USOO5662878A

United States Patent (19 11 Patent Number: 5,662.878

54 PROCESS FOR THE PRODUCTION OF 2,215,883 9/1940 Riedl et al. ............................. 423,588
HYDROGEN PEROXDE 3,009,782 11/1961 Porter ................. ... 42.3/588
3,923,967 12/1975 Kirchner et al. ... ... 42.3/588
: 0 inn r^s it S. 5,147,628 9/1992 Simon et al. ...... ... 42.3/588
75 Inventors GE ESSEE 5,538,640 7/1996 Wijmans et al. ....................... 210/640
Naperville, all of Ill. FOREIGN PATENT DOCUMENTS
73 Assignee: University of Chicago, Chicago, Ill. 293524 10/1992 Japan ..................................... 423,588
21 Appl. No.: 637,864 Primary Examiner Wayne A. Langel
Attorney, Agent, or Firm-Cherskov & Flaynik
22 Filled: Apr. 25, 1996
6 57 ABSTRACT
511 Int. Cl. ............................................. CO1B 15/023
52 423/588; 210/640 An integrated membrane-based process method for produc
58 Field of Search .................................... 423/588, 589, ing hydrogen peroxide is provided comprising oxidizing
423/590,584; 210/640,641 hydrogenated anthraquinones with air bubbles which were
created with a porous membrane, and then contacting the
56 References Cited oxidized solution with a hydrophilic membrane to produce
U.S. PATENT DOCUMENTS
an organics free, H2O laden permeate.
g 2V2
2,158,525 5/1939 Riedl et al. ............................. 423/588 20 Claims, 1 Drawing Sheet

