History of The Development of Low Dosage Hydrate Inhibitors

VOLUME 20, NUMBER 3 MAY/JUNE 2006
© Copyright 2006 American Chemical Society
ReViews
History of the Development of Low Dosage Hydrate Inhibitors
Malcolm A. Kelland*
Department of Mathematics and Natural Sciences, Faculty of Science and Technology,
UniVersity of StaVanger, 4036 StaVanger, Norway
ReceiVed December 21, 2005. ReVised Manuscript ReceiVed March 2, 2006
Low dosage hydrate inhibitors (LDHIs) are a recent and alternative technology to thermodynamic inhibitors
for preventing gas hydrates from plugging oil and gas production wells and pipelines. LDHIs are divided into
two main categories, kinetic inhibitors (KHIs) and anti-agglomerants (AAs), both of which are successfully
being used in field applications. This paper reviews the research and development of LDHIs with emphasis on
the chemical structures that have been designed and tested. The mechanisms of both KHIs and AAs are also
discussed.
Introduction
Gas hydrates are ice-like clathrate solids that are formed from
water and small hydrocarbons at elevated pressures and at lower
temperatures (Figure 1).1 The temperature below which hydrates
can form increases with increasing pressure and can sometimes
be as high as 30 °C. Gas hydrates are a problem to the oil and
gas industry as they can block flow lines, valves, wellheads,
and pipelines, causing loss of production. Low dosage hydrate
inhibitors (LDHIs) have been researched and developed over
the past 15 years as an alternative method to control gas
Figure 1. Two commonest clathrate hydrates, structure I (McMullan
hydrates. They are now established tools for the prevention of and Jeffrey, 1965) (left) and structure II (Mak and McMullan, 1965)
gas hydrate plugging of oil and gas pipelines and gas wells. A (right).
wide range of OPEX savings, possible extended field lifetime
and multi-million dollar CAPEX savings, are economic drivers previously unpublished work from RF-Rogaland Research (RF,
for choosing LDHIs instead of other hydrate prevention now International Research Institute of Stavanger, IRIS). Some
methods.2 qualitative theory regarding the mechanism of LDHIs is also
This paper documents the chemistry and history of the provided.
development of LDHIs. It is written from a somewhat Norwe- Due to the confidential nature of much of the research, very
gian perspective, where the author is based, and includes few research papers on the chemistry of LDHIs have been
published in the public domain. Consequently, this paper has
* Telephone: +47 51 83 18 23. Fax: +47 51831750. E-mail: made extensive use of the patent literature. In particular, patent
malcolm.kelland@uis.no. applications (and not just awarded patents) give a good
(1) Sloan E. D. Clathrate Hydrates of Natural Gases, 2nd ed.; Marcel indication of what each research group was working on at the
Dekker: New York, 1998. time. To give a full flavor of the chemistries investigated, both
(2) Frostman, L. M.; Thieu, V.; Crosby, D. L.; Downs, H. H. In
Proceedings of the SPE International Symposium on Oilfield Chemistry, successful and unsuccessful attempts to commercialize LDHIs
Houston, TX, February 5-8, 2003; SPE 80269. are described.
10.1021/ef050427x CCC: $33.50 © 2006 American Chemical Society
Published on Web 04/01/2006
826 Energy & Fuels, Vol. 20, No. 3, 2006 ReViews
crystal.3,4 THF forms structure II hydrate, the same structure

that is usually formed by natural gas hydrates. A second
apparatus is the ball-stop rig or rocker rig. These are small cells
or test tubes that are placed in a cooling bath within which a
metal ball rocks back and forth. When the balls stop moving,
the cell has plugged with hydrates. The time to hydrate
formation (induction time) is determined as the time when the
liquid goes cloudy and/or as the time when gas consumption
due to hydrate formation is observed. Both THF hydrate5,76 and
natural gas hydrate6,76 can be made in such ball-stop cells. The
rocker rig using natural gas hydrate is a simple but excellent
test equipment for AAs. A third commonly used apparatus is
(3) Makogon, T. Y.; Larsen, R.; Knight, C. A.; Sloan, E. D. J. Crystal

Growth 1997, 179, 258-262.
(4) Zeng, H.; Wi, L. D.; Walker, V. K.; Ripmeester, L. A. In Proceedings
Figure 2. Pressure-temperature graph for a typical natural gas hydrate. of the 4th International Conference on Natural Gas Hydrates, Yokohama,
Japan, May 19-23, 2002.
(5) Jussaume, L.; Canselier, J. P.; Montfort, J. P. In Proceedings of the
Before we delve into the history, it will help to explain a AICHE Spring National Meeting, Houston, TX, March 14-18, 1999.
few terms and types of equipment that are used in the research (6) Deaton, W. M.; Frost, E. M. Oil Gas J. 1937, 36 (1), 75.
stages. The term LDHI was coined in the mid 1990s to (7) Arjmandi, M.; Ren, S.-R.; Yang, J.; Tohidi, B. In Proceedings of
differentiate these inhibitors from the more well-known ther- the 4th International Conference on Natural Gas Hydrates, Yokohama,
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usually dosed at a concentration of ca. 0.1-1.0 wt % (active Hellsten, M. In Proceedings of the SPE International Symposium on Oilfield
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ReViews Energy & Fuels, Vol. 20, No. 3, 2006 827
the high-pressure stirred cell or autoclave.7 The cell is placed windows for visual observations or may be entirely made of
in a cooling bath, and the pressure, temperature, and sometimes sapphire. Recently, mini-autoclaves have been developed for
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2004/042190, 2004. Petroleum Society’s Canadian International Petroleum Conference, Calgary,
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(150) Talley, L. D. Nucleation Workshop; Ecole Nationale Superior de C.; Arjmandi, M.; Danesh, A.; Ren, S. R.; Todd, A.; Tohidi, B.; Storr, M.
Mines: St. Etienne, France, June 2003. T.; Jussaume, L.; Montfort, J.-P.; Rodger, P. M. Chemistry in the Oil
(151) Glenat, P.; Peytavy, J. L.; Jones, N. H.; Grainger, M. In Proceed- Industry, Symposium VIII, Manchester, England, 2003.
ings of SPE Middle East Conference, Abu Dhabi, U.A.E, 2004; SPE 88751 (189) Dahlmann, U.; Feustel, M.; Holtrup, F.; Jestel, M.; Fuss, R.-W.;
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Technology Conference, Marseille, France, November 19-21, 2003. 03/087532, 2003.
(154) Mehta, A. P. Shell Global Solutions, personal communication, (191) Kelland, M. A.; Iversen, J. E. Unpublished results.
2005. (192) Makogon, T.; Sloan, E. D. In Proceedings of the 4th International
(155) Petrie, M. Clariant, personal communication, 2005. Conference on Gas Hydrates, Yokohama, Japan, 2002; pp 498-563.
(156) Swanson, T. A.; Petrie, M.; Sifferman, T. R. Flow Assurance (193) Frostman, L. M. In Proceedings of the SPE International Sympo-
Forum, Galveston, TX, 2004. sium on Oilfield Chemistry, Houston, February 13-16, 2001; SPE 65006.
high-pressure loops using natural gas, condensate, or oil and worked, but it is the first recorded example of using a low
an aqueous phase. They can range from the mini-loop (e.g., dosage of a chemical to prevent hydrate plugging.
1/4 in. i.d.) to the full scale pilot loop of 4 in. i.d. or more.13,76 We have to go forward to the mid 1980s before any further
A disadvantage is that in some cases the pump can crush work on LDHIs took place. Conoco patented the use of scale
hydrates making AA experiments difficult to interpret. inhibitors as gas hydrate inhibitors.15 They cited an example
using a fairly high concentration of scale inhibitor to prevent
Early History of the Development of LDHIs gas hydrate in the gas well. The use of scale inhibitors at these
concentrations is uneconomical for pipeline use, and no further
The history of LDHIs actually begins in the early 1970s with work was reported.
a Russian engineer called Kuliev, who was well before his In 1987, IFP (The French Petroleum Institute) filed a series
time.14 He was experiencing gas hydrate problems in his gas of patent applications on using surfactants as LDHIs.16-19 They
wells. He decided to try adding commercial surfactants to the listed a wide range of surfactants and basically claimed all
top part of the wells and discovered that the hydrate problem surface-active chemicals as hydrate inhibitors. This last claim
went away. It is unclear from his paper how the surfactants was to cause some concern to oil companies developing or using
LDHIs and not wishing to be dependent on IFP’s patent. It was
(194) Crosby, D. Baker Petrolite, personal communication, 2005. not clear from IFP’s patents which surfactants they were
(195) Boyne, K.; Horn, M.; Bertrane, D.; Fournie, F.; Cooper, T.; Quinn,
P.; Coudeville, F.; Buchan, D.; Allan, K.; Arnott, S. In Proceedings of the
focusing on or the mechanism for their ability to prevent hydrate
Offshore Europe Conference, Aberdeen, UK, September 2-5 2003; SPE agglomeration. Later, it became apparent that the surfactants
83975. were producing a special kind of water-in-oil emulsion. (The
(196) Panchalingham, V.; Rudel, M. G.; Bodnar, S. H. U.S. Patent surfactant dosage was ca. 0.8 wt % based on the water phase.)
Application 20050081714, 2005.
(197) Panchalingham, V.; Rudel, M. G.; Bodnar, S. H. U.S. Patent This emulsion confined hydrates to form within the water
Application 20050081432, 2005. droplets, and the hydrates never agglomerated. The end product
(198) Panchalingham, V.; Rudel, M. G.; Bodnar, S. H. U.S. Patent was a slurry of hydrate particles in a hydrocarbon phase. This
Application 20050085396, 2005.
(199) Panchalingham, V.; Rudel, M. G.; Bodnar, S. H. U.S. Patent we shall call the IFP AA mechanism. IFP calls their AAs
Application 20050085675, 2005. dispersant additives. Examples of surfactants in IFP’s patents
(200) Panchalingham, V.; Rudel, M. G.; Bodnar, S. H. U.S. Patent include diethanolamides, dioctylsulfosuccinates, sorbitans, ethox-
Application 20050085676, 2005. ylated polyols, ethoxylated fatty acids, and ethoxylated amines.
(201) Maximilian, A.; Neubecker, K.; Sanner, A. U.S. patent 6867262,
2005. They also gave examples of polymeric surfactants based on
(202) Dalhlmann, U.; Feustel, M. U.S. Patent Application 20050101495. polyalkenyl succinic anhydride. The products in the examples
(203) Moon, C.; Taylor, P. C.; Rodger, P. M. J. Am. Chem. Soc. 2003, in their patents showed only weak KHI effects.
125, 4706.
(204) Høiland, S.; Askvik, K. M.; Fotland, P.; Alagic, E.; Barth, T.; Also, in the late 1980s the Colorado School of Mines (CSM)
Fadnes, F. J. Colloid. Interface Sci. 2005, 287, 217. was carrying out research on gas hydrates. CSM noticed that
(205) Karaaslan, U.; Parlaktuna, M. Energy Fuels 2002, 16, 1387. some materials catalyzed hydrate formation at low dosages and
(206) Zanota, M. L.; Dicharry, M.; Graciaa, A. Energy Fuels 2005, 19,
584. were encouraged by their consortium members to look for
(207) Angel, M.; Stein, S.; Neubecker, K. U.S. Patent 6878788, 2005. materials that would have the opposite effect. This initiated a
(208) Ohtake, M.; Yamamoto, Y.; Kawamura, T.; Wakisaka, A.; de long program on searching for kinetic hydrate inhibitors. CSM
Souza, W. F.; de Freitas, A. M. V. J. Phys. Chem. 2005, 109, 16879.
(209) Pakulski, M.; Qu. Q.; Pearcy, R. SPE International Symposium constructed a THF hydrate ball-stop rig and began screening a
on Oilfield Chemistry, The Woodlands, TX, February 2-4, 2005; SPE vast range of commercial products.
92971. One other initiative on LDHIs began in the late 1980s in
(210) Szymczak, S.; Sanders, K.; Pakulski, M.; Higgins, T. SPE Annual
Technical Conference and Exhibition, Dallas, October 9-12, 2005; SPE Norway within the state-funded PROFF research program. The
96418. program included two projects on gas hydrates. The first, carried
(211) Dong Lee, J.; Englezos, P. In 5th International Conference on Gas out at SINTEF, studied the consistency of hydrates under
Hydrates, Trondheim, Norway, June 13-16, 2005; p 44.
(212) Zeng, H.; Brown, A.; Wathen, B.; Ripmeester, J. A.; Walker, V. flowing conditions. They observed that at low water conversion
K. In 5th International Conference on Gas Hydrates, Trondheim, Norway, the hydrates were sticky and liable to agglomerate and deposit
June 13-16, 2005; p 1. on the pipe walls. However, at high water conversion the
(213) Hawtin, R. W.; Moon, C.; Rodger, P. M. In 5th International
Conference on Gas Hydrates, Trondheim, Norway, June 13-16, 2005; p
hydrates were a nonsticky powder that appeared to be transport-
118. able in the hydrocarbon phase. Thus if a chemical could be
(214) Grainger, N.; Hawtin, R.; Moon, C.; Rodger, P. M.; Rogers, S. In found to prevent the hydrates from agglomerating during the
5th International Conference on Gas Hydrates, Trondheim, Norway, June early stages of water conversion, it should be possible to produce
13-16, 2005; p 317.
(215) Arla, D.; Dicharry, C, Graciaa, A.; Hurtevent, C.; Jussaume, L.; a transportable slurry of hydrates.
Peytavy, J. L.; Sinquin, A. In 5th International Conference on Gas Hydrates, The second gas hydrate project in the PROFF program was
Trondheim, Norway, June 13-16, 2005; p 322.
(216) Vebenstad, A.; Larsen, R.; Straume, E.; Argo, C. B.; Fung, G. In
carried out at RF. RF began screening additives in high-pressure
5th International Conference on Gas Hydrates, Trondheim, Norway, June cells to observe any inhibiting effects. The best product from
13-16, 2005; p 1193. RF’s studies was a quaternary corrosion inhibitor from Black-
(217) Camargo, R. M. T.; Concalves, M. A. L.; Montesami, J. R. T.; smith, which showed some positive AA effect, but the work
Cardoso, C.; Minami, K. Offshore Technology Conference, Houston, 2004;
OTC 16687. was not taken further. In 1991, at the end of the PROFF
(218) Palermo, T.; Mussomeci, A.; LePorcher, E. Offshore Technology program, Esso Norge (now ExxonMobil Norge) began sponsor-
Conference, Houston, 2004; OTC 16681. ing RF on a 3-year program to develop LDHIs. The results were
(219) Arjmandi, M.; Ren, S. R.; Tohidi, B. In 5th International
Conference on Gas Hydrates, Trondheim, Norway, June 13-16, 2005; p to be fed into Exxon’s own internal program on LDHIs at Exxon
1178. Production Research (EPR, now ExxonMobil Upstream Re-
(220) Clark, L. W.; Anderson, J. In 5th International Conference on Gas search Company) in Houston. Meanwhile, Shell and BP were
Hydrates, Trondheim, Norway, June 13-16, 2005; p 1249. also putting together their own programs for developing LDHIs.
(221) Oskarsson, H.; Uneback, I.; Navarrete, R. C.; Hellsten, M.; Lund,
A.; Hjarbo, K. W. In 5th International Conference on Gas Hydrates, Thus, at the beginning of the 1990s, three institutes and three
Trondheim, Norway, June 13-16, 2005; p 1283. oil companies were involved in the search for LDHIs.
Figure 3. Structure of poly(vinylpyrrolidone).

