US 20190055477A1

( 19) United States

(12 ) Patent Application Publication ( 10) Pub . No.: US 2019 /0055477 A1
LAMBERTSSON et al. (43) Pub . Date : Feb . 21, 2019
(54 ) PROCESS FOR REMOVING MERCURY Publication Classification
FROM CRUDE OIL (51) C10G
Int. Ci29. /20 (2006 .01)
(71 ) Applicants :ConocoPhillips Company, Houston , B01D 3 /06 (2006 .01)
TX (US ); Umeå University, Umea (SE ) B01D 3 / 14 (2006 .01 )
(72 ) Inventors: Lars T . LAMBERTSSON , Umea ( SE );
(52 ) U .S . CI.
CPC ........... C10G 29 /20 ( 2013.01) ; B01D 3 / 06
Charles J. LORD , III, Bartlesville , OK ( 2013 .01); B01D 3 / 14 ( 2013 . 01); CIOG
(US ); Erik L . BJÖRN , Umea ( SE ); 2300 /205 (2013.01); B01D 2257/ 602
Wolfgang FRECH , Umea (SE ) (2013.01); CIOG 2300 / 104 (2013 .01) ; CIOG
2300 / 1044 (2013 .01); CIOG 2300 / 1048
( 2013 .01 ); B01D 2256 /24 (2013 .01); CIOG
(21) Appl. No.: 16 /051,973 2300/ 1033 ( 2013.01)
(57 ) ABSTRACT
Methods, systems and designs are provided for removing
(22 ) Filed : Aug. 1, 2018 mercury from crudes. Crude oil containing a synthetic
reducing agent is heated to a temperature above 100° C . and
held at that temperature for a specified period of time to
Related U .S . Application Data convert all of the forms of mercury in the oil into the
elemental mercury form . The elemental mercury is then
(60 ) Provisional application No. 62/545 ,653 , filed on Aug . stripped from the crude oil by e. g., flashing the hot oil and /or
15 , 2017 . contacting it with a gas phase .

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Patent Application Publication Feb. 21, 2019 Sheet 1 of 5 US 2019/0055477 A1

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Patent Application Publication Feb. 21, 2019 Sheet 2 of 5 US 2019/0055477 A1

FIGURE 2

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Patent Application Publication Feb. 21, 2019 Sheet 3 of 5 US 2019/0055477 A1

FIGURE 3

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100 120 140 160 180 200 220 240
Reaction Temperature (°C )
Patent Application Publication Feb. 21, 2019 Sheet 4 of 5 US 2019/0055477 A1

FIGURE 4

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°C
(
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100 150 200 250

Reducing Agent Conc (ppm )
Patent Application Publication Feb. 21, 2019 Sheet 5 of 5 US 2019/0055477 A1

FIGURE 5

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100 120 140 160 180 200 220 240

