CA2036084A1 - A method for preventing hydrates - Google Patents
A method for preventing hydratesInfo
- Publication number
- CA2036084A1 CA2036084A1 CA002036084A CA2036084A CA2036084A1 CA 2036084 A1 CA2036084 A1 CA 2036084A1 CA 002036084 A CA002036084 A CA 002036084A CA 2036084 A CA2036084 A CA 2036084A CA 2036084 A1 CA2036084 A1 CA 2036084A1
- Authority
- CA
- Canada
- Prior art keywords
- fluid
- hydrates
- alkyl aryl
- cell
- alkyl
- 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.)
- Abandoned
Links
- 150000004677 hydrates Chemical class 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012530 fluid Substances 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 alkyl aryl sulphonic acid Chemical compound 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000000979 retarding effect Effects 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 125000006755 (C2-C20) alkyl group Chemical group 0.000 claims 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- UVGCAWDXQWPTEK-UHFFFAOYSA-N ethane;hydrate Chemical class O.CC UVGCAWDXQWPTEK-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/328—Oil emulsions containing water or any other hydrophilic phase
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A B S T R A C T
A METHOD FOR PREVENTING HYDRATES
The invention relates to a method for preventing or retarding the formation of hydrates or for reducing the tendency of hydrates to agglomerate in a stream of fluid comprising water and hydrocarbon during transport of the fluid through a conduit, which method comprises adding to the fluid an alkyl aryl sulphonic acid or an alkali metal- or ammonium salt thereof substantially in the absence of glycol flowing in the stream.
VMl.T5398FF
A METHOD FOR PREVENTING HYDRATES
The invention relates to a method for preventing or retarding the formation of hydrates or for reducing the tendency of hydrates to agglomerate in a stream of fluid comprising water and hydrocarbon during transport of the fluid through a conduit, which method comprises adding to the fluid an alkyl aryl sulphonic acid or an alkali metal- or ammonium salt thereof substantially in the absence of glycol flowing in the stream.
VMl.T5398FF
Description
2 ~
A METHOD FOR PREVENTING HYDRATES
The invention relates to a method for preventing or retarding the formation of hydrates or for reducing the tendency of hydrates to agglomerate during the transport of a fluid through a conduit.
It is well known in the art that the formation of hydrates in a conduit, e.g. a pipeline, during the transport of oil and gas can be a serious problem, especially in areas with a low temperature in the winter season or in the sea. Generally the temperatures are so low that hydrate fcrmation, due to the inevitable presence of coproduced water in the wells, takes place if no special steps are taken. It is possible to insulate a pipeline when during transport from the well, the temperature of the fluid in the pipeline ,~ decreases. Insulation decreases the chance of hydrate formation,but on the other hand it is expensive. If the field is relatively small and at long distance from the production platform the costs of insulation may be too high to make the field economically attractive.
: It is also known to control the hydrate formation by addition of chemical compounds in the fluid which is transported, e.g. by the use of glycols, e.g. ethylene glycol or diethylene glycol. A
disadvantage thereof is that large amounts of glycol are needed (in the order of 30~ by weight calculated on the amount of water).
In the U.S.S.R. Inventor's Certificate 697696 is disclosed a composition suitable for the prevention of hydrate formation, which composition comprises diethylene glycol with a minor amount of alkyl aryl sulphonate (in a quantity of 0.3-0.5~ based on the weight of the diethylene glycol).
Surprisingly it has been found that alkyl aryl sulphonic acids or alkali metal- or ammonium salts thereof can be used without glycols, to control hydrate formation.
.
~, , , !
' ' ' ' ~ '~;' ' ';
2~3~8~ ~
The invention relates to a method for preventing or retarding the formation of hydrates or for reducing the tendency of hydrates to agglomerate in a stream of fluid comprising water and hydrocarbon during transport of the fluid through a conduit, which method comprises adding to the fluid an alkyl aryl sulphonic acid or an alkali metal- or ammonium salt thereof substantially in the absence of glycol flowing in the stream.
The hydrocarbon may be a liquid or a gas, but is preferably a gas such as methane, ethane, propane, isopropane, butane or isobutane. The fluid may be produced from oil wells as well as from gas wells. The fluid may also include natural gas.