Figure 6. Structures of polyethylacrylamide, polyvinyl-N-methyl
acetamide, and polyethyloxazoline.
Shell’s Research and the Discovery of Quaternary Sur-

factant AAs. In the early 1990s, Shell became aware of certain
fish, such as the winter flounder, which contained anti-freeze
proteins and glycoproteins (AFPs and AFGPs).25,26 These AFPs
and AFGPs prevent ice crystals from forming in the fish by
Figure 4. Monomer units in the terpolymer Gaffix VC-713. binding to the surface of ice nuclei. This allows the fish to
survive in sub-zero temperatures. It occurred to Shell that
artificial AFPs and AFGPs might bind to the surface of gas
hydrate nuclei. The AFPs and AFGPs themselves were found
to be expensive and fairly poor KHIs, but a screening of
perceived “protein-like” water-soluble polymeric amides led
Shell to independently (although somewhat later than CSM)
Figure 5. Structure of polyvinylcaprolactam. discover PVP. Shell tested PVP and a polymer called Antaron
P-904 or Agrimer P-904 (butylated PVP) in its own laboratories.
Early 1990s
They discovered that the butylated PVP performed better than
Discovery of PVP and PVCap at CSM. The first break- PVP. They patented the results in 1992 but later reassigned the
through in KHI technology came at CSM in 1991. In their ball- rights to CSM.27
stop rig tests they came across a polymer, poly(vinylpyrrolidone) After studying AFPs and PVPs, and based on the results of
(PVP), which delayed the formation and the agglomeration of a field trial in Michigan and in the Groningen field in which
THF hydrates (Figure 3).20,21 PVP failed to prevent hydrate formation, Shell realized that
The apparent AA effect of PVP as noted by CSM does not kinetic inhibitors would not give them the high subcooling
transfer to real hydrocarbon systems, which plug rapidly once performance they desired for their oncoming deepwater projects.
a certain amount of gas hydrate is formed, but the KHI effect They calculated using standard nucleation theory that you could
does. They also found that hydroxyethylcellulose (HEC) not stop hydrates nucleating indefinitely at subcoolings above
performed moderately in the ball-stop rig, but PVP was better. 10 °C.28 Since Shell was mostly interested in deepwater
PVP is the five-ring member of the series of polyvinyllactams, applications with high subcoolings, they concentrated on
which have two main suppliers, ISP and BASF. Nippon developing AAs. The first useful class of AAs they came across
Shokubai also manufactures PVP. CSM kept to this series and were the alkylarylsulfonates.29 (Interestingly, these surfactants
tested a hair-care product from ISP called Gaffix VC-713 a were chosen among others by Kuliev back in the early 1970s.)
terpolymer, which contains a high proportion of the seven-ring However, it was found that their performance was mediocre,
monomer, vinylcaprolactam (VCap) as well as vinyl pyrrolidone so Shell moved on to other products.
(VP) and dimethylaminoethyl methacrylate (DMAEMA) (Figure The next class of products that was patented by Shell were
4). alkyl glucosides.30 The multi-hydroxyl headgroup was envisaged
This polymer outperformed PVP in the ball-stop test. CSM to bond to water molecules on the hydrate surface. However,
then set up a collaboration agreement with ISP to develop better after further testing, it appeared that these surfactants gave very
KHIs. Realizing that VCap was the key monomer in Gaffix limited AA performance, and Shell moved on to what was to
VC-713, CSM tested the homopolymer polyvinylcaprolactan be a major breakthrough.
(PVCap) (Figure 5). Shell reasoned that quaternary ammonium surfactants would
PVCap gave a similar performance to Gaffix VC-713 and be ideal candidates as AAs as they are known to be good particle
became a standard by which other KHIs would be compared. dispersants. Shell was also aware of the work on quateranry
This early high molecular weight version of PVCap (or Gaffix ammonium and phosphonium salt clathrates as reported by
VC-713) gave 24 h hydrate nucleation delays up to a subcooling Jeffrey.230 In particular, they noticed that tetrabutylammonium
of 8-9 °C at a dosage of 0.5 wt %. The results from CSM’s bromide (TBAB) and tetrapentylammonium bromide (TPAB)
work were patented22,23 and communicated to their consortium
members, who began to test the polyvinyllactams in their own (222) Zeng, H.; Walker, V. K.; Ripmeester, J. A. In 5th International
laboratories. CSM also discovered that other polymers could Conference on Gas Hydrates, Trondheim, Norway, June 13-16, 2005; p
act as synergists increasing the performance of the polyvinyl- 1295.
lactams, particularly PVCap.24 In their patent applications in (223) Pakulski, M.; Hurd, D. In 5th International Conference on Gas
Hydrates, Trondheim, Norway, Norway, June 13-16, 2005; p 1444.
1994, they claimed polyelectrolytes, polyether block copolymers, (224) Cowie, L.; Bollavaram, P.; Erdogmus, M.; Johnson, T.; Shero, W.
polyvinylamides, polyalkylacrylamides, and polyalkyloxazolines Offshore Technology Conference, 2005; OTC 17328.
as synergists for polyvinyllactams. The examples included (225) Pakulski, M.; Dawson, J. C. U.S. Patent Application, 2004/
0231848, 2004.
polyethylacrylamide, poly(N-methyl-N-vinyl acetamide), and (226) Pakulski, M.; Dawson, J. C. U.S. Patent 6756345, 2004.
polyethyloxazoline (Figure 6). (227) Kvamme, B.; Huseby, G.; Førrisdahl, O. K. Mol. Phys. 1997, 90
Each of these polymers was shown to be a hydrate growth (6), 979.
inhibition synergist for PVCap. In the patent application, the (228) Lee, J. D.; Englezos, P. Chem. Eng. Sci. 2005, 60, 5323.
(229) Lee, J. D.; Englezos, P. Chem. Eng. Sci. 2006, 61, 1368.
amide polymers were claimed to have C1-4 alkyl groups, (230) Jeffrey, J. Inclusion Compounds, Vol. 1; Academic Press: New
although no examples were given with C3-4 alkyl groups. York, 1984; pp 159-190.
polyvinyllactam KHIs. They were also collaborating with Shell

in the mid 1990s and had access to their quaternary AA
technology. They combined a polyvinyllactam with small
quaternaries such as tetrabutylammonium bromide (TBAB) and
Figure 7. Structure of good quaternary ammonium or phosphonium found they gave a synergistic KHI effect.36 (Actually, Shell had
hydrate growth inhibitors, where M ) N or P and at least two of the
included blends of Gaffix VC-713 and tetrapentylammonium
R groups are n-butyl, n-pentyl, or isopentyl.
bromide (TPAB) in their AA patent but was not so interested
in the KHI effect.) BP called their blends “threshold hydrate
inhibitors”, but perhaps since the acronym THI could be
confused with thermodynamic hydrate inhibitors, it did not catch
on. BP patented the results along with blends with other
production chemicals.37,38 BP had their sights set on using their
synergistic KHI blends on their Southern North Sea gas fields
Figure 8. Structure of Shell’s quaternary AAs (R1 ) long chain where the subcooling was less than 10 °C and ideal for KHIs.
hydrocarbon tail; R2 ) n-butyl, n-pentyl, or isopentyl; M ) N or P; X
BP was also thinking ahead to a planned field in the ETAP
is an optional spacer group).
province where the subcooling was about 6-8 °C. BP licensed
their KHI technology to TR Oil Services (TROS, now Clariant
had clathrate hydrate structures with the 51264 cage, the same
Oilfield Services), who were used to bring the technology to
cage found in structure II gas hydrate. They tested a large range
the field. TROS built their own pressure cells based on BP’s
of quaternary salts and found that salts with two or more n-butyl,
design and worked on finding the optimum blends for BP’s
n-pentyl, and isopentyl groups were the best at delaying the
fields.
growth of THF hydrate crystals (Figure 7).
Shell’s next inspiration was to replace one or two of the small BP also initiated molecular modeling studies of PVP on gas
alkyl groups with a long hydrophobic tail (8-18 carbon atoms). hydrate surfaces at the University of Reading, U.K.39 The results
These materials are not anti-nucleators, so they are poor KHIs. show that the pyrrolidone ring bonded to the structure I hydrate
In fact, some of these small quaternary ammonium and also surface via hydrogen bonding to the amide and van der Waals
phosphonium salts can promote hydrate nucleation by being interaction between the ring and the hydrate surface. At that
templates. Shell called these chemicals “hydrate growth inhibi- time, no studies were carried out showing interactions with or
tors” (HGIs). These quaternary surfactants salts with two or three penetration of structure II cavities.
n-butyl, n-pentyl, and isopentyl groups performed extremely well It is thought that TPAB (or TBAB) works synergistically with
as hydrate AAs (Figure 8). Shell patented their results at the PVCap because of their different geometries. Thus, TPAB and
end of 1993.31 PVCap should attach to different sites on the hydrate crystal
The mechanism for Shell’s quaternary AAs is not the same surface. So what is happening at the molecular level with TPAB?
as that for IFP’s water-in-oil emulsifying AAs. Shell’s AAs are Molecular modeling carried out at the University of Reading
designed with a hydrate-philic (hydrate seeking) headgroup and for RF in the mid 1990s shows that TPAB penetrates a 51264
a hydrophobic tail. Being surfactants, the AAs will accumulate cavity on the 1,1,1 structure II hydrate surface. Two of the other
at the water-oil interface, where hydrate formation first occurs. pentyl groups lay in channels on the hydrate surface where new
The hydrate-philic headgroup, which is the quaternary center, 51264 cages would normally be formed. It therefore seems
will bind to hydrate particles. The butyl/pentyl groups penetrate possible that these cages could partially form, trapping or
open 51264 cavities on the hydrate surface and can even become imbedding the pentyl groups in the hydrate surface. Below the
embedded in the surface as the hydrate grows around the alkyl critical nuclear size, growth of the nuclei is energetically
groups. The long hydrophobic tail prevents the hydrate from unfavorable (∆G is positive). So, TPAB will not be embedded
continuing to grow on that surface. The hydrophobic tail also in the surface of the nuclei but will more easily detach. Above
makes the surface more attractive to the hydrocarbon phase. the critical nuclear size, TPAB can become embedded in the
Once several AA molecules have attached to the surface, the hydrate surface as partial hydrate cages form around the pentyl
particle is easily dispersed in the hydrocarbon phase. The groups, but further structure II growth is prevented by the
quaternary AA will also be attracted to the pipe walls (also remaining pentyl groups.
indicated by the fact that some of these AAs are very effective The embedding mechanism for the quaternary salts explains
corrosion inhibitors). The hydrophobic tails will then help why tetrapropylammonium bromide (TPrAB) and tetrahexyl-
prevent hydrate from growing or adhering to the pipe walls. ammonimum bromide (THAB) are poor hydrate growth inhibi-
All in all, the Shell AAs are well-designed molecules for their tors. TPrAB has an even weaker van der Waals interaction with
task, and it seemed like Shell was on to a winner, perhaps even cavities and channels on the hydrate surface than TBAB. TPrAB
the silver bullet. Shell divided up the development work. Shell will more easily detach from the surface even if some water
Houston was to develop the more water-soluble single-tailed molecules start to build cavities at the ends of the propyl groups
quaternary AAs, while Shell Amsterdam was to optimize the (i.e., it is less quickly embedded in the surface). On the other
more oil-soluble twin-tailed quaternary AAs. hand, THAB has alkyl groups that are too long to give strong
BP’s Research. BP’s own work on LDHIs began with the van der Waals interactions with more than one cavity on the
study of amino acids. Tyrosines and related chemicals gave surface and will therefore detach easily. In fact, THAB cannot
some weak KHI effect, and the results were patented.32 BP also easily get embedded in the surface of structure I or II hydrate.
patented various blends containing vinyl polymers such as PVP RF-Rogaland Research (RF) Projects for Esso/Exxon (now
and synergists.33-35 The synergists included corrosion inhibitors, ExxonMobil) and Elf (now Total). Back at the beginning of
amino alcohols, amino carbohydrates, lactones, amino acids, the 1990s, RF began their research program with Essso Norge
hydroxyacids, and glycol ethers. Some of the patent applications and Exxon Production Research (now ExxonMobil Upstream
were later withdrawn in favor of better KHIs. BP was a member Research Company, EMURC). RF carried on from where they
of the CSM consortium and therefore had access to the left off in the PROFF project by looking for a better AA than
Figure 9. Structure of poly-L-proline. Figure 10. Structure of N-methyl-N-vinylacetamide:vinyl caprolactam

1:1 copolymer (VIMA:VCap) where a ) b.
the Blacksmith corrosion inhibitor. Tests were carried out on a
condensate with 20% water cut in stirred sapphire cells. The
cell was cooled from 20 to 4 °C over 2 h at a pressure of ca. 90
bar at 700 rpm stirring rate. RF tested a range of surfactants
with varying headgroups, ionicity, and tail-lengths. Some
surfactants with multiple hydroxyl or carboxylic acid headgroups
were prepared in-house hoping to find hydrate-philic surfactants. Figure 11. Structures of polyacryloylpyrrolidine, polydiethylacryla-
Positive results were obtained with some neutral and cationic mide, and polyisopropylacrylamide.
surfactants, but only at low subcooling. (An n-butylpolyglycol
from Witco gave a slower growth of hydrates but was not
identified as a synergist for KHI polymers at the time). RF had
the right idea for making AAs, but not the right hydrate-philic
headgroups such as those found by Shell.
In their work on looking for surfactant AAs, RF observed Figure 12. Structures of polyethylmaleimide, ring-opened polyeth-
that products with a high degree of propoxylation gave beneficial yloxazoline, and ring-closed polyethyloxazoline.
effects. This initiated a study of over 30 polypropoxylated
products. Polypropoxylates are interesting molecules. They are performance with structure I hydrates relates to the higher
not as hydrophilic as polyethoxylates, which tend to surround symmetry of structure I hydrate crystals. On a suggestion from
themselves with water molecules, neither are they like alkyl- Exxon to test VCap copolymers, RF synthesized and tested
chains, which tend to partition in nonpolar solvents. Because N-methyl-N-vinylacetamide:VCap 1:1 copolymer (VIMA:VCap
of this amphiphilic behavior, polypropoxylates often end up at 1:1) (Figure 10). This copolymer performed better than PVCap
the interface between the aqueous and nonpolar phase. This by 2-3 °C subcooling in a sapphire cell test. Exxon, who had
makes them useful as defoamers and demulsifiers. commissioned the work at RF and owned the results, synthesized
The best AA was an amine polyalkoxylate having a molecular similar copolymers in their own laboratories. Tests in Exxon’s
weight of approximately 6000. This product gave excellent mini-loop confirmed RF’s findings, subsequently Exxon and a
dispersion of hydrates in the hydrocarbon phase at subcoolings researcher at RF jointly patented the copolymer as a KHI in
below ca. 10-13 °C at 700 rpm stirring. It is interesting to 1995.44
observe that BJ Unichem patented related polyether/polyamines RF synthesized and tested other VCap copolymers such as
as LDHIs in the late 1990s and that Akzo Nobel patented VCap:vinyl imidazole. This also gave good performance, but
polyalkoxylated amines in the new millennium. the work was not taken further. The last polymer of note that
RF carried out two smaller projects on LDHIs for Elf (now RF tested was a ring-opened polyethyloxazoline, which contains
Total) in the early 1990s.40-42 The first project looked at natural ethylamide groups in the repeating unit. Although the perfor-
and biodegradable surfactants as potential AAs. The best product mance in the THF hydrate ball-stop rig was only moderate,
was Plantaren 600 CPUS, an alkyl glucoside from Henkel. This interestingly it belonged to a different class of KHIs than the
product worked well at moderate subcooling at 0.5 wt %. It is vinyl lactam polymers.
interesting that Shell patented similar surfactants as AAs called LDHIs from Exxon Production Research (EPR). Esso
alkyl glycosides. The second project tested various water-in- Norge and Exxon Production Research (EPR, now EMURC)
oil emulsions made with commercial monomeric surfactants. discontinued their support of RF’s work at the end of 1994 and
No good results were obtained, indicating that compounds that decided to continue the work on their own. Exxon had deduced
are effective in creating water-in-oil emulsions do not necessarily that a key element in many KHI polymers was the presence of
show good AA performance. an amide group attached to a hydrophobic group in the repeating
Returning to the Exxon/Esso program, RF moved away from unit. Exxon had their own theory for KHIs which involved
studying AA surfactants and looked more at water-soluble maximizing the hydration volume of the polymer in water. The
polymers as potential KHIs. The first class of polymers that hydrophobic group would form hydrate cavities around it while
gave results were polyamino acids, which are related to fish- the carbonyl oxygen atom of the amide group would form
anti-freeze proteins. The best results were obtained with poly- hydrogen bonds with water molecules. Several of these interac-
L-proline (Figure 9). This polymer gave a subcooling of only a tions would be needed; hence, a polymer or oligomer was
few degrees Celcius, but its structural relationship to PVP was required. The inhibitor could thus interrupt nucleation of
the most important feature. Both poly-L-proline and PVP hydrates in the water phase. Exxon used molecular modeling
contained a five-member ring and an amide group in the to deduce the best inhibitor structures. Their theory is somewhat
repeating unit. related to that of other modelers.45-47,213,214,227
During RF’s work for Exxon/Esso, RF did indeed discover Exxon filed patents on a number of classes of polymer-
PVP as a KHI giving about 5 °C subcooling and shortly containing amide groups. These included polyalkylacrylamides48
thereafter PVCap, which gave about 8-9 °C subcooling.43 These (Figure 11), polydialkylacrylamides48 (Figure 11), polyvinyl-
discoveries were made independently of, but later than those amides,49 polyallylamides,50 polymaleimides51 (Figure 12),
of CSM and Shell (PVP only). RF showed that PVCap gave a polymers of cycliciminoethers52 such as polyacylalkyleneimines
lower subcooling performance with structure I methane hydrates and polyalkyloxazolines (ring-opened and ring-closed) (Figure
as compared to structure II natural gas hydrates.80 A reduced 12), and amides or esters of N-acyldehydroalanine.53 The best
that the butyrate groups in the VIMA:vinyl butyrate copolymer