Reaction Temperature (°C)
US 2019/0055477 A1 Feb . 21, 2019

PROCESS FOR REMOVING MERCURY [00091. Several processes for removing mercury from
FROM CRUDE OIL crude oil have been disclosed in U . S . Pat. No . 6 , 350 ,372 ,
U .S . Pat. No. 6 ,537 ,443, U .S . Pat. No. 6 ,685,824 , and U .S .
PRIOR RELATED APPLICATIONS Pat. No . 6 , 806 ,398 and in an article by Salva ( 2010 ). All of
these processes essentially involve reacting the crude oil
[0001] This application claims priority to U .S . Ser. No. with a sulfur compound to precipitate HgS and then sepa
62 /545,653 , filed Aug . 15 , 2017 , which is incorporated rating the HgS particles from the oil by filtration or another
herein in its entirety for all purposes. technique for solids removal. In some cases , the process
requires an additional filtration step prior to contacting the
FEDERALLY SPONSORED RESEARCH oil with the sulfur compound .
STATEMENT 10010 ] Such processes require the addition of reagent
[ 0002 ] Not applicable . chemicals as well as filtration of the crude oil. The filtration
step in particular is problematic because of filter plugging by
REFERENCE TO MICROFICHE APPENDIX other components in the crude oil such as waxes and
sediments. The HgS will only comprise a small percentage
[0003 ] Not applicable . of the total solids removed by filtration . The maintenance of
a crude oil filtration unit can thus become cost prohibitive in
FIELD OF THE DISCLOSURE terms of manpower , filtration media , and disposal.
[0004] The disclosure generally relates to removing mer [0011 ] The process disclosed in U .S . Pat. No. 8 ,080 , 156 ,
cury from crude oils . by contrast, involves the use of natural gas to strip mercury
from the crude oil . However, this process is only effective
BACKGROUND OF THE DISCLOSURE for the removal of elemental mercury . The efficiency of this
process is thus limited by the ratio of elemental mercury to
[0005] Coal is the largest source of human - generated totalmercury in the oil, and , in some cases, the efficiency of
mercury emissions in the United States. Coal- fired power mercury removal can be very low .
plants release about 48 tons ofmercury annually, according [0012 ] In U .S . Pat. No . 9,574 , 140 , incorporated herein in
to EPA data . In contrast, the total amount of mercury in its entirety for all purposes, Applicant disclosed a method for
crude oil processed in the U . S . annually is less than five determining the forms of mercury and their respective
percent of the amount contained in U . S . coal produced and concentrations in a crude oil sample , which allowed for the
consumed annually . development of a reaction rate expression for that particular
[0006 ] Mercury concentrations in crude oil have been crude oil feed and allowed the calculation of optimum
reported from as low as < 1 ng/ g to as high as 50 ,000 ng/ g design specifications for removal of mercury. Applicant
of oil ( see e . g ., FIG . 1 ). Some of the variability observed in found that crude oil can be heated to a temperature above
crude oilmercury data is due to difficulties encountered in 100° C ., and held at that temperature for a specified period
performing the analyses. A wide variety of measurement of time, to convert all of the forms of mercury in the oil into
techniques, including neutron activation and many types of the elemental mercury form . The elemental mercury can
sample preparation systems coupled with detectors as then be stripped from the crude oil by e. g., flashing the hot
diverse as mass spectrometers , ICP /MS, atomic absorption , oil and/ or contacting it with a gas phase . Typically , tem
and atomic fluorescence have been used to perform these peratures of 180° C . or higher are required to achieve
analyses . As such , it can be very difficult to compare commercially useful reaction rates . The reaction rate is also
mercury analysis results obtained in different laboratories strongly influenced by the composition of the crude oil.
using different analytical techniques. The handling of Condensates, for example , reactmore slowly than black oils.
samples can also significantly affect the measured results . A The ability to use the lower 100° C . temperature saves
recent study found that the number of times a sample bottle energy costs, and avoids undesired degradation of hydro
had been opened could significantly affect the measured carbons.
concentration . [0013] Further improvements to methods of removing
[0007] Although analytical difficulties are responsible for mercury are desired as companies are producing hydrocar
some of the variability in crude oilmercury data , geological bons from deeper and hotter reservoirs , which contain
factors such as depositional environment and thermal history increasing concentrations of mercury , and in regions in the
are a more important influence on the concentrations of North Sea , Asia -Pacific , and South America , which also
mercury that are observed in currently produced oils . The have elevated concentrations of mercury . Significant finan
mercury concentrations shown in FIG . 1 vary by more than cial and environmental advantages exist for lowering the
a factor of 1000 , which is indicative of the wide variety of composition of the mercury in crude oil prior to sale .
environments from which these oils originate . [0014] Thus , what are needed in the art are bettermethods
[0008] Mercury has come under increasing scrutiny in of removing mercury from crude hydrocarbons . Ideally , the
recent years because its presence in oil creates problems methods will be simple , yet robust and applicable to all types
throughout the production , transportation , storage and refin of hydrocarbons, including crude oils, natural gas , and light
ing systems. These problems include environmental con condensates .
cerns, contamination of refinery products , catalyst poison
ing , corrosion of equipment, health risks for personnel, as SUMMARY OF THE DISCLOSURE
well as expenses for disposal of contaminated tank sludge , [0015 ] This disclosure is directed to a relatively inexpen
cleaning of contaminated equipment, shipping restrictions, sive , robust and simple process for removing mercury that is
etc . These issues have led companies to search for methods not significantly affected by the crude oil compositional
of reducing the mercury content of crude oil . variations.
US 2019/0055477 A1 Feb . 21, 2019