Depending upon the pressure hydrates may be formed at temperatures well above the freezing point of water. Ethane hydrates, for example, are formed at pressures between 10 and 30 bar (1 and 3 MPa) and temperatures between 4 C and 14 C.
Formation and agglomeration of hydrate crystals will thus easily occur in pipelines surrounded by a cold atmosphere.
The problem of formation and agglomeration of gas hydrates is not limited to gas wells, but also occurs in oil wells, if water and gas are present in the fluid.
The alkyl aryl sulphonic acids or their salts preferably have an aryl group derived ~rom benzene, toluene, ortho-, meta- or para-xylene. The alkyl group is preferably a long chain alkyl group, which may be branched or straight. The alkyl group may be e.g. a c8-C22-alkyl group-Preferred compounds are those of the chemical formula ~01' R
wherein X is H, Na or K and R is a C8-C22 alkyl ~roup.
More preferred compounds are those wherein R is a C13 and/or C14 alkyl or a C18-alkyl group, such as thoqe known under the trade name DOBANAX-320, DOBANAX-313 and DOBANAX-205.
```:
2 ~
A METHOD FOR PREVENTING HYDRATES
The invention relates to a method for preventing or retarding the formation of hydrates or for reducing the tendency of hydrates to agglomerate during the transport of a fluid through a conduit.
It is well known in the art that the formation of hydrates in a conduit, e.g. a pipeline, during the transport of oil and gas can be a serious problem, especially in areas with a low temperature in the winter season or in the sea. Generally the temperatures are so low that hydrate fcrmation, due to the inevitable presence of coproduced water in the wells, takes place if no special steps are taken. It is possible to insulate a pipeline when during transport from the well, the temperature of the fluid in the pipeline ,~ decreases. Insulation decreases the chance of hydrate formation,but on the other hand it is expensive. If the field is relatively small and at long distance from the production platform the costs of insulation may be too high to make the field economically attractive.
: It is also known to control the hydrate formation by addition of chemical compounds in the fluid which is transported, e.g. by the use of glycols, e.g. ethylene glycol or diethylene glycol. A
disadvantage thereof is that large amounts of glycol are needed (in the order of 30~ by weight calculated on the amount of water).
In the U.S.S.R. Inventor's Certificate 697696 is disclosed a composition suitable for the prevention of hydrate formation, which composition comprises diethylene glycol with a minor amount of alkyl aryl sulphonate (in a quantity of 0.3-0.5~ based on the weight of the diethylene glycol).
Surprisingly it has been found that alkyl aryl sulphonic acids or alkali metal- or ammonium salts thereof can be used without glycols, to control hydrate formation.
.
~, , , !
' ' ' ' ~ '~;' ' ';
2~3~8~ ~
The invention relates to a method for preventing or retarding the formation of hydrates or for reducing the tendency of hydrates to agglomerate in a stream of fluid comprising water and hydrocarbon during transport of the fluid through a conduit, which method comprises adding to the fluid an alkyl aryl sulphonic acid or an alkali metal- or ammonium salt thereof substantially in the absence of glycol flowing in the stream.
The hydrocarbon may be a liquid or a gas, but is preferably a gas such as methane, ethane, propane, isopropane, butane or isobutane. The fluid may be produced from oil wells as well as from gas wells. The fluid may also include natural gas.
Depending upon the pressure hydrates may be formed at temperatures well above the freezing point of water. Ethane hydrates, for example, are formed at pressures between 10 and 30 bar (1 and 3 MPa) and temperatures between 4 C and 14 C.
Formation and agglomeration of hydrate crystals will thus easily occur in pipelines surrounded by a cold atmosphere.
The problem of formation and agglomeration of gas hydrates is not limited to gas wells, but also occurs in oil wells, if water and gas are present in the fluid.
The alkyl aryl sulphonic acids or their salts preferably have an aryl group derived ~rom benzene, toluene, ortho-, meta- or para-xylene. The alkyl group is preferably a long chain alkyl group, which may be branched or straight. The alkyl group may be e.g. a c8-C22-alkyl group-Preferred compounds are those of the chemical formula ~01' R
wherein X is H, Na or K and R is a C8-C22 alkyl ~roup.
More preferred compounds are those wherein R is a C13 and/or C14 alkyl or a C18-alkyl group, such as thoqe known under the trade name DOBANAX-320, DOBANAX-313 and DOBANAX-205.
