CN104479660A - Composite hydrate inhibitor - Google Patents
Composite hydrate inhibitor Download PDFInfo
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- CN104479660A CN104479660A CN201410655310.7A CN201410655310A CN104479660A CN 104479660 A CN104479660 A CN 104479660A CN 201410655310 A CN201410655310 A CN 201410655310A CN 104479660 A CN104479660 A CN 104479660A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
- F17D1/17—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity by mixing with another liquid, i.e. diluting
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Abstract
The invention discloses a composite hydrate inhibitor. The composite hydrate inhibitor is formed by configuring a kinetic inhibitor and ionic liquid according to the mass ratio of 1:1, wherein the kinetic inhibitor is polyvinylcaprolactam with the weight-average molecular weight of 900-40000. The hydrate inhibitor disclosed by the invention has high inhibition activity, small using amount, low cost and environmental friendliness, is easy to recover and applicable to an oil-gas-water three-phase or oil-water or gas-water two-phase coexistence system, is applied to generation of inhibition hydrates in oil-gas production, processing and conveying processes and has broad prospects.
Description
Technical field:
The present invention relates to chemical technology field, be specifically related to a kind of Compound Water compound inhibitors.
Background technology:
In oil-gas mining, processing and transportation, in system, water generates hydrate with some lighter hydrocarbons are as easy as rolling off a log in pipeline cryogenic high pressure position, if do not take braking measure, these hydrates will blocking pipeline, valve and equipment, affect normal production running, cause tremendous economic to lose, more can threaten the safety of whole production system.Therefore, how water prevention compound becomes one of gas industries issues that need special attention, and especially for deepwater field exploitation, Hydrate Plugging problem is more outstanding.
Hydrate prevention and controls main at present, comprises except water law, heating method, voltage drop method and interpolation hydrate inhibitor method.Except water law cost is higher, and there is very large limitation, because the existence of the generation of the hydrate free aqueous phase that is not absolute demand, if hydrate nucleus or free water are adsorbed in the places such as wall, although liquid hydrocarbon mutually in water concentration very low, hydrate also can from liquid hydrocarbon mutually growth.Heating method makes pipe temperature generate temperature higher than hydrate, easily cause line fracture even hydrate eruption, and the water decomposing generation must remove, otherwise again can form hydrate again.Voltage drop method is by reducing system pressure, and require too high to pressure-controlling, application difficulty is very large.Therefore, interpolation hydrate inhibitor method is simple, economical, effective, is that water prevention compound generates the most widely used method of blocking.
Hydrate inhibitor mainly contains thermodynamic inhibitor and low-dosage inhibitor.Thermodynamic inhibitor, as the alcohols such as methyl alcohol, ethylene glycol or inorganic salt etc., changes the phase balance condition of hydrate, make hydrate formation curve towards lower temperature or more high pressure move, inhibition is very effective.But the method add-on is large, general strength of solution 10 ~ 60wt%, the costs such as corresponding storage, transport, injection and recovery are high, and methyl alcohol is toxic simultaneously, is unfavorable for safety and environmental protection.Low-dosage inhibitor comprises kinetic inhibitor and stopper.Wherein kinetic inhibitor is nucleation time by delaying hydrate crystal or the further growth stoping crystal, thus suppresses it to generate, and does not occur Hydrate Plugging phenomenon.But kinetic inhibitor (>10 DEG C) inhibition when pipeline (or oil well) is closed or condensate depression is larger is not very effective.On the other hand, kinetic inhibitor is all generally high molecular weight water soluble polymer, and when the temperature increases, solvability is deteriorated, and rejection reduces.Stopper adds some low concentration surfactants or polymkeric substance, changes the form of hydrate crystal size and gathering, makes its conveying in slurries in leading fluid, realize safe fluid conveying.But stopper dispersing property is limited, just can only work when there being oil phase, application scenario is limited.