contribute to the inhibition performance since it is known that
polyVIMA is a fairly poor KHI. As a hydrate crystal growth
inhibitor, the propyl part of the butyrate group may be interacting
with open large cavities on the structure II hydrate surface. It
remains unclear whether the ester groups as well as the amide
group in the VIMA units form hydrogen bonds with the hydrate
Figure 13. Polyisobutylacrylamide. surface. It is probable that both do, but hydrogen bonding with
the ester group is probably weaker than with the amide. We
can deduce this since polyvinyl esters are not water-soluble (low
hydrophilicity), but polyvinylamides are water-soluble. (For
example, polyvinyl acetate is not water-soluble at room tem-
perature, but polyvinylacetamide is. Again, polyethylacrylate
is not water-soluble but polyethylacrylamide is.) In fact, the
reduced hydrophilicity of VIMA:vinylbutyrate polymer probably
Figure 14. Polyisopropylmethacrylamide.
contributes to the increased KHI performance relative to
polyVIMA. This is because, compared to polyVIMA, the
copolymer will favor interactions with the hydrate surface more
than with free water. Several research groups believe that the
hydrophilicity of a polymer (measured as its cloud point) is
related to its performance as a KHI, but no systematic study
has been published. In addition, no group has studied water-
soluble vinyl ester copolymers as KHIs. Exxon did carry out a
Figure 15. Structure of polyisopropylmethacrylamide:N-vinyl-N-
study that concluded that cloud point is not a sufficient condition
methyl acetamide copolymer (VIMA:iPMA).
for increasing KHI performance.111 Cloud point can be adjusted
by total carbon in the monomer or by salinity of the solution.
KHI performance was obtained with the acrylamide polymers,
Exxon found there was no change in rank order of subcooling
probably because the optimum size alkyl group was not used
for various structures when salinity greater than seawater was
for the other classes of polymer. (For example, it is difficult to
scanned. Increasing carbon in the monomer only resulted in an
synthesize N-vinyl amides with the wide variety of alkyl groups
that is possible for acrylamides.) The best acrylamide ho- insoluble polymer that cannot inhibit hydrates. Exxon concluded
mopolymer was polyacryloylpyrrolidene (polyAP) followed by that the exact positioning of carbon in a monomer or polymer
polydiethylacrylamide and then polyisopropylacrylamide (poly- is more important than the cloud point. This is the point of their
iPAm). methylated backbone patent where a carbon on the backbone
was more effective than another carbon in the pendant amide
Polyisobutylacrylamide was not tested because it is insoluble
in water (Figure 13). (In 1996, RF tested some copolymers of group.
isobutylacrylamide with VIMA and VP with KHI performance Exxon obtained one of the polyalkyloxazolines from Nippon
results similar to polyisopropylacrylamide.) Shokubai in Japan (NS). After discussions with Exxon, NS
Exxon found that the addition of a methyl group to the became interested in LDHIs and built their own THF hydrate
backbone of the acrylamide polymers increased their perfor- ball-stop rig. NS synthesized polyAP and found that it gave a
mance. For example, the subcooling performance of polyiso- very good performance in their rig. They patented the results
propylmethacrylamide (Figure 14) was found to be approxi- in Japan in 1994,56 not knowing that Exxon had already done
mately 2 °C greater than that of polyisopropylacrylamide. that a few weeks before. NS and RF remained unaware of this
Exxon patented this idea of adding a small alkyl group to until 1996. NS also filed a patent application on alkyl acrylate:
the backbone of a KHI polymer to increase its performance.54 VP copolymers.57 They found, for example, that butyl acrylate:
The only polyvinylamide to be tested by EPR was polyVIMA, VP gave increased KHI performance as compared to PVP. The
which was found to be a poor KHI. However, copolymers of argument for its increased performance is identical to that given
VIMA with other alkylamide polymers gave surprisingly high above for VIMA:vinyl butyrate copolymer tested by Exxon (i.e.,
subcoolings, very much like what RF had seen with the VIMA: a higher “hydrate-philicity” of the copolymer as compared to
VCap copolymer. For example, compared to polyiPMAM,55 a PVP and interaction of the butyl ester group with the hydrate
1:1 VIMA:iPMA copolymer (Figure 15) gave a 4.2 °C higher surface).
subcooling. For this copolymer, Exxon reported an actual Exxon applied for two further patents in 1994 and 1995. The
subcooling of 17.5 °C. However, it should be noted that a first patent covered surfactants with a hydrophobic tail of 12
subcooling of 4 °C was obtained by a test with no additives, carbons or less as AAs,59 while the second patent covered their
and Exxon’s test method is different from that of others. use as synergists with KHI polymers.60 Examples given included
Other interesting results were obtained with ring-closed butyl sulfate, sodium valerate, zwitterionics such as butyldi-
oxazoline polymers. These represent the first class of polymers methylammonium butylene sulfonate, and N-dodecylpyrroli-
that do not contain amide groups and still show substantial KHI done. On their own, these products gave reasonable performance
(anti-nucleation) performance. in the THF hydrate ball-stop rig. When combined with alkyl-
Exxon also found that a VIMA:vinyl butyrate copolymer gave amide polymer KHIs, they gave good synergistic results. This
a surprisingly high performance both as an anti-nucleator in can be explained by their function as hydrate growth inhibitors.
the high-pressure mini-loop and as a hydrate crystal growth The butyl group or pyrrolidone group can interact with open
inhibitor with THF hydrates. The mini-loop performance was 51264 cavities on the hydrate surface. RF confirmed that butyl
better than PVCap, polyiPMAM, and polyAP. (At that time none sulfate is indeed a hydrate growth inhibitor, although weaker
of the polymers were optimized for molecular weight.) It is clear than TBAB, in the single-crystal THF hydrate growth test.
Exxon conducted two mini-loop AA tests on butyl sulfate. At synergy with some other polymer classes. CSM carried out a
0.25 wt % no effect was observed, but at 0.5 wt % the blocking range of studies on PVCap, PVP, and VP:VCap copolymers
temperature of the loop was over 13 °C below the equilibrium supplied by ISP and BASF.75 They showed for example that
temperature. RF tested butyl sulfate as an AA in their sapphire laboratory autoclave experiments could be correlated with
cells but obtained very poor results. It seems that these small experiments in a pilot loop, in this case EPR’s loop.76,239 They
surfactants are best used as synergists for KHI polymers. also showed that the performance of PVCap was negatively
IFP and Emulsion AAs. The last institute to be mentioned impacted by methanol and a low concentration of salt.77,238
in the early 1990s is IFP. IFP continued to patent classes of Higher salt concentrations (> 5.5 wt %) were actually beneficial
AAs in the early 1990s.61-67 It was difficult to tell what to the performance of PVCap. In addition, CSM carried out
chemistry they were focusing on, but IFP had begun to narrow studies on the dependence of the performance of PVCap on
their choice of dispersants to just a few products by 1994. It molecular weight.78 CSM found that the highest subcooling
seemed from their patent application that they were concentrat- performance was obtained with a PVCap having a molecular
ing on polymeric emulsifiers such as polyglycol derivatives of weight of 900. Samples of PVCap were made at the University
polyalkenylsuccinic anhydride. Early conference talks in Sta- of Akron in Ohio. The University only measured the number
vanger, Norway, in 1992 described the use of 0.5-2.0 wt % average molecular weight, not the weight average molecular
dispersant additives.68 IFP later gave a talk at a seminar in weight, which is the more common figure to quote. It is therefore
Trondheim, Norway, in 1994 where they showed successful difficult to say how many monomer units are in CSM’s low
results of an AA at 0.8 wt %.69 In addition, Norsk Hydro tested molecular weight PVCap polymers. Even so, at these low
IFP’s products in autoclaves and got promising results using a molecular weights, it is probably best to use the term oligomer
dosage of 2.0 wt %. rather than polymer.
CSM also carried out extensive studies on THF hydrates
Mid 1990s giving structure II and ethylene oxide hydrate giving structure
I.79 They confirmed RF’s findings80 with gas hydrates that
At the beginning of the 1990s, LDHI technology was just a PVCap gave a lower subcooling performance on structure I
good research idea with a lot of potential. By the mid 1990s, hydrate as compared to structure II hydrate at the same dosage.
many of the classes of LDHIs used today had been discovered, In addition, work carried out at CSM on the growth of single
although there was plenty more chemistry yet to come. The THF hydrate crystals showed that stirred solutions needed a
service companies and several chemical companies began to lower dosage of KHI to totally inhibit crystal growth as
get actively involved in designing and formulating LDHIs compared to static solutions. This has implications in pipelines
hoping to get a slice of the market that was opening up. By during shut-in situations. The dosage necessary to inhibit
1995 Shell, BP, and Exxon had decided on their strategies for hydrates will be higher in a shut-in than under flowing
developing their LDHIs. Shell had their quaternary surfactant conditions. This is because polymer diffusion to the hydrate
AAs (“quat AAs”), which gave high subcoolings, BP had settled surface is slower under static conditions. This also implies that
for KHI blends that gave moderate subcooling, and Exxon had a low molecular weight polymer with high mobility will perform
a range of KHIs that could give a fairly high subcooling in their better than a larger polymer.
mini-loop. ISP and BASF. CSM’s agreement with ISP was not
First KHI Field Trials. The polyvinyllactams discovered by satisfactory for ISP, who wanted better control of the market
CSM were beginning to reach the market via the chemical for their KHI polymers. Consequently, ISP ended their col-
suppliers, ISP and BASF, and the service companies. One laboration with CSM and built their own autoclave equipment.
service company even advertised PVP under a new brand name In this way, ISP could test any new polymers synthesized in
as an effective KHI at 50 ppm at the exhibition hall of the SPE their laboratories and patent any new LDHI inventions. The first
Technical Conference in 1994. It remained to be seen who patent that ISP filed concerned the use of small alcohols and
would be first to try out these new LDHIs in the field. Who glycol ethers with a tail of 3-5 carbon atoms as synergists for
would dare risk using these new products with no track record? vinyl caprolactam polymers.81 The main synergist example was
The first pioneers to report their field trials were Arco,70 butyl glycol ether (BGE). BGE was not only a good synergist
Texaco,71 and BP.72 Arco was the first to go offshore in 1995 for polymers such a PVCap, it could also be used as the solvent.
with a KHI when they tested Gaffix VC-713 on a Southern This patent application was a problem to ISP’s competitor
North Sea gas field. The trials showed that 0.5 wt % of polymer BASF. At the time BASF had been using small alcohols and
could handle 8-9 °C of subcooling. Texaco tested PVP in glycol ethers in the manufacture of VCap polymers. Now BASF
Wyoming and Texas showing it is useful at limited subcooling was forced to find other solvents. In the end, BASF ended up
only. BP carried out six field trials on another Southern North
Sea gas field (Ravensburn-Cleeton) in 1995-1996 using their (231) Crosby, D. L.; Rivers, G. T.; Frostman, L. M. U.S. Patent
KHI blends formulated by TR Oil Services (now Clariant). The Application 2005/0261529, 2005.
(232) Kelland, M. A.; Svartaas, T. M.; Øvsthus, J.; Tomita, T.; Mizuta,
KHI blends were based on mixtures of TBAB and VCap K. Chem. Eng. Sci. Submitted for publication.
polymers. (Besides being a synergist, TBAB has the additional (233) Kelland, M. A.; Svartaas, T. M.; Øvsthus, J.; Tomita, T.; Chosa,
beneficial effect of increasing the cloud point of the VCap J. Chem. Eng. Sci. Submitted for publication.
(234) Arjmandi, M.; Tohidi, B.; Danesh, A.; Todd, A. C. Chem. Eng.
polymer). In addition, TBAB is roughly half the price of PVCap. Sci. 2005, 60, 1313.
The field trials were successful up to the maximum subcooling (235) Koh, C. A.; Westacott, R. E.; Zhang, W.; Hirachand, K.; Creek,
of 10 °C. This success led BP to switch from glycol to KHI on J. L.; Soper A. K. Fluid Phase Equilib. 2002, 192, 4, 143.
(236) Koh, C. A.; Wisbey, R. P.; Wu, X. P.; Westacott, R. E.; Soper A.
their West Sole/Hyde, 69 km wet gas pipeline in 1996 where K. J. Chem. Phys. 2000, 113, 6390.
the subcooling was a maximum of 8 °C.73,74 This became the (237) Kvamme, B.; Kuznetsova, T.; Aasoldsen, K. J. Mol. Graphics
first offshore field application of a KHI and, in fact, any LDHI. Modell. 2005, 23, 524.
CSM’s Consortium. CSM continued to screen potential (238) Sloan, E. D.; Subramanian, S.; Matthews, P. N.; Lederhos, J. P.;
Khokhar, A. A. Ind. Eng. Chem. Res. 1998, 37, 3124.
LDHIs up until the mid 1990s, but they did not make any further (239) Lederhos, J. P.; Sloan, E. D. In SPE Annual Technical Conference
KHI discoveries besides that of the polyvinyl lactams and their and Exhibition, October 5-9, 1996, Denver; SPE 36588.
using ethylene glycol and water as solvents for their products.

