WO2001038694A1 - Method and system for preventing hydrate formation by reinjecting hydrocarbon gas including methanol - Google Patents
Method and system for preventing hydrate formation by reinjecting hydrocarbon gas including methanol Download PDFInfo
- Publication number
- WO2001038694A1 WO2001038694A1 PCT/NO2000/000395 NO0000395W WO0138694A1 WO 2001038694 A1 WO2001038694 A1 WO 2001038694A1 NO 0000395 W NO0000395 W NO 0000395W WO 0138694 A1 WO0138694 A1 WO 0138694A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- production
- hydrocarbon gas
- methanol
- gas
- oil
- Prior art date
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 228
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 87
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 87
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 86
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 claims abstract description 70
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 28
- 150000004677 hydrates Chemical class 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 90
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 35
- 239000003921 oil Substances 0.000 description 32
- 238000005755 formation reaction Methods 0.000 description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 14
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- -1 hydrocarbon hydrates Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B37/00—Methods or apparatus for cleaning boreholes or wells
- E21B37/06—Methods or apparatus for cleaning boreholes or wells using chemical means for preventing or limiting, e.g. eliminating, the deposition of paraffins or like substances
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/34—Arrangements for separating materials produced by the well
- E21B43/40—Separation associated with re-injection of separated materials
Definitions
- the present invention relates to a method of preventing hydrate formation when transporting untreated hydrocarbon gas .
- the invention relates to the use of a slip stream from a hydrocarbon gas stream separated from oil in the production of oil in a production well for the synthesis of methanol to be added to the remaining hydrocarbon gas stream to prevent the formation of hydrocarbon gas hydrates when said hydrocarbon gas stream is to be further transported.
- hydrocarbon gas When hydrocarbon gas is subjected to high pressures and low temperatures in the presence of water in liquid or gaseous form hydrocarbon hydrates in the form of solid products can be formed. If such hydrates are formed in sufficient high amounts they can clog pipelines in which the gas is flowing and thereby prevent the intended gas flow.
- most reservoir fluids In the production of crude oil most reservoir fluids also produce associated gas. In order to meet the crude oil specification with respect to flash point, the gas must be flashed off from the crude oil through a sequence of separation steps.
- gas pipeline infrastructure is normally not present close to the production area to which the gas could be exported. Neither would the field economy allow for installing a new pipeline of any length. Consequently, the gas must be flared or reinjected into the reservoir at an injection pressure ranging normally from 250- 350 bar to enhance the production of further oil. In most developed country areas flaring of larger amount of gas would not be permitted due to resource and environmental considerations.
- the dehydration Prior to the injection of such gas the gas has to be compressed.
- the water due point is controlled by the use of glycol dehydration towers.
- the dehydration is performed to remove free water to eliminate the possibility of hydrate formation when the gas is cooled.
- the dehydration systems comprise at least one stripper column wherein the gas is countercurrently contacted with the glycol stripping the water from the gas into the glycol phase.
- the water rich on glycol is then transferred to a glycol reboiler in which the water is stripped off and the glycol stripped of water is recycled to the above mentioned at least one stripping column.
- the system for processing the glycol comprises several heat exchanges, degassing vessels, pumps etc..
- the glycol system must be considered as a heavy system contributing severely to the costs of gas treatment and compression.
- the gas treatment (dehydration) cost is estimated to:
- the dehydration plant also has a high OPEX cost due to its complexity and continuous need for make-up glycols.
- the conventional chemicals used for this purpose are methanol, monoethylene glycol, diethylene glycol and three ethylene glycol.
- the addition of chemicals, specifically methanol and ethylene glycol, is disclosed in E.D. Sloan Jr., Clathrate Hydrates of Natural Gases, Marcel Dekker, Inc., New York, 1998, pp 164-170. These antifreezes expand the pressure- temperature-area of the safe operation. However, large quantities thereof are required, and 50% of such additives in the water liquid fraction is not unusual in productions rich on water.
- the use of methanol in the North Sea may thus approach 3 kg per 1000 Sm 3 of gas extracted. This implies severe demands on the logistics of the transport and storage.
- the object of the present invention is thus to provide a more economic and efficient way of preventing the formation of gas hydrates during transport of gas and/or reinjection of gas.
- the problem is solved by using part of the gas separated from the oil produced in an oil production well for the production of a dirty (impure) methanol which is combined with the rest of the gas stream, which combined stream is subjected to gas compression and exported or reinjected into a suitable reservoir.
