GB2185995A - Removal of hydrogen sulphide from oil - Google Patents
Removal of hydrogen sulphide from oil Download PDFInfo
- Publication number
- GB2185995A GB2185995A GB08701374A GB8701374A GB2185995A GB 2185995 A GB2185995 A GB 2185995A GB 08701374 A GB08701374 A GB 08701374A GB 8701374 A GB8701374 A GB 8701374A GB 2185995 A GB2185995 A GB 2185995A
- Authority
- GB
- United Kingdom
- Prior art keywords
- hydrogen sulphide
- compound
- isocyanate
- oil
- feedstock
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000010779 crude oil Substances 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 3
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 6
- -1 aromatic isocyanate Chemical class 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 3
- 230000002000 scavenging effect Effects 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 abstract description 3
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 abstract description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 21
- 239000003921 oil Substances 0.000 description 19
- 239000012071 phase Substances 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000002516 radical scavenger Substances 0.000 description 4
- 238000005201 scrubbing Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- YNKLTNGQZXMIFC-UHFFFAOYSA-N isocyanatobenzene;1-isocyanatooctadecane Chemical compound O=C=NC1=CC=CC=C1.CCCCCCCCCCCCCCCCCCN=C=O YNKLTNGQZXMIFC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000009420 retrofitting Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Hydrogen sulphide is scavenged from a feedstock comprising crude oil and hydrogen sulphide by adding a compound of general formula R<1>-N=C=X-R<2> to the feedstock. R<1> is an alkyl group containing 1 to 18 carbon atoms, a cycloalkyl or alkyl cycloalkyl group containing 3 to 18 carbon atoms, an aryl group which may be substituted e.g. an alkyl aryl group wherein the alkyl moiety contains 1 to 18 carbon atoms, or a hydrogen atom, X is a nitrogen atom or an oxygen atom, and R<2> is R<1> and X is a nitrogen atom, or zero when X is an oxygen atom. Preferred scavengers include phenyl isocyanate, toluene-2,4-di-isocyanate, octadecyl isocyanate and dicyclohexyl carbodiimide.
Description
SPECIFICATION
Removal of hydrogen sulphide
This invention relates two a method for removing hydrogen sulphide from crude oil.
A petroleum reservoir is formed by a suitably shaped porous stratum of rock sealed with an impervious rock. The nature of the reservoir rock is extremely important as the oil is present in the small spaces or pores which separate individual rock grains.
Crude oil is generally found in a reservoir in association with water, which is often saline, and gas. Dependent upon the characteristics of the crude, the temperature and the pressure, the gas may exist in solution in the oil or additionally as a separate phase in the form of a gas cap. The oil and gas occupy the upper part of the reservoir and below there may be a considerablevolume of water, known asthe aquifer, which extends throughout the lower levels of the rock.
For oil to move through the pores of the reservoir rock and into a well,the pressure underwhich the oil exists in the reservoir must be greater than the pressure at the well.
The water contained in the aquifer is under pressure and is one source of drive. The dissolved gas associated with the oil is another and so is the free gas in the gas cap when this is present.
When oil is produced from a well, it is forced from the reservoir by natural pressure in the bottom ofthe well up which it rises to the surface. As the oil rises the pressure becomes less and gas associated with the oil is progressively released from solution.
After emerging from the well, it is necessary to treat the multi-phase mixture of oil, gas and possiblywater, hereinafter termed "produced well fluid", in separators to remove free or potentially free gas, mainly methane and ethane. By potentially free gas is meant gas which would be likely to come out of solution if the oil were maintained at about atmospheric pressure, for example, during transport in a tanker or in storage tanks, without treatment.
Some crude oils contain not only dissolved hydrocarbon gases, but also appreciable quantities of hydrogen sulphide. This problem is particularly associated with "watered out" reservoirs approaching the end oftheir life, although it is not confined to them.
Hydrogen sulphide is a toxic, evil-smelling and corrosive gas and is unacceptable in quantity from both safety and environmental considerations. When hydrogen sulphide is present, it is necessary to provide furthertreatmentto reducethe concentration of hydrogen sulphide in all products to an acceptably low level.