[ 0016 ] Specifically , a synthetic reducing agent is added to synthetic reducing agent can be utilized to further decrease
and mixed with a crude oil ( or other type of hydrocarbon the reaction temperature and simultaneously increase the
matrix ) that contains various forms ofmercury . The mixed reaction rate . Additionally , these moderate temperatures also
composition is then heated to convert the various forms of provide flexibility in the concentration of organic phosphites
mercury in the crude oil into elemental mercury during a needed for highly efficient mercury removal.
mercury conversion process . The synthetic reducing agent [0025 ] Preferably , the heating occurs for a time sufficient
acts as a catalyst for this conversion reaction . This allows to convert at least 95 % all mercury forms to elemental
lower conversion temperatures and pressures to be used . mercury. Preferably 96 , 97 , 98 , 99 or nearly 100 % of the
Further, the synthetic reducing agent is able to accelerate the mercury is converted . The amount of time needed is vari
mercury conversion in slow reacting matrices , such as light able, because the reaction rate depends on the type of
condensates. hydrocarbon , the composition of the forms of mercury , the
[0017 ] This process allows for the removal of all mercury conversion temperature and the amount of reducing agent.
forms at a moderate conversion temperature and within a 10026 ]. Following the converting step , the elemental mer
commercially feasible timeframe. The lower conversion cury is transferred from the oil phase into a gas phase by,
temperature reduces the capital and operating expenses that preferably , flashing or gas stripping, but any other method of
would be required for building and operating a mercury removal can be used , and the various methods can be
removal unit, while maintaining or increasing the output of combined .
reduced -mercury or mercury - free hydrocarbons. 10027 ] The removing of the elemental mercury from the
[ 0018 ]. In addition to crude oil, this reducing agent and gas phase after the conversion process can be by any known
process is also applicable to most hydrocarbon matrices such in the art or to be developed in the future , and in addition to
as natural gases, condensates, naphthas, middle distillates, the above, includes condensation , precipitation , or absorp
and waxes . tion , adsorption , and combinations thereof.
[0019 ] The synthetic reducing agent converts all formsof [0028 ] For instance, elemental mercury can be removed
mercury , including ionic mercury, into elemental mercury by precipitation as HgS . Another method includes treating
using an organic phosphite (P (OR )3 ). These organic phos the mercury rich stream with an adsorption agent. Yet
phite reducing agents are relatively inexpensive chemicals another method includes removing mercury from the mer
that are commonly available worldwide in bulk quantities. cury rich stream by precipitation as HgSe after contacting
The use of organic phosphite reducing agents also facilitates the mercury rich stream with a filter containing selenium . If
mercury conversion in otherwise difficult matrices such as desired , some or all of the stripping gas can be recycled back
condensates and refined petroleum products . into the process to save costs .
[0020 ] The phosphite can have any alkyl or phenyl sub [0029 ] Key advantages of the process disclosed herein
stituents, including methyls, ethyls, propyls, butyls, phenyls, include :
and the like. Exemplary phosphites include triphenyl phos [0030] The process is inherently simple and robust.
phite, tributyl phosphite , dibutyl phosphite , triethyl phos [ 0031] Only one chemical reagent is required to speed
phite , diethyl phosphite, trimethyl phosphite , dimethyl phos the conversion process .
phite or combinations thereof. Further, a combination of R [ 0032 ] No filtration is required .
groups with different numbers of carbons in their chain [ 0033 ] Relatively low reaction temperatures are needed ,
length can be used on the phosphite (i.e. P (OR ) (OR ') (OR " )) which reduces operating costs and the risk of thermally
as well as having a hydrogen in place of at least one R group . degraded hydrocarbon components.
[ 0021] While all alkyl/ phenyl-substituted phosphites were [0034 ] High removal efficiency is ensured by the con
able to convert the ionic mercury to elemental mercury, the version of non -volatile mercury species into the strip
size of the sub stituents did affect the reaction rate . Thus , pable elemental form of mercury.
smaller alkyl substituents on the phosphite are preferred as [0035 ] This summary is provided to introduce a selection
they react more quickly with ionic mercury . Further, per of concepts that are further described below in the detailed
formance tests also revealed that the di-substituted phosphi description . This summary is not intended to identify key or
tes performed better than the tri -substituted phosphites. This essential features of the claimed subject matter, nor is it
appears to be due to the fact that the di-substituted phos intended to be used as an aid in limiting the scope of the
phites have significantly better thermal stability compared to claimed subject matter .
their tri -substituted counterparts . 10036 ] As used herein , the term “ elemental mercury ”
[0022 ] As such , the most preferred phosphite is dimethyl means Hgºt, which is a metallic , silvery liquid that readily
phosphite ((OME), P ( O ) H ). breaks into droplets and easily vaporizes at room tempera
[0023 ] By using the reaction rate expressions specific to ture. Elemental mercury is not the only volatile form of
the crude oil feed , developed in U .S . Pat. No. 9 ,574 , 140 , mercury , and the term does not include inorganic or organic
users can calculate optimum design specifications such as forms of mercury .
process temperature , vessel sizes, oil feed rate , synthetic [0037 ] As used herein , the term “ ionic mercury ” refers to
reducing agent feed rate , etc . for commercial- scale mixing mercury ( II) or Hg2 + . Ionic mercury is very soluble in crude
units . oils and is a non -volatile form ofmercury . Elemental mer
[0024 ] After the synthetic reducing agent is added to the cury , in contrast, is less soluble in crude oils and more
mercury rich hydrocarbon , both are heated to 100° C . to volatile .
convert all forms of mercury to elemental mercury . While [0038 ] In addition to ionic mercury , the reducing agent can
conversion temperatures below 100° C . are possible with the convert other non - volatile forms of mercury , such as
use of the reducing agent, a temperature range of 100- 200° Hg(CH3) 2 (dimethylmercury ), HgCH2X (monomethylmer
C . proved optimal for establishing flexibility in designing cury ), that are commonly found in hydrocarbons into ele
the mercury removal unit . Higher concentrations of the ment mercury .
US 2019/0055477 A1 Feb . 21, 2019

