CN104263340A - Kinetic natural gas hydrate inhibitor and preparation method thereof - Google Patents
Kinetic natural gas hydrate inhibitor and preparation method thereof Download PDFInfo
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
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- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/22—Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers
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Abstract
The invention belongs to the technical field of preparing chemical reagents and in particular relates to a kinetic natural gas hydrate inhibitor and a preparation method thereof. The hydrate inhibitor is obtained by performing a free radical solution polymerization reaction on N-vinyl pyrrolidone (NVP), acrylamide (AM) and acrylonitrile (AN) which are used as synthesis monomers in the presence of ammonium persulfate and sodium sulfite which are used as initiators. The kinetic natural gas hydrate inhibitor is capable of reducing the hydrate generation temperature to a larger extent and prolonging the induction time and is suitable for the recovery and transportation of oil and gas fields; besides, the kinetic natural gas hydrate inhibitor is convenient to synthesize, low in cost, prone to biodegrade, and wide in application prospect.
Description
Technical field
The invention belongs to the preparing technical field of chemical reagent, particularly relating to is a kind of gas hydrate kinetic inhibitor and preparation method.
Background technology
Natural gas extraction, collect defeated and in the course of processing, due to the change of temperature, pressure, velocity of flow etc., cryogenic high pressure turbulent flow of being everlasting place forms gas hydrate, and this is the major cause causing Sweet natural gas production equipment exception and line of pipes blocking, even can cause security incident.
At present, for the control of hydrate mainly through physical method and chemical process two kinds.Physical method mainly makes Oil and Gas System not possess the thermodynamic condition generating hydrate, has the conbined usage except water law, heating method, voltage drop method and this several method.Along with reality drops into the use generated, the problems such as physical method cost is high, application limitation is large highlight all the more, and chemical process water prevention compound becomes main flow gradually.
Chemical process water prevention compound is the character changing the balancing each other of system, crystal nucleation, crystal growth or gathering aspect by adding chemical reagent, is the method that water prevention compound generates most widely used, has the advantages such as simple, economic, efficient.It mainly comprises hydrate thermodynamic inhibitor, hydrate dynamic inhibitor and anti polymerizer.
The normal hydrate thermodynamic inhibitor (solubility alcohols is as methyl alcohol, ethanol, ethylene glycol, inorganic salt etc.) adopted in the actual generation of oil and gas industry, but thermodynamic inhibitor using dosage is large, cause storage and injection device huge, cost of winning increases, and produce large amount of sewage contaminate environment, improve the cost of application.
Take hydrate dynamic inhibitor as the major inhibitors additive that the low dosage hydrate inhibitor of representative is just becoming application and oil-gas field.Kinetic inhibitor is generally the low-molecular weight polymer that some have side chain amide group ring texture, is usually about 1% ~ 2% and by suppressing the formation of hydrate in aqueous phase to play a role adding concentration.
Summary of the invention
The object of the invention is to: design and prepare a kind of hydrate dynamic inhibitor, this inhibitor is used not only not affect the thermodynamic condition of hydrate generation, but also the hydrate nucleation time can be delayed, reduce the speed of growth, stop the further growth of crystal, thus to make in pipeline fluid in its temperature lower than hydrate-formation temperature (condensate depression △ T) current downflow, and there is not Hydrate Plugging phenomenon, belong to the generation by chemical process water prevention compound.
Technical scheme of the present invention is as follows: a kind of synthetic natural gas hydrate dynamic inhibitor, and this inhibitor label is that H is composed of the following components: A:N-vinyl pyrrolidone, B: acrylamide, C: propylene is fine, D: deionized water, E: mercaptothiols, F: specification is ammonium persulfate solution, the G of 10%: specification is the S-WAT of 10%; Wherein the mass percent of monomer A, B, C is: A:70 ~ 90%, B:5 ~ 20%, C:5 ~ 10%; The per-cent of E, F, G and D relative monomer total mass is: E:0.5 ~ 1.5%, F:2.5 ~ 3.5%, G:2.5 ~ 3.5%, D:100 ~ 200%.