f3
-N- 17
ABC

10

19 /
12 14 18 AR

r 2O
15 16
|

24 25
U.S. Patent Sep. 2, 1997 5,662,878

O
CN

s s
SQ
SN &
O
Q

Y, S

9. so
5.V. SN
CN

wt N
 5,662,878
1. 2
PROCESS FOR THE PRODUCTION OF Conventional processes to extract HO from reaction
HYDROGENPEROXDE liquor also has several drawbacks. Such processes utilize
counter-current, multi-stage, liquid-liquid extraction of the
CONTRACTUAL ORIGIN OF THE INVENTION anthraquinone working solution (AQS) with water.
The United States Government has rights in this invention 5 However, these procedures result in a very low (1:20, i.e.,
pursuant to Contract No. W-31-109-ENG-38 between the one part water extract to 20 parts of AQS) phase ratio
U.S. Department of Energy and the University of Chicago, between water extract and the AQS. HO concentration in
representing Argonne National Laboratory. the aqueous fraction has to be high in these processes so that
Subsequent HO isolation steps can proceed more economi
BACKGROUND OF THE INVENTION 10 cally. As such, typical extractors are multi-stage, very large
1. Field of the Invention in volume and difficult to scale down. These systems can be
highly unstable and thus require a high degree of operational
This invention relates to amethod for producing hydrogen control. Finally, a certain amount of the polar solvents also
peroxide, and more specifically, this invention relates to a enters the final aqueous phase in these processes. This
method for producing hydrogen peroxide via the utilization 15 results in contamination of the HO phase and ultimately,
of advanced membrane technology loss of the solvent. Typical extraction equipment has 23
2. Background of the Invention countercurrent stages and is approximately 100 feet tall.
Environmental considerations and regulations continue to Efforts have been made to minimize ancillary reducing
prompt industries to use compounds which are less detri reactions (leading primarily to nuclear hydrogenation of the
mental to the ecosystem. One example is the dramatic 20 aromatic nuclei of the working solution) to prevent loss of
increase in the use of hydrogen peroxide for pulp and paper solvent and anthraquinone feedstock (U.S. Pat. No. 3,009,
industry applications. Instead of relying on chlorine and 782 to Porter). However, final fractions of HO, still contain
chlorine dioxide bleaching processes, many paper producers high levels of organic contaminants that require further
now utilize chemithermo-mechanical pulping where hydro isolation and polishing.
gen peroxide facilitates pulp brightness. The use of hydro 25 Finally, and not surprisingly, the costs associated with the
gen peroxide in this industry has increased-to approximately typical highly capital- and energy-intensive, large scale
300,000 metric tons, which is 50 percent of current North hydrogen peroxide processes are passed on to low-volume
American production capacity. Such usage will continue to end users. These end users would benefit from methods for
increase significantly. producing hydrogen peroxide more economically.
The use of hydrogen peroxide is expanding quickly in 30 A need exists in the art for a process to produce hydrogen
other markets as well, such as in water and waste treatment, peroxide without the concomitant capital costs and handling
mining, chemical processing, textiles and industrial clean problems associated with current production schemes. The
ing. Current world wide production annually is 1.4 million process would allow effective HO production in small
metric tons, with a 7 percent annual growth rate. plant environments and therefore would have a small size or
Hydrogen peroxide production is controlled by a few 35 footprint compared to the footprint of the "host” industrial
chemical companies that produce it in large scale plants as site. Finally, the H2O process would be as modular as
a 70 percent concentrate. However, the highly oxidative possible with the ability for quick start-up, shut-down and
characteristics of that level of concentration requires nearly turnaround, while also accommodating variability in pro
immediate dilution to 50 percent concentration for safe duction rates.
transport. Ultimately, hydrogen peroxide is used in concen 40
trations of approximately 5-10 percent. Typical HO pro SUMMARY OF THE INVENTION
duction processes are based on anthraquinone reduction It is an object of the presentinvention to provide a method
oxidation chemistry. The typical process steps are (1) for producing hydrogen peroxide that overcomes many of
hydrogenation of anthraquinone working solution in a fixed the disadvantages and shortcomings of the prior art.
bed reactor; (2) separation of the catalyst fines; (3) oxidation 45 It is another object of the present invention to provide a
