CN101235278A - Ionic liquid type hydrate inhibitor - Google Patents
Ionic liquid type hydrate inhibitor Download PDFInfo
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- CN101235278A CN101235278A CNA2008100560173A CN200810056017A CN101235278A CN 101235278 A CN101235278 A CN 101235278A CN A2008100560173 A CNA2008100560173 A CN A2008100560173A CN 200810056017 A CN200810056017 A CN 200810056017A CN 101235278 A CN101235278 A CN 101235278A
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Abstract
The invention relates to ion liquid type hydrate inhibitor, which is diluting solution or mixture which is prepared through dissolving one kind of ion liquid, two kinds of ion liquid, or more than two kinds of ion liquid in solvent, wherein the mass concentration of ion liquid in solution is 0.005-0.05wt%, ion liquid is combined with organic cation and organic or inorganic anion through ionic bond according to the molar ratio of 1:1, solvent is water, salt water and alcohols and mixtures. As the inhibitor has especial unit structure, the inhibitor can form space steric hindrance and electric barrier steric hindrance for the generation of clathrate hydrate in fluid, can inhibit the nucleation, growth and agglomeration of hydrate, has higher inhibiting activity, can reduce viscosity of fluid, and improves flowability of fluid. Compared with common thermodynamics inhibitor, the inhibiting property and inhibiting time are increased, the additive dose is largely reduced, the additive condition is mild, recycling is convenient, and solvent loss is small, and the inhibitor is an environment-friendly product.
Description
Technical field
The present invention relates to a kind of ionic liquid type hydrate inhibitor that in oil or gas extraction, processing and course of conveying, suppresses the generation of cage type gas hydrate.
Background technology
Gas hydrate are in oil, Natural gas extraction, processing and transportation, under certain temperature and pressure, by some the micro-molecular gas (CO in the Sweet natural gas
2, CH
4, C
2H
6, C
3H
8, H
2S etc.) the ice and snow shape crystal that forms with liquid water.In hydrate, the water molecules that is connected by hydrogen bond forms cage structure, and gas molecule is enclosed in the lattice under the Van der Waals force effect.
The generation of gas hydrate is main relevant with following three aspects: contain liquid water in (1) Sweet natural gas or contain the steam of hypersaturated state, with the formation void structure; (2) low temperature and condition of high voltage; (3) gaseous tension fluctuation or flow direction sudden change produce disturbance or have nucleus to exist.The formation of hydrate mainly comprises nucleation stage, slow growth stage and growth phase (wherein really to production of hydrocarbons and to carry what threaten be quick growth phase) fast.Theoretically, when forming hydrate, not necessarily need free-water, there is the component that forms hydrate to exist jointly in gas phase or the condense hydrocarbon as long as exist, the pressure and temperature condition satisfies (being high pressure and low temperature), and water and some components will form solid hydrate.It is generally acknowledged that the critical temperature that hydrate forms is the top temperature that hydrate exists, be higher than this temperature, pipe pressure is not much, can not form hydrate yet.
Each component of table 1 Sweet natural gas generates the critical formation temperature (pressure 3MPa) of hydrate
| The component title | Critical temperature/℃ |
| CO 2 CH 4 | 10.0 21.5 |
| C 2H 6 C 3H 8 H 2S | 14.5 5.5 29.0 |
The temperature of system is low more, the metastable lattice framework of the easy more formation of water; Pressure is high more, and the easy more gas molecule that makes enters in the lattice cavity, so temperature is low more, the high more easy more generation hydrate of pressure.For example, be lower than under 4 ℃ the temperature at ethane under the pressure of about 1MPa and forming the vaporous water compound, be lower than under 14 ℃ the temperature at ethane under the pressure of 3MPa and can form the vaporous water compound.This temperature and pressure scope all often runs into for many operating environments of production and transport gas and other petroleum fluids.