[0039] As used herein , the phase " conversion ofmercury DESCRIPTION OF EMBODIMENTS OF THE
to elemental mercury ” or “ conversion of mercury in various DISCLOSURE
forms to elemental mercury ” means that all of the various [0058 ] The invention provides a novel method of remov
forms of mercury found in the hydrocarbon matrix are ing all forms of mercury from hydrocarbon sources. Spe
converted to elemental mercury . This includes all non cifically , a synthetic reducing agent comprising a phosphite
volatile forms of organic mercury and ionic mercury , and is added to a hydrocarbon source containing various forms
any other forms that may be present. of mercury . The hydrocarbon /phosphite mixture is then
10040 ] The total concentration of mercury will be equal to heated to convert the various forms ofmercury to elemental
the sum of the contributions from each of the various forms mercury , which can then be removed from the hydrocarbon
of mercury as shown below : source .
HgrotalHgº+Hg²+complex+Hgads+Hgother [00591. The present methods includes any of the following
where : embodiments in any combination (s ) of one ormore thereof:
[0041 ] Hgtotai – the sum total of all the species ofmercury [ 0060 ] A method of removing mercury from a hydro
[0042] Hgº = elemental mercury (can exist in gaseous, liq carbon wherein a synthetic reducing agent is mixed
uid , or solid phases) with a hydrocarbon comprising mercury in various
[ 0043] Hg2+ complex = organically -complexed ionic mercury forms, then heated to at least 100° C . and less than 2009
(mercury -thiols , etc .) C . until at least 95 % of the mercury in various forms is
converted to elemental mercury . The elemental mer
[ 0044 ] Hgads= mercury adsorbed to solid particles or cury can then be converted to gaseous elemental mer
metallic surfaces cury before removal from the hydrocarbon/reducing
[0045 ] Hgother = other forms of mercury not listed above agent mix .
[0046 ] The use of the word “ a” or “ an ” when used in [0061] A method of removing mercury from a hydro
conjunction with the term “ comprising " in the claims or the carbon that comprises various forms of mercury ,
specification means one or more than one , unless the context wherein the mercury speciation is first determined and
dictates otherwise. a reaction rate expression is created to express the
[ 0047] The term “ about” means the stated value plus or conversion of ionic mercury to elemental mercury .
minus the margin of error ofmeasurement or plus or minus Once the conversion information is determined , the
10 % if no method of measurement is indicated . hydrocarbon can be mixed with a synthetic reducing
10048 ] The use of the term “ or ” in the claims is used to agent, then heated to about 100 - 200° C ., depending on
mean " and /or” unless explicitly indicated to refer to alter the conversion information , until at least 90 % of the
natives only or if the alternatives are mutually exclusive. mercury in various forms is converted to elemental
[ 0049 ] The terms“ comprise ” , “have ”, “ include ” and “ con mercury , as calculated using the reaction rate expres
tain ” (and their variants ) are open -ended linking verbs and sion . The elemental mercury can then be converted to
allow the addition of other elements when used in a claim . gaseous elemental mercury before removal from the
[0050 ] The phrase " consisting of is closed , and excludes hydrocarbon /reducing agent mix .
all additional elements. [0062 ] An improved method of removing mercury from
[ 0051] The phrase " consisting essentially of” excludes a liquid hydrocarbon stream that is mercury rich ,
additional material elements , but allows the inclusions of wherein a synthetic reducing agent is mixed with the
non -material elements that do not substantially change the liquid hydrocarbon stream , then heating the reducing
nature of the invention . agent/ liquid hydrocarbon stream to at least 100° C . and
less than 200° C . until at least 90 % of the mercury in
[0052 ] The following abbreviations are used herein : various forms is converted to elemental mercury . The
elemental mercury can then be converted to gaseous
ABBREVIATION TERM elemental mercury.
methyl
[0063] The gaseous elemental mercury can then be
Me
Et Ethyl stripped from the hydrocarbon stream by contacting the
stream with gas stream , such as nitrogen ,methane , ethane ,
propane , butane , natural gas or combinations thereof. This
results in a treated liquid hydrocarbon stream and a mercury
BRIEF DESCRIPTION OF THE DRAWINGS rich gas stream . The mercury can there be removed from the
mercury rich gas stream by precipitation as HgS if the gas
[0053 ] FIG . 1. Literature values of concentrations ofmer stream contains hydrogen sulfide . Alternatively , mercury
cury in crude oil, from Hollebone 2007. can there be removed from the mercury rich gas stream by
[0054 ] FIG . 2. Schematic of a process for removal of precipitation as HgO .
mercury from crude oil. 0064 ] A method of removing mercury from a hydro
[0055 ] FIG . 3 . Ionic to elemental mercury conversion in carbon that contains various formsofmercury, wherein
crude oil with various concentrations of dimethyl phosphite the hydrocarbon is fed into a mixer at a predetermined
as the reducing agent. The reaction time was 5 minutes . flow rate , along with an organic phosphite that is also
100561. FIG . 4 . Decrease in the ionic mercury reduction fed into the mixer at predetermined flow rate. The
reaction temperature in crude oil with increasing amounts of hydrocarbon and organic phosphite can then be mixed ,
dimethyl phosphite as the reducing agent. and fed into a thermal soak vessel. The mixture can be
[0057] FIG . 5 . Comparison of relative reaction rate in heated in the thermal soak vessel to at least 100° C . and
direct response to increasing dimethyl phosphite concentra less than 200° C . until at least 90 wt % of the mercury
tion . in various forms is converted to elementalmercury . The
US 2019/0055477 A1 Feb . 21, 2019