of the hydrogenated anthraquinone working solution by air process for economically producing hydrogen peroxide. A
in a multi-stage packed bed tower while simultaneously feature of the invention is the utilization of membrane
producing H2O in the organic stream; (4) extraction of the technologies to isolate hydrogen peroxide from the process
HO, from the anthraquinone working solution by water in reaction liquid. An advantage of the invention is the render
a multistage counter-current extraction column process; (5) 50 ing of hydrogen peroxide that is virtually free of organics.
recovery and polish purification of the anthraquinone work Another advantage of the invention is the ability to retain
ing solution, the accompanying solvents, and their recycle to expensive organic solvents in reaction liquors for reuse.
the hydrogenator; and (6) recovery, polish purification and Yet another object of the present invention is to provide a
stabilization of the HO product. modularized process for producing hydrogen peroxide. A
The typical process outlined above, disclosed in U.S. Pat. 55 feature of the process is supplanting multi-stage packed bed
Nos. 2,158.525 and 2,215,883 to Pfiderer and Riedel, oxidation towers found in typical peroxide production sys
respectively is suitable for large scale production of H2O. tems with membrane systems. An advantage of the invention
However, the process is unsuitable for small scale produc is the minimization of the footprint and costs associated with
tion (500-1,000 metric tons per year) and medium scale the production of hydrogen peroxide.
production (5,000 metric tons per year). This is because the Briefly, a method for producing hydrogen peroxide is
packed tower used for oxidation, and the column for HO, provided comprising supplying an anthraquinone
extraction are very large and do not easily scale up or down containing solution; subjecting the solution to hydrogen to
for modularity and operational flexibility. For example, for hydrogenate the anthraquinone; mixing air with the solution
a nominal 5,000 metric ton per year mini-plant, the containing hydrogenated anthraquinone to oxidize the solu
oxidation-tower will have three beds 4.5 feetin diameter and 65 tion; contacting the oxidized solution with a hydrophilic
15 feet tall, stacked in series. The height of the equipment for membrane to produce a permeate; and recovering hydrogen
this single oxidation process is more than 60 feet. peroxide from the permeate.
 5,662,878
3 4
BRIEF DESCRIPTION OF THE DRAWING This starter material 12 is solubilized via a ternary solvent
These and other objects and advantages of the present system into an initial stream 13 to yield a homogenous liquid
invention will become readily apparent upon consideration phase 14. This phase 1-4 is subjected to a hydrogenation
of the following detailed description and attached drawing, step 15. The hydrogenation step converts 2-ethyl
wherein anthraquinone to 2-ethyl anthrahydroquinone and tetrahydro
FIG. 1 is a schematic diagram of a method for producing 2-ethyl anthraquinone to tetrahydro 2-ethyl anthrahydro
hydrogen peroxide, in accordance with the present inven quinone to comprise a hydrogenated solution 16. The hydro
tion. genated solution 16 is then subjected to a particulate
DETALED DESCRIPTION OF THE 10
removal step 18 so as to remove any catalyst fines. The now
INVENTION filtered hydrogenated solution is oxidized via a membrane
The present invention provides an improved process for perfusion reactor 20, which consists of a porous membrane
production of HO via mini-plants by the use of advanced system to produce finely divided air bubbles to saturate the
membrane technologies of perfusion, perstraction and per solution with oxygen. As can be noted in Equation 2, Supra,
vaporation. 15 this oxidation step regenerates the starter anthraquinone
The invented process revolves around the well known materials and the desired product, hydrogen peroxide.
successive hydrogenation and oxidation of alkytan The oxidized solution 21, now containing hydrogen
thraquinones depicted below in Equations 1 and 2. peroxide, is contacted with a pervaporation membrane 23
associated with a pervaporation and/or perstraction process
O Eq. 1 20 22 so as to produce a permeate 25 containing polar, volatile
compounds, namely water and hydrogen peroxide. This
R
+H2 - Catalyst
alyst e permeate 25 can be subjected to further polishing 26 such as
distillation so as to boil off water and other lower fractions,
25
thereby leaving the hydrogen peroxide. Materials retained
O by the pervaporation membrane 23, such as solvents and
OH anthraquinones are recirculated via a recirculation means 24
back to the make-up stream step 13, noted supra, for reuse.