```:
2 ~
Other groups of preferred compounds are dialkyl benzene sulphonates of the chemical structura so3~ S03X
Rl or ~ R
wherein X i5 an alkali metal and Rl and R2 are the same or different C2-c20-alkyl groups, preferably C6-C14-alkyl groups The alkyl aryl sulphonates are added in quantities from O.1 per cent to 3 per cent by weight, calculated on the weight oE the water present in the fluid. A preferred range is from 0.2 to 1 percent, more preferred in the range of from 0.3 to 0.6 per cent.
To study the influence of a small quantity of alkyl aryl sulphonates on the nucleation temperacure, kinetics of the crystal : growth and morphology of the crystals, a high pressure, jacketed visual cell was built. The cell was made of stainless steel and had a cooling jacket to allow a good and easy temperature control of the cell. Two sapphire windows allowed visual observation of the cell content. The cell was provided with two valves one for the . introduction of liquid and one for gas. At the bottom of the cell a stirring bar cared for good mixing of the cell content. The inner volume of the cell was 66.4 ml and dead volumes were reduced to a minimum. The cell was further tested together with its loading system at a pressure of ].00 bar over a period of 80 hours without any pressure drop being observed. The cell usually worked at a pressure of below 30 bar. The cell was located in a plexiglass cage.
A personal computer based data acquisition system allowed the measurement of the temperature and pressure inside the cell once per minute. The set point of a thermostated bath, connected to the cooling jacket, could be set automatically by the computer. A steel well went deeply inside the cell in which a platinum resistance thermometer was introduced. On the cell was mounted a pressure .~ . . . ~ ~ , .
`' ' ~ ; ` ' . " ' ' ~ ':
.
. .
2 ~
Rl or ~ R
wherein X i5 an alkali metal and Rl and R2 are the same or different C2-c20-alkyl groups, preferably C6-C14-alkyl groups The alkyl aryl sulphonates are added in quantities from O.1 per cent to 3 per cent by weight, calculated on the weight oE the water present in the fluid. A preferred range is from 0.2 to 1 percent, more preferred in the range of from 0.3 to 0.6 per cent.
To study the influence of a small quantity of alkyl aryl sulphonates on the nucleation temperacure, kinetics of the crystal : growth and morphology of the crystals, a high pressure, jacketed visual cell was built. The cell was made of stainless steel and had a cooling jacket to allow a good and easy temperature control of the cell. Two sapphire windows allowed visual observation of the cell content. The cell was provided with two valves one for the . introduction of liquid and one for gas. At the bottom of the cell a stirring bar cared for good mixing of the cell content. The inner volume of the cell was 66.4 ml and dead volumes were reduced to a minimum. The cell was further tested together with its loading system at a pressure of ].00 bar over a period of 80 hours without any pressure drop being observed. The cell usually worked at a pressure of below 30 bar. The cell was located in a plexiglass cage.
A personal computer based data acquisition system allowed the measurement of the temperature and pressure inside the cell once per minute. The set point of a thermostated bath, connected to the cooling jacket, could be set automatically by the computer. A steel well went deeply inside the cell in which a platinum resistance thermometer was introduced. On the cell was mounted a pressure .~ . . . ~ ~ , .
`' ' ~ ; ` ' . " ' ' ~ ':
.
. .
2 ~
transducer, with a very small temperature hysteresis and a high accuracy.
Before a run was made, the cell was rinsed with demineralized water, rinsed with ethanol and vacuum dried, all without dismounting the cell.
To carry out the experiment demineralized water and decane were introduced as liquid into the cell. The water contained 0.5~
per cent by weight of alkyl aryl sulphonic acid or salt thereof, if desired. Ethane was introduced as a gas into the cell. The run started at 20 C and the temperature in the cell was dropped, via the jacket connected to the thermostatic bath by lowering its temperature. The amounts of water, decane and ethane were 25, 5.8 ; and 4.7 grams respectively. The pressure was 25 bar at 20 C, and no ethane hydrates were formed.
The thermometer sent a digital signal, the pressure meter an analog signal, to ~he computer. The computer could also send a set point command to the thermostatic bath. During each experiment the temperature and the pressure of the cell were recorded, together with the time, at every minute. Of a given composition, comprising water, decane and ethane and if desired the alkyl aryl sulphonic acid or salt thereof, a temperature-time and a pressure-time curve could be made.