elemental mercury can then be converted to gaseous [0073] U .S . Pat. No. 5 ,384,040 discloses a catalytic pro
elemental mercury before removal from the hydrocar cess for transforming mercury compounds contained in a gas
bon /reducing agent mix . condensate liquid into elemental mercury . Although not the
[0065 ] In any of the above methods, the synthetic preferred embodiment, a non -catalytic heat treatment pro
reducing agent is an organic phosphite and can be cess in the absence of hydrogen is also disclosed . The
selected from a group including , but not limited to , elemental mercury formed by the catalytic process is
triphenyl phosphite , tributyl phosphite, dibutyl phos removed from the gas condensate liquid using a solid phase
phite, triethyl phosphite , diethyl phosphite , trimethyl sorbent.
phosphite, dimethyl phosphite, ethylmethyl phosphite , [0074 ] In this disclosure , a process is described for con
or combinations thereof. Dimethyl phosphite is pre verting the various forms of mercury in a crude oil to the
ferred . elemental form using a reducing agent and heat so that the
[0066 ] The heating range in the above methods is mercury can be subsequently removed from the oil by gas
expected to fall between 100 and less than 200° C . stripping.
Depending on the type of hydrocarbon , heating ranges [0075 ] A range of different compounds with antioxidant/
can include 100° C .- 180° C . or 120 - 150° C . However, reducing properties was tested for their ability to reduce
it can also be less than 100° C ., e.g , 95°, 90°, 850, or Hg2 + and other forms of mercury in crude oil . Not all
even 80° , depending on crude components, amount of reducing agents were effective for converting ionic mercury
mercury, and plant design considerations . to elemental mercury in crude oil matrices . A variety of
amines, phenols , and phosphites were evaluated . Phosphites
[0067] In any of the above methods, the elemental demonstrated good performance . However, the phenol and
mercury can be converted to gaseous elemental mer amine reducing agents did not prove to be as effective .
cury by flashing or gas stripping . The gaseous elemen 10076 ) To further evaluate the use of phosphites as a
tal mercury can then be removed by condensation , reducing agent, a series of di- and tri -substituted alkyl and
precipitation, or absorption , adsorption, or combina aryl phosphites with varying chain lengths or phenyl sub
tions thereof. stituents were evaluated using a continuous flow reactor. The
[0068 ] In any of the above methods, the hydrocarbon performance tests revealed that the rate of ionic mercury
can be most hydrocarbon matrices, including but not conversion increased as the size of the hydrocarbon sub
limited to crude oil, natural gases, condensates, naph stituents on the phosphite molecule decreased . In other
thas, middle distillates , and waxes. words, the methyl - substituted phosphites reacted faster than
[0069 ] In crude oil, the elemental mercury redox equilib the ethyl, butyl, and phenyl - substituted compounds. How
rium , Hgº < > Hg2 + + 2e , is shifted towards the oxidized state ever, increasing the concentrations of the large alkyl-substi
(Hg2- + 2e ) at temperatures below 100° C . The equilibrium tuted phosphites narrowed the gap between reaction rates .
begins to shift towards the reduced state at temperatures [0077 ] The performance tests also revealed that the di