OH
OOO". OH
Eq. 2
30
Solvent System Detail
In the pure state, 2-ethyl anthraquinone (EAQ) and tet
rahydro 2-ethyl anthraquinone (THEAQ) are solids and
must be pretreated by being dissolved in an appropriate
solvent system. The EAQ and THEAQ are soluble in one
type of solvent and their hydrogenation products 2-ethyl
R 35 anthrahydroquinone (EAHO) and tetrahydro 2-ethyl
+ O: -G) anthrahydroquinone (THEAHQ), respectively, are soluble in
another type of solvent. The mix of the EAQ and THEAQ,
OH and their hydrogenation products, all dissolved in their
40
appropriate solvents, is called the anthraquinone working
O
solution (AQS).
R The initial stream 13 results from the use of a ternary
- H2O2 solvent mix solvent A, B and C. Solvent A is chosen to
dissolve EAQ and THEAQ, which are readily soluble in
45 alkylated aromatic solvents. Solvent B is chosen to solubi
O lize the hydrogenated intermediates EAHQ and THEAHQ,
which are polar compounds. Solvent C provides more com
where R connotes an alkyl group, such as ethyl, and the patibility between the two solvent systems, and also
hydrogenation catalyst is any suitable catalyst that fosters improves the rate and selectivity of the hydrogenation step.
the reduction of the quinone group to the hydroquinone 50
Solvent A is a mixture of alkylated aromatics. A suitable
group. mixture, commercially available from Shell Oil Co., is
An exemplary embodiment of the invented process is CYCLO-SOL 63TM. This trade name compound is typically
designated as numeral 10, in FIG. 1. Briefly, starter bench-marked as having 80 percent C-10 and C-11 alkyl
anthraquinone material 12 is first selected. While a myriad benzenes, 3.2 percent C-8, C-9 and C-12 alkyl benzenes,
of alkyl anthraquinones are suitable for HO production, 55
13.3 percent cycloalkylbenzenes, and 3.5 percent naphtha
the inventors choose to illustrate their process using 2-ethyl lene. Other suitable alkylated aromatics are commercially
anthraquinone and-tetrahydro 2-ethyl anthraquinone as the available from Exxon Corp., as Aromatic 150TM and Aro
starter anthraquinone material 12. However, the choice of matic 100TM.
starter materials here should not be construed as limiting the Solvent B is a polar solvent, such as Tri(w-ethylhexyl)
invented process to these species. Rather, a myriad of 60
phosphate (TOF). Another suitable polar solvent for solu
Working materials are suitable, including, but not limited to, bilizing the hydrogenated anthraquinone materials is
2-ethylanthraquinone, 2-isopropylanthraquinone, 2-sec disobutylcarbinol.
butylanthraquinone, 2-t-butylanthraquinone, 2-sec
amylanthraquinone, 1,3-dimethylanthraquinone, 2,3- Solvent C candidates include tetra alkyl ureas such as
dimethyl-anthraquinone, 14 dimethylanthraquinone, 2.7- 65 N,N-Diethyl-N,N-Di-n-Butyl-urea (DEDBU).
dimethylanthraquinone, amylanthraquinone, A typical composition of the working solution (AQS) is
tetrahydroamylanthraquinone and combinations thereof. disclosed in Table 1, below:
 5,662,878
5 6
reactor volumes and heights. However, the invented method
TABLE 1. utilizes more compact membrane-based perfusion contac
tOS.
Composition of an Exemplary Anthraquinone Working Solution Membranes with very high porosity that can enable the
Component Weight Percent' dispersion of very fine gas bubbles into a liquid stream are
used to mix an oxygen containing fluid, such as air, oxygen
2-ethyl anthraquinone (EAQ) 4.5 gas, or some other oxygen-containing gas, into the hydro
tetrahydro 2-ethyl anthraquinone (THEAQ) 13.5
Polar Solvent 100 genated AQS and oxidize it. One such membrane, comprised
Tetra alkyl urea 0-10 mainly of polypropylene, is manufactured by Hoechst
Inerts + miscellaneous
Alkylated aromatic solvent
40
remainder
10 Celanese Inc. and sold under the trade name Celligard TM.
Oxidation via the Cellgard TM membrane occurs in the oxi
'Values to add to 100. dation step 20 when liquid contacts a first side of the
A suitable polar solvent is tri (w-ethylhexyl) phosphate. membrane and the oxygen-containing fluid (e.g. gas such as
A suitable urea compound is N,N-Diethyl-N,N-Di-n-Butyl urea. air or oxygen) contacts a second side of the membrane. The
Inerts generally are epoxides of anthraquinones. 15 gas which may be compressed, first flows through microtu
Such as Cyclo-sol-63. bules contained on the second side of the membrane. The
The above exemplary composition should not be con microtubule structure allows the gas to pass through the fine
Strued as limiting the anthraquinone working solution to pores of the first side of the membrane to mix with the liquid.
certain weight percent values. Rather, a myriad of weight Generally, the average residence time of the liquid in the
percents for the AQS working solution produce good results. 20 perfusion membrane can range from between approximately
For example, suitable ranges for 2-ethyl anthraquinone is 0.5 minutes to 5 minutes. Oxygen-containing gas pressures