- the present invention provides a method of preventing hydrate formation by reinjecting hydrocarbon gas from an oil production in a production well, wherein part of the hydrocarbon gas stream from the oil production is reacted to produce raw methanol, which is subsequently added to the remaining hydrocarbon gas which is reinjected in the same production well or injected in other production wells.
- said part of the hydrocarbon gas stream from the oil production is split off from the main stream of the hydrocarbon gas and fed to a methanol synthesis plant separate from the main stream, to which steam and the energy required is supplied, said plant having a downstream connection back to the main stream.
- said part of the hydrocarbon gas stream is fed to a methanol synthesis plant situated integrated in the main hydrocarbon stream, to which steam and the energy required is supplied, the product of which synthesis being discharged in the main stream flowing by.
- One option of this embodiment involves that the methanol synthesis plant is located subsea.
- methanol synthesis plant is located onboard a production platform or on board a vessel.
- a further aspect of the instant invention relates to a method of preventing hydrate formation by reinjecting hydrocarbon gas from an oil production in a production well, wherein oil and hydrocarbon gas from an oil production is reacted in a subsea methanol synthesis plant to produce raw methanol, which is subsequently added to hydrocarbon gas which is reinjected in the same production well or injected in another production well.
- MeOH will be hydrofile and hence suitably be dissolved in water.
- said part of the hydrocarbon gas stream is preferably converted to methanol by a sequence of a reformation reaction and a Fischer Tropsch reaction.
- the reformation reaction is performed in the presence of a reformation catalyst, at a low pressure of about 5 to 50 bar, and an outlet temperature of about 400 to 650 °C in the absence of O 2 .
- a commercially available reforming catalyst may be used.
- the methanol synthesis may be effected by feeding a synthesis gas comprising mainly hydrogen and carbon monoxide to a methanol synthesis reactor run e.g. at a temperature of between 170 °C and 240 °C and at a pressure of between 5 and 20 MPa in the presence of a catalyst based on Zn and Cu oxides, such as the catalyst sold by Haldor Tops ⁇ e A/S, Denmark, under the trade-name "MK-101".
- a catalyst based on Zn and Cu oxides such as the catalyst sold by Haldor Tops ⁇ e A/S, Denmark, under the trade-name "MK-101".
- the present invention relates to the use of a slip stream from a hydrocarbon gas stream, separated from an oil in the production of oil in a production well, for the synthesis of methanol to be added to the remaining hydrocarbon gas stream to prevent the formation of hydrocarbon gas hydrates when said hydrocarbon gas stream is reinjected in oil production wells.
- said part of the hydrocarbon gas stream from the oil production is split off from the main stream of the hydrocarbon gas and fed to a methanol synthesis plant separate from the main stream, to which steam and the energy required is supplied, said plant having a downstream connection back to the main stream.
- said part of the hydrocarbon gas stream is fed to a methanol synthesis plant situated integrated in the main hydrocarbon stream, to which steam and the energy required is supplied, the product of which synthesis being discharged in the main stream flowing by.
- the last option involves that the methanol synthesis plant may be located subsea.
- methanol synthesis plant may be located onboard a production platform or onboard a vessel.
- the present invention also relates to the use of the lower molecular hydrocarbon part of an oil and hydrocarbon gas mixture for the production of methanol to be used for preventing hydrate formation when reinjecting hydrocarbon gas from an oil production in a production well, wherein oil and hydrocarbon gas from an oil production is reacted in a subsea methanol synthesis plant to produce raw methanol, which is thereby dissolved in the produced water, which is subsequently added to hydrocarbon gas which is reinjected in the same production well or injected in another production well.
- Preferably said part of the hydrocarbon gas stream is converted to methanol by a sequence of a reformation reaction and a Fischer Tropsch reaction.
- the reformation reaction is performed in the presence of a reformation catalyst, at a low pressure of about 5 to 50 bar, and an outlet temperature of about 400 to 650 °C in the absence of O .
- the pressure is kept at about 20 bar and the temperature is kept at about 650 °C.
- a commercially available reformation catalyst can be used for this purpose.
- Preferably said part of the hydrocarbon gas stream is converted to methanol by a so called “black box” comprising a sequence of reformation reaction and Fischer Tropsch reaction.
- the reformation reaction is performed at a low pressure of about 20 bar and an outlet temperature of about 650DC in the absence of O 2 .