above 100° C . Although the Hg2 + reduction rate is too small substituted phosphites performed better than the tri -substi
at 100° C . to be commercially useful, the conversion to Hgº tuted phosphites. This appears to be due to the fact that the
will be complete in a petroleum reservoir at that temperature di- substituted phosphites have significantly better thermal
because of the geologic timescale that applies to that envi stability compared to their tri - substituted counterparts .
ronment (> 10 million years ). As such , the mercury concen [0078 ] Thus, the extent of mercury reduction in a given
tration and speciation in wellhead crude oil is a function of hydrocarbon matrix is therefore a function of the reaction
reservoir geology and temperature . temperature , the chemical composition of the reducing
[0070 ] Additionally , mercury speciation undergoes pre agent, the reducing agent concentration , and the length of
dictable changes as the physical and chemical conditions time that the oil is allowed to react.
change during oil production and transport. In crude oil [0079 ] The present methods are exemplified with respect
reservoirs at temperatures above 100° C .,mercury is present to crude oil in FIG . 2 -5 . However , this is exemplary only,
only as Hgº. After the crude is extracted from the reservoir
and its temperature falls below 100° C ., the spontaneous
and the invention can be broadly applied to any type of
hydrocarbon matrix . In view of the initial findings on the
oxidation of Hgº to Hg2+ will occur. reducing agent, Applicant performed a series of experiments
[0071 ] Hg2 + is very soluble in crude oils and is a non using a di - substituted phosphite with smaller alkyl chains:
volatile form ofmercury ,making its removal more difficult. dimethyl phosphite . However, other organic phosphites are
Thus, preheating oils to about 100° C . or 100 -200° C . with expected to work well, too .
a phosphite will convert Hg + + to Hg' , and simplify extrac [0080] The following examples are intended to be illus
tion because processes to remove elementalmercury already trative only , and not unduly limit the scope of the appended
exist. claims.
[0072 ] For example, U .S . Pat. No . 4 ,962, 276 and U . S . Pat. [0081] A block flow diagram of the disclosed mercury
No. 8 ,080, 156 disclose processes that employ gas stripping removal process is shown in FIG . 2 . A mercury -containing
to remove mercury from condensates and crude oils . These crude oil and the reducing agent is introduced into an in -line
processes, however, only work if the mercury is already in mixer to be mixed . From there, the mixed composition is
the gas strippable elemental form . As noted above , a sig introduced into a heater to quickly and efficiently preheat the
nificant portion of the mercury in a crude oil can be present crude oil to at least 100° C .
in the non -volatile ionic form , and the non - volatile ionic [0082] The heated oil is then moved into a thermal soak
mercury cannot be removed from a crude oil by gas strip vessel that is heated to a pre - determined temperature above
ping. Each of these methods can be used however, if 100° C . The crude remains in the heated soak vessel while
proceeded by the preheat stage described herein , which the mercury species are being converted into elemental
converts various forms of mercury to elementalmercury. mercury .
US 2019/0055477 A1 Feb . 21, 2019