ISP applied for several further patent applications in the late
1990s, which will be discussed later.
In contrast to ISP, their competitor in vinyl lactam polymers,
BASF, took a less active stance in trying to capture the market
for their KHI polymers. During the mid 1990s they did not test
their own polymers as LDHIs, nor did they file patent applica- Figure 16. Structure of modified AMPS polymers where R1 is an alkyl
tions for any of their own products. (BASF did patent vinyl tail of 1-6 carbon atoms and R2 is H or Me.
formamide copolymers with more hydrophobic monomers, but
the performance of them appears to be poor.82) Instead, BASF of this modified AMPS monomer with VCap gave even better
relied on synthesising polymers at the request of any customer performance. However, it does not appear that ExxonMobil has
using their extensive experience in polymer chemistry, which sought to commercialize this technology.
went beyond the polyvinyllactams. Later BASF began to be Shell’s Quaternary AAs. While the first KHI field trials were
more active in testing and patenting their own discoveries. taking place, Shell was preparing the first generation of the
ExxonMobil Research. Exxon (now ExxonMobil) ap- quaternary AAs. The Shell U.S. team was responsible for the
proached BASF because they wanted to commercialize the development of the single-tail quaternary AA. The preferred
VIMA:VCap copolymer that had been patented in 1995. BASF molecules in their patents contained a hydrophobic tail of 10-
made samples of VIMA:VCap, which ExxonMobil tested in 14 carbon atoms, a tributylammonium or tripentylammonium
their loops. When ExxonMobil was convinced of the improved headgroup, and a counterion. (A tripentylammonium headgroup
performance of VIMA:VCap copolymer, they signed a license would give a better hydrate growth inhibitor, but the precursor
agreement with Nalco Exxon Energy Chemicals (now Nalco) tripentylamine is roughly twice the price of tributylamine.) This
to commercialize the technology. ExxonMobil began using KHIs quaternary AA performed extremely well coping with subcool-
in the field from 1996.83,84 ExxonMobil and Nalco reported ings of 20+ °C in systems containing saline (> 1.5 wt % salt)
several field applications in 1999-2001 including the first water. However, the AA did not perform so well in freshwater.
deepwater application of an LDHI.85,86 Royalties from the use This may be due to the strength of the ion pairing in an aqueous
of VIMA:VCap copolymer were paid by Nalco to ExxonMobil phase of low ionicity. Second, the concentration needed for
and CSM because the copolymer contained VCap monomer. optimum performance was fairly high at 0.6-1.0 wt % actives.
Sales of the copolymer were low until a North Sea application Baker Petrolite was given a worldwide license to commercialize
greatly increased the volume. Today however, VIMA:VCap is the technology. They spent the mid and late 1990s building their
no longer commercially available due to the difficulty in own LDHI test equipment and getting up to speed on testing
obtaining the VIMA monomer and its high price. In the mid procedures.
1990s Clariant was the only manufacturer of VIMA monomer, Shell and Baker Petrolite’s biggest hurdle in getting the single-
which was used for making cheese wrap. Nalco bought a tail water-soluble quaternary AA to the field was its environ-
quantity of this monomer from Clariant to make VIMA:VCap mental impact. Quaternary surfactants are known to be toxic,
copolymer, but they have not bought anymore since then. BASF and the quaternary AA was no exception. Added to that, the
and ISP have both been approached by Nalco to make further majority of the quaternary AA partitioned into the aqueous phase
quantities of VIMA:VCap copolymer, but it seems that neither and would therefore be discharged into the sea (although the
company has delivered this product. single-tail quaternary AA is seen to phase separate in a warm
The other class of polymer that ExxonMobil wanted to oil-water separator containing high salinity produced water.
commercialize was based on alkylacrylamides. They had used Therefore in such cases very little of it may be discharged in
a proprietary theory to deduce that isopropylmethacrylamide the overboard water). Second, being a tetraalkyl quaternary AA,
(IPMA) polymer was the most potent KHI of the alkylacryl- it had low biodegradability. This meant that the toxic molecule
amides. Since it performed better than isopropylacrylamide would survive in the sea for a considerable time and could
polymer, ExxonMobil deduced that adding a methyl group to possibly bioaccumulate. The environmental impact of the
the backbone was beneficial. The same benefit was found for quaternary AA made Baker Petrolite initially unsure about its
other polymer classes such as polyvinyloxazolines. ExxonMobil commercial viability. Being a new molecule, it had to go through
patented the idea of adding a methyl group to the backbone to pre-market notification, and Baker Petrolite was unsure whether
increase polymer performance.54 this was worth the trouble. But eventually the green light was
ExxonMobil’s theory, that led them to the conclusion that given to go ahead with its manufacture and commercialization.
the IPMA polymer is the most effective alkylacrylamide However, no field trials were reported in the 1990s, indicating
polymer, is proprietary. The theory has to do with maximizing that field implementation was a fairly long process.
the hydration volume of the polymer in order to perturb the The development of the twin-tailed quaternary AA was the
nucleation of hydrates. Clearly IPMA and VCap polymers must responsibility of the Dutch Shell team. They enlisted the help
be perturbing water molecules around the side chain functional of a neighboring chemical company, Akzo Nobel, to make their
groups at some distance so that they are unavailable for forming AAs. The first prototype molecules were based on tetraalkyl-
hydrate clusters, thereby preventing hydrate nucleation. They ammonium salts with two tails such as dicocoyldibutylammo-
exploited this idea in a new patent application on modified nium bromide.88 This quaternary AA performed well up to a
AMPS (acrylamidopropylsulfonic acid) polymers. (Figure 16).87 subcooling of ca. 14 °C in Shell’s flow loop in several
PolyAMPS is a poor KHI, but ExxonMobil found that the hydrocarbon fluids at 0.25 wt %. In contrast to the single-tail
addition of a hydrophobic tail between the amide and the quaternary AAs, it also worked in freshwater systems. The
sulfonic acid group increased the performance of the polymer. biggest drawback with the tetraalkylammonium salts was their
The optimum size of the tail was 5 carbon atoms long. A environmental impact. These quaternary AAs gave almost zero
homopolymer of this monomer gave a performance in Exxon- biodegradation in standard OECD (Organization for Economic
Mobil’s mini-loop, similar to PVCap. Moreover, copolymers Cooperation and Development) tests. Added to that they were
toxic and even more bioaccumulative than the single-tail

quaternary AAs. Akzo Nobel went back to the laboratory and
synthesized diester quaternary AAs instead. These were diesters
Figure 17. Example of a polyetherdiamine.
of dibutyldiethanolammonium halides and 2 mol of a long-chain
alkyl carboxylic acid. These products biodegraded ca. 50% in IFP and Project EUCHARIS. Another JIP that started in
28 days. The ester groups degrade within 5 days, leaving a small, the mid 1990s centered on the technology and facilities at IFP.
less surface active, and less toxic quaternary ammonium salt. The project was called EUCHARIS and was supported by six
The optimum chain length for the carboxylic acid appeared to oil companies and the HSE Department of the U.K. The main
be coconut fatty acids with 12-14 carbon atoms. This cocoyl aim of the project was to be a springboard for IFPs emulsion
diester quaternary AA performed well up to subcooling of 15 AA technology. After almost a decade of laboratory research,
°C in the tests described by Shell in their patent. The product IFP had narrowed down the choice of AA candidates to just a
performed equally well in freshwater as in saline water. The few products, largely polymeric surfactants. One of them called
concentration necessary was only 0.25 wt % based on the Emulfip 102b made by FINA (now Total) was the preferred
aqueous phase. In addition, this diester quaternary AA parti- product. Emulfip 102b is a 50% solution of polymerized fatty
tioned ca. 95% into the liquid hydrocarbon phase. This meant acids and amides in rapeseed oil. Although no environmental
that the active concentration in the bulk water phase was only data was published, this product was expected to be considerably
approximately 125 ppm. This seems surprisingly low for such greener than Shells quaternary AAs. To test Emulfip 102b
a powerful product. However, the concentration of the AA at further, IFP used their newly completed pilot-scale flow-loop.
the liquid hydrocarbon/water interface, where hydrate formation The product was tested at two concentrations and a range of
first takes place, is undoubtedly a lot higher. Akzo Nobel conditions.91 At 0.4 wt % the results were poor, but at 0.8 wt
formulated the cocoyl diester quaternary AA as a 33% solution % the tests were much more successful. Fine slurries of
in a hydrocarbon solvent. This was made available to the service transportable hydrates were formed up to the maximum sub-
companies for commercialization. cooling of 13 °C. There were, however, a couple of drawbacks
to the emulsion AA technology. First, the water phase had to
One oil company interested in Shell’s quaternary AAs was
be thoroughly emulsified before entering hydrate-forming
Statoil. Statoil had been collaborating with the Dutch Shell team conditions, otherwise hydrate agglomeration and deposition is
in the mid 1990s testing Shell’s/Akzo Nobel’s twin-tail qua- likely. Could this be guaranteed in the field? Second, hydrates
ternary AAs in their wheel-loops. Statoil was impressed by their formed from condensed water on the upper walls of the pipe
performance and went ahead with a field trial on their Tom- during laminar flow or during shut down. Nevertheless the JIP
meliten field in 1995. Only a few details have been published committee recommended IFP to go ahead with field trials, which
on the field trial, the results of which do not appear to have took place in the late 1990s.
dampened Statoil’s enthusiasm for using the quaternary AAs.89 IFP also carried out studies on KHIs for the first time. They
In fact, Statoil wanted to use the twin-tail quaternary AA on a tested a BP KHI blend commercialized by TROS (now Clariant
new field development called Kvitebjørn. The most economical Oilfield Services) in their pilot loop. They also filed two patent
solution was a tie-back using multiphase transportation. The applications on new KHIs.92,94 The first patent application
subcooling for hydrate formation was calculated to be under claimed polymers with at least one sulfonate group. The best
15 °C and ideal for the twin-tail quaternary AA. Statoil asked examples were acrylamide:AMPS copolymers.93 But these gave
TROS (now Clariant Oilfield Services) to make an application only moderate performance, no better than PVP. The second
to the Norwegian environmental authorities (SFT) to use the patent application claimed polymers with at least one nitrogen
diester quaternary AA on the Kvitebjørn field.90 Unfortunately, containing monomer such as the dimethylaminomethylacrylate
the SFT turned down TROS and Statoil’s application. It seems monomer. These gave a similar fairly weak performance as the
that the reason given was that the diester quaternary AA was sulfonated copolymers.
insufficiently biodegradable. The SFT did not like the fact that BJ Unichem and Gas Well AAs. The only service company
the degraded product, dibutyldiethanolammonium bromide, did to be actively involved in inventing LDHIs in the 1990s was
not degrade any further in a 28 day OECD test even though BJ Unichem Chemical Services. A one-man effort has seen new
this degraded product was far less toxic. TROS submitted further products taken through from laboratory research all the way to
data to show that the degraded quaternary does degrade several field applications. The laboratory test rig used was a 1
eventually in a 70 day test, but it was to no avail, the SFT stood mm i.d., 64 m long flowline. The liquid phase was THF in 3.6%
by their decision. This meant that Statoil had to cancel their brine, and the flow rate was slow at less than 1 mm/s. BJ
plans for developing the Kvitebjørn field since no alternative Unichem found that polyetherpolyamines and polyetherdiamines
economical solution could be found. The field still remains (particularly of the oxypropylene type) lowered the blocking
undeveloped to this day. But the failure to get the twin-tail temperature or gave a longer time to blocking than a test with
quaternary AA accepted for use on the Kvitebjørn field had no additives.95,96 Examples were taken from the Jeffamine range
wider repercussion. It meant that no quaternary AAs, single- by Huntsman Corporation (Figure 17) and Ethoduomeen by
or twin-tail would ever be allowed in Norwegian waters. Statoil Akzo Nobel.
then began to look elsewhere for alternative LDHI technology. BJ Unichem also patented quaternized polyetherpolyamines
They joined the CSM consortium as a late participant hoping by reaction of polyamines with a long-chain alkyl bromide.97
to find a high-performing KHI. They also joined a new industry These products performed better in the THF hydrate flowline
project (JIP), which started at RF in April 1995. They also than PVCap, TBAB, and several Shell-type quaternary AAs.
carried out a field trial on BP’s PVCap/TBAB KHI technology At least four field applications have been reported in gas wells
commercialized by TROS (now Clariant).89 The field trial lasted both offshore and one onshore.98-101 One report included details
only 3 h as the subcooling at 9 °C was just outside the of an autoclave test in which the polyetherpolyamine was a good
performance limit of the KHI at 0.5 wt %. Meanwhile, the Dutch synergist for PVCap. The same product dispersed gas hydrates
Shell team had to look elsewhere for field trials of their diester in the remaining unconverted water. Use of the polyetheramines
quaternary AA. in completion and fracturing fluids has also been patented.226
It is difficult to know how to categorize BJ’s products or