By lowering the temperature, which was accompanied by a pressure drop, to below the equilibrium temperature point at which hydrates and liquid were in equili~rium, ethane hydrates were formed. The rather sudden formation of hydrates was read from the temperature- and pressure-time curve. A relatively steep rise in temperature (about 0.5 C) and a pressure drop (about 1 to 5 bar) occurred.
At the same time the formation of hydrates was seen through a . sapphire window. The formation of hydrate crystals consumes the free ethane molecules. The progressive drop of the cell pressure ` that occurs after nucleation has started is a good indication of the quantity of hydrate formed as a function of time.
:`'`
"`' - ~.
' ' ` ' :~ , ` ` ` `
.` ` ~ ~ .
~3~
Before a run was made, the cell was rinsed with demineralized water, rinsed with ethanol and vacuum dried, all without dismounting the cell.
To carry out the experiment demineralized water and decane were introduced as liquid into the cell. The water contained 0.5~
per cent by weight of alkyl aryl sulphonic acid or salt thereof, if desired. Ethane was introduced as a gas into the cell. The run started at 20 C and the temperature in the cell was dropped, via the jacket connected to the thermostatic bath by lowering its temperature. The amounts of water, decane and ethane were 25, 5.8 ; and 4.7 grams respectively. The pressure was 25 bar at 20 C, and no ethane hydrates were formed.
The thermometer sent a digital signal, the pressure meter an analog signal, to ~he computer. The computer could also send a set point command to the thermostatic bath. During each experiment the temperature and the pressure of the cell were recorded, together with the time, at every minute. Of a given composition, comprising water, decane and ethane and if desired the alkyl aryl sulphonic acid or salt thereof, a temperature-time and a pressure-time curve could be made.
By lowering the temperature, which was accompanied by a pressure drop, to below the equilibrium temperature point at which hydrates and liquid were in equili~rium, ethane hydrates were formed. The rather sudden formation of hydrates was read from the temperature- and pressure-time curve. A relatively steep rise in temperature (about 0.5 C) and a pressure drop (about 1 to 5 bar) occurred.
At the same time the formation of hydrates was seen through a . sapphire window. The formation of hydrate crystals consumes the free ethane molecules. The progressive drop of the cell pressure ` that occurs after nucleation has started is a good indication of the quantity of hydrate formed as a function of time.
:`'`
"`' - ~.
' ' ` ' :~ , ` ` ` `
.` ` ~ ~ .
~3~
It was further observed that in the hydrate formation the crystals agglomerated in case that alkyl aryl sulphona~e was not added.
In the method according to the invention, however, the addition of an alkyl aryl sulphonate prevented the formation of agglomerates of hydrates.
E~MPLE 1 25 g of water, 5.8 g of decane, 4.7 g of ethane and 0.5~ by weight, based on the water, of di-linear C8-C10-alkyl benzene sulphonate (sodium salt), were used as described above in the cell.
The experiment started at 20 C and after lowering the temperature to 8.4 C crystallization occurred, while at the same time the pressure in the cell decreased from 22 bar to 13 bar. No agglomeration of the hydrate was observed.
25 g of water, 5.8 g of decane, 4.7 g of ethane and 0.5% by weight, based on the water, of sulphonated "SOMIL SH" (SOMIL is a Trade Mark) were used as described above in the cell. The experiment started at 20 C and after lowering the temperature to 8.4 C crystallization occurred, while at the same time the pressure in the cell decreased from 22 bar to 16 bar. No agglomeration of the hydrate was observed.
25 g of water, 5.8 g of decane, 4.7 g of ethane and 0.5% by weight, based on the water, of Cl~-alkyl benzene sulphonic acid were used as described above in the cell. The experiment started at 20 C and after lowering the temperature to 8.4 C crystallization occurred while at the same time the pressure in the cell dropped from 22 bar to 16 bar. No agglomeration of the hydrate was observed.
Comparative Example A
: 25 g of water, 5.8 g of decane and 4.7 g of ethane were used as described above in the cell. Also in this case the experiment started at 20 C and after lowering the temperature to 9.4 C
crystallization occurred and was followed by agglomeration of the crystals.
~`
:
`: ` , ::
, .