- Such a plant which is required for effecting said processes would be situated on a production platform. Thus, no transport or storage logistic requirements will be involved.
- the reaction is normally performed in the presence of a reformation catalyst.
- the subsequent Fisher Tropsch reaction can be effected under the usual Fischer Tropsch reaction conditions (useful temperature intervals and pressure intervals should be defined) and catalysts (some examples should be mentioned).
- a further advantage of the method of the present invention is the elimination or at least reduction of omission of glycol, volatile organic compounds and ETEX from a glycol reboiler.
- a glycol reboiler On conventional offshore plants one of the greatest contributions to hydrocarbon emission outside the power generation is normally the glycol reboiler system.
- the instant method of the invention thus provides a significant contribution to the reduction of pollution of the environment.
- the enclosed figures shows the plants used for performing the method of the invention integrated in an oil production and gas injection stream.
- Figure 1 shows the conversion of a slip gas stream from a hydrocarbon main stream being converted to methanol in an isolated "black box", the dirty methanol obtained subsequently being reintroduced in the hydrocarbon main stream downstream, whereupon said methanol containing hydrocarbon main stream is injected in an oil reservoir.
- Figure 2 shows the conversion of part of a hydrocarbon main gas stream being converted to methanol in an isolated "black box" within a hydrocarbon main stream pipeline topside the sea surface, the dirty methanol obtained subsequently being reintroduced in the hydrocarbon main stream downstream, whereupon said methanol containing hydrocarbon main stream is injected in an oil reservoir.
- Figure 3 shows the conversion of part of a hydrocarbon main stream comprising oil and gas being converted to methanol in an isolated "black box" within a hydrocarbon main stream pipeline subsea, the dirty methanol obtained subsequently being reintroduced in the hydrocarbon main stream downstream, whereupon said methanol containing hydrocarbon main stream is injected in an oil reservoir (not shown on this figure).
- Figure 4 shows the conversion of part of a hydrocarbon main gas stream being converted to methanol in an isolated "black box" within a hydrocarbon main stream pipeline subsea, the dirty methanol obtained subsequently being reintroduced in the hydrocarbon main stream downstream, whereupon said methanol containing hydrocarbon main stream is injected in an oil reservoir (not shown on this figure).
- the object of the present invention is to provide a more economic and efficient way of preventing the formation of gas hydrates for evacuation/transport of hydrocarbon gas.
- the problem is solved by using part of a flowing hydrocarbon (HC) gas for the production of a dirty (impure) methanol, which is combined with the rest of the gas stream thus preventing hydrates to form.
- HC flowing hydrocarbon
- the present invention provides a method of preventing hydrate formation wherein part of the hydrocarbon gas stream from the oil production is reacted to produce raw methanol.
- the methanol is subsequently added to the remaining hydrocarbon gas stream which will be transported or injected into one or more suitable reservoirs.
- said part of the hydrocarbon gas stream is converted to methanol by a MeOH converter, comprising a sequence of reformation reaction and Fischer Tropsch reaction.
- a MeOH converter comprising a sequence of reformation reaction and Fischer Tropsch reaction.
- the location of the MeOH converter could be:
- Any well known reformation reaction conditions may be used.
- Preferred reaction conditions are, however, the SOLCO TEPS conversion of nature gas to methanol system. This involves a low pressure system of about 20 bar, a low outlet temperature of about 650°C, whereas other reformers/reactors typically utilise temperatures of 1000-1200°C. Further, only limited amount of steam input is required in addition to the hydrocarbon gas fed to the process. No oxygen gas or carbon-dioxide is required. In fact, this SOLCO process yields a quality which is superior to what the dirty methanol operation requires.
- a further advantage of the method of the present invention is the elimination of emission of glycol, volatile organic compounds and BTEX from a glycol reboiler.
- a glycol reboiler On conventional offshore plants one of the greatest contributions to hydrocarbon emission outside the power generation is normally the glycol reboiler system.
- the instant method of the invention thus provides a significant contribution to the reduction of pollution of the environment.
- the enclosed figure 1 shows a typical plant used for performing the method of the invention integrated in an oil and gas production with a gas injection stream.
- a mixture of oil and gas is produced from an oil reservoir. This is subjected to an oil and gas separation in a plant as indicated in the figure.
- the gas fraction separated is transferred to a gas compression train.