Summary of the invention:
The object of this invention is to provide a kind of new and effective Compound Water compound inhibitors.
The present invention is achieved by the following technical programs:
A kind of Compound Water compound inhibitors, is formed according to mass ratio 1:1 configuration by kinetic inhibitor and ionic liquid; Described kinetic inhibitor to be weight-average molecular weight be 900 ~ 40000 polyvinyl caprolactam (PVCap).
Described ionic liquid is combined into ionic linkage by the mol ratio of 1:1 by organic cation and organic or inorganic negatively charged ion.
Described ionic liquid is preferably the one of the ionic liquid of alkyl guanidine salt shown in formula I:
Wherein, R
1be selected from normal-butyl, R
2be selected from methyl, R
3be selected from methyl, negatively charged ion X is selected from the one in halide-ions, tetrafluoroborate, acetate moiety, trifluoroacetic acid root, trifluoromethane sulfonic acid root.
Described composite inhibitor working concentration is low, and consumption is few, is 0.05 ~ 0.5% relative to the mass concentration of water during use.
Principal feature of the present invention is that the ionic liquid added has the effect of thermodynamics and kinetics double inhibition to hydrate, can reduce hydrate and generate temperature or improve hydrate generation pressure, reduce condensate depression to the negative impact of high molecular polymer rejection; Also can suppress the speed of the nucleation of hydrate, growth and agglomeration, suppress time lengthening, and nontoxic, corrosion-free, environmentally friendly, corrosion will be caused broken to pipeline; Biodegradable, later stage Separation and Recovery treatment process is simple; There is the adjustable characteristic of anion/cation, by adjusting its polarity and hydrophilic/lipophilic, inhibitor can be made to be applicable to oil gas water three phase or profit or air water two-phase coexistent system.
Compared with traditional Hydrate Suppression, the advantage that the combination water compound inhibitors combined by ionic liquid and kinetic inhibitor Vinylcaprolactam homopolymer of the present invention has is as follows:
(1) inhibit activities is higher: the inhibition being used alone ionic liquid generation generally will be weaker than kinetic inhibitor PVCap, but single power inhibitor PVCap is large by the impact of condensate depression, after condensate depression is more than 10 DEG C, inhibition can become very poor.By inciting somebody to action both compound uses, the electric charge restraining effect of the ion in ionic liquid and the characteristic of self surfactant, to a certain degree improve surroundings, reduce the impact of composite inhibitor by condensate depression, act synergistically between the two, can produce and compare the better inhibition of one-component inhibitor, even, not bad than the effect of one-component inhibitor effect sum.
(2) consumption is few, and cost reduces: the add-on of composite inhibitor is far smaller than conventional heat inhibitor, and run-of-the-mill concentration is about 0.05 ~ 0.5wt%, and reagent cost reduces greatly.
(3) environmental protection, is easy to reclaim.Ionic liquid chemical stability and Heat stability is good, nonflammable, corrosion-free, overcome the corrodibility that conventional heat inhibitor causes pipeline.And ionic liquid does not have volatility, large with the boiling-point difference of fluid, the later stage easily reclaims, and can reduce the loss amount of inhibitor.
In a word, the present invention is applicable to oil gas water three phase or profit or air water two-phase coexistent system, is applied to the generation suppressing hydrate in oil-gas mining, processing and course of conveying, has broad prospects.
Embodiment:
Below further illustrate of the present invention, instead of limitation of the present invention.
The hydrate reaction system of the present embodiment mainly comprises nucleus equipment autoclave, low temperature thermostat bath, vacuum pump, gas cylinder and data collecting instrument etc.Wherein autoclave comprises reactor body, magnetic stirring apparatus, intake valve, vacuum valve, tapping valve, safety valve and temperature/pressure sensor etc.Described autoclave adopts Stainless steel 316 material to make, and kettle front and back belt form, maximum working pressure can reach 10MPa.Low temperature thermostat bath provides the refrigerant circulation liquid of-20 ~ 100 DEG C for autoclave chuck, and agitator speed regulation range is 0 ~ 2200r/min.Temperature in the kettle is measured by Pt100 platinum resistance temperature sensor, temperature measurement accuracy ± 0.1 DEG C, and pressure is the determination of pressure sensor of 0.5% by precision.The parameters such as still internal pressure, temperature and rotating speed can automatically be gathered by data collecting system and store.