[0083] After conversion , the crude oil flows into a gas Arrhenius equation used to calculate the effect of tempera
stripping vessel with an optional packing therein to facilitate ture ( T ) on the reaction rate constant.
contact between a stripping gas and crude oil. As shown in
FIG . 2 , the stripping gas flows from the bottom of the vessel [0091 ] The kinetics, fluid flow and heat transfer of a
through the oil. Any gas, such as nitrogen ,methane, ethane, process are important when upscaling for large -scale
propane, butane, or natural gas, can be used . designs. To retain the same reaction rate , the other variables
[ 0084 ] As the stripping gas contacts the crude oil, the in the process design must be decreased or increased as
elemental mercury is removed in the form of mercury gas. necessary . For instance , increasing vessel sizes could
The stripping gas plus mercury vapor is drawn from the top decrease the rate , such that the temperature of the conversion
of the vessel and passed through a mercury removal unit, must be increased to return the rate to its original value .
wherein the mercury can be removed from the stripping gas [0092 ] In the presently described method , the reaction rate
using an adsorption method ( filter or scrubber ). Alternative , is accelerated through the use of a reducing agent. FIG . 3
mercury can be removed from the stripping gas via precipi depicts the increase in mercury conversion at lower reaction
tation with a filter containing selenium or a gas containing temperatures and increasing concentrations of the reducing
hydrogen sulfide . agent, dimethyl phosphite. Each reaction was 5 minutes
[0085 ] The mercury -free stripping gas can then be long. As expected , the higher concentration reducing agent
recycled . The stripped crude oil will be discharged for (200 ppm ) reached at least a 90 % conversion efficiency at a
further processing. much lower temperature than the reaction without any
[0086 ] Obtaining mercury speciation and kinetic informa reducing agent.
tion , per the methods described in U .S . Pat. No. 9 ,574 ,140,
are beneficial first steps in the mercury conversion process. [0093 ]. Even when a small amount of reducing agent was
Speciation of the mercury provides information for under used , the reaction temperature was at least 40° C . less . This
standing the fate and distribution of mercury throughout the is very usefulbecause higher reaction temperatures can lead
petroleum system from reservoir rock to consumer products to degradation of hydrocarbon components or the loss of
and how to structure the conversion . Each of the mercury lower molecular weight hydrocarbons due to evaporation .
species is characterized by a unique set of properties that
define its toxicity , solubility, volatility, thermal stability , and [0094 ] As an example , in U . S . Pat.No . 9 ,574 ,140 , increas
reactivity . Thus , the amount of reducing agent, mixing ing reaction temperature increased the amount and rate of
times , and conversion temperature and time used in the mercury conversion . However, a balance had to be struck to
process depicted in FIG . 2 should be augmented for the prevent thermal degradation of other components in the
relative concentrations of various mercury species in a given crude oil or destruction of processing equipment.
hydrocarbon source to improve efficient conversion inex
pensively. [0095 ] Here, the reducing agent can be utilized to reduce
[0087 ] The process for obtaining kinetic data for the the temperature needed for the conversion process, such that
conversion of mercury to the elemental form was previously thermal degradation of hydrocarbons and /or evaporation of
described in U . S . Pat . No. 9 ,574 , 140 . The rate at which lighter weight hydrocarbons less problematic.
mercury is thermally reduced to elemental mercury is also [0096 ] FIG . 4 illustrates the decrease in reaction tempera
strongly influenced by the composition of the crude oil . ture after the addition of the synthetic reducing agent for a
Therefore, for process design purposes, it is beneficial to conversion efficiency of 95 % . The reducing agent signifi
experimentally determine the kinetics of the mercury reduc cantly lowers the reaction temperature compared to crude oil
tion reaction for the specific oil feed to the process . with no addition . At a reducing agent addition of 200 ppm
[0088 ] Kinetic data for the mercury reduction reaction for example , the reaction temperature is lowered by about
were obtained by spiking the oil with an enriched stable 70° C . FIG . 5 illustrates the relative effect of reducing agent
isotope of ionic mercury (e.g. 198Hg2+ or 201 Hg2 +). To concentration on the rate of the ionic mercury conversion
accomplish this , an enriched isotope, in the form of HgCl2 reaction .
or Hgo for example , is dissolved in the oil and the rate of
conversion of this ionic mercury standard to elemental [0097 ] Though shown with crude oil, the method can be
mercury is monitored as a function of time and temperature . applied to any hydrocarbon source . Lower molecular weight
The use of an enriched isotope allows the reduction reaction hydrocarbons such as those contained in condensates have
to be monitored accurately even though naturally occurring inherently slow mercury conversion rates . By adding a
mercury may also be present in the oil. reducing agent to these feedstocks, commercially attractive
[0089] The conversion of Hg2+ to Hgº was monitored processing rates can be achieved .
using enriched isotopic tracers and the mercury speciation [0098 ] Further, the ability to convert ionic mercury to the
procedure that was described above . elemental form at lower temperatures has significant advan
[0090 ] The results of the kinetic measurements can be tages in termsof reducing the capital and operating expenses
used to define a reaction rate expression for a specific oil that that would be required for building and operating a mercury
might have a form such as: removal unit.
[Hg2 +),=[Hg2+),eht 100991. The reducing agent's ability to accelerate the reac
k = Ae -Ea/RT tion and not be significantly affected by oil compositional
variations is an unexpected advantage. Thus , by adding an
where : k = apparent first -order rate constant; t= time; [Hg2+ ] organic phosphite reducing agent to a hydrocarbon source , a
i concentration of ionic mercury at time zero ; [Hg2 + ] simple , robust and cost- effective method for removing all
Fconcentration of ionic mercury at time t; Ae - Ear ? is the forms of mercury is obtained .
US 2019/0055477 A1 Feb . 21, 2019