indeed understand the mechanism for their action. (See also
results in the early 1990s by RF on propylene glycols.) They
are clearly not KHIs, as BJ’s autoclave tests on polyether-
polyamines gave zero induction time. (However, a later paper
does show significant anti-nucleation effect for some poly- Figure 18. Structure of polyallyl isopentanamide.
etheramines, as well as good synergy with a polymeric KHI223.)
Neither are they true AAs because they have not been proven
to work at full water conversion with a liquid hydrocarbon
phase. In both the laboratory studies and the field applications,
gas hydrates that form are being dispersed in unconVerted water
(or water plus a minor % of hydrocarbon phase). Therefore,
when used alone it is probably best to call these products gas
well AAs (GWAAs) in order to distinguish them from true AAs, Figure 19. Structures of VP:isobutylacrylamide and VIMA:isobuty-
which work in pipelines with a hydrocarbon phase at full water lacrylamide copolymers.
conversion. They are also synergists for KHI polymers such as
PVCap.225 Regarding their mechanism as synergists, the poly-
etherpolyamine may be interacting with cavities on the hydrate
surface via the amine headgroups. The polyether chain may
interact weakly with the hydrate surface or just act as a barrier
to prevent the hydrate nuclei from growing. Many small amines Figure 20. Structure of VP:butyl acrylate copolymer.
are known to form clathrate hydrates. This includes ethylamine,
which is the same size as the ethyleneamine groups on the ends
of the polyetherpolyamines.
RF JIP: KI Studies. When Exxon dropped out of supporting
RF’s studies at the end of 1994, this left RF briefly without
any LDHI work. However, by April 1995, RF had launched its
own JIP. The JIP was supported by seven oil companies, TR
Oilfield Services (now Clariant Oilfield Services), Hoechst (now Figure 21. Structures of polypyrrolidinyl aspartate (polyAS) and
Clariant), and the Norwegian Research Council (NFR). The aim polyglyoxylpyrrolidine (polyGP).
of the project was to design better LDHIs (both KHI and AA)
alkylamide a greater degree of rotational freedom as compared
than were previously available. RF’s approach was to use
to polyvinyl amides. This means polyallylamides will lose this
molecular modeling and a good deal of intuition to design
rotational freedom (entropy) on binding two hydrate surfaces
improved products. The modeling work was carried out at the
making the process less favorable than with polyvinylamides.
University of Reading. The goal was to find functional groups
The next class of polymers with alkylamide groups that RF
that would interact strongly with structure II hydrate surfaces.102
investigated were polyalkylacrylamides. Polyisopropylacryla-
These functional groups could then be placed into water-soluble
mides (polyiPA), synthesized in house, performed better than
polymers to make KHIs and into surfactants to make AAs.
polyethylacrylamides but a little worse than Gaffix VC-713.
Functional groups investigated by modeling included alkyla-
Polyisobutylacrylamide (polyiBA) was also synthesized but
mides, lactams and many other heterocyclic groups, amine
found to be water-insoluble. Therefore, 1:1 copolymers of iBA
oxides, quaternary ammonium salts, and betaines. The alkyl
with VIMA and VP were prepared with cloud points of 30 °C
amides with the strongest structure II hydrate interactions were
(Figure 19). Both these copolymers performed somewhat better
found to contain alkyl groups with 3-4 carbon atoms. Moreover,
than polyiPA and similar to Gaffix VC-713. No further
the interaction was strongest when the alkyl group was branched
polyalkylacrylamides were synthesized in house as RF began
(i.e., isopropyl and isobutyl).
to be supplied with this class of polymer by Nippon Shokubai
To confirm the modeling results, RF sought to make KHI Company Ltd. of Japan (NS).
polymers containing optimum alkylamide groups. They em- NS had independently discovered polyacryloylpyrrolidine
ployed the University of Oslo to make vinyl alkyl amide (polyAP) as a KHI and had patented the result in 1995.56 RF
polymers. The University succeeded in making N-vinyl-N-propyl later became a co-owner of the patent along with a second patent
propanamide, but this monomer refused to polymerize, even on VP:alkyl acrylates, which performed better than PVP, (e.g.,
with comonomers such as VP. Clariant also tried to make VP:butyl acrylate copolymer) (Figure 20).57
polyvinylalkylamides. They synthesized N-vinyl-N-isobutyl ac- Besides polyAP, the first patent also included other polymers
etamide, but this also refused to polymerize. with carbonyl pyrrolidine groups in the side chains (e.g..
Stumped by the lack of access to polyvinylamides, RF looked polypyrrolidinyl aspartate (polyAS) and polyglyoxyl pyrrolidine
for other polymers containing alkylamide groups. Polyallyla- (polyGP)) (Figure 21). Bayer later patented polyaspartate and
mides with pendant alkyl groups of 1-5 carbon atoms were related polymers with succinyl units.58
made available to RF by Nitto Boseki of Japan. The most RF tested NS’s polyAP and found it to be an excellent KHI,
effective KHI in this class was polyallyl isopentanamide, with superior to Gaffix VC-713. (PolyGP performed equally as well
a pendant isobutyl on the amide (Figure 18). This result was in as polyAP and polyAS a little less so.) Extensive work was
agreement with the modeling studies. The performance was carried out optimizing polyAP. The optimum molecular weight
significantly less than Gaffix VC-713 for two reasons. First, (Mw) for best performance was found to be 1000-3000. This
the degree of amidation of the original polyallylamine was only represents only eight monomers in the chain of the shortest
40%. Second, the alkylamide groups are separated from the polymers (oligomers). Only one copolymer, AP:VCap copoly-
polyvinyl backbone by methylene spacer groups. This gives the mer, was found that performed better than polyAP. The best of
Figure 23. Structure of one of Clariant’s synergists for maleic

anhydride copolymers.
Figure 22. Structure of the active monomer unit in amidated maleic
anhydride copolymers. R+ is H+, a metal ion or a quaternary ammonium mance. RF patented the results in 1997. Unknown to RF at the
ion. The isobutyl group can be exchanged with isopropyl. time, Clariant, who had heard RFs initial results at a JIP meeting,
had patented a modification of RF’s technology. Clariant had
the other AP copolymers was 1:1 AP:acrylamide copolymer. noted that RF’s maleic copolymers had low cloud points, a
AP:VIMA copolymers were not investigated, although Exxon- feature, which at the time was thought to be a disadvantage.
Mobil’s results with methacryloylpyrrolidine:VIMA (MAP: Clariant’s idea was to substitute some of the alkylamine for a
VIMA) copolymers suggest they could outperform polyAP. diamine in the amidation process. For example, reaction of a
Molecular modeling of AP monomer indicated that it 80:20 blend of isobutylamine:dimethylaminopropylamine with
interacted strongly with the deep holes on the (1,1,1) structure a maleic anhydride:vinyl acetate copolymer gave a useful KHI
II hydrate surface. VCap did not interact well with the surface, with a high cloud point. The pendant dimethylamino groups
and VP interacted in a different way to AP. This suggested to help solubilize the copolymer in water to higher temperatures.
RF that PVCap and PVP might be synergists for polyAP. This The performance of the copolymer is a little less than a polymer
was confirmed through laboratory experiments. The best amidated with isobutylamine alone but is still useful to a
synergistic blend that was formulated was a 4:1:1 triple blend subcooling of approximately 8 °C at 5000 ppm (this is without
of polyAP (Mw ) 5000):PVCap (Mw ) 19000):Antaron P904 added synergists). RF and Clariant decided to combine their
(Mw ) 16000). A 6000 ppm solution of this triple blend two patents at a later stage.105,106 Clariant continued to carry
prevented hydrates from forming for at least 17 h at 16 °C out studies on amidated maleic anhydride copolymers with the
subcooling in autoclave and wheel tests. The conditions were German Petroleum Institute at Clausthal. Clariant also developed
90 bar and 2 °C while the fluids were 3.6% synthetic seawater, synergists for these polymers, which have been patented
Exxol D60, and a natural gas blend (C1-C4, CO2, and N2). separately.107 These consist of small, surfactant-like molecules
By this time, RF and NS were aware that ExxonMobil had with alkylamide headgroups (Figure 23). The technology has
beaten them to the patent office for polyAP and other poly- been successfully field trialled and is now commercially
alkylacrylamides. Therefore, RF and NS took out a joint patent available through Clariant Oilfield Services.
on their synergistic blend technology hoping that ExxonMobil Clariant. Clariant filed three further patent applications
would give them a license to commercialize them.103 Two during their time in the RF JIP. The first application claimed
hurdles got in the way of commercializing polyAP and the use of amphiphilic polymers as KHIs.108 The polymers
synergistic blends. First, ExxonMobil would not give RF and contained equal amounts of cationic and ionic monomers. Initial
NS a license before having tested the technology themselves. results were obtained through the JIP and used in the patent
Second, it was discovered that pyrrolidine, the starting material application. RF later tested Clariants polymers as KHIs but
for making polyAP, was prohibitively expensive (ca. 12 euro/ obtained poor performance. Sometime later Clariant withdrew
kg). Therefore, NS and RF decided to switch strategies and its patent application.
concentrate on polyiPA, which was expected to be cheaper to The second patent application claimed the use of isobutyl
manufacture than PVCap. PVCap was found to be a synergist glycol ether (iBGE) as a synergist solvent for KHI polymers.109
for polyiPA but not to the same degree as for polyAP. The best Clariant noted that ISP had already patented small alcohols and
synergistic blend was found to be a 2:1 blend of 90/10 iPA/ glycol ethers as synergists for their VCap polymers. ISP’s
AMPS:PVCap. A 6000 ppm solution of this blend delayed preferred synergist was n-butyl glycol ether (BGE), a com-
hydrates for over 1 day, including a 6 h shut-in at 12 °C mercial product. Clariant found that iBGE was a better synergist
subcooling in autoclave and wheel tests.104 A sample of this for the amidated maleic copolymers than BGE. Presumably, the
blend was sent to ExxonMobil for testing. A similar subcooling isobutyl group interacts better with hydrate cavities than the
was obtained in loop tests as RF had found in the autoclave n-butyl, which fits with RF’s observations on alkylamides.
and wheel tests. ExxonMobil’s prior licensing agreements However, iBGE did not become a commercial product, and the
precluded a license to NS and RF. Not being able to com- patent application lapsed. It seems that the marginal performance
mercialize AP or iPA polymers, NS decided to synthesize new improvement of iBGE over BGE was outweighed by the cost
classes of surfactant AAs that RF would test. This chapter in of commercializing a new solvent in limited quantities.
the history of LDHIs is discussed later in the section entitled The third patent application from Clariant appeared to hold
“The Late 1990s”. a lot of promise.110 At that time, 1996, Clariant was selling
In mid-1996, RF discovered a new class of KHIs based on PVCap/TBAB blends to BP through their daughter company
amidation of maleic anhydride copolymers. Maleic anhydride TROS (now also called Clariant Oilfield Services). Neither
does not easily polymerize by itself but does so with a variety PVCap or TBAB were manufactured by Clariant, who were
of vinylic comonomers giving regular ABAB copolymers. keen to sell their own chemicals. In talks between RF and
Reaction of these copolymers with alkylamines (cyclic imines) Clariant the idea arose of using amine oxides as a substitute
opens the anhydride ring to give two different neighboring side for TBAB. TBAB, TPAB, and tributyl phosphine oxide were
chains: first, an alkylamide group and, second, a carboxylic all known to form clathrate hydrates, so it was assumed that
acid or carboxylate group (Figure 22). tributylamine oxide (TBAO) and tripentylamine oxides (TPAO)
RF made a series of amidated copolymers using various would do the same. Clariant synthesized these amine oxides
amines. They found that isobutylamine gave a copolymer with by simple oxidation of the corresponding trialkylamines.
marginally better performance than a copolymer made using RF found that TBAO performed at least as well as TBAB in
isopropylamine. Copolymers made from n-propylamine, n- inhibiting the growth of single crystals of THF hydrates. TPAO
butylamine, and tetrahydrofurfurylamine gave poorer perfor- performed even better but was not studied further since the cost
of tripentylamine was rather high and would make the price of

TPAO uneconomic. TBAO proved to be an excellent synergist
for VCap polymers. Optimized blends produced some of the
most powerful KHIs tested at RF in the 1990s, superseded only
by the best polyAP triple blends. However, TBAO did not
Figure 24. Structure of dodecyl-2-(2-caprolactamyl) ethanamide.
become a commercial product, and the patent application on
amine oxides was withdrawn. The problem was its poor
of them being a Span sorbitan surfactant that prevented
biodegradability. At less than 20% in a 28 day OECD test,
agglomeration at 2 wt % concentration at up to 11.5 °C
TBAO was no better than TBAB and therefore offered no
subcooling. The synthetic surfactants were designed to contain
advantage to the best available technology at the time.
headgroups found in KHIs. The caprolactam ring was an obvious
Due to the high performance of TBAO, RF was convinced
choice, as it was known from CMS’s studies to attach to hydrate
that there was more mileage in amine oxide products. In
crystal surfaces. The best AAs were mono-tail surfactants
particular, they thought surfactants amine oxides would make
containing the caprolactam headgroup as well as polymeric
good AAs. These are discussed in the next section under “RF
surfactants based on vinyl caprolactam oligomer or N,N-
JIP: AA Studies”.
dialkylacrylamides with alkyl thioether end groups. The single
best product was dodecyl-2-(2-caprolactamyl) ethanamide (Fig-
Late 1990s ure 24) At 0.75 wt % this AA prevented hydrate agglomeration
In the late 1990s a few research groups were still actively at 11.5 °C subcooling including a 3-day shut-in/start-up test.
pursuing KHI technology, but it was becoming increasingly clear ISP KHI Patents. ISP filed a number of patent applications
that this was not going to be an economic solution for high on KHIs in the late 1990s. They were all based on VCap
subcooling conditions. Improvements in KHI technology were polymer technology. Three of the patent applications claimed
few and incremental, and no big breakthroughs occurred. Thus, very low molecular weight PVCap (i.e., PVCap oligomer).113-115
as far as LDHIs are concerned, deepwater applications were The lowest molecular weight PVCap oligomer that gave the
the domain of AAs only. Perhaps the only company that might best performance had a molecular weight (Mw) of 1500. This
justifiably argue with this conclusion is ExxonMobil. They had represents about 11 monomer units in the oligomer. Some of
produced experimental data from their mini-loop to suggest that the experimental work was carried out in collaboration with
KHIs could be used at 15+ °C subcooling. At 1 wt % their BP. The fourth and fifth patent applications claimed copolymers
best inhibitor VIMA:IPMA 1:1 low molecular weight copolymer of VCap with small amounts of dimethylaminoethylacrylate or
(oligomer) failed at a subcooling of 22-23 °C.111 The experi- N-(3-dimethylaminopropyl)methacrylamide.116 The function of
mental method is to slowly cool the mini-loop 1 °C at a time this comonomer in aiding KHI performance is not given, but it
until the line is blocked. With no additives, the line was blocked may be related to the comonomers’ ability to open out polymer
at a subcooling of 4 °C. It should also be added that ExxonMobil chains that might otherwise curl up on themselves in aqueous
has not used any synergists or synergist solvents in these solution. The sixth and seventh patent applications claimed the
experiments. It is difficult to say how long the induction time use of VCap:vinyl pyridine copolymers.117,118 The function of
is at any one subcooling at this high concentration as this the second monomer in one patent application was to give the
information is not available; but the data obtained is still copolymer KHI and corrosion inhibition properties. An eighth
impressive. patent application claimed the use of polyoxyalkylenediamines
ExxonMobil spent 3 years from 1998 to 2001 looking for as synergists for VCap polymers.119 This synergy was originally
manufacturers of their alkylacrylamide polymers. IPMA mono- discovered by BJ Unichem a couple of years earlier. Two further
mer was not commercial then and still is not today. ExxonMobil patents claimed a KHI synergist effect between VCap polymers
first looked for a manufacturer of VIMA:IPMA copolymer and an alcohol containing 3-5 carbon atoms and one hydroxy
rather than VIMA:IPMA oligomer and then finally IPMA group.120,121
homopolymer. Their sources told them that IPMA monomer KHIs for the Eastern Trough Area Project (ETAP). The
would cost 2-3 times the price of VCap monomer. Even at last report on KHIs in the late 1990s concerns their use on the
this high price ExxonMobil still believes they have an applica- BP-operated Eastern Trough Area Project (ETAP) in the British
tion for an IPMA polymer, and they wish to explore this avenue sector of the North Sea.122,123 ETAP consists of several fields
further. ExxonMobil finished their research program in 1998, tied back to a central processing unit. Plans for ETAP began in
and one or two patent applications are still to be released. the early 1990s, and production began in 1998. Fluids from two
CSM also carried out studies on KHIs into the late 1990s. In of the fields were expected to be operating 6-8 °C into the
particular, they showed that PVCap oligomer performed better hydrate region. Both fields were therefore ideal for using BP’s
than higher molecular weight PVCap.3 Samples were obtained KHI technology, which was being field-trialed in the Southern
from BASF and the University of Akron, Ohio. BASF’s PVCap North Sea Gas Basin. (Shell, who is a partner in ETAP, hoped
oligomer became a commercial product through the service to use their AA technology in one of the fields, but this never
company Nalco. Nalco now uses polymers supplied by ISP. materialized.) The use of KHI gave BP and their partners a
CSM Studies on AAs. CSM’s consortium members could CAPEX saving of 40 million U.S. dollars as compared to using
see that PVCap oligomer was not going to be good enough for methanol. The main cost saving was due to eliminating a
deepwater applications at higher subcooling. They therefore methanol regeneration plant and the platform space it required.
encouraged CSM to study AAs as the only LDHI alternative. TROS (now Clariant) who had the license for BP’s KHI were
CSM responded by setting up equipment and test procedures asked to formulate KHI products for ETAP. They had to
for studying AAs. They then tested a range of commercial overcome compatibility issues such as the combined use of
surfactants with different headgroups and HLB (hydrophilic corrosion and scale inhibitors. Injection of KHI began in 1998
lipophilic balance) values as well as about 70 new surfactant and the field has been operating smoothly since. The originally
AAs synthesized at the University of Akron, Ohio.112 None of KHIs were based on BP’s PVCap/TBAB synergists blend
the commercial surfactants performed particularly well, the best technology (A similar product was used by Elf, now Total, to
Petrolite had overcome any environmental hurdles for the Gulf