Much ofthe hydrogen sulphide associates with the gases resulting from the gas-oil separation process and this may be removed by scrubbing the gases, for example with amines. This requires expensive gas/liquid contacting, regeneration and conversion facilities. The cost of this extra treatment is considerable and in some cases, e.g., offshore fields, gas scrubbing may not be feasible since space may not be available on the field platforms for retrofitting the necessary equipment.
Even where gas scrubbing is possible, this still leaves some hydrogen sulphide associated with the oil and aqueous phases, however.
It would clearly be more convenient to treat the produced well fluid with a scavenger for hydrogen sulphide before the various phases are separated.
We have now discovered that certain compounds containing contiguous double bonds are capable of reacting with hydrogen sulphide under mixed phase conditions and forming relatively harmless thiol compounds.
Thus according to the present invention, there is provided a method for scavenging hydrogen sulphide from a feedstock comprising crude oil and hydrogen sulphide which method comprises adding a compound of general formula: R1 -N=C=X-R2 wherein R1 is an alkyl group containing 1 to 18 carbon atoms, a cycloalkyl or alkyl cycloalkyl group containing 3to 18 carbon atoms, an aryl group, an alkyl aryl groupwhereinthealkyl moiety contains 1 to 18carbon atoms or a hydrogen atom, Xis a nitrogen atom or an oxygen atom, and R2 is R1 when Xis a nitrogen atom, or zero when Xis an oxygen atom, to the feedstock and allowing the compound to react with the hydrogen sulphide contained therein.
Preferred compounds are isocyanates, most preferably aromatic isocyanates and di-isocyanates.
The feedstock may be produced well fluid as hereinbefore defined.
Although the above defined scavengers are particularly useful in treating produced well fluids since they can withstand the severe environment of the latter, they are also suitable for treating crude oil or petroleum fractions under milder conditions, for example, in pipelines, storage tanks, railcars, tankers, etc., afterthe produced wel I fl uid has been dewatered and degassed.
When water is present, the partitioning of hydrogen sulphide between the various phases depends largely upon the pH and redox potential of the aqueous phase. These will normally be such that the hydrogen sulphide is concentrated in the oil and aqueous phases, i.e., in the ranges 4to 9.5 and -0.2 to -0.3 Vwith reference to hydrogen potential, respectively.
Preferably the scavengers are oil soluble and react with the hydrogen sulphide in the oil phase. By mass transferthis also reduces the concentration of hydrogen sulphide in the gaseous and aqueous phases. The oil soluble scavengers should also be stable in the presence of water and thermally stable since fluids are often produced at elevated temperatures.
Suitable scavengers include
octadecyl isocyanate phenyl isocyanate CeH13-N = C = N Cg H13 dicyclohexyl carbodi-imide
The scavenger is suitably used in amount 1 to 50, preferabiy 5 to 15, times the amount of hydrogen sulphide present, on a molar basis.
The length oftime required to scavenge the hydrogen sulphide is generally ofthe order of 1 to 15 minutes.
The invention is illustrated with reference to the following Examples.
Examples 1-5 Aflaskwas charged with 309 crude oil (from the Welton oil field in the English Midlands), and 8g water, buffered to a pH of 7 and sealed. 2 ml of 0.7% Na2S.9H2O were then injected by means of a syringe, giving a potential H2S content of 0.029.
The resulting oil/aqueous liquid/gas system was allowed two equilibratefor 15 minutes after which in Example 2-5 the scavenger was injected in solution into the flask and the latterwas shaken.
After a further 15 minutes a sample of the gas was removed to a "Gas-Tec" detection tube and the hydrogen sulphide concentration was determined. Thefollowing results were obtained:
Example Scavenger Concentration of H2S (ppm) 1 Control 700
(no additive) 2 Phenylisocyanate 20 (0.1g in lgtoluene) 3 Dicyclohexylcarbodi-imide 100 (0.1g in lgtoluene) 4 Octadecylisocyanate 400 (0.1g in lgtoluene) 5 Toluene-2,4-di-isocyanate 20 (0.1g in lgtoluene)
Claims (9)
1. A method for scavenging hydrogen sulphide from a feedstock comprising crude oil and hydrogen sulphidewhich method comprises adding a compound of general formula: R1 ~ N = C = XR2 wherein R1 is an alkyl group containing 1 to 18 carbon atoms, a cycloalkyl or alkyl cycloalkyl group containing 3to 18 carbon atoms, an aryl group, an alkyl aryl groupwhereinthealkyl moiety contains 1 to l8carbon atoms or a hydrogen atom, Xis a nitrogen atom or an oxygen atom, and R2 is R1 when Xis a nitrogen atom, or zero when Xis an oxygen atom, to thefeedstock and allowing the compound to react with the hydrogen sulphide contained therein.