approximately 3.5 to 6 weight percent. Suitable ranges for applied to the second side of the membrane can range from
the tetrahydro 2-ethyl anthraquinone is approximately 10 between approximately 1-4 atmospheres (15-60 psi).
and 15 weight percent. A suitable range for the polar solvent The use of these types of membranes results in very high
is approximately 8 to 12 weight percent. 25 contact efficiency between liquid and gas. Furthermore,
Hydrogenation Detail unlike typical oxidation modules, Small volume structures
The hydrogenation step 15 is carried out in a fixed bed provide suitable oxidation rates, with oxidation reactor
reactor at pressures ranging from approximately 3 to 10 volumes reduced by approximately 90 percent. This type of
atmospheres, and at temperatures ranging from between oxidation module 20 provides tremendous operational flex
approximately 35° C. and 70° C., with preferred tempera 30 ibility for easy start up and shut down while also accom
tures ranging from between approximately 40° C. and 50° C. modating variations in production rates.
The catalyst in the hydrogenation reactor is comprised of
any of the suitable catalysts known to foster the reduction of Other suitable membranes can, be made from finely
the quinone group to the hydroquinone group, as for instance sintered metals, ceramic and polymeric materials, such as
Raney nickel, or one of the noble metals such as ruthenium, polysulfonic and polyvinylidenefluoride.
rubidium, platinum, rhodium or palladium. Palladium, as 35 HO, Separation Detail
one of the more common catalysts employed, is used herein The nominal concentration of HO, in the oxidized AQS
at 0.3-0.35 weight percent dispersed on alumina, wherein solution 21 is 10-20 grams per liter. As noted above, it is the
the alumina used is delta or theta alumina and therefore separation of this low concentration of H2O from the
substantially free of alpha, gamma, or alpha alumina mono reaction liquor, and concomitantly obtaining the same H2O2
hydrate. concentration in the permeate, that proves to be problematic
The hydrogen feed 17 is substantially free of catalyst with conventional production processes.
poisoning chemicals, such as sulfur compounds, carbon The invented extraction process 22 utilizes pervaporation
monoxide, and chlorine compounds. Also, to maintain a membranes 23 to greatly simplify the extraction process,
positive output at bleed-offs and through the hydrogenation particularly for Small or mini-plant operations. In this per
reactor, between approximately 1 and 10 percent of the 45 vaporation process step, hydrophilic membranes enable the
hydrogen feed 17 is an inert carrier gas such as nitrogen, permeation of aqueous and volatile hydrophilic constituents
argon, neon, helium and noble fluids, generally. of the mixture while retaining the non-hydrophilic and
Fresh hydrogen is mixed with recycled hydrogen and fed non-volatile constituents for recycle.
with the AQS in a down-flow mode to the packed bed Generally, the pervaporation membranes 23 employed
hydrogenation reactor 15 where the catalyst particles are 50 consist of a nonporous polyvinyl alcohol active layer on a
dispersed in vertical cylindrical tubes arranged to provide a porous supporting layer. For example, membranes manufac
high degree of contacting efficiency. Generally, from 20 to tured by GFT, Inc. in Neunkirchen-Heinitz, Germany, hav
200 liters per minute per square foot of catalyst bed cross ing the GFT PerVap 1001 or 1005 trade names consist of a
area is a suitable range. After hydrogenation occurs in the non-porous polyvinyl alcohol active layer on a porous
tubular reactors, the converted gas is re-compressed and 55 supporting layer made of polyester and polyacrylonitrile
recycled via a gas recirculation loop 19 while the AQS is which are resistant to organics. Another membrane which
passed through in-line filters in the particulate removal step has alkali resistance is marketed as GFTPerVap 2001. Here,
18 to remove any hydrogenation catalyst fines. In as much the porous supporting layer is poly-acrylonitrile, only.
as the hydrogenation step is somewhat exothermic, the Another Manufacturer of such membranes is Texaco, Inc. of
hydrogenated AQS may need to be cooled prior to feeding White Plains, N.Y., and a typical hydrophilic membrane is
the solution to the next phase of the process, which is the TexSep 1B. Membranes made of Nafion (Dupont) which is
oxidation step, discussed below. Solution temperatures hydrophilic-derivatized Teflon also can be used.
adjusted to between approximately 20° C. and 70° C. are The oxidized AQS, which contains low concentration of
suitable for the next step of the process. hydrophilic compounds and volatile H2O, is fed to the
Oxidation Detail 65 pervaporation unit where HO and HO selectively perme
As noted above, conventional oxidation processes employ ates through the membrane. The organics, including the
packed bed or bubble column reactors which require large polar but nonvolatile solvent tri (w-ethylhexyl) phosphate,