[0100 ] The following references are incorporated by ref 12. The method of claim 10, wherein said organic phos
erence in their entirety . phite is dimethyl phosphite .
10101] Salvá et al ( 2010 ) SPE 138333 . 13. The improved method of claim 10 , wherein said gas
[0102] Hollebone, B . P. and C . X . Yang, “Mercury in stream is nitrogen , methane , ethane , propane, butane , or
Crude Oil Refined in Canada " , Environment Canada , natural gas .
Ottawa, ON , 2007 . 14 . The improved method of claim 10 , wherein said gas
10103 ] U . S . Pat. No. 3 , 194 ,629 stream is a natural gas stream .
0104 ] U . S . Pat. No . 4 , 962, 276 15 . The improved method of claim 10, further comprising
10105 ] U . S . Pat. No. 5 ,384 ,040 removing mercury from said mercury rich gas stream .
10106 ) U . S . Pat. No. 6 , 350 ,372 16 . The improved method of claim 10 , further comprising
[ 0107] U .S . Pat. No. 6 ,537 ,443 removing mercury from said mercury rich gas stream by
10108 ] U . S . Pat. No. 6 ,685 ,824 precipitation as Hgs , wherein said gas stream contains
10109 ] U . S . Pat. No . 6 ,806 , 398 hydrogen sulfide.
[0110] U . S . Pat. No. 8 ,080 ,156 17 . The improved method of claim 10 , further comprising
10111 ] U . S . Pat. No. 9 , 574 , 140 removing mercury from said mercury rich gas stream by
1. A method of removing mercury from crude oil , com precipitation as HgO .
prising: 18 . A method of removing mercury from crude oil ,
a ) mixing a synthetic reducing agent with a crude oil comprising :
comprising mercury in various forms to form a crude
oil mixture ; a ) determining the mercury speciation in said crude oil ;
b ) heating said crude oil mixture to at least 100° C . and b ) calculating a reaction rate expression , wherein said
less than 200° C . until at least 95 % of the mercury in reaction rate expresses the conversion of ionic mercury
various forms is converted to elemental mercury ; into elemental mercury ;
c ) converting the elemental mercury to gaseous elemental c) mixing a synthetic reducing agent with a crude oil
mercury ; and comprising mercury in various forms to form a crude
d ) removing the gaseous elemental mercury from said oil mixture ;
crude oil. d ) heating said crude oil mixture to about 100° C . - 200° C .
2 . The method of claim 1, wherein said synthetic reducing until at least 90 % of the mercury in various forms is
agent is an organic phosphite. converted to elemental mercury, wherein said 90 %
3 . The method of claim 2 , wherein said organic phosphite conversion is calculated using said reaction rate expres
is selected from a group comprising triphenyl phosphite , sion ;
tributyl phosphite, dibutyl phosphite , triethyl phosphite , e ) converting said elementalmercury to gaseous elemen
diethyl phosphite, trimethyl phosphite , dimethyl phosphite tal mercury ; and
or combinations thereof. f ) removing said gaseous elemental mercury.
4 . The method of claim 3, wherein said organic phosphite 19 . A method of removing mercury from crude oil ,
is dimethyl phosphite . comprising:
5. The method of claim 1, wherein said heating is between a ) feeding a crude oil comprising mercury in various
100° C - 180° C . forms into a mixer at a predetermined flow rate ;
6 . The method of claim 1,wherein said heating is between b ) feeding an organic phosphite in said mixer at prede
120 - 150° C . termined flow rate;
7. The method of claim 1, where said converting step is
by flashing.
c ) mixing said crude oil and said organic phosphite to
form a crude oil mixture ;
8 . The method of claim 1, where said converting step is d ) feeding said crude oil mixture into a thermal soak
by gas stripping . vessel;
9 . Themethod of claim 1 , where said removing step is by e ) heating said crude oil mixture a first time period in said
condensation , precipitation , or absorption , adsorption , or thermal soak vessel to at least 100° C . and less than
combinations thereof. 200° C . until at least 90 wt % of the mercury in various
10 . An improved method of removing mercury from forms is converted to elemental mercury ;
crude oil, the method comprising contacting a liquid hydro f) converting the elementalmercury to gaseous elemental
carbon stream having mercury contaminants with a gas mercury; and
stream to thereby form a treated liquid stream and a mercury g ) removing the gaseous elemental mercury from said
rich gas stream , wherein the improvement comprises first
mixing the liquid hydrocarbon stream with an organic phos crude oil.
phite before heating the mixed liquid hydrocarbon stream 20 . The improved method of claim 19 , wherein said
having mercury contaminants at 100 -200° C . until 90 % of organic phosphite is selected from a group comprising
said mercury contaminants are converted to elemental mer triphenyl phosphite , tributyl phosphite, dibutyl phosphite,
cury , and then contacting said heated liquid hydrocarbon triethyl phosphite , diethyl phosphite , trimethyl phosphite ,
stream with a gas stream to thereby form a treated liquid dimethyl phosphite or combinations thereof.
stream and a mercury rich gas stream . 21 . The method of claim 19 , wherein said organic phos
11 . The improved method of claim 10 , wherein said phite is dimethyl phosphite .
organic phosphite is selected from a group comprising 22 . A method of removing mercury from crude oil ,
triphenyl phosphite , tributyl phosphite, dibutyl phosphite, comprising:
triethyl phosphite , diethyl phosphite , trimethyl phosphite , a ) mixing dimethyl phosphite with a crude oil comprising
dimethyl phosphite or combinations thereof. mercury in various forms to form a crude oil mixture ;
US 2019/0055477 A1 Feb . 21, 2019

b ) heating said crude oil mixture to at least 100° C . and

less than 200° C . until at least 95 % of the mercury in
various forms is converted to elemental mercury ;
c ) converting the elemental mercury to gaseous elemental
mercury ; and
d ) removing the gaseous elemental mercury from said
crude oil.