The action effect of composite inhibitor of the present invention can according to the induction time of hydrate, completely rise time and pressure drop comprehensive descision.Wherein hydrate induction time for gaseous tension from initial value to pressure decline time of experiencing.The time of having reacted finally stablizes for hydrate starts to be generated to pressure and temp the time experienced.
Specific implementation process:
First experiment cleans autoclave three to five times with deionized water before running repeatedly, then by nitrogen purging autoclave and experiment piping system, guarantees that system is dry.Autoclave is vacuumized, sucks the compound inhibitor aqueous solution of the different concns prepared.For getting rid of air in still, first passing into experimental gas, and then vacuumizing, 3 times so repeatedly, finally passing into the experimental gas being less than 0.5MPa, ensure malleation in autoclave still and do not reach the condition that hydrate generates.Experiment starts low temperature thermostat bath and lowers the temperature to autoclave, until temperature in the kettle reaches setting experimental temperature.When after temperature-stable, open intake valve, open gas cylinder valve, pass into experimental gas to the required pressure of experiment.Start magnetic stirring apparatus, and keep 500rmp rotating speed.Due to the dissolving of gas, experiment start time slight pressure declines.Hydrate generates, and pressure can progressively decline.Adopt form observation and temperature, pressure change curve method simultaneously, judge whether hydrate generates.When temperature and pressure long-time stable is constant, think that reaction reaches balance, hydrate generates and terminates completely.Close agitator, stop experiment.
Reaction experiment temperature is set to 4 DEG C, experimental pressure 7.5MPa, and experimental gas is gas mixture (by volume mark meter, methane 91.95%, ethane 5.00% and propane 3.05%).
Comparative example 1
Add in reactor by 200g pure water, according to above-mentioned experimental procedure, result shows that hydrate generation induction time is under these conditions 35min, and the reaction deadline is 1500min, and in reaction, pressure drop is 3.5MPa.
Comparative example 2
Be that 900 ~ 40000PVCap aqueous solution adds in reactor by the weight-average molecular weight of 200g mass concentration 0.25%, experimental procedure is the same, result shows, it is 105min that hydrate under this system generates induction time, reaction deadline 3105min, in reaction, pressure drop is 1.68MPa, has good inhibition.
Comparative example 3
Be that 900 ~ 40000PVCap aqueous solution adds in reactor by the weight-average molecular weight of 200g mass concentration 0.5%, experimental procedure is the same, result shows, it is 219min that hydrate under this system generates induction time, reaction deadline 3915min, in reaction, pressure drop is 1.43MPa, has good inhibition.
Comparative example 4
By the N of 200g mass concentration 0.5%, N, N ﹐, N ﹐ ,-tetramethyl--N "-methyl-N "-butyl guanidine villaumite ([MBTMG] Cl) aqueous solution adds in reactor, experimental procedure is the same, result shows, it is 155min that the hydrate under this system generates induction time, reaction deadline 2508min, in reaction, pressure drop is 1.73MPa, has good inhibition.
Embodiment 1
Be PVCap and N of 900 ~ 40000 by weight-average molecular weight, N, N ﹐, N ﹐ ,-tetramethyl--N "-methyl-N "-butyl guanidine villaumite ([MBTMG] Cl) compound aqueous solution that is configured to 200g mass concentration 0.05% according to mass ratio 1:1 adds in reactor, experimental procedure is the same, result shows, it is 67min that the hydrate under this system generates induction time, reaction deadline 2219min, in reaction, pressure drop is 2.37MPa, has good inhibition.
Embodiment 2
Be PVCap and N of 900 ~ 40000 by weight-average molecular weight, N, N ﹐, N ﹐ ,-tetramethyl--N "-methyl-N "-butyl guanidine villaumite ([MBTMG] Cl) compound aqueous solution that is configured to 200g mass concentration 0.25% according to mass ratio 1:1 adds in reactor, experimental procedure is the same, result shows, it is 319min that the hydrate under this system generates induction time, reaction deadline 4327min, in reaction, pressure drop is 1.55MPa, has good inhibition.
Embodiment 3
Be 900 ~ 40000PVCap and N by weight-average molecular weight, N, N ﹐, N ﹐ ,-tetramethyl--N "-methyl-N "-butyl guanidine villaumite ([MBTMG] Cl) is configured to 200g mass concentration 0.5% compound aqueous solution according to mass ratio 1:1 and adds in reactor, experimental procedure is the same, result shows, it is 522min that the hydrate under this system generates induction time, reaction deadline 6950min, in reaction, pressure drop is 0.85MPa, has good inhibition.
Embodiment 3 contrasts known with comparative example 3,4, by by kinetic inhibitor PVCap and ionic liquid compound use, can produce and compare the better inhibition of one-component inhibitor: the induction time prolongs of hydrate, the reaction deadline is longer, and in reaction, pressure drop reduces; Even, not bad than the effect of one-component inhibitor effect sum, this is the characteristic of electric charge restraining effect due to the ion in ionic liquid and self surfactant, to a certain degree improves surroundings, reduces the impact of composite inhibitor by condensate depression.
Embodiment 4
Be PVCap and N of 900 ~ 40000 by weight-average molecular weight, N, N ﹐, N ﹐ ,-tetramethyl--N "-methyl-N "-butyl guanidine a tetrafluoro borate ([MBTMG] BF
4) according to mass ratio 1:1 be configured to 200g mass concentration be 0.25% compound aqueous solution add in reactor, experimental procedure is the same, result shows, it is 387min that hydrate under this system generates induction time, reaction deadline 4579min, in reaction, pressure drop is 1.1MPa, has good inhibition.
Embodiment 5
Be PVCap and N of 900 ~ 40000 by weight-average molecular weight, N, N ﹐, N ﹐ ,-tetramethyl--N "-methyl-N "-butyl glucocyamine salt ([MBTMG] CH
3cOO) compound aqueous solution being configured to 200g mass concentration 0.25% according to mass ratio 1:1 adds in reactor, experimental procedure is the same, result shows, it is 217min that hydrate under this system generates induction time, reaction deadline 3778min, in reaction, pressure drop is 1.38MPa, has good inhibition.
Embodiment 6
Be PVCap and N of 900 ~ 40000 by weight-average molecular weight, N, N ﹐, N ﹐ ,-tetramethyl--N "-methyl-N "-butyl guanidine trifluoroacetate ([MBTMG] CF
3cOO) compound aqueous solution being configured to 200g mass concentration 0.25% according to mass ratio 1:1 adds in reactor, experimental procedure is the same, result shows, it is 235min that hydrate under this system generates induction time, reaction deadline 3950min, in reaction, pressure drop is 1.32MPa, has good inhibition.
Embodiment 7
Be PVCap and N of 900 ~ 40000 by weight-average molecular weight, N, N ﹐, N ﹐ ,-tetramethyl--N "-methyl-N "-butyl guanidine trifluoromethyl sulfonic acid ([MBTMG] CF
3sO
3) be configured to 200g mass concentration 0.25% compound aqueous solution according to mass ratio 1:1 and add in reactor, experimental procedure is the same, result shows, it is 268min that hydrate under this system generates induction time, reaction deadline 4095min, in reaction, pressure drop is 1.25MPa, has good inhibition.