In exploitation, processing and the transmission course of Sweet natural gas, oil, particularly transfer pressure is generally higher in the long-distance transmission pipeline, forms hydrate in the pipeline easily.After in a single day hydrate forms, fluid retrogradation, system viscosity are increased, and the minimizing of the circulation area of pipeline, forming throttling, the formation of hydrate is further quickened in meeting, can stop up equipment such as pit shaft, pipeline, valve and instrument in the time of seriously.From the field that taps natural gas both at home and abroad through examining, hydrate all takes place in the pit shaft and stops up in nearly all gas field to some extent.Perhydrate just occurring as gas field, China northern Shensi in the pilot production process stops up; At the beginning of 1999, the problem that gas hydrate influence the normal gas transmission of pipeline also appearred in capital, Shan natural gas line.In addition, in the marine petroleum exploitation process, gas hydrate can form the ring-type shutoff between probing and preventer, stop up preventer, choker-line and kill line.Therefore, to the control of hydrate become need to be resolved hurrily in the oil and gas industry one of key issue.
For this reason, various countries' oil gas circle and academia have carried out long-term and unremitting effort, and develop evaporation, heating method and interpolation inhibitor method in succession.Dehydration technique has three kinds of treatment processs: moisture absorption solvent, chemisorption and physical adsorption.
The moisture absorption solvent is generally chosen triglycol, and can absorb water molecules by hydrogen bond after fluid contacts; Physical adsorption is with solid selective adsorption water moleculess such as molecular sieve, aluminum oxide or silica gel; Chemisorption can't be regenerated because of sorbent material and no longer be adopted.The cost of evaporation is higher, and the nucleus of hydrate or free water can be adsorbed in places such as wall, although the water concentration of liquid hydrocarbon in mutually is very low, hydrate also can be at an easy rate from liquid hydrocarbon mutually growth, so the application of dehydration technique has very big limitation.
The difficult point of heating method is to be difficult to determine the position of hydrate obstruction, when finding blocking position, must heat gradually to the centre from the two ends of hydrate piece, in order to avoid, cause the eruption of line fracture even hydrate owing to the decomposition of hydrate sharply increases pressure, temperature.And decompose the water that produces and to remove, otherwise, be easy to form again hydrate owing to comprise a large amount of hydrate remaining structure in the water.This method is to long inapplicable apart from the seabed gas transmission.
Therefore, it is the simplest, economical to add inhibitor in air-flow, uses also extensively, and it is the effective ways that prevent the hydrate generation near wellbore formation, pit shaft, ore deposit factory gathering system and the gas pretreatment device before entering long-distance transport pipes.Generally in pipeline, inject alcohols inhibitor or inorganic salt inhibitor such as methyl alcohol, ethanol, Virahol or ethylene glycol traditionally, this class inhibitor can destroy the hydrogen bond of hydrate, change the partial potential of the aqueous solution or hydrate phase, make the decomposition curve of hydrate shift to lesser temps or elevated pressures, suppress the purpose that hydrate generates thereby reach, thereby be referred to as the thermodynamics inhibitor.Only be characterized in that under high density (more than the 6wt%) could reduce the formation speed (can improve the formation speed of hydrate under the lower concentration on the contrary) of hydrate.Because add concentration height (10-60wt%), consumption is big, therefore required cost height (the inhibitor cost accounts for the 5-8% of total production cost).Particularly methyl alcohol is toxic, and aerial limits of explosion only is 6.0-31.5 %, is unfavorable for safety and environmental protection, might be disabled.In addition, the loss of inhibitor is also bigger, and processing, storage, recovery and fluidic purify all to be needed to consider.
Therefore, entered since the nineties, countries in the world oil gas circle and academia are active day by day to the development of novel hydrates inhibitor.New inhibitor comprises hydrate kinetic inhibitor and anti polymerizer.
Kinetic inhibitor is some water-soluble or aqueous dispersion polymers, and they only suppress the formation of hydrate at aqueous phase, the concentration of adding very low (at aqueous phase usually less than 1%), and it does not influence the thermodynamic condition that hydrate generates.At the initial stage of crystal of hydrate nucleation and growth, they are adsorbed in the surface of hydrate particle, the ring texture of inhibitor is by the crystal combination of hydrogen bond and hydrate, delay the hydrate crystal nucleation time or stop crystalline further to be grown up, fluid is lower than hydrate-formation temperature (promptly at certain condensate depression Δ t) current downflow in its temperature in the pipeline thereby make, and the hydrate latch up phenomenon do not occur.