- the outlet gas stream 1 from the compressor train is split into two streams of which a slip stream 2 is fed to a MeOH converter, comprising one or more reformation reactors and one or more Fischer Tropsch reactors.
- the slip stream hydrocarbon gas is together with steam fed to the reformation reactors. The required energy is also fed to the system.
- the product stream 4 is combined with the remaining hydrocarbon gas stream 1 and fed to a gas compressor.
- the pressurised composition comprising the dirty methanol is then injected in an export solution preventing formation of hydrocarbon hydrates prone to plugging the injection gas pipelines.
- a slip stream 2 of 3500 SM 3 gas is required on a daily basis for the required methanol conversion to prevent hydrocarbon hydrate formation. Additionally, 2 tonnes of steam is required. The energy supply 5 will be required only in sufficient amounts to achieve the sufficient reaction temperature.
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- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0212267A GB2374364A (en) | 1999-11-24 | 2000-11-23 | Method and system for preventing hydrate formation by reinjecting hydrocarbon gas including methanaol |
AU15616/01A AU1561601A (en) | 1999-11-24 | 2000-11-23 | Method and system for preventing hydrate formation by reinjecting hydrocarbon gas including methanol |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NO19995756 | 1999-11-24 | ||
NO19995756A NO311187B1 (en) | 1999-11-24 | 1999-11-24 | Formation of methanol from hydrocarbon gas in which the methanol is injected back into the gas stream for gas hydrate prevention |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001038694A1 true WO2001038694A1 (en) | 2001-05-31 |
Family
ID=19904018
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NO2000/000395 WO2001038694A1 (en) | 1999-11-24 | 2000-11-23 | Method and system for preventing hydrate formation by reinjecting hydrocarbon gas including methanol |
Country Status (4)
Country | Link |
---|---|
AU (1) | AU1561601A (en) |
GB (1) | GB2374364A (en) |
NO (1) | NO311187B1 (en) |
WO (1) | WO2001038694A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7216712B2 (en) | 2003-12-10 | 2007-05-15 | Praxair Technology, Inc. | Treatment of oil wells |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3348614A (en) * | 1965-06-23 | 1967-10-24 | Mobil Oil Corp | Hydrate prevention in gas production |
US4036247A (en) * | 1976-03-15 | 1977-07-19 | Vetco Offshore Industries, Inc. | Multi-pressure, single line supply system |
GB2255102A (en) * | 1990-02-02 | 1992-10-28 | Kvaerner Subsea Contracting | Subsea piping method and plant |
US5262443A (en) * | 1990-03-19 | 1993-11-16 | Haldor Topsoe A/S | Method of preparing methanol |
WO2000040835A1 (en) * | 1998-12-31 | 2000-07-13 | Shell Internationale Research Maatschappij B.V. | Method for removing condensables from a natural gas stream |
-
1999
- 1999-11-24 NO NO19995756A patent/NO311187B1/en unknown
-
2000
- 2000-11-23 AU AU15616/01A patent/AU1561601A/en not_active Abandoned
- 2000-11-23 GB GB0212267A patent/GB2374364A/en not_active Withdrawn
- 2000-11-23 WO PCT/NO2000/000395 patent/WO2001038694A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3348614A (en) * | 1965-06-23 | 1967-10-24 | Mobil Oil Corp | Hydrate prevention in gas production |
US4036247A (en) * | 1976-03-15 | 1977-07-19 | Vetco Offshore Industries, Inc. | Multi-pressure, single line supply system |
GB2255102A (en) * | 1990-02-02 | 1992-10-28 | Kvaerner Subsea Contracting | Subsea piping method and plant |
US5262443A (en) * | 1990-03-19 | 1993-11-16 | Haldor Topsoe A/S | Method of preparing methanol |
WO2000040835A1 (en) * | 1998-12-31 | 2000-07-13 | Shell Internationale Research Maatschappij B.V. | Method for removing condensables from a natural gas stream |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7216712B2 (en) | 2003-12-10 | 2007-05-15 | Praxair Technology, Inc. | Treatment of oil wells |
Also Published As
Publication number | Publication date |
---|---|
NO995756L (en) | 2001-05-25 |
GB0212267D0 (en) | 2002-07-10 |
NO995756D0 (en) | 1999-11-24 |
NO311187B1 (en) | 2001-10-22 |
AU1561601A (en) | 2001-06-04 |
GB2374364A (en) | 2002-10-16 |
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