of Mexico (GoM) at least. Here the environmental law is not
so restrictive as it is for example in the North Sea. In the GoM,
it is the toxicity of the discharged water and its dilution that
are the critical factors. In the North Sea it is the toxicity,
biodegradability, and bioaccumulation of the injected chemicals
that are evaluated. On top of this, the British sector demands
20% biodegradability for new chemicals, something the single-
tail quaternary AA does not have but the twin-tail quaternary
AA does. The Norwegian sector normally demands 60+%
biodegradability on new chemicals, which rules out all LDHIs
commercialized to date.
Some news about the single-tail quaternary AA did filter
through on the grapevine. For example, Amoco (now BP) had
Figure 25. Early version of the twin-tail diester quaternary AA (A),
been testing it in their high-pressure autoclave and found it gave
improved version of the AA where R ) Me or Et (B), and a worse excellent results, especially in saline water.128 The single-tail
version of the AA with propylene spacer groups (C). quaternary AA was also tested as part of the Deep Star program
alongside other LDHIs. Deep Star was a series of deepwater
replace methanol in an onshore multiphase transport line124). technology projects funded by most of the major oil companies
The PVCap was supplied by BASF and amounted to ap- and managed by Texaco (now Chevron Texaco). Westport
proximately 100-120 ton per year. This made ETAP the biggest Technology (now Intertek Westport Technology Centre) un-
KHI application anywhere in the world. (The later RasGas KHI dertook the test program using a high-pressure autoclave. The
application in Qatar in the Middle East is of similar magnitude.) single-tail quaternary AA outperformed all the other LDHIs
In 2001 Clariant lost the contract to Nalco for topside chemical giving transportable hydrate slurries at 16+ °C subcooling. It
injection on ETAP. Nalco also used PVCap technology for their was clearly a product the oil companies wanted to see used in
KHIs, but they chose to source the polymer from BASF’s the field.
competitor ISP. This cut BASF’s sales of PVCap in half. DeepStar also began funding the reconstruction of an on-
(Clariant’s current biggest sale of KHI is for seasonal use of land pipeline in Wyoming for LDHI testing. Unfortunately, the
ca. 70 ton/year for a Middle East application.155) Thus we can budget got out of control and the project was never finished.
estimate that at the beginning of the new millennium sales of
IFP Patents and Field Trials on Emulfip 102b. As part of
PVCap-based polymers for KHI applications were ca. 300-
the EUCHARIS project, IFP carried out two field trials on their
500 ton per year.
emulsion AA, Emulfip 102b, in 1998-1999.129 The site was a
Oil-Soluble Twin-Tail Quaternary AA. Compared to KIs,
3 in., 2.5 km onshore pipeline as part of Total’s Canadon field
progress in getting AAs into full field applications was slow.
in southern Argentina. The pipe pressure was 40 bar, water cut
One of the main reasons was that all the AAs were new
20%, and the salinity 10 g/L. The subcooling in the first field
chemicals and had to go through manufacturing regulations
trial was a maximum of 10-12 °C. The AA was pumped in
beginning with Pre-Market Notification (PMN). The twin-tail
pulses rather than using continuous injection. IFP deemed the
quaternary AA also had to undergo a small but important
first field trials as a success. A downstream emulsion was
modification. The first version of the AA was made from
formed in the separator caused by Emulfip 102b, but this
N-butyl diethanolamine and had ethylene spacer groups between
problem was not addressed by IFP.
the ester groups and the quaternary nitrogen atom (Figure 25,
molecule A). Shell found that addition of a small alkyl branch A second field trial was carried out in June-July 1999 at
(methyl or ethyl) to the spacer group improved the performance Total’s Canadon field. The subcooling varied from 10 to 20 °C
of the AA (Figure 25, molecule B).125 Specifically, the depending on the time of the day. The product worked for a
performance of shut-in/start-up loop test with preformed hy- short time but then failed, resulting in the plugging of the line.
drates slurries were improved. A longer spacer group such as Two plugging mechanisms were proposed. First, accumulation
propylene (molecule C) gave a worse performance. The twin- of hydrate particles in the line, not necessarily at low points.
tail quaternary AA also contained a certain amount of unquat- Second, deposition of hydrate at the upper pipe walls from
ernized amine in the finished product from Akzo-Nobel. The condensed water. NB: The flow is stratified flow and Emulfip
amine actually improves the performance of the AA as well as 102b is not in the gas phase. This effect was seen in IFP’s loop
helping break emulsions. test, but being a loop the deposits did not build up.
Field trials on the oil-soluble twin-tail quaternary AA were Thus, it appears that Emulfip 102b was able to disperse the
carried out in Holland, Great Britain, and New Zealand from hydrates formed. The condensed water problem and slurry
the mid to late 1990s.126 A first field application was planned transportation difficulties may be overcome when the flow is
on a British North Sea gas/condensate field in the Sole Pit not stratified (higher liquid volumes and flow rates).
area.127 However, the produced water became so saline that a IFP filed several patent applications in the late 1990s on both
hydrate inhibitor was not required anymore. Shell had to wait KHIs and AAs.130-133 The first patent application claimed water-
a few more years for the first field application of the oil-soluble soluble polyoxyalkylene macromers and/or polymacromers
twin-tail quaternary AA. alone or in combination with known KHIs such as Gaffix VC-
Water-Soluble Single-Tail Quaternary AA. No data were 713 as KHIs. A second patent application claimed water-soluble
published in the open literature in the late 1990s by either Shell KHI polymers characterized by a specific number of rotational
or Baker Petrolite concerning progress with the water-soluble degrees of freedom and degree of polymerization. Examples
single-tail quaternary AA. The supplier Baker Petrolite was are polymers of propylene glycol alginate, poly(ethylene glycol)
undoubtedly going through the motions of getting the product monomethacrylate, and AMPs. A third patent application
ready for field trials, which began in 1999. It seemed that Baker claimed AAs based on mixtures of copolymers of polyisobu-
Figure 26. Structure of amine oxide surfactant AAs.
tylene succinate/poly(ethylene glycol) and alkyl (meth)acrylate: Figure 27. Structures of carbonylpyrrolidine and isopropylamide
VP copolymers. A fourth patent application claimed amphiphilic carboxylic acid surfactants tested by RF. R ) C8-14.
nonionic polymeric surfactants as AAs formed by reacting a
polymerized unsaturated oil and an amino alcohol (e.g., flax
oil and diethanolamine).
RF JIP: AA Studies. The RF JIP began searching for new
AAs as early as 1995. However, it was not until the late 1990s
that they concentrated their efforts on this class of LDHI. They
Figure 28. Structure of betaines tested by RF. R is a long alkyl chain
set a goal of finding an AA that at 0.5 wt % in 3.6% brine with various spacer groups.
would perform as well as Shell/Akzo Nobel’s oil-soluble
quaternary AA but was more environmentally friendly. This the Shell quaternary AAs, further work on the alkylamide
meant lower toxicity or higher biodegradability or both. surfactants was dropped and the patent application withdrawn.
Almost all the potential AAs were new surfactants synthesized The last AA idea RF investigated in their JIP was to take the
by various chemical companies under collaboration agreements. single-tail quaternary AA and place the anion in the molecule
A range of polymeric surfactants with pendant alkyl- and thereby making it zwitteronic.135,233 Nippon Shokubai made a
dialkylamide groups were tested, but they gave poor results. range of these betaine surfactants, which RF tested (Figure 28).
Better performance was obtained with monomeric surfactants. The results were fairly promising in cell and wheel tests, but
The first noteworthy AA was a triester quaternary ammonium the subcooling limit at 0.5 wt % was approximately 13 °C.
salt with one long tail made by Stepan Europe. It performed Clearly, the anion was best separated from the quaternary
well up to 10 °C subcooling and had >60% biodegradability. nitrogen atom. RF concluded that Shell’s original idea of using
However, the performance of this class could not be improved quaternary surfactant AAs with two or three butyl or pentyl
so RF looked elsewhere. groups in the head was still the best class of AAs discovered
The next class of surfactants that gave positive AA results yet.
were the cationic caprolactams. They contained a caprolactam Following this conclusion, RF did get a chemical company
head and a quaternary nitrogen spacer group. They worked well to make a new class of quaternary AA. They were only briefly
up to 10-11 °C subcooling but were toxic and were not tested with good results in RF cells before RF turned to other
investigated further. studies in the new millenium. Stavanger University is now
Tributylamine oxide had been shown by RF to be an excellent testing this promising class.
THF hydrate growth inhibitor on a par with TBAB. It was
therefore of great interest to investigate amine oxide surfactants
Into the New Millenium
as AAs. Commerical surfactants from Clariant with dimethyl-
amine oxide headgroups gave poor results. Better results were Polyesteramide LDHIs. By the end of the millennium, all
obtained with two surfactants synthesized by Clariant although three LDHI JIPs were coming to a close. CSM and RF had
neither had an optimum structure. The first surfactant was seen new KHIs brought to commercialization whereas IFP had
dodecylbutylmethylamine oxide (DDBMAO) (Figure 26). By still to see their AAs and KHIs reach full application. Exxon
having only one butyl group rather than two at the head, it was had shut down its R&D program and were no longer investigat-
not ideal. As expected it gave moderate results in the cell and ing new chemistry. So one may be excused for thinking that
wheel. The second surfactant is also shown in Figure 26 and after all this effort the best chemistry had been discovered.
has a diethylamine oxide headgroup. However, it also gave only However, Shell was still open for new LDHI ideas when they
moderate results in the cell and wheel. The surfactant also turned came across a new class of polymer marketed by the Dutch
out to be very toxic to skeletonema. For these reasons Clariant company, DSM, under the tradename Hybranes. Hybranes are
decided not to synthesize further amine oxide surfactants, and hyper-branched polyesteramides. Shell found that certain poly-
the patent application on amine oxide was dropped. More esteramides performed well as KHIs while others showed AA
recently, Stavanger University has synthesized the more desir- behavior. They patented the results in 2002.136 The basic
able surfactants with dibutylamine oxide headgroups. polyesteramides are fairly cheap to manufacture, cheaper than
In 1998-1999 RF and Nippon Shokubai prepared and tested PVCap according to Shell. They are made by condensing a
monomeric surfactants with alkylamide or dialkylamide groups cyclic acid anhydride with a dialkanolamine in a ratio of n:n +
in the head.232 This led to a patent application in 1999.134 The 1 where n is an integer. (By varying n one can vary the
groups were mostly carbonylpyrrolidine and isopropylamide molecular weight of the polymer.) This gives a polymer with
groups that had been shown to perform well in KHI polymers. hydroxyl groups at the tips. The hyper-branching is caused by
Several classes of these surfactants performed fairly well in cell the dialkanolamine, which has three reactive groups. By adding
tests, but two classes stood out for also having low environ- a third molecule to the reaction mixture, such as a secondary
mental impact. These are shown in Figure 27. Both surfactant amine, the tips of the polymer can be modified to become more
classes have a branching carboxylic acid group which gives them or less hydrophilic. In their patent application, Shell used
high biodegradability. Further, the higher the HLB (the shorter polymers made from di-2-propanolamine as the dialkanolamine.
the tail) the lower the toxicity of the surfactants. Both classes The best choice for the cyclic acid anhydride appears to be
performed very well in cell and wheel tests at 13 °C subcooling. hexahydrophthalic anhydride. This combination gives polymers
Statoil also tested the isopropylamide surfactant in their wheel with the structural units shown in Figure 29.
and obtained similar results. However, both classes failed at 15 The resemblance of the polyesteramide with earlier KHIs such
°C subcooling. As there seemed no performance advantage over as PVCap and polyIPMA is now apparent. All three KHI
KHIs for Drilling and Completion Fluids. Gas hydrate