Develop the hydrate kinetic inhibitor abroad since the nineties.Duucum etc. have set forth hydrate kinetic inhibitor one tyrosine and derivative thereof first in its patent (Eur.Pat.536950) in 1993.Subsequently, Anselme etc. has confirmed the restraining effect of multiple polymers to the growth velocity of tetrahydrofuran (THF) hydrate crystal on the ice crystal crystal seed in its patent (World Pat.WO 93/25798).Polymkeric substance that they try comprises the NVP polymkeric substance, as homopolymer N-vinyl pyrrolidone (PVP) and butyl derivative---Agrinerp-904 thereof.Sloan had introduced NVP (five-ring), hydroxy vitamin (six-ring) and N-caprolactam (seven-membered ring) the polymkeric substance situation as the hydrate kinetic inhibitor in its patent (World Pat.WO 94/12761) in 1994.Nineteen ninety-five Kelland etc. has checked the inhibition usefulness of multiple polymers kinetic inhibitor again, and has confirmed that trimer Gaffix VC-0713 by olefin(e) acid methyl esters in NVP, N-caprolactam and the dimethylin is best a kind of of effect in the inhibitor of being tested.The common feature of above-mentioned kinetic inhibitor is to add concentration less than 1wt%.
At present, kinetic inhibitor is tested and is used at the oil-gas field of the U.S. and Britain.Texaco lnc.s etc. adopt PVP at U.S.'s onshore oil gas field.British Petroleum Company p.l.c. has adopted the higher kinetic inhibitor of another kind of activity in the Xi Suole gas field in south, the North Sea.The rejection of GaffixVC-713 has been tested by Atlantic Richfield Co. at sea gas field.
One of it is main that kinetic inhibitor exists at present, and problem is to be subjected to the influence of condensate depression very big, and it suppresses active on the low side.Maximum subcooled temperature as the inhibitor of Atlantic Richfield Co. test is 4 ℃, and the condensate depression that the inhibitor that adopt in the Xi Suole gas field is suitable for also only is 8-9 ℃.And the condensate depression that most of oil and gas industry marine and cold season (area) obviously requires inhibitor to use should be 2 times of above-mentioned condensate depression at least.Because the condensate depression that is suitable for of kinetic inhibitor is minimum in theory can be greater than 10 ℃, therefore, current driving force is learned the development also far immature (molecular structure that mainly is presented as inhibitor is undesirable) of inhibitor.The solvability variation of kinetic inhibitor when two of problem is the temperature rising, thus its due inhibition usefulness reduced.
Summary of the invention
The objective of the invention is to propose a kind of gas hydrate kinetic inhibitor of ion liquid type, in the hope of under the guidance of reliable mechanism, optimize the molecular structure of hydrate kinetic inhibitor, it is bigger to make it suppress higher, the suitable condensate depression scope of activity, and manages to improve its solvability in fluid.
Ionic liquid has the new liquid of special property as a class, under low temperature (less than 100 ℃), promptly be in a liquid state, therefore be also referred to as low-temperature molten salt, generally constitute by organic cation and organic or inorganic negatively charged ion, compare with spe medium with traditional organic solvent, have a lot of unrivaled advantages:
(1) ion liquid yin, yang ion can be selected according to design requirements, can regulate its selectivity to inorganics, water, organism and polymkeric substance;
(2) ionic liquid does not almost have vapour pressure under normal pressure, can not volatilize;
(3) most inorganic, organic and macromolecular material is shown good dissolving ability, and because its structure difference, also different with the intermiscibility of different solvents, have high resolution and weak coordination or non-coordination, be the fine solvent of many organic and inorganic things;
(4) thermostability, chemical stability are higher, have very wide liquid temperature scope (can widely reaching-96～400 ℃), can avoid decomposing, the generation of side reaction such as disproportionation;
(5) nontoxic, no burn into incombustible, viscosity is low.
