US4064040A
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US
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Sour water treating process utilizing liquid membranes having a sulfonated polymer exterior oil phase
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1976-05-03
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Granted: 1977-12-20
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Expires: 1996-05-03
Abstract
Abstract This invention relates to novel liquid membrane formulations which are water-in-oil emulsions wherein the oil phase comprises a sulfonated polymer having a backbone which is substantially nonaromatic, for example, less than 10 mole % aromatic, and uses thereof in high temperature liquid membrane processes. The emulsions are useful in liquid membrane water treating processes, especially in water treating processes which are desirably run at high temperatures. In the most preferred embodiment, these compositions are used in a liquid membrane sour water treating process wherein a waste water stream containing ammonium sulfide is contacted with a liquid membrane emulsion, i.e. the emulsions of the instant invention, at conditions whereby ammonia permeates through the external phase of the emulsion into an acidic internal phase wherein it is converted to a nonpermeable form, e.g. ammonium ion, while H 2 S is continuously stripped out of the waste water solution by means of an inert gas, e.g. steam. Processes of this sort are most effectivey carried out at temperatures greater than 80° C. wherein the emulsions of the instant invention have excellent stability.
Inventors
- 👤 Gopal H. Singhal
- 👤 Martin L. Gorbaty
- 👤 Richard M. Minday
- 👤 Norman N. Li
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 02:42
CPC Classifications
C; C08; C08J; C08J3/00; C08J3/02; C08J3/09; B; B01; B01D; B01D61/00; B01D61/38; B01D61/40
Claims Analysis
Total Claims: 49
Claim 1
Independent Claim
189 words
A process for the removal of the salts of a weak acid and a weak base from an aqueous solution which comprises contacting said solution with a water-in-oil emulsion, said emulsion comprising from 10 to 90 weight % of an oil exterior phase, the balance of the emulsion being an aqueous interior phase, said exterior phase being characterized as immiscible with said solution and permeable to said weak base, said exterior phase comprising a sulfonated polymer and a solvent for said polymer, said sulfonated polymer having an average molecular weight of at least 1,000, said sulfonated polymer comprising a substantially nonaromatic backbone and from 0.25 to 20 mole % sulfonic acid groups, said polymer being present in said exterior phase from 0.05 to 40 weight % based upon solvent weight, said interior phase comprising a reactant which is capable of converting said weak base to a nonpermeable form, whereby said weak base permeates through said exterior phase into said interior phase wherein it is converted to a nonpermeable form, and removing said weak acid by passing an inert gas through said solution or subjecting the system to subatmospheric pressures.
Claim 2
Dependent Claim
189 words
A process for the removal of the salts of a weak acid and a weak base from an aqueous solution which comprises contacting said solution with a water-in-oil emulsion, said emulsion comprising from 10 to 90 weight % of an oil exterior phase, the balance of the emulsion being an aqueous interior phase, said exterior phase being characterized as immiscible with said solution and permeable to said weak base, said exterior phase comprising a sulfonated polymer and a solvent for said polymer, said sulfonated polymer having an average molecular weight of at least 1,000, said sulfonated polymer comprising a substantially nonaromatic backbone and from 0.25 to 20 mole % sulfonic acid groups, said polymer being present in said exterior phase from 0.05 to 40 weight % based upon solvent weight, said interior phase comprising a reactant which is capable of converting said weak base to a nonpermeable form, whereby said weak base permeates through said exterior phase into said interior phase wherein it is converted to a nonpermeable form, and removing said weak acid by passing an inert gas through said solution or subjecting the system to subatmospheric pressures.
Claim 3
Dependent Claim
11 words
The process of claim 1 wherein said inert gas is steam.
Claim 4
Dependent Claim
29 words
The process of claim 1 wherein said weak acid is selected from the group consisting of H 2 S, SO 2 , CO 2 , HCN, HF, and phenol.
Claim 5
Dependent Claim
19 words
The process of claim 1 wherein said weak base is selected from the group consisting of ammonia and amines.
Claim 6
Dependent Claim
11 words
The process of claim 1 wherein said salt is ammonium sulfide.
Claim 7
Dependent Claim
11 words
The process of claim 5 wherein said inert gas is steam.
Claim 8
Dependent Claim
29 words
The process of claim 6 wherein said removal is carried out at a temperature of from 75° to 220° F. and a pressure of from 0.2 to 1 psig.
Claim 9
Dependent Claim
20 words
The process of claim 7 wherein said ammonium sulfide comprises from 20 to 10,000 ppm by weight of said solution.
Claim 10
Dependent Claim
24 words
The process of claim 8 wherein said reactant comprises an acid selected from the group consisting of phosphoric acid, sulfuric acid, and hydrochloric acid.
Claim 11
Dependent Claim
29 words
The process of claim 8 wherein said reactant comprises an acid selected from the group consisting of benzene polycarboxylic acids, aliphatic polycarboxylic acids, sulfocarboxylic acids and acid salts thereof.