formation can be a hazard in deep water drilling if gas
breakthrough occurs. To avoid hydrates from forming the
drilling fluid can be formulated with salts and glycols, which
act as thermodynamic inhibitors. However, there are some
Figure 29. Repeat unit in a polyesteramide made from di-2- situations in which the drilling fluid will be under-inhibited.
propanolamine and hexahydrophthalic anhydride. For example, the density of the fluid required, so that the fracture
gradient is not exceeded, might limit the amount of salt that
polymers have a hydrophobic group attached to an amide group. can be added. Second, in ultra-deep water drilling, it may be
The hydrophobic group forms a van der Waals interaction with impossible to avoid hydrate formation with some types of water-
hydrate surfaces (and/or perturbation of free water), while the based drilling fluids. Westport Technology Center International,
amide hydrogen bonds to water molecules in the hydrate surface. RF, MI, and Norsk Hydro140 have all carried out projects to
This disrupts further growth of the hydrate particles. In the case investigate the use of KHIs in under-inhibited drilling fluids.
of the polyesteramide shown in Figure 29, the hydrophobic
PVCap and other KHI polymers with low cloud points cannot
group is the cyclohexyl ring, although the methyl group of the
be used, as they will not be compatible with highly saline drilling
di-2-propanolamine may make a contribution. The ester groups
muds at the maximum circulation temperature of the mud (often
may also take part in hydrogen bonding. The feature that singles
40-50 °C). Hence it has been necessary to design the KHI with
out the polyesteramides from all other KHI polymers is their
a higher cloud point in saline solutions. Westport carried out a
hyper-branching. All other KHI polymers are linear snake-like
molecules with a polyvinyl backbone. To use an analogy for matrix of tests on KHIs for drilling fluids for a consortium of
KHI bonding to hydrate surfaces, the polyesteramides are like oil companies and mud companies. They determined that the
a hand clutching a hydrate ball, whereas other KHIs are like a KHIs lost performance probably by adsorption onto clay (mud)
single long finger attached to the ball. The molecular weight of particles in the drilling fluid. RF carried out several projects
the polymer does not need to be very high either. Shell found for oil companies and MI Swaco. They also noted the effect of
that polymers with molecular weights of 1500 gave good KHI clay particles on some KHI polymers. However, they did
performance. This is roughly the same figure found for identify two polymers that were useful KHIs for drilling fluids
polyvinyl-based KHIs such as PVCap. giving an extra 8-10 °C subcooling protection with a 24 h
In Shell’s patents on polyesteramides, they found that some nucleation delay at 0.6 wt %. MI Swaco found a KHI polymer
hydrophobically modified polymers gave moderate AA perfor- that gave 8 °C added subcooling protection with a 10 h
mance. Shell has spent considerable effort exploring polyes- nucleation delay at a concentration of 1 wt %.140 However, no
teramides as AAs, but in May 2004 they discontinued research clay was used in these tests. BJ Chemical Services has used a
concluding that the performance was not good enough to make proprietary blend of thermodynamic inhibitor, KHI and GW
a commercial AA product.139 AA in a packer fluid for a Gulf of Mexico application.209
Baker Petrolite and Polyesteramide KHIs. Polyesteramide KHIs Based on PVCap. Low molecular weight PVCap-
KHIs are commercially available through Baker Petrolite. They based products with added synergists are probably the best KHIs
will give PVCap some competition on the KHI market. Baker for structure II hydrate inhibition on the market today. ISP and
Petrolite has also patented new KHIs137 and synergists138 for Nalco reported that such a KHI blend gave at least 48 h hydrate
polymers including polyesteramide dendrimers. In one example inhibition at a subcooling of 13 °C.141 This represents an
given in the synergist patent application, polyethyleneimine is improvement of about 5-6 °C subcooling since the VCap-based
reacted with formaldehyde and caprolactam. This gives polymers terpolymer Gaffix VC-713 was first discovered. ISP and Nalco
with pendant caprolactam rings just as one finds in PVCap. had their low molecular weight PVCap-based KHI tested in the
Although PVCap is also a synergist for the polyesteramides, it wheel loop by Statoil. The results were some of the best
seems that Baker Petrolite is avoiding the use of PVCap in their recorded for any KHI.142,143 The KHI was tested using two shut-
KHI products. This gives them PVCap-free KHI technology, in/start-ups. For one condensate the KHI passed the test at 17-
which is only rivalled by Clariant’s amidated maleic anhydride 19 °C subcooling, whereas for another condensate the maximum
copolymers with ether carboxamide surfactant synergists. subcooling was only 8-12 °C. The maximum subcooling in a
Another KHI synergist from Baker Petrolite is made by reacting crude was 13-16 °C whereas in a gas/water system the
N-methyl butylamine with formaldehyde and polyacrylamide.
maximum subcooling was 11-12 °C. This underlines the
Other synergists mentioned are nonpolymeric surfactants with
dependency of the KHI on the liquid hydrocarbon phase and
caprolactam or alkylamide headgroups. A small amount of a
the need to test a KHI in the actual fluids from the field. It
quaternary AA can also be formulated with the KHI blend to
would be interesting to determine what a condensate or crude
improve the performance. In their patent application, Baker
contains that has such a beneficial effect on a KHI and then
Petrolite also mentions a typical polyesteramide as being made
build this into improved KHIs.
from di-2-propanolamine, hexahydrophthalic anhydride and bis-
(dimethylaminopropyl)imine. The latter molecule gives the Nalco also showed that KHI polymer cloud point is not such
polymer pendant dimethylamino groups, which help to make a critical issue for field implementation.141 Earlier it was thought
the polymer more water-soluble. Baker Petrolite has carried out that the polymer had to be soluble up to the maximum
two field trials on the polyesteramides in 2004, and several field temperature in the well stream, which is usually at the injection
applications have already begun. In addition, Baker Petrolite site. Otherwise it might precipitate out in the pipeline. This made
has found that their polyesteramide-based KHIs have better it difficult to use PVCap, which has a cloud point of ap-
performance on structure I hydrates than other KHI chemistries proximately 30-42 °C in freshwater. Nalco ran tests to show
such as PVCap.194 Some fields have such a high percentage of that PVCap polymer will remain within solvent droplets in the
methane that structure I hydrate is formed rather than structure hydrocarbon phase until the temperature of the aqueous phase
II. Baker Petrolite is already looking at structure I field drops below the cloud point of the polymer. At this point the
applications for their polyesteramides. polymer will dissolve in the aqueous phase.
Even with the good KHI results mentioned above Statoil discussed in the patent application. RF had the same idea in
could not use PVCap technology in their Norwegian fields. The the late 1990s carrying out studies on mixtures of high and low
reason is that the Norwegian Pollution Authority (SFT) demands molecular weight polyAP. They observed some increase in
that all new chemicals offshore have 60+ % biodegradability. performance relative to a low molecular weight sample only.
Nalco’s PVCap-based KHI has very poor biodegradability, RF postulated that the increase in KHI performance is related
although it is low in toxicity like all water-soluble polymers. to the size and mobility of the different molecular weight
Since quaternary AAs were already banned from use in Norway, samples. The low molecular weight sample, like a motorbike,
and now KHIs could not be used either, this led Statoil to shut moves quickly in solution to the site of hydrate nuclei growth.
down their LDHI research program in 2001. ExxonMobil Norge It will adsorb onto the surface of the hydrate but only weakly.
has a potential KHI application on their Ringhorn field where The high molecular weight sample, like a lorry, moves slowly
the subcooling was fairly low. However, the SFT would not but can then replace the low molecular weight sample on the
allow the use of poorly biodegradable polymers, so the plan surface adsorbing more strongly and preventing hydrate nuclei
was dropped. growth for longer periods. The motorbike-lorry analogy can
The British environmental authorities demand only 20+ % also be used for the synergistic blend of TBAB (motorbike)
biodegradability for new offshore chemicals. However, even and PVCap (lorry) discussed earlier. In fact, RF has showed
this is higher than the biodegradation of normal PVCap. This that TBAB is a better KHI synergist with high molecular weight
has led BASF, Clariant and ISP to search for more biodegradable PVCap than with low molecular weight PVCap.
polymers. So far, BASF has reported that they have managed ExxonMobil also presented a paper in 2003 at a nucleation
to synthesize a low molecular weight lactam-based polymer with workshop on the results of mini-loop experiments of KHI hold
approximately 20% biodegradability, which performs as well time versus subcooling at fixed KHI concentrations in a gas
as earlier KHI VCap-based products.144 condensate system.150 The hold time, which is repeatable, is
Recently, BASF took out a patent application on water-soluble the time from when the loop fluids reach the constant cooldown
vinyl lactam copolymers.145 A preferred polymer was 80:20 VP: temperature until hydrates are first detected. The data fitted an
butyl acrylate which performed better than a PVCap sample in exponential function in subcooling at all KHI concentrations
the THF hydrate ball-stop rig. The copolymer is very similar of the form y ) mx + b where y ) ln(1/hold time), x )
to copolymers patented earlier by Nippon Shokubai and RF. A subcooling, m was a constant at all KHI concentrations making
second patent application by BASF concerns the use of ethylene the curves of hold time versus subcooling have the same shape,
glycol as a high flash point solvent for VCap polymers.207 differing only in intercept, and b was dependent in a nonlinear
Although not a manufacturer of the VCap monomer, Clariant fashion on KHI concentration. The function b versus KHI
has also filed a patent application on copolymers where the bulk concentration was similar to the function maximum subcooling
of the examples concern VCap:alkyl(meth)acrylate ester co- versus KHI concentration that approaches an asymptote above
polymers.146 With short-chain alkyl methacrylates, such as 0.5 wt % active polymer.
methyl methacrylate, the VCap copolymer gave improved KHI KHI Applications Continue to Increase. By 2005, it is
effect over PVCap samples. With long chain alkyl methacrylates, estimated that there are about 40-50 KHI applications world-
such as oleyl methacrylate the VCap copolymer gave some AA widespread between a handful of service companies. Recently,
effect. the first application in the Middle East was reported by Clariant
A new synergist for PVCap has been identified as high and Total for a field called West Pars. Injection of KHI was
molecular weight poly(ethylene oxide) (PEO).211,228 However, successful throughout a 10-month period.151 Nalco has also
it does not perform as well as butoxyethanol.51 A small amount reported that they have a KHI application for RasGas in the
of PEO added to a PVCap solution also dramatically reduced Middle East.152
the hydrate memory effect.229 A new field called Otter in the British sector of the North
KHIs Based on Isopropylmethacrylamide (IPMA). The Sea and operated by Total will become only the second field,
high performance of polyIPMA, discovered by ExxonMobil, following ETAP, where a KHI application is planned during
and its possible competition with PVCap has been recognized the field development. Otter is an oil field tied back in a 10 in.
by Mitsubishi and ISP as they have both filed patent applications line to existing infrastructure. Production began in 2003.153,195
on polyIPMA. ISP claimed that polyIPMA synthesized in butyl KHI is injected during planned shutdowns or short-term low
glycol gave a far better performance than polyIPMA synthesized flow.
in 2-propanol.147 Mitsubishi patented polyIPMA with hydroxyl Another hurdle the service companies have had to overcome
end groups, claiming it to be a better KHI polymer than normal is combining KHIs with other production chemicals in a single
polyIPMA.148 injection line. On ETAP and a southern North Sea Gas field,
In 2003, ExxonMobil (EMURC) filed a patent application KHIs have been successfully combined with corrosion and scale
claiming KHIs that are polymers with a bimodal molecular inhibitors by Clariant.155 Clariant also recently reported the
weight distribution.149 The bimodal distribution can be made successful use of KHI combined with paraffin inhibitor,156,157
from a single polymerization or by mixing two polymers with while Baker Petrolite has reported studies on KHI/corrosion
unequal molecular weight distributions. The preferred polymer inhibitor blends.220
is polyIPMA although PVCap and other polymers are also Another application area for KHIs is their combination with
claimed. The increase in performance over a polymer with a thermodynamic inhibitors. For example, late in field life the
monomodal molecular weight distribution is most striking for water cut may be too high (> 50%) to use AAs. The subcooling
polyIPMA. For example, a hold time of 20 h was possible at may also be too high for commercial KHIs alone. Boosting the
43.5 °F (24.1 °C) subcooling using 0.5 wt % of a poly IPMA subcooling performance by combining the KHI with methanol
with a bimodal molecular weight distribution. The bulk of the or glycol is a possibility. A West African field that is due to
polymer has a molecular weight average of ca. 1000-3000. start up soon, and for which Shell is the operator, has been
This result is the highest subcooling recorded to date for a KHI planned in this way. Baker Petrolite plans the early life of the
product. The mechanism for the increased performance is not field with application of a quaternary AA.154 BJ Chemical
Services has published a paper on the use of KHI combined Two methods to reduce the environmental impact of quater-
with methanol for a subsea production line in the Gulf of nary surfactant AAs have been patented. Shell has patented a
Mexico.210 method to phase separate a quaternary AA by adding sufficient
Novel LDHIs. In 2003 BP filed a novel patent application inorganic salt to the produced water to render the AA insoluble.
for a method of delaying hydrate formation.158 The method Baker Petrolite has patented methods to detoxify quaternary AA
comprises mixing a polymeric emulsifier and optionally a surfactants by the addition of anionic polymers or anionic
nonionic nonpolymeric co-emulsifier with the hydrocarbon and surfactants.240-242
aqueous fluids so as to generate a water-in-oil emulsion. The Very recently a new patent application from Baker Petrolite
emulsifiers form a substantially gas impermeable interfacial (Baker Hughes Incorporated) was laid open.231 They found that
layer, which prevents hydrate from forming in the encapsulated, the effective concentration of a quaternary surfactant AA could
aqueous droplets. Nucleation delays of over 16 h were obtained be reduced by the addition of a minor amount of an anionic,
at 12 °C subcooling. The concentration of the emulsifiers used nonionic, or amphoteric compound. The mixture, called an ion
was 2 wt %. BP recommends recovering and reusing the pair, allows lower concentrations of the quaternary surfactant
emulsifiers in order to make the process economically viable. to be used in practice, which reduces the treatment cost as well
However, no suggestions are made as to how this should be as the environmental impact. For example, the effective
done. concentration of quaternary ammonium surfactant AA was
RF investigated two novel LDHI ideas in 2000. The first idea reduced from 0.75 wt % to 0.15 wt % by the addition of 0.12
was to use super water-adsorbent polymers to take out all the wt % alcohol ether sulfate (AES) for AA tests with a GoM
water before hydrate formation occurred. The experiments failed condensate. In another example with a GoM condensate, the
because a suspension of water-adsorbed polymer particles could effective concentration of the quaternary AA could be reduced
not be maintained. Coagulation may have been avoided with from 0.59 wt % to 0.30 wt % by the addition of 0.04 wt %
polymer particles with membranes but this is too expensive. sodium dodecyl sulfate (SDS). Both AES and SDS are known
However, the second idea gave some success. The idea was to to have little or no AA hydrate inhibiting ability.
use an ion pair blend of ionic KHI polymer and surfactant with In another version of the invention, Baker Petrolite found
the opposite charge to give an AA effect. The KHI would control that mixing dodecylbenzenesulfonic acid (DDBSA) with a small
hydrate growth and the surfactant would drag the hydrate KHI- quaternary ammonium compound with appendages containing
coated particles to the hydrocarbon phase by electrostatic forces. less than 6 carbon atoms, to give an ion pair, also gave a product
An anionic IPA:AMPS copolymer with a cationic surfactant that performed as an AA. Neither the ammonium compound or
worked well at 14 °C and 90 bar but failed at higher subcoolings. DDBSA showed any appreciable AA activity individually. An
No further work was carried out after the project finished at example of a small quaternary compound could be TPAB,
the end of 2000. known to be a hydrate crystal growth inihibitor. Baker Petrolite’s
idea is similar to RF’s idea of using an ion pair AA made from
First Field Trials and Field Applications of the Quater-
an anionic KHI with a cationic surfactant discussed earlier.
nary AAs. In the year 2000, Baker Petrolite presented a paper
Baker Petrolite has reversed the charges using a cationic hydrate
discussing the first field trials with the water-soluble quaternary
growth inhibitor with an anionic surfactant.
AA.159 The first trial actually took place in the Gulf of Mexico
(GoM) in 1999 and was a success. Later AAs have been used The first application for which the field was specifically
in the GoM to mitigate against hydrate plugging during shut- designed to use an AA was Shell’s K7-FB field in the Dutch
in/start-up situations in black oil systems. The first field sector of the North Sea in 2003.167 The oil-soluble quaternary
application with continuous injection of AA was in 2002, again AA from Akzo Nobel is presently supplied through Clariant
in the GoM on a Shell field called Popeye.160 Since then the Oilfield Services. The field produces gas condensate and
number of AA applications particularly in the GoM has freshwater and the subcooling is a maximum of 8-9 °C. One
increased rapidly.161-163 For example, ExxonMobil ran the Diana of the drawbacks of the oil-soluble quaternary AA is that it has
field oil flowlines with a Baker Petrolite AA from 2002 to 2003; a shelf life at ca. 20 °C of about 1 year. One of the tails of the
oil production ended on high watercut.111 A field application surfactant gradually degrades off leaving a mono-tail quaternary
in West Africa is also planned.153 surfactant, which has much poorer AA performance. Conse-
quently, the operator has to make sure that the turnover of the
Baker Petrolite claimed at an SPE Forum that 1 wt % actives quaternary AA, especially in a hot climate, is kept to under a
of the water-soluble quaternary could treat any subcooling.164 year.
It seems like this product is the proverbial silver bullet. So far
LDHIs from IFP. By 2005, IFP had still not managed to
it has been lab tested successfully up to 7000 psi (500 bar) and
find a field application for their emulsion AA, Emulfip 102b,
22 °C (40 °F) subcooling, and used successfully in the field at
following mixed results from the field trials in Argentina. The
ca. 14 °C (25 °F) subcooling. Along with KHIs they have also
tendency for the hydrates to drop out during shut-in was an
been found to work in highly sour systems where the H2S has
issue that they addressed in a new patent application.168 This
been thought to affect the hydrate equilibrium properties.165
claimed the use of hydrophobic oil-soluble block copolymers
Finally, compatibility with materials193 and other production
that when used together with an emulsion AA would prevent
chemicals such as corrosion and wax inhibitors appears to have
the settling out of hydrates during shut-in. A typical block
been overcome for both KHIs and AAs.
copolymer mentioned is made from styrene/ethylene/propylene.
Baker Petrolite has also patented a method to increase the A typical emulsion AA is made by reacting a polyalkenylsuc-
performance of the water-soluble quaternary AA.166 The water- cinic anhydride with a monoether of poly(ethylene glycol).
soluble quaternary AA (onium compound) is formulated with
an amine salt and optionally a solvent. The amine salt will (240) Blytas, G. C.; Kruka, V. R. International Patent Application WO
increase the ionic strength of the water phase, which may make 01/38695.
the AA perform better in freshwater. The amine salt contained (241) Rivers, G. T.; Downs, H. H. U.S. Patent Application 20040144732,
2004.
preferably alkyl or hydroxyalkyl groups with 1-3 carbon atoms (242) Rivers, G. T.; Frostman, L. M.; Pryzbyliski, J. L.; McMahon, J.
or an ammonium salt could be used. A. U.S. Patent Application 20030146173, 2003.
Figure 30. Structure of alkyl ether tributylammonium bromide AAs.