 5,662,878
7 8
are retained and recirculated via a recirculation loop 24. A 2-ethyl anthraquinone, tetrahydro 2-ethyl anthraquinone,
number of advantages are realized as a result of the utiliza and combinations thereof.
tion of the pervaporation unit. First, the selectivity of the 7. A method for producing hydrogen peroxide compris
membrane is very high (>>100) and hence the resulting Ing:
HO permeate 25 is essentially organic free. Furthermore, a.) Supplying an anthraquinone-containing solution;
solvent losses are negligible. These low solvent concentra b.) subjecting said solution to hydrogen to hydrogenate
tions in the permeate also results in the elimination of the the anthraquinone;
formation of undesirable emulsions in permeate streams, c.) mixing an oxygen-containing gas stream with said
which is typical in conventional processes. solution containing hydrogenated anthraquinone to oxi
HO, flux rates through the pervaporation membrane of 10 dize the solution;
0.1 to 1.0 kilograms per minute per square meter are d.) contacting said oxidized solution with a hydrophilic
obtained in the invented process. Desired flux rates, and membrane to produce a permeate; and
desired concentrations of HO, (i.e. 10-50 percent H2O in e.) recovering the hydrogen peroxide from said permeate
water) can be maintained by the addition of water to the wherein the step of mixing an oxygen-containing gas
AQS stream during pervaporation. One preferable final 15 with the solution containing hydrogenated anthraquino
target HO concentration is approximately 40 percent H.O. nes further comprises:
in Water. f) supplying a perfusion membrane having a first side and
Water also can be added to the permeate side of the a second side;
membrane. Given that water has an affinity to pull H2O2 out g) contacting the solution with the first side of said
of solution, this modified process essentially becomes a 20 perfusion membrane; and
pervaporation/perstraction stage whereby the added water h.) contacting the second side of the perfusion membrane
enhances the H2O, extraction from the AQS. The amount of with an oxygen-containing gas so as to cause the gas to
water added to the AQS stream is determined by the desired pass through the-membrane and mix with the solution.
final concentration of H2O. Alternatively, only a first 8. The method as recited in claim 7 wherein the oxygen
amount of water can be added to the AQS process stream, 25 containing gas, stream is air that is compressed.
with a second amount of water to be added to the permeate, 9. The method as recited in claim 7 wherein the step of
to achieve desired H2O2 dilutions. contacting the oxidized solution with a hydrophilic mem
While the invention has been described with reference to brane further comprises adding an amount of water to the
details of the illustrated embodiment, these details are not oxidized solution prior to contacting the oxidized solution
intended to limit the scope of the invention as defined in the 30 with the hydrophilic membrane to facilitate the permeation
appended claims. of hydrogen peroxide, thereby resulting in the permeate
The embodiment of the invention in which an exclusive containing a predetermined concentration of hydrogen per
property or privilege is claimed is defined as follows: oxide in water.
1. A method for producing hydrogen peroxide comprising 10. The method as recited in claim 7 wherein the step of
a.) supplying an anthraquinone-containing solution; 35 contacting the oxidized solution with a hydrophilic mem
b.) subjecting said solution to hydrogen to hydrogenate brane further comprises:
the anthraquinone; a.) determining a final amount of water necessary to
c.) mixing an oxygen-containing gas stream with said render a predetermined hydrogen peroxide concentra
solution containing hydrogenated anthraquinone to oxi tion in the permeate, said final amount of water the sum
dize the solution; of a first amount of water and a second amount of
water;
d) contacting said oxidized solution with a hydrophilic b.) adding said first amount of water to the oxidized
membrane and adding water to a permeate side of the solution prior to contacting the oxidized solution with
hydrophilic membrane to produce a permeate contain the hydrophilic membrane;
ing hydrogen peroxide; and 45
e.) recovering the hydrogen peroxide from said permeate. c.) contacting the water and oxidized solution mixture
2. The method as recited in claim 1 wherein the with the hydrophilic membrane; and
anthraquinone-containing solution contains anthraquinones d.) adding the second amount of water to the permeate.
and a ternary solvent mixture. 11. A method for producing hydrogen peroxide compris
1ng:
3. The method as recited in claim 2 wherein the ternary 50
a.) Supplying a homogenous liquor containing
solvent mixture solubilizes the anthraquinones and hydro anthraquinones and a ternary solvent mixture;
genated anthraquinones into a homogenous liquor.