Claim 12
Dependent Claim
66 words
The process of claim 10 wherein said emulsion is separated from said solution after the acid is substantially neutralized and conveyed to a regeneration zone wherein said emulsion is contacted with steam at a temperature of from 230 to 450° F. and at a pressure of from 5 to 300 psig for a period sufficient to convert said acid substantially back to a less neutralized form.
Claim 13
Dependent Claim
61 words
The process of claim 1 wherein said solvent for the sulfonated polymer is selected from the group consisting of pertroleum distillates having a boiling point of greater than 200° C; paraffinic solvents having substituents selected from the group consisting of halogen, benzene, and cycloalkyl ring; isoparaffins having an average carbon number of from about 10 to about 100; and combinations thereof.
Claim 14
Dependent Claim
22 words
The process of claim 1 wherein said sulfonated polymer has an average molecular weight of from at least 1,000 to about 50,000.
Claim 15
Dependent Claim
19 words
The process of claim 1 wherein said sulfonated polymer comprises up to about 4.0 mole % sulfonic acid groups.
Claim 16
Dependent Claim
20 words
The process of claim 12 wherein the sulfonated polymer has an average molecular weight of from 5,000 to about 50,000.
Claim 17
Dependent Claim
22 words
The process of claim 1 wherein the exterior oil phase constitutes from 30 to 60 weight % of the total emulsion composition.
Claim 18
Dependent Claim
22 words
The process of claim 1 wherein said sulfonated polymer is present at from 0.1 to 30 weight % based on solvent weight.
Claim 19
Dependent Claim
189 words
A process for the removal of the salts of a weak acid and a weak base from an aqueous solution which comprises contacting said solution with a water-in-oil emulsion, said emulsion comprising from 10 to 90 weight % of an oil exterior phase, the balance of the emulsion being an aqueous interior phase, said exterior phase being characterized as immiscible with said solution and permeable to said weak acid, said exterior phase comprising a sulfonated polymer and a solvent for said polymer, said sulfonated polymer having an average molecular weight of at least 1,000, said sulfonated polymer comprising a substantially nonaromatic backbone and from 0.25 to 20 mole % sulfonic acid groups, said polymer being present in said exterior phase from 0.05 to 40 weight % based upon solvent weight, said interior phase comprising a reactant which is capable of converting said weak acid to a nonpermeable form, whereby said weak acid permeates through said exterior phase into said interior phase wherein it is converted to a nonpermeable form, and removing said weak base by passing an inert gas through said solution or subjecting the system to subatmospheric pressures.
Claim 20
Dependent Claim
189 words
A process for the removal of the salts of a weak acid and a weak base from an aqueous solution which comprises contacting said solution with a water-in-oil emulsion, said emulsion comprising from 10 to 90 weight % of an oil exterior phase, the balance of the emulsion being an aqueous interior phase, said exterior phase being characterized as immiscible with said solution and permeable to said weak acid, said exterior phase comprising a sulfonated polymer and a solvent for said polymer, said sulfonated polymer having an average molecular weight of at least 1,000, said sulfonated polymer comprising a substantially nonaromatic backbone and from 0.25 to 20 mole % sulfonic acid groups, said polymer being present in said exterior phase from 0.05 to 40 weight % based upon solvent weight, said interior phase comprising a reactant which is capable of converting said weak acid to a nonpermeable form, whereby said weak acid permeates through said exterior phase into said interior phase wherein it is converted to a nonpermeable form, and removing said weak base by passing an inert gas through said solution or subjecting the system to subatmospheric pressures.
Claim 21
Dependent Claim
61 words
The process of claim 18 wherein said solvent for the sulfonated polymer is selected from the group consisting of petroleum distillates having a boiling point of greater than 200° C; paraffinic solvents having substituents selected from the group consisting of halogen, benzene, and cycloalkyl rings; isoparaffins having an average carbon number of from about 10 to about 100; and combinations thereof.
Claim 22
Dependent Claim
22 words
The process of claim 18 wherein said sulfonated polymer has an average molecular weight of from at least 1,000 to about 50,000.
Claim 23
Dependent Claim
20 words
The process of claim 18 wherein the sulfonated polymer has an average molecular weight of from 5,000 to about 50,000.
Claim 24
Dependent Claim
19 words
The process of claim 18 wherein said sulfonated polymer comprises up to about 4.0 mole % sulfonic acid groups.
Claim 25
Dependent Claim
22 words
The process of claim 18 wherein the exterior oil phase constitutes from 30 to 60 weight % of the total emulsion composition.
Claim 26
Dependent Claim
22 words
The process of claim 18 wherein said sulfonated polymer is present at from 0.1 to 30 weight % based on solvent weight.
Claim 27
Dependent Claim
11 words
The process of claim 18 wherein said inert gas is steam.
Claim 28
Dependent Claim
30 words
The process of claim 18 wherein said weak acid is selected from the group consisting of H 2 S, SO 2 , acetic acid, CO 2 , HCN and phenol.
Claim 29
Dependent Claim
19 words
The process of claim 18 wherein said weak base is selected from the group consisting of ammonia and amines.
Claim 30
Dependent Claim
11 words
The process of claim 18 wherein said salt is ammonium sulfide.