R has 12-14 carbon atoms.
Figure 31. Structure of a preferred polyalkoxylated amine where a +
IFP has since put Emulfip 102b back on the shelf and instead b + c ) 14.9.
are trying to promote another polymeric surfactant emulsion
AA called IPE 202b, which they hope to commercialize through
the service company Shrieve in the GoM.169 IFP’s KHIs such
as AMPS:acrylamide are also in a stand-by situation and which
they hope to be commercialized through a new partner.
Natural LDHIs. It has been known since the mid 1990s that
natural surfactants in crude oils affect hydrate plugging tenden- Figure 32. Structure of tributylammoniumpropylsulfonate (TBAPS).
cies. Attempts to isolate these natural AAs have been carried
out by chromatography but have led to very complicated similar claims covers alkylaminoalkyl/alkoxy monoesters. A
mixtures.170 For crudes it seems the maltene fraction (which fourth patent application with similar claims covers alkoxylated
are surfactants) and possibly asphaltenes are responsible for the amine ether carboxylic acids and their quaternized products.
AA effect. Later work seems to show that there are two types These surfactants could in theory contain dibutylammonium
of crude oil, only one of which has hydrate-plugging tenden- headgroups, as originally claimed by Shell for AAs, although
cies.171-173,215-218 no examples are given. Their synergy with PVCap is also
New Quaternary AAs. By the new millennium it was claimed. A fifth patent application covers alkenylsuccinimi-
becoming clear to the chemical manufacturers and service doalkylamines as KHI synergists and corrosion inhibitors with
companies that the only surfactants that gave high AA perfor- improved water solubility and biodegradability.
mance were quaternary surfactants with 2 or 3 butyl or pentyl Besides various quaternary ammonium surfactants Champion
groups, first discovered by Shell. The research work of CSM, Technologies’ patent applications196-200 also cover amine oxides
RF, and others had not provided any better AAs. Since the turn and betaine surfactants, a subject first researched by RF in the
of the millenium Nalco,175 Goldschmidt,176 Clariant,177-181,202 late 1990s.
and Champion Technologies196-200 have all filed patent ap- There was a reluctance by operators to use the early
plications on new quaternary surfactant AAs. Both Nalco and quaternary AAs since their unit price per barrel of water treated
Clariant already have commercially available quaternary AAs was about the same as methanol. However, the later quaternary
that will compete with the Shell quaternary AAs available AAs are now much more competitive and can be dosed at lower
through Baker Petrolite and Akzo Nobel. concentrations.224,231
New KHIs. In 2003, Akzo Nobel filed a patent application
Nalco appears to have found a way around the original Shell
on a new class of LDHI called polyalkoxylated amines.184,185
patents allowing them to use the desired surfactants with a
The alkoxylation is preferably done with propylene oxide (PO).
quaternary center with butyl or pentyl groups. After 2 years of
A preferred amine for making KHIs is triethanolamine but
testing at Nalco and Westport Technology Centre, the new AA
ammonia and other alkanolamines can be used. The amine can
is already being used in a field application on BP’s Horn
also be quaternized. The best example given in the patent
Mountain in the GoM.182 Injection is continuous and began in
application is triethanol with a total of 14.9 PO units (Figure
2003. Other applications have recently been reported.183
31). At 1.0 wt % this reduced the hydrate onset temperature
Goldschmidt’s patent application176 claims the use of qua- from ca. 42 °F (5.6 °C) in a blank test to 32.9 °F (0.5 °C). AAs
ternary ammonium salt surfactants as AAs with an ether spacer are covered in the patent application by adding a long
group between the quaternary nitrogen atom and the long alkyl hydrophobic tail to the polyalkoxylated amine, but no examples
tail (Figure 30). The AAs are claimed to have improved water are given.
dispersibility over tetraalkylammonium salts such as hexade- Molecular modeling work carried out at the Universities of
cyltributylammonium bromide. There appears to be no public Warwick and Reading, England, and hydrate testing at ENSI-
information as to whether Goldschmidt’s AAs have been ACET & LGC, Toulouse, France, and Heriot-Watt University,
commercialized. Edinburgh, Scotland, has led to a class of zwitterionic KHI
Clariant now has its own quaternary AA, which has been synergists.186,187(They also have potential as AAs.219) The only
successfully field-trialled and is commercially available. Clariant chemical mentioned in detail is tributylammoniumpropylsul-
has filed several patent applications on surfactant AAs, some fonate (TBAPS), which performed only slightly better than PVP
products of which can also be used as synergists for KHI in the THF hydrate ball-stop rig (Figure 32). Instead of binding
polymers such as PVCap. For example, alkylaminoalkyl mono- inside potholes on the hydrate surface, TBAPS and related
and diesters are claimed in one patent application and shown compounds lie along the surface and actually cap the pothole.
to work as AAs as well as synergists for KHI polymers such as The modeling was carried out in a vacuum and does not take
PVCap. The products also exhibited good corrosion inhibition into account free water-LDHI interactions. A later paper
properties. In a second patent application N,N′-dialkylaminoalkyl mentions a product called J3 designed using molecular model-
ether carboxylates are claimed as corrosion and gas hydrate ing, which performed significantly better than a commercial
inhibitors with improved water solubility and biodegradability. PVCap blend, giving an induction time of over 4000 min with
Examples are shown to work as AAs as well as synergists for structure II hydrates.188 It will be interesting to see how this
KHI polymers such as PVCap. A third patent application with class of KHI develops.
LDHI testing. The effect of pressure, and not just the subcooling,
on the performance of LDHIs also needs further investiga-
tion.80,234
Conclusion
Figure 33. Structure of poly(vinyl alcohol) based KHIs where R1 has Low dosage inhibitors for mitigating other oilfield problems
1-6 carbon atoms, R2 or R3 is H, COOH, C1-10 alkyl or C6-C12 are well-known and include wax, scale, corrosion, and asphalt-
aryl, and R4 is H or CH3. ene inhibitors. Low dosage inhibitors for the prevention of
plugging by gas hydrates are the latest tools to have been
Kuraray Specialties Europe filed a patent application in 2001
developed. This paper has reviewed the development of LDHIs
on a new class of polymer KHI.189 The polymers are based on
with focus on the various chemistries that have been investi-
derivatives of poly(vinyl alcohol) by reaction with aldehydes.
gated. Both commercial and unsuccessful attempts have been
The structure of a typical product is shown in Figure 33. It
included for completeness. Since the start of LDHI research in
contains vinyl ester acetal functionalities besides some unreacted
the late 1980s over 240 documents have been published. The
vinyl alcohol monomer units. A preferred aldehyde is butyral-
fact that nearly 100 of these are patent applications gives some
dehyde, giving pendant propyl groups. Some of the polymers
idea of the interest in this subject. However, there have been
are also claimed to work as AAs.
far fewer patent applications in the last 2-3 years.
Since the early 1990s, it has been known that anti-freeze
The use of LDHIs is now rapidly becoming an accepted
proteins not only inhibit ice growth but also inhibit hydrate
method for preventing hydrate plugging in gas wells and oil
formation.26,28 Queen’s University, Kingston, Canada, has sought
and gas pipelines. Already LDHIs are a million dollar business
to commercialize the idea by claiming anti-freeze proteins, active
for some of the oilfield service companies. By the end of 2005,
fragments of these anti-freeze proteins, and mimetics thereof,
there are and have been ca. 50-70 field applications of LDHIs,
as KHIs. The anti-freeze proteins or active fragments are derived
the majority of them related to KHIs although the number of
from insects, plants, fungi, protests, or bacteria presumably in
AA applications are now increasing almost as rapidly. Most
a process that allows for large-scale manufacture since isolation
LDHI applications to date have been retrofits (i.e., methanol or
of large quantities of anti-freeze proteins from these sources is
glycol use has been exchanged with the more economical use
prohibitively expensive.190,212
of an LDHI). However, as the technology becomes more well-
In 2001 BASF patented the use of grafted polymers as
known, more fields will be planned with the use of LDHIs since
KHIs.201 The backbone is preferably a polyalkylene glycol, a
the CAPEX savings can be very significant.224
polyalkyleneimine, a polyether, or a polyurethane, and the active
functional side groups are made by grafting VP or VCap to the KHIs will continue to dominate the market for applications
backbone using radical initiators. The heteroatoms in the where the hydrate subcooling is below 10 °C. Some commercial
backbone should help to increase the biodegradability of the KHIs when dosed at >5000 ppm have been used in the field at
polymer. subcoolings up to approximately 15 °C.155 Other KHIs have
Although quaternary ammonium salts with 2 or 3 butyl or been shown to work at much higher subcoolings, but they are
pentyl groups had been known for over a decade from Shell’s not commercially available. The best example is ExxonMobil’s
work to work as hydrate growth inhibitors and as AAs, no one VIMA:IPMA oligomer. Blends of thermodynamic inhibitors and
it seems had tried to make polymer KHIs with quaternary KHIs are also being used in the field.210 AAs can of course
ammonium groups. In 2004 RF and Stavanger University also be used at low subcoolings where the water cut is under
rectified this situation by testing polyquaternaries with pendant 50%, and in some cases they may be more economical than
tributylammonium groups.191 Perhaps not unexpectedly they also KHIs.
turned out to be excellent synergists for VCap polymers such The mechanism for kinetic hydrate inhibition (nucleation
as Gaffix VC-713 performing better than TBAB as synergist. inhibition) by water-soluble polymers is still not fully under-
So far the work, which is still ongoing, has not been taken stood, at least in the public domain, although models have been
beyond the laboratory stage. presented. Usually these relate to adsorption of the polymer onto
hydrate embryos or crystal structures,192 although some work
now suggests that water pertubation is also critical.188,213,214
Future LDHI Research
More work is needed on molecular modeling of hydrate-
LDHI R&D appears to have come near to the top of the water-polymer interactions in an aqueous environment not just
S-curve. As of late 2005, there is relatively little activity by oil hydrate-polymer interactions in vacuo. In addition, ExxonMo-
companies, institutes, and the academic community in designing bil’s proprietary theory related to maximizing the hydration
higher performing products. It now seems to be primarily the volume of the KHI polymer in water needs investigating further.
job of the service companies and chemical manufacturers in After all, their polymers (e.g., VIMA:IPMA oligomer) appear
fine-tuning existing chemistries. However, a number of new to have the highest performance of KHIs reported to date.
academic research groups have taken up the batton and are Finally, the mechanism of the effect of the hydrocarbon phase
beginning to explore LDHIs, some in collaboration with service on the performance of a KHI needs investigating.
companies. This may also lead to new or greener versions of For high subcooling applications, AAs seem the only com-
known LDHI classes. Further, fundamental studies on the mercial LDHI alternative. Applications of AAs are expected to
mechanisms of nucleation and agglomeration of hydrates are move to higher subcoolings as operators and service companies
also being carried out, either as molecular modeling203,213,214,237 become experienced with their use. Single-tailed quaternary AAs
or as experimental work.204-208,222,235,236 These studies will surely appear to be the only LDHIs that can consistently perform at
help our understanding of the mechanisms of LDHIs but are 15+ °C subcooling. So far they have only been field proven in
unlikely to result in fundamentally new commercial LDHIs. flow lines to 14 °C subcooling, although laboratory experiments
Better experimental procedures that match the true field condi- suggest that 20+ °C subcoolings can be obtained (BP’s Holstein
tions (not just a single subcooling limit) are also needed for field did use an AA at start-up where the subcooling could have
been as high as 25 °C224). Emulsion-based AAs have yet to like to thank my wife, Evy, who patiently typed a large part of the
reach field applications. There is still a need for greener AAs manuscript while I was recovering from a long-term illness.
for use in environmentally sensitive waters such as offshore
Norway. GWAAs are different from pipeline AAs and have so Nomenclature
far only been shown to work at low water-to-hydrate conversion AA ) anti-agglomerant
in gas wells. They are however good synergists for PVCap- AFP ) anti-freeze protein
based KHI polymers. AFGP ) anti-freeze glycoprotein
AMPS ) acrylamidopropylsulfonic acid
CSM ) Colorado School of Mines
Acknowledgment. I would like to thank my fellow LDHI EMURC ) ExxonMobil Upstream Research Company
researchers at RF-Rogaland Research: Thor Martin Svartaas, Knut IFP ) Institut Francais du Petrole
Lekvam, Svante Nilsson, Lindy Dybvik, Jorunn Øvsthus, and Jan IPA ) isopropylacrylamide
Erik Iversen during the years 1991-2001. I would also like to thank IPMA ) isopropylmethacrylamide
the participants in LDHI projects carried out at RF-Rogaland KHI ) kinetic hydrate inhibitor
Research. They include Larry Talley (ExxonMobil Upstream LDHI ) low dosage hydrate inhibitor
Research Company), Nick Wolf and Stan Swearingen (Conoco- NS ) Nippon Shokubai Company Ltd.
Phillips), George Shoup (BP), Emil LePorcher and Jean-Louis OECD ) Organization for Economic Cooperation and Development
Peytavy (Total), Keijo Kinnari and Anita Rasch (Statoil), Finn PolyAP ) polyacryloylpyrrolidine
Fadnes (Norsk Hydro), Agostino Mazzoni and Carla Consoloni PVP ) poly(vinylpyrrolidone)
(ENI), Nick Phillips (Clariant Oilfield Services, now Baker Petro- PVCap ) polyvinylcaprolactam
lite), and Peter Klug (Clariant). Yuji Sugiura, Takashi Tomita, RF ) RF-Rogaland Research
Takashi Namba, Yoshihiro Arita, Jun-ichi Chosa, and Keiichiro THF ) tetrahydrofuran
Mizuta at Nippon Shokubai Company Ltd, are also acknowledged TROS ) TR Oil Services (now Clariant)
for their collaboration and excellent synthetic skills. I thank Larry TPAB ) tetrapentylammonium bromide
Talley and Ulfert Klomp (Shell Global Solutions) for reading the TBAB ) tetrabutylammonium bromide
manuscript and making helpful comments. I am also grateful for VIMA ) N-vinyl-N-methyl acetamide
the help of Piers Crocker who read to me many LDHI articles and
reports while I was unable to do so. Finally, but not least, I would EF050427X

History of The Development of Low Dosage Hydrate Inhibitors

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VOLUME 20, NUMBER 3 MAY/JUNE 2006

© Copyright 2006 American Chemical Society

crystal.3,4 THF forms structure II hydrate, the same structure

(3) Makogon, T. Y.; Larsen, R.; Knight, C. A.; Sloan, E. D. J. Crystal

Figure 3. Structure of poly(vinylpyrrolidone).

Shell’s Research and the Discovery of Quaternary Sur-

polyvinyllactam KHIs. They were also collaborating with Shell

Figure 9. Structure of poly-L-proline. Figure 10. Structure of N-methyl-N-vinylacetamide:vinyl caprolactam

that the butyrate groups in the VIMA:vinyl butyrate copolymer

using ethylene glycol and water as solvents for their products.

toxic and even more bioaccumulative than the single-tail

It is difficult to know how to categorize BJ’s products or

Figure 23. Structure of one of Clariant’s synergists for maleic

of tripentylamine was rather high and would make the price of

Petrolite had overcome any environmental hurdles for the Gulf

Figure 26. Structure of amine oxide surfactant AAs.

KHIs for Drilling and Completion Fluids. Gas hydrate

Figure 30. Structure of alkyl ether tributylammonium bromide AAs.

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