4. The method as recited in claim 3 wherein the ternary b.) subjecting said liquor to hydrogen to produce hydro
solvent mixture is comprised of solvents selected from the genated anthraquinones;
group consisting of alkylated aromatics, polar solvents, tetra 55 c.) exposing said liquor containing said hydrogenated
alkyl ureas, and combinations thereof. anthraquinones to oxygen-containing gas via a perfu
5. The method as recited in claim 1 wherein the Sion reactor to produce a mixture containing hydrogen
anthraquinones are selected from the group consisting of peroxide and to regenerate said anthraquinones;
2-ethyl anthraquinone, tetrahydro 2-ethyl anthraquinone, d) contacting said mixture containing hydrogen peroxide
2-isopropylanthraquinone, 2-sec-butylanthraquinone, 2-t- 60 and regenerated anthraquinones with a pervaporation
butylanthraquinone, 2-sec-amylanthraquinone, 1.3-di membrane and adding water to a permeate side of the
methylanthraquinone, 2,3-dimethyl-anthraquinone, 1.4 membrane so as to create a hydrogen peroxide perme
dimethylanthraquinone, 2,7-dimethylanthraquinone, ate and a working solution retentate; and
amylanthraquinone, tetrahydroamylanthraquinone and com e.) recovering the hydrogen peroxide from the permeate.
binations thereof. 65 12. The method as recited in claim 11 wherein the
6. The method as recited in claim 1 wherein the anthraquinones are selected from the group consisting of
anthraquinones are selected from the group consisting of 2-ethyl anthraquinone, tetrahydro 2-ethyl anthraquinone.
 5,662,878
9 10
13. The method as recited in claim 11 wherein the ternary hydrogenated anthraquinones to oxygen-containing gas
solvent liquor contains solvents selected from the group via a perfusion reactor to produce a mixture containing
consisting of alkylated aromatics, polar solvents, tetra alkyl hydrogen peroxide and to regenerate said anthraquino
ureas, and combinations thereof. nes further comprises:
14. The method as recited in claim 13 wherein the
aklykated aromatics are capable of dissolving f) supplying a perfusion membrane having a first side and
anthraquinones, the polar solvents are capable of dissolving a second side;
hydrogenated anthraquinones, and the tetraalkyl ureas are g) contacting the liquor with the first side of said perfu
selected to homogenize the ternary solvent system. sion membrane; and
15. The method as recited in claim 11 wherein the O
h.) contacting the second side of the perfusion membrane
hydrogenated anthraquinones are selected from the group with an oxygen-containing gas so as to cause the gas to
consisting of 2-ethyl anthrahydroquinone, tetrahydro 2-ethyl
anthrahydroquinone, and combinations thereof. pass through the membrane and mix with the liquor.
16. The method as recited in claim 11 wherein the 18.The method as recited in claim 17 wherein the step of
pervaporation membrane is hydrophilic. 15 contacting said mixture containing hydrogen peroxide and
17. A method for producing hydrogen peroxide compris regenerated anthraquinones with a pevaporation membrane
Ing: so as to create a hydrogen peroxide permeate and a working
a.) supplying a homogenous liquor containing solution retentate is preceded by combining said mixture
anthraquinones and a ternary solvent mixture; containing hydrogen peroxide and regenerated anthraquino
b.) subjecting said liquor to hydrogen to produce hydro nes with an amount of water so as to result in the permeate
genated anthraquinones; containing a predetermined concentration of hydrogen per
c.) exposing said liquor containing said hydrogenated oxide in water.
anthraquinones to oxygen-containing gas via a perfu 19. The method as recited in claim 18 wherein the
sion reactor to produce a mixture containing hydrogen 25 predetermined concentration of hydrogen peroxide is
peroxide and to regenerate said anthraquinones; selected from a range of between 10 percent and 50 percent
d) contacting said mixture containing hydrogen peroxide hydrogen peroxide in water.
and regenerated anthraquinones with a pervaporation 20. The method as recited in claim 18 wherein the
membrane so as to create a hydrogen peroxide perme predetermined concentration of hydrogen peroxide is
ate and a working solution retentate; and 30 approximately 40 percent hydrogen peroxide in water.
e.) recovering the hydrogen peroxide from the permeate,
wherein the step of exposing said liquor containing said * : * : :
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 5, 662,878
DATED : September 2, 1997
INVENTOR(S) : Datta et al.

it is certified that error appears in the above-indentified patent and that said Letters Patent is hereby
corrected as shown below:

Column 8, line 25, after the word "containing," delete "gas," and insert
the Word --gas--.

Column 10, line 16, after the word "a," delete "pevaporation" and insert
the word --pervaporation--.

Signed and Sealed this

Attest: 6. (east
BRUCE LEHMAN

Attesting Officer Commissioner of Patents and Tradenaarks