2. A method according to claim 1 wherein the compound is an isocyanate.
3. A method according to claim 2 wherein the compound is an aromatic isocyanate.
4. A method according to claim 3 wherein the aromatic isocyanate is phenyl isocyanate ortoluene-2, 4-di-isocyanate.
5. A method according to any ofthe preceding claims wherein the feedstock is produced well fluid as hereinbefore defined.
6. A method according to any of claims 1 to 3 wherein the feedstockis dewatered and/or degassed crude petroleum.
7. A method according to any of the preceding claims wherein the compound is used in amount 1 to 50 times the amount of hydrogen sulphide present on a molar basis.
8. A method according to claim 7 wherein the compound is used in amount 1 to 50 times the amount of hydrogen sulphide present on a molar basis.
9. A method for scavenging hydrogen sulphide from a feedstock comprising crude oil and hydrogen sulphide according to claim 1 as hereinbefore described with reference to Examples 2 to 5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB868602319A GB8602319D0 (en) | 1986-01-30 | 1986-01-30 | Removing hydrogen sulphide from crude oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8701374D0 GB8701374D0 (en) | 1987-02-25 |
| GB2185995A true GB2185995A (en) | 1987-08-05 |
Family
ID=10592245
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB868602319A Pending GB8602319D0 (en) | 1986-01-30 | 1986-01-30 | Removing hydrogen sulphide from crude oil |
| GB08701374A Withdrawn GB2185995A (en) | 1986-01-30 | 1987-01-22 | Removal of hydrogen sulphide from oil |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB868602319A Pending GB8602319D0 (en) | 1986-01-30 | 1986-01-30 | Removing hydrogen sulphide from crude oil |
Country Status (2)
| Country | Link |
|---|---|
| GB (2) | GB8602319D0 (en) |
| NO (1) | NO870352L (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0411750A3 (en) * | 1989-06-06 | 1992-03-04 | Rohm And Haas Company | Organic stabilizers for isothiazolones |
| RU2312070C2 (en) * | 2005-02-03 | 2007-12-10 | Общество с ограниченной ответственностью "Инжиниринговая компания "ИНКОМП-НЕФТЬ" | Hydrogen sulfide neutralization composition |
| RU2404175C2 (en) * | 2008-06-03 | 2010-11-20 | Учреждение Российской Академии Наук Институт Нефтехимии И Катализа Ран | Two-component hydrogen sulphide scavenger and preparation method thereof |
-
1986
- 1986-01-30 GB GB868602319A patent/GB8602319D0/en active Pending
-
1987
- 1987-01-22 GB GB08701374A patent/GB2185995A/en not_active Withdrawn
- 1987-01-28 NO NO870352A patent/NO870352L/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0411750A3 (en) * | 1989-06-06 | 1992-03-04 | Rohm And Haas Company | Organic stabilizers for isothiazolones |
| RU2312070C2 (en) * | 2005-02-03 | 2007-12-10 | Общество с ограниченной ответственностью "Инжиниринговая компания "ИНКОМП-НЕФТЬ" | Hydrogen sulfide neutralization composition |
| RU2404175C2 (en) * | 2008-06-03 | 2010-11-20 | Учреждение Российской Академии Наук Институт Нефтехимии И Катализа Ран | Two-component hydrogen sulphide scavenger and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8602319D0 (en) | 1986-03-05 |
| NO870352D0 (en) | 1987-01-28 |
| NO870352L (en) | 1987-07-31 |
| GB8701374D0 (en) | 1987-02-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |