CN106190060A - A kind of Compositional type hydrate inhibitor for natural gas - Google Patents
A kind of Compositional type hydrate inhibitor for natural gas Download PDFInfo
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- CN106190060A CN106190060A CN201510265936.1A CN201510265936A CN106190060A CN 106190060 A CN106190060 A CN 106190060A CN 201510265936 A CN201510265936 A CN 201510265936A CN 106190060 A CN106190060 A CN 106190060A
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- caprolactam
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Abstract
The invention discloses a kind of Compositional type hydrate inhibitor for natural gas compositions, be made up of with thermodynamic inhibitor the polymer shown in structure formula (I), polymer is 1:1 ~ 1:10, wherein R with the mass ratio of thermodynamic inhibitor1For C1～C10Alkyl, cycloalkyl, aromatic hydrocarbons, described thermodynamic inhibitor is selected from methanol, ethanol, ethylene glycol, butanol, butyl glycol ether, butyl, ethylene glycol phenyl ether, Polyethylene Glycol.Low cost of the present invention, the built agent of selection is that some are cheap, the alcohol that is easy to get and ether etc., and addition is little, greatly reduces the cost that gas industries generates due to suppression hydrate.
Description
Technical field
The present invention relates to a kind of highly efficiency compositional type hydrate inhibitor, belong to oil gas field additive technology field.
Technical background
In oil-gas mining and transport, especially under the operating mode of cryogenic high pressure, the gas molecule in natural gas can be combined with water and form the crystal being similar to ice, referred to as gas hydrates.Nineteen thirty Hammerschmidt is found that gas hydrates block up the phenomenon of natural gas transportation pipeline and gas well, and gas hydrates problem gradually causes the close attention of industrial quarters.The huge puzzlement that hydrate brings to production of hydrocarbons becomes problem demanding prompt solution.
The approach that suppression gas hydrates are formed mainly has: the moisture in (1) removing natural gas；(2) pipeline is heated, because it is possible to be formed less than uniform temperature hydrate；(3) pressure is controlled, because it is possible to be formed higher than certain pressure hydrate；(4) interpolation has the chemicals of given efficacy, i.e. hydrate inhibitor for natural gas.The most most widely used general, most efficient method is through adding chemical inhibitor to prevent the generation of pipeline gentle WIH compound.
Adding hydrate inhibitor for natural gas is to be easily formed in the operating mode of hydrate to pipeline and gas well etc. to add inhibited chemicals, in order to change the thermodynamical equilibrium condition of natural gas-aqueous systems, the generation of prevention hydrate nucleus, to slow down in the speed grown up of nucleus, the generation stoping hydrate cage and gas molecule entrance hydrate cage or the gathering of prevention tiny crystals, thus play the effect of suppression hydrate generation.At present, hydrate inhibitor for natural gas is broadly divided into following a few class: thermodynamic inhibitor (THI), anti polymerizer (AA), kinetic inhibitor (KHI).
The mechanism of action of thermodynamic inhibitor is, changes the thermodynamic equilibrium constant of system so that the pressure forming hydrate is bigger, and temperature is lower, but the concentration of thermodynamic inhibitor is the highest, usually 10%-60%.The problems such as the use of heavy dose of inhibitor, brings such as cost increase, and injected system is huge, and operation is complicated, the most often can bring environmental problem, the most at sea or during seabed operation.
Dynamic hydrate inhibitor, it is impossible to stop the generation of hydrate nucleus, but the growth even stopping nucleus can being slowed down, thus play the effect of suppression.It is little that kinetic inhibitor has consumption, performance advantages of higher, but in the face of the field working conditions of oil gas field complexity, still shows the deficiency of rejection ability, it is impossible in large-scale application to actual production.
Summary of the invention
It is an object of the invention to for the deficiencies in the prior art, it is provided that a kind of new and effective, Compositional type hydrate inhibitor.
The present invention is on the basis of the advantage taking into full account various gas hydrates suppressing method and deficiency, synthesize a kind of new polymers kinetic inhibitor, and with this kinetic inhibitor as host, add certain built agent, the rejection of inhibitor can be significantly improved.
It is as follows that the present invention realizes process:
A kind of Compositional type hydrate inhibitor for natural gas compositions, is made up of with thermodynamic inhibitor the polymer shown in structure formula (I), and polymer is 1:1 ~ 1:10 with the mass ratio of thermodynamic inhibitor,
(I)
Wherein R1For C1～C10Alkyl, cycloalkyl, aromatic hydrocarbons；
Described thermodynamic inhibitor is selected from methanol, ethanol, ethylene glycol, butanol, butyl glycol ether, butyl, ethylene glycol phenyl ether, Polyethylene Glycol.
Shown Polymer average molecular weights is 8,000 ~ 400,000 g/mol, the most poly-(caprolactam-ethyl methacrylate) copolymer of shown polymer or poly-(caprolactam-methyl methacrylate) copolymer.
Method for producing polymer shown in said structure formula (I) is: with N-caprolactam, methacrylate as monomer, azodiisobutyronitrile is initiator, carry out free radical solution polymerization reaction in aqueous, obtain described poly-(caprolactam-methacrylate) copolymer；Described monomer N-vinyl caprolactam, the mass ratio of methacrylate are 12:1-1:1, and the consumption of initiator is the 5-10% of described monomer mass, and polymeric reaction temperature is 40-90 DEG C, and the response time is 2-12h.
Advantages of the present invention and good effect:
(1) action effect is good: the new polymers kinetic inhibitor of synthesis is poly-(caprolactam-methacrylate) copolymer, longer than the supression time of existing kinetic inhibitor Vinylcaprolactam homopolymer, polyvinylpyrrolidone when being used alone.With this kinetic inhibitor as host, compound with thermodynamic inhibitor, can significantly extend the supression time.Kinetic inhibitor can only extend the generation time of hydrate, the growing amount of hydrate can not be reduced, and inhibitor hydrate is except extending the generation time of hydrate, the growing amount of hydrate can also be reduced, its action effect is strengthened in terms of two, makes the hydrate more difficult obstruction pipeline of generation.
(2) application is more extensive: separate power inhibitor problems faced in the application is that inhibitory activity is on the low side, it is affected by the external environment bigger, poor universality, application has the biggest limitation, owing to the effect of compound inhibitor is greatly improved, and the generation of hydrate can also be reduced, therefore versatility is higher.
(3) cost is lower, more economical: the built agent selected by the present invention is that some are cheap, the alcohol that is easy to get and ether etc., and addition is also little, the consumption of compounding rear kinetic inhibitor can be lower, thus greatly reduces the cost that gas industries generates due to suppression hydrate.
Detailed description of the invention
The synthesis of poly-(caprolactam-methacrylate) copolymer:
With N-caprolactam, ethyl methacrylate as monomer, azodiisobutyronitrile is initiator, carries out free radical solution polymerization reaction in aqueous, obtains described poly-(caprolactam-ethyl methacrylate) copolymer；Described monomer is 1:2-1:10 with the mass ratio of described solvent, and described monomer N-vinyl caprolactam, the ratio of ethyl methacrylate are 12:1-1:1, and the consumption of described initiator is the 5-10% of the quality of described monomer.The reaction temperature of described polyreaction is 40-90 DEG C, and the response time is 2-12h.
The product used prepared by said method carries out infrared spectrum analysis, and contrast monomer and the infrared spectrum of polymer, at the 1625cm of product infared spectrum-1The peak produced by-C=C key stretching vibration disappears, 3105cm-1 place's olefinic carbon protonCharacteristic absorption also disappear, 1721cm-1Place is the stretching vibration peak of ester C=O, 1625cm-1It is the stretching vibration peak of cyclic amides C=O, therefore can be determined that product is exactly poly-(caprolactam-ethyl methacrylate) copolymer.
Product carries out nmr analysis, and the hydrogen atom chemical shift of deuterated water is at 4.8.At 6, the chemical shift of hydrogen atom is between 4.3-4.6, at 5, the chemical shift of hydrogen atom is between 3.0-3.5, at 8 be connected with ester carbonyl group, the chemical shift at hydrogen atom and 1 overlaps between 2.3-2.5, at 9 in CH2 O hydrogen atom chemical shift near 4.1, remaining hydrogen atom chemical shift everywhere is between 1.2-2.0, and at 10, the chemical shift of terminal methyl group hydrogen atom is 0.95.
Acrylic acid containing ester based monomer is: CH2=C(CH3)CO2R1, wherein R1: C1～C10Alkyl, cycloalkyl, aromatic hydrocarbons.
Poly-(caprolactam-ethyl methacrylate) copolymer and inhibitor performance evaluation use THF test method(s), particularly as follows:
(1) preparation of poly-(caprolactam-ethyl methacrylate) copolymer suppression solution.
Poly-(caprolactam-ethyl methacrylate) copolymer accurately weighing certain mass is put in 100ml round-bottomed flask, add the deionized water of certain volume, put into stirrer stirring, it is made fully to dissolve, it is made into poly-(caprolactam-ethyl methacrylate) aqueous copolymers solution that mass fraction is 1%, 3%, 5%, standby.
(2) poly-(caprolactam-ethyl methacrylate) copolymer accurately pipetting 10 ml suppresses liquid in round-bottomed flask, adds 2.65ml oxolane, puts into stirrer, stopper bottle stopper, shake flasks, make suppression liquid mix homogeneously with THF.
(3) in order to get rid of the impact of room temperature, pre-adjust refrigerator temperature, flask is put in refrigerator so that it is constant temperature 15min at 8 DEG C so that it is original state keeps consistent as far as possible.
(4) temperature being pre-adjusted reactive bath technique is 0 DEG C, is fixed on iron stand by the flask after constant temperature 15min, puts in the cold well of cryogenic thermostat reactive bath technique, opens the agitating device of reactive bath technique simultaneously, starts stirring.
(5) observe the reading of thermometer, reach to start when 0 DEG C timing, the most constantly the state of mixed liquor in observation flask.When hydrate occurs, stop timing, calculate induction time.
Thermodynamic inhibitor used time compounding is mainly methanol, ethanol, ethylene glycol, butanol, butyl glycol ether, butyl, ethylene glycol phenyl ether, Polyethylene Glycol etc..
Embodiment 1
Based on the quality of water in system, preparation is containing poly-(caprolactam-benzyl methacrylate) copolymer quality concentration 1% and the composite hydrate inhibitor of methanol quality concentration 5%, add a certain amount of THF so that it is concentration is 19wt%, utilize THF method to carry out performance evaluation.At ambient pressure, reaction temperature maintains 0 DEG C, and the rotating speed of each experimental stirring all keeps consistent, and the suppression time is more than 75h.
Embodiment 2
Based on the quality of water in system, preparation is containing poly-(caprolactam-benzyl methacrylate) copolymer quality concentration 3% and the composite hydrate inhibitor of butyl glycol ether mass concentration 5%, add a certain amount of THF, making its concentration is 19wt%, utilizes THF method to carry out performance evaluation.At ambient pressure, reaction temperature maintains 0 DEG C, and the rotating speed of each experimental stirring all keeps consistent, and the suppression time is more than 65h.
Embodiment 3
Based on the quality of water in system, preparation is containing poly-(caprolactam-benzyl methacrylate) copolymer quality concentration 3% and the composite hydrate inhibitor of quality of glycol concentration 5%, add a certain amount of THF so that it is concentration is 19wt%, utilize THF method to carry out performance evaluation.At ambient pressure, reaction temperature maintains 0 DEG C, and the rotating speed of each experimental stirring all keeps consistent, and the suppression time is more than 55h.
Embodiment 4
Weigh 3% poly-(caprolactam-methacrylate) aqueous copolymers solution of 10ml, add 2.65ml oxolane, utilize THF method to carry out performance evaluation.At ambient pressure, reaction temperature maintains 0 DEG C, generates hydrate after suppression 140min.
Comparative example 1
The THF solution 10g of configuration 19wt% utilizes THF method to carry out performance evaluation, and at ambient pressure, reaction temperature maintains 0 DEG C, generates hydrate after reaction 3min.
Comparative example 3
Weigh in the round-bottomed flask that the deionized water of 10g puts into 100ml, then pipette a certain amount of methanol, be configured to 1.0%(wt) aqueous solution, then the THF pipetting 2.65ml adds in round-bottomed flask.At ambient pressure, reaction temperature maintains 0 DEG C, generates hydrate after reaction 7min.
Comparative example 4
Measure the suppression time of 1% Polyethylene Glycol according to the method described above.At ambient pressure, reaction temperature maintains 0 DEG C, generates hydrate after reaction 46min.
Claims (5)
1. a Compositional type hydrate inhibitor for natural gas compositions, it is characterised in that be made up of with thermodynamic inhibitor the polymer shown in structure formula (I), polymer is 1:1 ~ 1:10 with the mass ratio of thermodynamic inhibitor,
(I)
Wherein R1For C1～C10Alkyl, cycloalkyl, aromatic hydrocarbons；
Described thermodynamic inhibitor is selected from methanol, ethanol, ethylene glycol, butanol, butyl glycol ether, butyl, ethylene glycol phenyl ether, Polyethylene Glycol.
Compositional type hydrate inhibitor for natural gas compositions the most according to claim 1, it is characterised in that: shown Polymer average molecular weights is 8,000 ~ 400,000 g/mol.
Compositional type hydrate inhibitor for natural gas compositions the most according to claim 1, it is characterised in that: shown polymer is poly-(caprolactam-ethyl methacrylate) copolymer or poly-(caprolactam-methyl methacrylate) copolymer.
Compositional type hydrate inhibitor for natural gas compositions the most according to claim 1, it is characterized in that the method for producing polymer shown in structure formula (I) is: with N-caprolactam, methacrylate as monomer, azodiisobutyronitrile is initiator, carry out free radical solution polymerization reaction in aqueous, obtain described poly-(caprolactam-methacrylate) copolymer；Described monomer N-vinyl caprolactam, the mass ratio of methacrylate are 12:1-1:1, and the consumption of initiator is the 5-10% of described monomer mass, and polymeric reaction temperature is 40-90 DEG C, and the response time is 2-12h.
5. compositions described in claim 1 is as the application of hydrate inhibitor for natural gas.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107795848A (en) * | 2017-09-30 | 2018-03-13 | 天津大学 | A kind of Compositional type hydrate inhibitor for natural gas of the amphipathic copolymer containing POSS and preparation method thereof |
| CN108219762A (en) * | 2016-12-14 | 2018-06-29 | 中国科学院广州能源研究所 | A kind of novel hydrates kinetic inhibitor and its preparation method and application |
| FR3087780A1 (en) * | 2018-10-31 | 2020-05-01 | Arkema France | COMPOSITION FOR DELAYING THE FORMATION OF GAS HYDRATES |
Citations (5)
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| WO1996037684A1 (en) * | 1995-05-26 | 1996-11-28 | Nippon Shokubai Co., Ltd. | Clathrate hydrate inhibitor and method of inhibiting the formation of clathrate hydrates using it |
| CN1157651A (en) * | 1994-09-15 | 1997-08-20 | 埃克森生产研究公司 | Method for inhibiting hydrate formation |
| CN101074361A (en) * | 2007-05-25 | 2007-11-21 | 东莞理工学院 | Efficient composite hydrate inhibitor |
| WO2007143489A2 (en) * | 2006-06-01 | 2007-12-13 | Isp Investments Inc. | Composition for inhibiting formation of gas hydrates |
| CN103194194A (en) * | 2013-03-22 | 2013-07-10 | 西北大学 | Composite type hydrate inhibitor |
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- 2015-05-25 CN CN201510265936.1A patent/CN106190060A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157651A (en) * | 1994-09-15 | 1997-08-20 | 埃克森生产研究公司 | Method for inhibiting hydrate formation |
| WO1996037684A1 (en) * | 1995-05-26 | 1996-11-28 | Nippon Shokubai Co., Ltd. | Clathrate hydrate inhibitor and method of inhibiting the formation of clathrate hydrates using it |
| WO2007143489A2 (en) * | 2006-06-01 | 2007-12-13 | Isp Investments Inc. | Composition for inhibiting formation of gas hydrates |
| CN101074361A (en) * | 2007-05-25 | 2007-11-21 | 东莞理工学院 | Efficient composite hydrate inhibitor |
| CN103194194A (en) * | 2013-03-22 | 2013-07-10 | 西北大学 | Composite type hydrate inhibitor |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219762A (en) * | 2016-12-14 | 2018-06-29 | 中国科学院广州能源研究所 | A kind of novel hydrates kinetic inhibitor and its preparation method and application |
| CN107795848A (en) * | 2017-09-30 | 2018-03-13 | 天津大学 | A kind of Compositional type hydrate inhibitor for natural gas of the amphipathic copolymer containing POSS and preparation method thereof |
| CN107795848B (en) * | 2017-09-30 | 2019-06-11 | 天津大学 | A kind of Compositional type hydrate inhibitor for natural gas of the amphipathic copolymer containing POSS and preparation method thereof |
| FR3087780A1 (en) * | 2018-10-31 | 2020-05-01 | Arkema France | COMPOSITION FOR DELAYING THE FORMATION OF GAS HYDRATES |
| WO2020089554A1 (en) * | 2018-10-31 | 2020-05-07 | Arkema France | Composition that can be used to delay the formation of gas hydrates |
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