.
,
In the method according to the invention, however, the addition of an alkyl aryl sulphonate prevented the formation of agglomerates of hydrates.
E~MPLE 1 25 g of water, 5.8 g of decane, 4.7 g of ethane and 0.5~ by weight, based on the water, of di-linear C8-C10-alkyl benzene sulphonate (sodium salt), were used as described above in the cell.
The experiment started at 20 C and after lowering the temperature to 8.4 C crystallization occurred, while at the same time the pressure in the cell decreased from 22 bar to 13 bar. No agglomeration of the hydrate was observed.
25 g of water, 5.8 g of decane, 4.7 g of ethane and 0.5% by weight, based on the water, of sulphonated "SOMIL SH" (SOMIL is a Trade Mark) were used as described above in the cell. The experiment started at 20 C and after lowering the temperature to 8.4 C crystallization occurred, while at the same time the pressure in the cell decreased from 22 bar to 16 bar. No agglomeration of the hydrate was observed.
25 g of water, 5.8 g of decane, 4.7 g of ethane and 0.5% by weight, based on the water, of Cl~-alkyl benzene sulphonic acid were used as described above in the cell. The experiment started at 20 C and after lowering the temperature to 8.4 C crystallization occurred while at the same time the pressure in the cell dropped from 22 bar to 16 bar. No agglomeration of the hydrate was observed.
Comparative Example A
: 25 g of water, 5.8 g of decane and 4.7 g of ethane were used as described above in the cell. Also in this case the experiment started at 20 C and after lowering the temperature to 9.4 C
crystallization occurred and was followed by agglomeration of the crystals.
~`
:
`: ` , ::
, .
.
,
Claims (10)
1. A method for preventing or retarding the formation of hydrates or for reducing the tendency of hydrates to agglomerate in a stream of fluid comprising water and hydrocarbon during transport of the fluid through a conduit, which method comprises adding to the fluid an alkyl aryl sulphonic acid or an alkali metal- or ammonium salt thereof substantially in the absence of glycol flowing in the stream.
2. A method as claimed in claim 1 wherein the fluid comprises one or more hydrocarbons consisting of the group: methane, ethane, propane, isopropane, butane and isobutane.
3. A method as claimed in claim 1 or 2 wherein the fluid comprises natural gas.
4. A method as claimed in one or more of the claims 1-3 wherein is added to the fluid a C8-C22-alkyl aryl sulphonic acid or an alkali metal- or ammonium salt thereof.
5. A method as claimed in claim 4 wherein a compound of the chemical structure wherein X is H, Na or K and R is a C8-C22 alkyl group, is used.
6. A method as claimed in claim 1 wherein a compound of the chemical structure and/or wherein X is an alkali metal and R1 and R2 are the same or different C2-C20-alkyl groups, preferably C6-C14-alkyl groups, is used.
7. A method as claimed in one or more of the claims 1-6 wherein the quantity of alkyl aryl sulphonate ranges from 0.1 per cent to 3 per cent by weight, calculated on the weight of the water present in the fluid.
8. A method as claimed in claim 7 wherein the quantity of alkyl aryl sulphonate lies in the range of from 0.2 to 1 per cent.
9. A method as claimed in one or more of the claims 1-8 characterized by the substantial absence of a glycol.
10. A method for preventing or retarding the formation of hydrates on for reducing the tendency of hydrates to agglomerate as claimed in claim 1 as hereinbefore described with special reference to the Examples 1-3.