A kind of preparation method of synthetic natural gas hydrate dynamic inhibitor, the method comprises the following steps: (a) puts into A, B and D in the ratio according to claims 1 that to be equipped with in the there-necked flask with reflux condensate device, then the there-necked flask filling A, B and D is put into magnetic force water-bath, heating makes temperature remain on 50 ~ 60 DEG C, being stirred to A and B dissolves with D completely, for subsequent use; B C adds in the solution for preparing in step (a) by (), stir, mix for subsequent use; Add E in c solution that () prepares in step (b), stir 2 ~ 3 minutes; Then solution G and solution F is added, with the rotating speed stirring reaction 3 ~ 5 hours of 600r/min at 50 ~ 60 DEG C, for subsequent use; D () step (c) reacts completely after, by the homopolymer of unreacted C and C be suspended in solution surface, after carrying out separation removal, carry out purification to surplus solution dry, can be inhibited agent H.The mass ratio of described F:G is 1:1.
The unit of the amount of above-mentioned substance is quality, unit is gram, raw material A is NVP, raw material B is acrylamide, raw material C is that propylene is fine, and raw material D is deionized water, and raw material E is mercaptothiols, raw material F is ammonium persulfate solution (ammonium persulphate of 10%), and raw material G is sodium sulfite solution (S-WAT of 10%).Wherein the mass ratio of F:G is 1:1.Preset raw material X is methyl alcohol simultaneously, and raw material Y is ethylene glycol, and raw material Z is sodium-chlor.Described raw material ethylene glycol, methyl alcohol, hydrochloric acid, sodium-chlor, ammonium persulphate, S-WAT are analytical pure, and Chengdu Ke Long chemical reagent factory produces; NVP is chemical pure, and Dongying City achievements of a ruler Chemical Co., Ltd. produces; Acrylamide is analytical pure, and good fortune chemical reagent factory in morning in Tianjin is produced; Vinyl cyanide is analytical pure, and Shanghai Secco Petrochemical Co., Ltd. produces; Mercaptothiols is analytical pure, and modern east (Beijing) development in science and technology company limited produces.
Beneficial effect of the present invention: the hydrate dynamic inhibitor that the present invention develops, rejection is remarkable, stability strong, easily reclaim and recycle, and be easy to biological degradation have no effect to geology, efficiently solve in the gas recovery of natural gas field the difficult problem delaying and even reduce gas hydrate and generate, the situation for the Hydrate Plugging run in industrialization actual production have found new solution route.The present invention adopts NVP (NVP), acrylamide (AM), propylene fine (AN) to become new and effective kinetic inhibitor for postponing and even stop the generation of gas hydrate for monomer polymerization, by specific embodiment and mensuration thereof, its result of use is splendid.
specific implementation method:
Embodiment 1: a kind of synthetic natural gas hydrate dynamic inhibitor, this inhibitor label is that H is made up of by ratio of weight and the number of copies following component: A:N-vinyl pyrrolidone 70 parts, B: acrylamide 20 parts, C: fine 10 parts of propylene, D: deionized water 100 parts, E: mercaptothiols 0.5 part, F: specification is ammonium persulfate solution 2.5 parts, the G of 10%: specification is the S-WAT 2.5 parts of 10%.
Prepare the preparation method of above-mentioned gas hydrate kinetic inhibitor, the method comprises the following steps: (a) puts into A, B and D in the ratio according to claims 1 that to be equipped with in the there-necked flask with reflux condensate device, then the there-necked flask filling A, B and D is put into magnetic force water-bath, heating makes temperature remain on 50 ~ 60 DEG C, being stirred to A and B dissolves with D completely, for subsequent use; B C adds in the solution for preparing in step (a) by (), stir, mix for subsequent use; Add E in c solution that () prepares in step (b), stir 2 ~ 3 minutes; Then solution G and solution F is added, with the rotating speed stirring reaction 3 ~ 5 hours of 600r/min at 50 ~ 60 DEG C, for subsequent use; D () step (c) reacts completely after, by the homopolymer of unreacted C and C be suspended in solution surface, after carrying out separation removal, carry out purification to surplus solution dry, can be inhibited agent H.The mass ratio of described F:G is 1:1.
Embodiment 2: a kind of synthetic natural gas hydrate dynamic inhibitor, this inhibitor label is that H is made up of by ratio of weight and the number of copies following component: A:N-vinyl pyrrolidone 80 parts, B: acrylamide 15 parts, C: fine 5 parts of propylene, D: deionized water 100 parts, E: mercaptothiols 0.5 part, F: specification is ammonium persulfate solution 2.5 parts, the G of 10%: specification is the S-WAT 2.5 parts of 10%.