Therefore, the present invention mainly is achieved in that
A kind of ionic liquid type hydrate inhibitor, this inhibitor be by ion liquid dissolving in certain solvent, make diluting soln or mixture.Ionic liquid is made of organic cation and organic or inorganic negatively charged ion, and ion liquid adding quality is in the concentration range of 0.005～0.05wt%, and preferred concentration is 0.005～0.01wt%.
Ion liquid positively charged ion is a glyoxaline cation; Its structural formula is:
(R
1=R
2=R
3=R
4=R
5=alkyl substituent or H.)
Negatively charged ion can be halide-ions, tetrafluoroborate, hexafluoro-phosphate radical, two (trifluoromethyl) sulfimide root, trifluoroacetic acid root or nitrate ion.Ion liquid solvent can be selected from water, salt solution, alcohols and composition thereof.
The ionic liquid that is dissolved in solvent can be a kind of ionic liquid, also can be that two or more is ion liquid composite.
Fluid separation in inhibitor and conveying or the process of manufacture reclaims and can carry out with vaporizer.
Because the similar of the five-membered ring structure of glyoxaline cation of the present invention and gas hydrate can play sterically hindered shielding effect to forming hydrate; And the ion in the ionic liquid also can destroy the hydrogen bond in the hydrate, plays electricity and builds the sterically hindered effect; Have again, ion liquid volume is bigger, effect with certain surface promoting agent, the surfactivity agent inhibitor is near under the micelle-forming concentration, to not significantly influence of thermodynamic property, but compare with pure water, mass transfer coefficient can reduce about 50%, thereby reduce the touch opportunity of water and guest molecule, reduce the generating rate of hydrate, and the characteristics of polymer inhibitor molecular chain are to contain a large amount of water soluble groups and have long fatty carbon chain, by eutectic or adsorption, can stop the growth of hydrate nucleus, or the hydrate particulate keep to be disperseed and not assemble, be suspended in the fluid and with fluid flow.Because these three reasons, this ionic liquid inhibitor can suppress nucleation, growth and the agglomerant speed of hydrate, higher to the inhibition activity of gas hydrate, the inhibition time is longer; By the synergy of chemistry and physics, can promote the dispersion of hydrate crystal in oil phase simultaneously, make it in oil phase, be pulpous state rather than lumphy structure, effectively reduce fluidic viscosity, improve liquidity, reduce blocked danger such as pipeline.
Ionic liquid has the advantages that zwitterion can be allocated, so can at the difference of the gas molecule that forms hydrate, optimize the unitary structure of inhibitor according to the mechanism that suppresses hydrate, adjusting reduces the influence that inhibitor is subjected to condensate depression to the selectivity and the solvability of hydrate molecule.
Simultaneously, this inhibitor be with ion liquid dissolving in water, salt solution, alcohols equal solvent liquid, make diluting soln or mixture.The main application of solvent is the carrier as inhibitor, so that inhibitor is absorbed in the aqueous phase of petroleum fluids.Any solvent that is suitable for inhibitor is delivered to the fluidic aqueous phase all can use.Inorganic salt, alcohols itself also have the effect of thermodynamics inhibitor, so can strengthen the inhibition effect.
The invention effect
Compare with the available dynamic inhibitor with thermodynamics inhibitor commonly used, the advantage of hydrate inhibitor of the present invention is:
(1) because the sterically hindered and electric base resistance effect of the activity unit structure among the present invention, ionic electric charge restraining effect and characteristics with tensio-active agent, nucleation, growth and the agglomerant speed that can effectively suppress hydrate, make it be pulpous state rather than lumphy structure is dispersed in the oil phase, can reduce fluidic viscosity, improve liquidity, reduce blocked danger such as pipeline, inhibition activity to gas hydrate is higher, and the inhibition time is longer.
(2) because ionic liquid has the advantages that zwitterion can be allocated, so can optimize modular construction, regulate selectivity and solvability to the hydrate molecule according to the mechanism that suppresses hydrate, reduce the influence that inhibitor is subjected to condensate depression.
(3) add dosage and be far smaller than the thermodynamics inhibitor, preferred concentration is about (0.005～0.01) wt%, and adding the agent cost can greatly reduce, and it is more gentleer than the inhibitor of other types to add the conditions such as injection mode of agent.
(4) because ionic liquid does not have volatility, big with the fluidic boiling-point difference, so reclaim easily, the loss of inhibitor is few.And ionic liquid is in very wide temperature range, and chemical stability and Heat stability is good are nonflammable, do not have corrosion, implements convenient, safety, satisfies growing environmental requirement easily.
Embodiment:
The THF test
The THF test is a kind of method of laboratory evaluation inhibitor efficient, so-called tetrahydrofuran (THF) or THF test.The general ASTM synthetic sea water (SSW) that uses the suppressant additive that contains aequum of 3ml tetrahydrofuran (THF) (THF) and 9ml of THF test.THF and SSW are packed in the test tube (15mm diameter * 12.5cm is long) that has only the 0.95cm Stainless Steel Ball and seal.Each pipe is put into ferriswheel type clamper and put near the cooling bath that remains on 0 ℃ together.The rotation test tube promotes the mixing of sample.This effective visual inspection and by camera record.Along with the carrying out that hydrate forms, the viscosity of THF/SSW solution raises.The viscosity of solution becomes very high in many cases, is enough to make the ball stop motion.Stainless Steel Ball needed time of stop motion on the whole length of test tube is known as trapping time or BST.
BST is the approximate representation of inhibitor efficient.Because it is miscible that THF/SSW solution has about 2～5 ℃ Teq and THF and water, with the petroleum fluids of carrying in pipeline under typical field conditions or the circulating tube comparatively speaking, promoted the hydrate of THF/SSW solution to form greatly.So BST test can be used for disclosing the inhibitor efficient under the condition in the open air.The BST that adds the THF/SSW solution of inhibitor is three times of BST of unconstrained dose contrast solution.Since the result of THF test to the temperature tested, manage to such an extent that the variation performance in the gap between rotation frequency, Stainless Steel Ball and the tube wall etc. is responsive, importantly the THF/SSW contrast solution is carried out each inhibitor evaluation, with the TIC that guarantees accurately to measure inhibitor with observe reliable inhibition effect.
Embodiment 1
When in the aqueous solution, not containing ionic liquid, carry out the THF test, the results are shown in table 2.
Embodiment 2-4
Ion liquid preparation:
By the halide salts of tertiary amines and the synthetic quaternary ammonium of haloalkane, for example 1-butyl-3-Methylimidazole villaumite ([C
4Mim] [Cl]) synthetic:
Reaction needs organic solvent, excessive haloalkane, and reflux was reacted and will have been removed the remaining haloalkane of organic solvent with rotatory evaporator after a few hours.React as follows:
mim+EtCl＝[C
4mim][Cl]
Compound concentration is respectively 0.005,0.01 and [the C of 0.05wt%
4Mim] [Cl] ionic liquid aqueous solution, carry out the THF test, the results are shown in Table 2.
Embodiment 5-7
1-ethyl-3-Methylimidazole bromine salt ([C
4Mim] [Br]) preparation process with similar among the embodiment 2-4, only need to replace EtCl and can obtain ([C with EtBr
4Mim] [Br]).Compound concentration is respectively 0.005,0.01 and ([the C of 0.05wt%
4Mim] [Br]) ionic liquid aqueous solution, carry out the THF test, the results are shown in Table 2.
Embodiment 8-10
Adopt Ag salt method (AgCl) preparation 1-butyl-3-Methylimidazole fluoroborate ([C
4Mim] [BF
4]), react as follows:
[C
4mim][Cl]+AgBF
4＝[C
4mim][BF
4]+AgCl
Solvent for use can be the mixture of methyl alcohol or methyl alcohol and water etc.AgCl precipitation is separated out, and removes by filter, and the residual solution heat phase is also removed to desolvate with rotatory evaporator and got final product.
Compound concentration is respectively 0.005,0.01 and ([the C of 0.05wt%
4Mim] [BF
4]) ionic liquid aqueous solution, carry out the THF test, the results are shown in Table 2.
Embodiment 11-16
With embodiment 2-4, but with 1-ethyl-3-Methylimidazole villaumite ([C
2Mim] [Cl]) and 1-hexyl-3-Methylimidazole villaumite ([C
6Mim] [Cl]) ionic liquid that is mixed with for inhibitor carries out the THF experiment.[C
2Mim] [Cl] and [C
6Mim] concentration of aqueous solution of [Cl] is respectively 0.005,0.01 and 0.05wt%.The results are shown in Table 2.
Embodiment 17-20
With embodiment 2-4, positively charged ion is constant, but is fluorophosphate ([PF with the negatively charged ion
6]
-), two (trifluoromethyl) sulfimide negatively charged ion ([Tf
2N]
-), trifluoroacetic acid salt anionic ([TA]
-) and nitrate anions ([NO
3]
-) ionic liquid carry out THF test, ionic liquid aqueous solution concentration is 0.01wt%.The results are shown in Table 2.
Table 2 THF test-results
| Embodiment | Ionic liquid | Concentration/(wt%) | Trapping time/(min) |
| 1 | Do not have | 0 | 6 |
| 2 3 | [C 4mim][Cl] [C 4mim][Cl] | 0.005 0.010 | 38.8 79 |
| 4 | [C 4mim][Cl] | 0.050 | 93 |
| 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 | [C 4mim][Br] [C 4mim][Br] [C 4mim][Br] [C 4mim][BF 4] [C 4mim][BF 4] [C 4mim][BF 4] [C 2mim][Cl] [C 2mim][Cl] [C 2mim][Cl] [C 6mim][Cl] [C 6mim][Cl] [C 6mim][Cl] [C 4mim][PF 6] [C 4mim][NTf 2] [C 4mim][TA] [C 4mim][NO 3] | 0.005 0.010 0.050 0.005 0.010 0.050 0.005 0.010 0.050 0.005 0.010 0.050 0.010 0.010 0.010 0.010 | 35.5 76 92 43.5 83 95 36 70 88 49 93 108 78 70 73 77 |
The present invention is applicable to and forms clathrate hydrate in the suppression fluid, particularly is being used for producing and/or the pipeline or the conduit of transport gas or other petroleum fluids.
Claims (3)
1, a kind of ionic liquid type hydrate inhibitor is characterized in that: inhibitor is diluting soln or the mixture of being made in solvent by a kind of ionic liquid, two kinds of ionic liquids or two or more ion liquid dissolvings; The mass concentration that ionic liquid adds solvent is 0.005～0.05wt%;
Ionic liquid by organic cation and organic or inorganic negatively charged ion by 1: 1 mol ratio with ionic linkage in conjunction with formation;
Solvent is water, salt solution, alcohols and composition thereof.
2, ionic liquid type hydrate inhibitor according to claim 1 is characterized in that: ion liquid positively charged ion is a glyoxaline cation.
3, ionic liquid type hydrate inhibitor according to claim 1 is characterized in that: negatively charged ion is halide-ions, tetrafluoroborate, hexafluoro-phosphate radical, two (trifluoromethyl) sulfimide root, trifluoroacetic acid root or nitrate ion.
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| US11192964B2 (en) | 2019-10-29 | 2021-12-07 | China University Of Petroleum (Beijing) | Ionic liquid shale inhibitor for drilling fluid and preparation method and application thereof |
| CN111154468A (en) * | 2020-01-06 | 2020-05-15 | 西南石油大学 | Selective water shutoff agent for oilfield water shutoff |
| CN111234794A (en) * | 2020-03-18 | 2020-06-05 | 北京大德广源石油技术服务有限公司 | Composite blocking remover and application method thereof |
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