VMl.T5398FF
VMl.T5398FF
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9003617.9 | 1990-02-16 | ||
| GB909003617A GB9003617D0 (en) | 1990-02-16 | 1990-02-16 | A method for preventing hydrates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2036084A1 true CA2036084A1 (en) | 1991-08-17 |
Family
ID=10671171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002036084A Abandoned CA2036084A1 (en) | 1990-02-16 | 1991-02-11 | A method for preventing hydrates |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0457375B1 (en) |
| CA (1) | CA2036084A1 (en) |
| DE (1) | DE69100197T2 (en) |
| DK (1) | DK0457375T3 (en) |
| GB (1) | GB9003617D0 (en) |
| NO (1) | NO180783C (en) |
| NZ (1) | NZ237020A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7585816B2 (en) | 2003-07-02 | 2009-09-08 | Exxonmobil Upstream Research Company | Method for inhibiting hydrate formation |
| US7958939B2 (en) | 2006-03-24 | 2011-06-14 | Exxonmobil Upstream Research Co. | Composition and method for producing a pumpable hydrocarbon hydrate slurry at high water-cut |
| US8430169B2 (en) | 2007-09-25 | 2013-04-30 | Exxonmobil Upstream Research Company | Method for managing hydrates in subsea production line |
| US8436219B2 (en) | 2006-03-15 | 2013-05-07 | Exxonmobil Upstream Research Company | Method of generating a non-plugging hydrate slurry |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994001684A1 (en) * | 1992-07-06 | 1994-01-20 | Eniricerche S.P.A. | Process for recovering and causing highly viscous petroleum products to flow |
| US5420370A (en) * | 1992-11-20 | 1995-05-30 | Colorado School Of Mines | Method for controlling clathrate hydrates in fluid systems |
| US5432292A (en) * | 1992-11-20 | 1995-07-11 | Colorado School Of Mines | Method for controlling clathrate hydrates in fluid systems |
| US5841010A (en) * | 1994-09-15 | 1998-11-24 | Exxon Production Research Company | Surface active agents as gas hydrate inhibitors |
| US5600044A (en) * | 1994-09-15 | 1997-02-04 | Exxon Production Research Company | Method for inhibiting hydrate formation |
| US6015929A (en) * | 1994-09-15 | 2000-01-18 | Exxon Research And Engineering Co. | Gas hydrate anti-agglomerates |
| USH1749H (en) * | 1994-09-15 | 1998-09-01 | Exxon Production Research Company | Method for inhibiting hydrate formation |
| US5491269A (en) * | 1994-09-15 | 1996-02-13 | Exxon Production Research Company | Method for inhibiting hydrate formation |
| US5583273A (en) * | 1994-09-15 | 1996-12-10 | Exxon Production Research Company | Method for inhibiting hydrate formation |
| US5744665A (en) * | 1995-06-08 | 1998-04-28 | Exxon Production Research Company | Maleimide copolymers and method for inhibiting hydrate formation |
| US5936040A (en) * | 1995-06-08 | 1999-08-10 | Exxon Production Research Company | Method for inhibiting hydrate formation using maleimide copolymers |
| US6194622B1 (en) | 1998-06-10 | 2001-02-27 | Exxonmobil Upstream Research Company | Method for inhibiting hydrate formation |
| US6359047B1 (en) | 2001-03-20 | 2002-03-19 | Isp Investments Inc. | Gas hydrate inhibitor |
| NO316295B1 (en) | 2002-05-07 | 2004-01-05 | Agr Group As | Method and apparatus for removing a hydrate plug |
| FR2879189B1 (en) * | 2004-12-13 | 2007-03-30 | Inst Francais Du Petrole | METHOD FOR TRANSPORTING SUSPENDED HYDRATES INTO PRODUCTION EFFLUENTS USING A NON-POLLUTANT ADDITIVE |
| US9988568B2 (en) | 2015-01-30 | 2018-06-05 | Ecolab Usa Inc. | Use of anti-agglomerants in high gas to oil ratio formations |
| WO2016133470A1 (en) | 2015-02-16 | 2016-08-25 | Göksel Osman Zühtü | A system and a method for exploitation of gas from gas-hydrate formations |
| FR3092331A1 (en) | 2019-02-06 | 2020-08-07 | Arkema France | COMPOSITION TO PREVENT AGGLOMERATION OF GAS HYDRATES |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU697696A1 (en) * | 1977-12-01 | 1979-11-15 | Всесоюзный Научно-Исследовательский И Проектный Институт По Подготовке К Транспортировке И Переработки Природного Газа | Composition for inhibiting paraffin-hydrate deposition |
| JPS5935960B2 (en) * | 1982-02-25 | 1984-08-31 | 株式会社 柏化学工業 | Cleaning agent for piping |