Prepare the preparation method of above-mentioned gas hydrate kinetic inhibitor with embodiment 1.
Embodiment 3: a kind of synthetic natural gas hydrate dynamic inhibitor, this inhibitor label is that H is made up of by ratio of weight and the number of copies following component: A:N-vinyl pyrrolidone 80 parts, B: acrylamide 10 parts, C: fine 10 parts of propylene, D: deionized water 150 parts, E: mercaptothiols 1 part, F: specification is ammonium persulfate solution 3 parts, the G of 10%: specification is the S-WAT 3 parts of 10%.
Prepare the preparation method of above-mentioned gas hydrate kinetic inhibitor with embodiment 1.
Embodiment 4: a kind of synthetic natural gas hydrate dynamic inhibitor, this inhibitor label is that H is made up of by ratio of weight and the number of copies following component: A:N-vinyl pyrrolidone 85 parts, B: acrylamide 10 parts, C: fine 5 parts of propylene, D: deionized water 150 parts, E: mercaptothiols 1 part, F: specification is ammonium persulfate solution 3 parts, the G of 10%: specification is the S-WAT 3 parts of 10%.
Prepare the preparation method of above-mentioned gas hydrate kinetic inhibitor with embodiment 1.
Embodiment 5: a kind of synthetic natural gas hydrate dynamic inhibitor, this inhibitor label is H
5be made up of by ratio of weight and the number of copies following component: A:N-vinyl pyrrolidone 85 parts, B: acrylamide 5 parts, C: fine 10 parts of propylene, D: deionized water 150 parts, E: mercaptothiols 1 part, F: specification is ammonium persulfate solution 3 parts, the G of 10%: specification is the S-WAT 3 parts of 10%.
Prepare the preparation method of above-mentioned gas hydrate kinetic inhibitor with embodiment 1.
Embodiment 6: a kind of synthetic natural gas hydrate dynamic inhibitor, this inhibitor label is that H is made up of by ratio of weight and the number of copies following component: A:N-vinyl pyrrolidone 90 parts, B: acrylamide 5 parts, C: fine 5 parts of propylene, D: deionized water 200 parts, E: mercaptothiols 1.5 parts, F: specification is ammonium persulfate solution 3.5 parts, the G of 10%: specification is the S-WAT 3.5 parts of 10%.
Prepare the preparation method of above-mentioned gas hydrate kinetic inhibitor with embodiment 1.
Detect and measure: the mensuration of inhibitor H effect prepared by (1) embodiment 1-6, the inhibitor H prepared by embodiment 1-6, label is set as H
1-H
6: at initial temperature 277.15K, under original pressure 8.0MPa condition, the solution that concentration is 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt% is respectively configured to respectively by D, measure the induction time that each hydrate inhibitor suppresses hydrate to generate respectively under different concns, and contrast with the induction time that hydrate under D system generates.Obtain data as follows;
D system: induction time is 18min.
H
1system: concentration is that the induction time of 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt% is respectively 423 min, 658 min, 710 min, 753 min, 787 min.
H
2system: concentration is that the induction time of 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt% is respectively 479 min, 692min, 740 min, 788 min, 820 min;
H
3system: concentration is that the induction time of 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt% is respectively 532 min, 785 min, 812 min, 840 min, 862 min;
H
4system: concentration is that the induction time of 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt% is respectively 546 min, 790 min, 832 min, 867 min, 880 min;
H
5system: concentration is that the induction time of 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt% is respectively 603 min, 867 min, 933 min, 972 min, 1002 min;
H
6system: concentration is that the induction time of 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt% is respectively 571 min, 829 min, 890 min, 932 min, 950 min.
Effect assessment: can be found by the contrast of induction time, the H of synthesis
1~ H
6all show concentration larger, induction time is longer, but the amplitude of time lengthening is constantly reducing.They all have the performance suppressing gas hydrate to generate preferably, and induction time all extends a lot than 18 min of D system.H in six kinds of inhibitor
5the induction time of each section is longer relative to other system.
(2) mensuration of inhibitor H effect prepared of embodiment 1-6, the inhibitor H prepared by embodiment 1-6, label is set as H
1-H
6: at initial temperature 277.15K, under original pressure 8.0MPa condition, first configure the Z solution of different salinity with D, add H respectively
1-H
6be configured to the solution that concentration is 1.0wt%.Under the temperature and pressure of same setting, measured the induction time of each hydrate inhibitor system by cryogenic high pressure still.Obtain data as follows;
Salinity 0 mg/L:H
1: 613 min, H
2: 753 min, H
3: 785 min, H
4: 832 min, H
5: 883 min, H
6: 869 min;
Salinity 10000 mg/L:H
1: 710 min, H
2: 841 min, H
3: 872 min, H
4: 928 min, H
5: 997 min, H
6: 950 min;
Salinity 20000 mg/L:H
1: 759 min, H
2: 880 min, H
3: 927 min, H
4: 990 min, H
5: 1049 min, H
6: 1013 min;
Salinity 40000 mg/L:H
1: 860 min, H
2: 1002 min, H
3: 1062 min, H
4: 1102 min, H
5: 1187 min, H
6: 1139 min;
Salinity 80000 mg/L:H
1: 1078 min, H
2: 1213 min, H
3: 1270min, H
4: 1335 min, H
5: 1463 min, H
6: 1405 min.
Effect assessment: can be found out by the contrast of induction time, along with the rising of salinity, induction time, in continuous increase, illustrates that the inhibition of salinity to hydrate inhibitor has promoter action.The generation of high salinity to hydrate is favourable, but the too high meeting of salinity causes corrosion or scale formation to pipeline.
(3) mensuration of inhibitor H effect prepared of embodiment 1-6, the inhibitor H prepared by embodiment 1-6, label is set as H
1-H
6: the hydrate inhibitor H that can be found out synthesis by (1) and (2)
5inhibition best, take H
5carry out combine experiment.The concentration preparing Y with D is the solution I of 20wt%, the solution J that the concentration of Y is 20wt% is prepared in addition with the Z that salinity is 4000 mg/L, system pressure is constant in 8.0MPa, utilizes the experimental technique of hydrate phase balance, measures hydrate dynamic inhibitor H in Y solution respectively by cryogenic high pressure still
5the generation temperature of system hydrate when concentration is 0wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%.And with reference to D system:
D system: 288.25K
Y system: 278.32K
I system: 0wt%H
5: 278.32K, 1.0wt%H
5: 275.78K, 1.5wt%H
5: 274.75K, 2.0wt%H
5: 274.15K, 2.5wt%H
5: 273.82K;
J system: 0wt%H
5: 277.55K, 1.0wt%H
5: 275.14K, 1.5wt%H
5: 274.05K, 2.0wt%H
5: 273.45K, 2.5wt%H
5: 273.11K;
Effect assessment: (1), compared with D system, I significantly reduces the temperature that hydrate generates, and embodies the rejection of hydrate thermodynamic inhibitor Y; (2) along with H in I, J solution
5the rising of concentration, hydrate generates the more of temperature reduction, but the amplitude reduced slows down gradually.
(3) H
5add and not only do not restrict the impact of Y on Hydrate Formation Conditions, slightly act synergistically on the contrary.
(4) mensuration of inhibitor H effect prepared of embodiment 1-6, the inhibitor H prepared by embodiment 1-6, label is set as H
1-H
6: the solution L by the concentration of D preparation X being 20wt%, the solution M that the concentration of X is 20wt% is prepared in addition with the Z that salinity is 4000 mg/L, system pressure is constant in 8.0MPa, utilizes the experimental technique of hydrate phase balance, measures hydrate dynamic inhibitor H in X solution respectively by cryogenic high pressure still
5the generation temperature of system hydrate when concentration is 0wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%.And with reference to D system:
D system: 288.25K
X system: 276.34K
L system: 0wt%H
5: 276.34K, 1.0wt%H
5: 274.42K, 1.5wt%H
5: 273.75K, 2.0wt%H
5: 272.87K, 2.5wt%H
5: 272.22K;
M system: 0wt%H
5: 275.42K, 1.0wt%H
5: 273.64K, 1.5wt%H
5: 272.65K, 2.0wt%H
5: 271.70K, 2.5wt%H
5: 271.32K.
Effect assessment: compare with Y system with D system, the effect that the solution adding X reduces the temperature that hydrate generates is more remarkable, and the performance of X is better than Y, but X itself has and reclaims the defect such as difficult, poisonous and in use receive multiple restriction.Therefore Y and hydrate inhibitor H is selected
5composite.
(5) mensuration of inhibitor H effect prepared of embodiment 1-6, the inhibitor H prepared by embodiment 1-6, label is set as H
1-H
6: select salinity to be that to prepare Y concentration be that the solution of 20wt%, 60wt%, 70wt%, 80wt% and 90wt% is designated as N for the Z of 4000mg/L
1, N
2, N
3, N
4, N
5, system pressure is constant in 4.0MPa and 8.0MPa respectively, utilizes the experimental technique of hydrate phase balance, measures N respectively by cryogenic high pressure still
1~ N
5middle hydrate inhibitor H
5the generation temperature of system hydrate when concentration is 0wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%; Under 8.0Mpa condition:
N
1:0wt%H
5:277.55K、1.0wt%H
5：275.14K、1.5wt%H
5：274.05K、2.0wt%H
5：273.45K、2.5wt%H
5:273.11K；
N
2:0wt%H
5:276.43K、1.0wt%H
5：273.97K、1.5wt%H
5：272.64K、2.0wt%H
5：271.57K、2.5wt%H
5:270.89K；
N
3:0wt%H
5:275.67K、1.0wt%H
5：272.05K、1.5wt%H
5：270.95K、2.0wt%H
5：269.71K、2.5wt%H
5:268.94K；
N
4:0wt%H
5:274.43K、1.0wt%H
5：270.68K、1.5wt%H
5：269.21K、2.0wt%H
5：268.34K、2.5wt%H
5:267.71K；
N
5:0wt%H
5:274.21K、1.0wt%H
5：269.48K、1.5wt%H
5：268.29K、2.0wt%H
5：267.80K、2.5wt%H
5:267.33K；
Under 4.0Mpa condition:
N
1:0wt%H
5:277.42K、1.0wt%H
5：274.82K、1.5wt%H
5：273.77K、2.0wt%H
5：273.02K、2.5wt%H
5:272.49K；
N
2:0wt%H
5:275.31K、1.0wt%H
5：272.77K、1.5wt%H
5：271.35K、2.0wt%H
5：270.37K、2.5wt%H
5:269.80K；
N
3:0wt%H
5:273.78K、1.0wt%H
5：270.39K、1.5wt%H
5：269.32K、2.0wt%H
5：268.70K、2.5wt%H
5:268.14K；
N
4:0wt%H
5:272.56K、1.0wt%H
5：268.92K、1.5wt%H
5：267.36K、2.0wt%H
5：266.72K、2.5wt%H
5:266.35K；
N
5:0wt%H
5:272.04K、1.0wt%H
5：268.42K、1.5wt%H
5：267.03K、2.0wt%H
5：266.32K、2.5wt%H
5:266.11K；
Effect assessment: (1) system pressure is certain, and the N of different concns is along with adding H
5the increase of dosage, its performance suppressing hydrate to generate is improving constantly, and hydrate generates temperature and reduces more;
(2) system pressure is certain, adds the H of different concns
5n all along with the increase of Y concentration contained by it, its suppress hydrate generate performance improving constantly;
(3) N of same concentrations, is better than high pressure system in the inhibition of low pressure system.Add the H of same concentrations
5also this rule is met;
(4) no matter be increase or the H of Y concentration
5the increase of concentration, inhibition has growth but the amplitude increased is declining, and integrated economics situation, draws best compatibility program: 1.0-2.0wt%H
5+ 80wt%Y.
In sum: (1) experimental example 1 ~ 6, different by the ratio of synthesized hydrate inhibitor monomer used, successfully synthesize H
1~ H
6, and all show good rejection, effectively can reduce the temperature that hydrate generates, the induction time that substantial delay hydrate generates, well keep rejection at high pressure low temperature environmental energy.And filter out the hydrate inhibitor H of best performance
5.
(2) from thermodynamics and kinetics two angles, hydrate dynamic inhibitor and the hydrate thermodynamic inhibitor (X and Y) of synthesis are carried out composite, both sides serve mutually promote, the effect of complementation, greatly improve rejection.The compound scheme that finishing screen is selected: 1.0-2.0wt%H
5+ 80wt%Y.
(3) experiment of lifting is only preferably example of the present invention, the protection domain be not intended to limit the present invention.All any amendments, improvement etc. done within principle of the present invention, all should be included within protection scope of the present invention.
The unit of the amount of above-mentioned substance is quality, unit is gram, and raw material A is NVP, and raw material B is acrylamide, raw material C is that propylene is fine, raw material D is deionized water, and raw material E is mercaptothiols, and raw material F is ammonium persulfate solution (ammonium persulphate of 10%), raw material G is sodium sulfite solution (S-WAT of 10%), raw material X is methyl alcohol, and raw material Y is ethylene glycol, and raw material Z is sodium-chlor; Wherein the mass ratio of F:G is 1:1.
Claims (3)
1. a synthetic natural gas hydrate dynamic inhibitor, is characterized in that: this inhibitor label is that H is composed of the following components: A:N-vinyl pyrrolidone, B: acrylamide, C: propylene is fine, D: deionized water, E: mercaptothiols, F: specification is ammonium persulfate solution, the G of 10%: specification is the S-WAT of 10%; Wherein the mass percent of monomer A, B, C is: A:70 ~ 90%, B:5 ~ 20%, C:5 ~ 10%; The per-cent of E, F, G and D relative monomer total mass is: E:0.5 ~ 1.5%, F:2.5 ~ 3.5%, G:2.5 ~ 3.5%, D:100 ~ 200%.
2. a preparation method for synthetic natural gas hydrate dynamic inhibitor, is characterized in that: the method comprises the following steps:
A () puts into A, B and D in the ratio according to claims 1 that to be equipped with in the there-necked flask with reflux condensate device, then the there-necked flask filling A, B and D is put into magnetic force water-bath, heating makes temperature remain on 50 ~ 60 DEG C, is stirred to A and B and dissolves with D completely, for subsequent use;
B C adds in the solution for preparing in step (a) by (), stir, mix for subsequent use;
Add E in c solution that () prepares in step (b), stir 2 ~ 3 minutes; Then solution G and solution F is added, with the rotating speed stirring reaction 3 ~ 5 hours of 600r/min at 50 ~ 60 DEG C, for subsequent use;
D () step (c) reacts completely after, by the homopolymer of unreacted C and C be suspended in solution surface, after carrying out separation removal, carry out purification to surplus solution dry, can be inhibited agent H.
3. the preparation method of a kind of synthetic natural gas hydrate dynamic inhibitor according to claim 2, is characterized in that: the mass ratio of described F:G is 1:1.
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Cited By (5)
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| CN105859963A (en) * | 2016-04-15 | 2016-08-17 | 西南石油大学 | Polycyclic polymerized natural gas hydrate dynamic inhibitor and preparation method |
| CN106281280A (en) * | 2016-08-08 | 2017-01-04 | 北京千永科技有限公司 | The composite inhibitor of a kind of gas hydrates and application thereof |
| CN106380541A (en) * | 2016-09-05 | 2017-02-08 | 路术松 | Preparation method of amide copolymer hydrate kinetic inhibitor |
| CN106404610A (en) * | 2016-10-20 | 2017-02-15 | 中国石油大学(北京) | Evaluation method for hydrate kinetic inhibitor and application of evaluation method in screening |
| CN111075397A (en) * | 2019-12-30 | 2020-04-28 | 南京惟真智能管网科技研究院有限公司 | Hydrate blockage removing method |
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| CN106380541B (en) * | 2016-09-05 | 2018-07-13 | 路术松 | The preparation method of amide analog copolymer hydrate dynamic inhibitor |
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| CN106404610B (en) * | 2016-10-20 | 2019-08-09 | 中国石油大学(北京) | A kind of evaluation method of hydrate dynamic inhibitor and its application in screening |
| CN111075397A (en) * | 2019-12-30 | 2020-04-28 | 南京惟真智能管网科技研究院有限公司 | Hydrate blockage removing method |
| CN111075397B (en) * | 2019-12-30 | 2024-02-13 | 南京惟真智能管网科技研究院有限公司 | Hydrate blocking and unblocking method |
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