Claims (4)
1. a Compound Water compound inhibitors, is characterized in that, is formed according to mass ratio 1:1 configuration by kinetic inhibitor and ionic liquid; Described kinetic inhibitor to be weight-average molecular weight be 900 ~ 40000 polyvinyl caprolactam.
2. Compound Water compound inhibitors according to claim 1, is characterized in that, described ionic liquid is combined into ionic linkage by the mol ratio of 1:1 by organic cation and organic or inorganic negatively charged ion.
3. Compound Water compound inhibitors according to claim 1 and 2, is characterized in that, described ionic liquid is selected from the one in the ionic liquid of alkyl guanidine salt shown in formula I:
Wherein, R
1be selected from normal-butyl, R
2be selected from methyl, R
3be selected from methyl, negatively charged ion X is selected from the one in halide-ions, tetrafluoroborate, acetate moiety, trifluoroacetic acid root, trifluoromethane sulfonic acid root.
4. Compound Water compound inhibitors according to claim 3, is characterized in that, is 0.05 ~ 0.5% relative to the mass concentration of water when described composite inhibitor uses.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410655310.7A CN104479660A (en) | 2014-11-17 | 2014-11-17 | Composite hydrate inhibitor |
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| CN201410655310.7A CN104479660A (en) | 2014-11-17 | 2014-11-17 | Composite hydrate inhibitor |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105090748A (en) * | 2015-08-14 | 2015-11-25 | 中国石油化工股份有限公司 | Efficient combination type hydrate inhibitor |
| CN105179942A (en) * | 2015-08-14 | 2015-12-23 | 中国石油化工股份有限公司 | Compound hydrate inhibitor |
| CN106641728A (en) * | 2016-12-28 | 2017-05-10 | 中国科学院广州能源研究所 | Compound hydrate inhibitor based on piperidine ionic liquid |
| CN106753300A (en) * | 2016-12-28 | 2017-05-31 | 中国科学院广州能源研究所 | A kind of double effect compound type hydrate inhibitor and preparation method thereof |
| CN107903884A (en) * | 2017-10-31 | 2018-04-13 | 常州大学 | A kind of combined gas hydrate inhibitor and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104039918A (en) * | 2011-10-11 | 2014-09-10 | Eco抑制剂公司 | Method of inhibiting the formation of gas hydrates using amidines and guanidines |
-
2014
- 2014-11-17 CN CN201410655310.7A patent/CN104479660A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104039918A (en) * | 2011-10-11 | 2014-09-10 | Eco抑制剂公司 | Method of inhibiting the formation of gas hydrates using amidines and guanidines |
Non-Patent Citations (1)
| Title |
|---|
| 孙力等: "高分子通报", 《高分子通报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105090748A (en) * | 2015-08-14 | 2015-11-25 | 中国石油化工股份有限公司 | Efficient combination type hydrate inhibitor |
| CN105179942A (en) * | 2015-08-14 | 2015-12-23 | 中国石油化工股份有限公司 | Compound hydrate inhibitor |
| CN105179942B (en) * | 2015-08-14 | 2018-05-18 | 中国石油化工股份有限公司青岛安全工程研究院 | A kind of Compositional type hydrate inhibitor |
| CN106641728A (en) * | 2016-12-28 | 2017-05-10 | 中国科学院广州能源研究所 | Compound hydrate inhibitor based on piperidine ionic liquid |
| CN106753300A (en) * | 2016-12-28 | 2017-05-31 | 中国科学院广州能源研究所 | A kind of double effect compound type hydrate inhibitor and preparation method thereof |
| CN106753300B (en) * | 2016-12-28 | 2019-10-08 | 中国科学院广州能源研究所 | A kind of double effect compound type hydrate inhibitor and preparation method thereof |
| CN107903884A (en) * | 2017-10-31 | 2018-04-13 | 常州大学 | A kind of combined gas hydrate inhibitor and preparation method thereof |
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Application publication date: 20150401 |