Claim 31
Dependent Claim
11 words
The process of claim 28 wherein said inert gas is steam.
Claim 32
Dependent Claim
29 words
The process of claim 29 wherein said removal is carried out at a temperature of from 75° to 220° F and a pressure of from 5 to 50 psia.
Claim 33
Dependent Claim
20 words
The process of claim 30 wherein said ammonium sulfide comprises from 100 to 10,000 ppm by weight of said solution.
Claim 34
Dependent Claim
20 words
The process of claim 31 wherein said reactant comprises a base selected from the group consisting of NaOH and KOH.
Claim 35
Dependent Claim
29 words
The process of claim 31 wherein said reactant comprises a base selected from the group consisting of alkaline and alkaline earth carbonates, phosphates and borates; and amines and hydroxyamines.
Claim 36
Dependent Claim
66 words
The process of claim 33 wherein said emulsion is separated from said solution after the base is substantially neutralized and conveyed to a regeneration zone where said emulsion is contacted with steam at a temperature of from 230° to 450° F and at a pressure of from 5 to 300 psig for a period sufficient to convert said base substantially back to a less neutralized form.
Claim 37
Dependent Claim
162 words
A process for the removal of a dissolved species from an aqueous solution which comprises contacting said aqueous solution with a water-in-oil emulsion, said emulsion comprising from 10 to 90 weight % of an oil exterior phase, the balance of the emulsion being an aqueous interior phase, said exterior phase being characterized as immiscible with said solution and permeable to said dissolved species, said exterior phase comprising a sulfonated polymer and a solvent for said polymer, said sulfonated polymer having an average molecular weight of at least 1,000, said polymer comprising a substantially nonaromatic backbone and from 0.25 to 20 mole % sulfonic acid groups, said polymer being present in said exterior phase from 0.05 to 40 weight % based upon solvent weight; said interior phase comprising a reactant which is capable of converting said dissolved species to a nonpermeable form, whereby said dissolved species permeates through said exterior phase into said interior phase wherein it is converted to a nonpermeable form.
Claim 38
Dependent Claim
162 words
A process for the removal of a dissolved species from an aqueous solution which comprises contacting said aqueous solution with a water-in-oil emulsion, said emulsion comprising from 10 to 90 weight % of an oil exterior phase, the balance of the emulsion being an aqueous interior phase, said exterior phase being characterized as immiscible with said solution and permeable to said dissolved species, said exterior phase comprising a sulfonated polymer and a solvent for said polymer, said sulfonated polymer having an average molecular weight of at least 1,000, said polymer comprising a substantially nonaromatic backbone and from 0.25 to 20 mole % sulfonic acid groups, said polymer being present in said exterior phase from 0.05 to 40 weight % based upon solvent weight; said interior phase comprising a reactant which is capable of converting said dissolved species to a nonpermeable form, whereby said dissolved species permeates through said exterior phase into said interior phase wherein it is converted to a nonpermeable form.
Claim 39
Dependent Claim
61 words
The process of claim 35 wherein said solvent for the sulfonated polymer is selected from the group consisting of petroleum distillates having a boiling point of greater than 200° C; paraffinic solvents having substituents selected from the group consisting of halogen, benzene, and cycloalkyl rings; isoparaffins having an average carbon number of from about 10 to about 100; and combinations thereof.
Claim 40
Dependent Claim
22 words
The process of claim 35 wherein said sulfonated polymer has an average molecular weight of from at least 1,000 to about 50,000.
Claim 41
Dependent Claim
19 words
The process of claim 35 wherein said sulfonated polymer comprises up to about 4.0 mole % sulfonic acid groups.
Claim 42
Dependent Claim
20 words
The process of claim 35 wherein the sulfonated polymer has an average molecular weight of from 5,000 to about 50,000.
Claim 43
Dependent Claim
22 words
The process of claim 35 wherein the exterior oil phase constitutes from 30 to 60 weight % of the total emulsion composition.
Claim 44
Dependent Claim
22 words
The process of claim 35 wherein said sulfonated polymer is present at from 0.1 to 30 weight % based on solvent weight.
Claim 45
Dependent Claim
12 words
The process of claim 35 wherein said dissolved species is an ion.
Claim 46
Dependent Claim
24 words
The process of claim 35 wherein said dissolved species are converted to a nonpermeable form by complexing with a reactant in the interior phase.
Claim 47
Dependent Claim
20 words
The process of claim 35 wherein said dissolved species are converted to nonpermeable forms in the interior phase by neutralization.
Claim 48
Dependent Claim
20 words
The process of claim 35 wherein said dissolved species are converted to nonpermeable forms by precipitating in the interior phase.
Claim 49
Dependent Claim
17 words
The process of claim 35 wherein said removal is conducted at a temperature up to 100° C.
References Cited (Backward Citations)
US3770682A
Cited
US3969265A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-12-19 | 1981-06-20 | 1981-12-20 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-12-19 | 1985-06-20 | 1985-12-20 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-12-19 | 1989-06-20 | 1989-12-20 | $7700.00 | Window Closed / Lapsed |