| FR2625548B1 (en) * | 1987-12-30 | 1990-06-22 | Inst Francais Du Petrole | PROCESS FOR DELAYING FORMATION AND / OR REDUCING THE TENDENCY TO AGGLOMERATION OF HYDRATES |
-
1990
- 1990-02-16 GB GB909003617A patent/GB9003617D0/en active Pending
-
1991
- 1991-02-05 NZ NZ237020A patent/NZ237020A/en unknown
- 1991-02-08 EP EP91200272A patent/EP0457375B1/en not_active Expired - Lifetime
- 1991-02-08 DK DK91200272.2T patent/DK0457375T3/en active
- 1991-02-08 DE DE91200272T patent/DE69100197T2/en not_active Expired - Fee Related
- 1991-02-11 CA CA002036084A patent/CA2036084A1/en not_active Abandoned
- 1991-02-15 NO NO910619A patent/NO180783C/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7585816B2 (en) | 2003-07-02 | 2009-09-08 | Exxonmobil Upstream Research Company | Method for inhibiting hydrate formation |
| US8436219B2 (en) | 2006-03-15 | 2013-05-07 | Exxonmobil Upstream Research Company | Method of generating a non-plugging hydrate slurry |
| US7958939B2 (en) | 2006-03-24 | 2011-06-14 | Exxonmobil Upstream Research Co. | Composition and method for producing a pumpable hydrocarbon hydrate slurry at high water-cut |
| US8430169B2 (en) | 2007-09-25 | 2013-04-30 | Exxonmobil Upstream Research Company | Method for managing hydrates in subsea production line |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69100197D1 (en) | 1993-09-02 |
| DK0457375T3 (en) | 1993-12-27 |
| EP0457375A1 (en) | 1991-11-21 |
| DE69100197T2 (en) | 1993-12-02 |
| GB9003617D0 (en) | 1990-04-11 |
| NO910619D0 (en) | 1991-02-15 |
| NO180783C (en) | 1997-06-18 |
| NO180783B (en) | 1997-03-10 |
| NZ237020A (en) | 1992-11-25 |
| NO910619L (en) | 1991-08-19 |
| EP0457375B1 (en) | 1993-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0457375B1 (en) | A method for preventing hydrates | |
| EP0736130B1 (en) | A method for inhibiting the plugging of conduits by gas hydrates | |
| US5648575A (en) | Method for inhibiting the plugging of conduits by gas hydrates | |
| Smelik et al. | Crystal-growth studies of natural gas clathrate hydrates using a pressurized optical cell | |
| US5879561A (en) | Method for inhibiting the plugging of conduits by gas hydrates | |
| Holdaway | Thermal stability of Al-Fe epidote as a function of and Fe content | |
| Zhong et al. | Surfactant effects on gas hydrate formation | |
| Bishnoi et al. | Experimental study on propane hydrate equilibrium conditions in aqueous electrolyte solutions | |
| GB2349889A (en) | A method for inhibiting gas hydrate formation using polymeric amides of molecular mass less than 1000 | |
| Assarsson | Equilibria in aqueous systems containing Sr2+, K+, Na+ and Cl− | |
| Brearley | An experimental and kinetic study of the breakdown of aluminous biotite at 800 C: reaction microstructures and mineral chemistry | |
| Fujiwara et al. | Colloidal properties of α-sulfonated fatty acid methyl esters and their applicability in hard water | |
| Van Den Berg et al. | Effect of glycerol and dimethyl sulfoxide on 0 changes in composition and ph of buffer salt solutions during freezing | |
| WO2003087532A1 (en) | Antifreeze proteins for inhibition of clathrate hydrate formation and reformation | |
| Weill et al. | The 1010° and 800° C Isothermal Sections in the System Na3 AIF 6‐AI 2 O 3‐SiO2 | |
| US4474710A (en) | Preparation of highly based magnesium sulfonate | |
| Jangkamolkulchai et al. | Multiphase equilibria behavior of nitrous oxide+ n-paraffin mixtures | |
| Myran et al. | Genetically-engineered mutant antifreeze proteins provide insight into hydrate inhibition | |
| CA1149411A (en) | Process for producing a mixture of branched and linear carboxylic acid salts | |
| US4910334A (en) | Recovery of overbased alkaline earth metal additives from centrifugates | |
| Pounder | Mechanical strength of ice frozen from an impure melt | |
| RU2016041C1 (en) | Hydrocarbon based drilling mud | |
| US5439614A (en) | Oxidation inhibited fluid compositions | |
| SU1733405A1 (en) | Composition for preventing salt deposition | |
| US2799648A (en) | Inhibition of corrosion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |