CN105042334A - Green natural type hydrate inhibitor and preparation method thereof - Google Patents
Green natural type hydrate inhibitor and preparation method thereof Download PDFInfo
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- CN105042334A CN105042334A CN201510309801.0A CN201510309801A CN105042334A CN 105042334 A CN105042334 A CN 105042334A CN 201510309801 A CN201510309801 A CN 201510309801A CN 105042334 A CN105042334 A CN 105042334A
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- hydrate
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- 239000003112 inhibitor Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 235000013399 edible fruits Nutrition 0.000 claims abstract description 7
- 150000004676 glycans Chemical class 0.000 claims abstract description 7
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 7
- 239000005017 polysaccharide Substances 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 49
- 229920002230 Pectic acid Polymers 0.000 claims description 18
- LCLHHZYHLXDRQG-ZNKJPWOQSA-N pectic acid Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)O[C@H](C(O)=O)[C@@H]1OC1[C@H](O)[C@@H](O)[C@@H](OC2[C@@H]([C@@H](O)[C@@H](O)[C@H](O2)C(O)=O)O)[C@@H](C(O)=O)O1 LCLHHZYHLXDRQG-ZNKJPWOQSA-N 0.000 claims description 18
- 239000010318 polygalacturonic acid Substances 0.000 claims description 18
- 238000005886 esterification reaction Methods 0.000 claims description 16
- 244000276331 Citrus maxima Species 0.000 claims description 13
- 235000001759 Citrus maxima Nutrition 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- WQZGKKKJIJFFOK-SVZMEOIVSA-N (+)-Galactose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-SVZMEOIVSA-N 0.000 claims description 8
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 claims description 8
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000284 extract Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- -1 D-wood sugar Chemical compound 0.000 claims description 5
- IAJILQKETJEXLJ-KKQCNMDGSA-N (2r,3r,4r,5s)-2,3,4,5-tetrahydroxy-6-oxohexanoic acid Chemical compound O=C[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O)C(O)=O IAJILQKETJEXLJ-KKQCNMDGSA-N 0.000 claims description 4
- LKDRXBCSQODPBY-IANNHFEVSA-N D-sorbose Chemical compound OCC1(O)OC[C@@H](O)[C@H](O)[C@H]1O LKDRXBCSQODPBY-IANNHFEVSA-N 0.000 claims description 4
- SHZGCJCMOBCMKK-PQMKYFCFSA-N L-Fucose Natural products C[C@H]1O[C@H](O)[C@@H](O)[C@@H](O)[C@@H]1O SHZGCJCMOBCMKK-PQMKYFCFSA-N 0.000 claims description 4
- SHZGCJCMOBCMKK-DHVFOXMCSA-N L-fucopyranose Chemical compound C[C@@H]1OC(O)[C@@H](O)[C@H](O)[C@@H]1O SHZGCJCMOBCMKK-DHVFOXMCSA-N 0.000 claims description 4
- PNNNRSAQSRJVSB-BXKVDMCESA-N aldehydo-L-rhamnose Chemical compound C[C@H](O)[C@H](O)[C@@H](O)[C@@H](O)C=O PNNNRSAQSRJVSB-BXKVDMCESA-N 0.000 claims description 4
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 4
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 4
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 235000009508 confectionery Nutrition 0.000 claims description 4
- 229920001277 pectin Polymers 0.000 claims description 4
- 239000001814 pectin Substances 0.000 claims description 4
- 235000010987 pectin Nutrition 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229960003487 xylose Drugs 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 241000219357 Cactaceae Species 0.000 claims description 2
- 235000005976 Citrus sinensis Nutrition 0.000 claims description 2
- 240000002319 Citrus sinensis Species 0.000 claims description 2
- 241000234272 Dioscoreaceae Species 0.000 claims description 2
- 244000020551 Helianthus annuus Species 0.000 claims description 2
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- 241000218995 Passifloraceae Species 0.000 claims description 2
- 241000220222 Rosaceae Species 0.000 claims description 2
- 241001093501 Rutaceae Species 0.000 claims description 2
- 244000061456 Solanum tuberosum Species 0.000 claims description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 230000021736 acetylation Effects 0.000 claims description 2
- 238000006640 acetylation reaction Methods 0.000 claims description 2
- 238000011938 amidation process Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000004804 polysaccharides Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000004781 supercooling Methods 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 3
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- 238000006703 hydration reaction Methods 0.000 description 31
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- 238000002474 experimental method Methods 0.000 description 13
- 230000005764 inhibitory process Effects 0.000 description 13
- 230000001629 suppression Effects 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
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- 229910052760 oxygen Inorganic materials 0.000 description 10
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- 230000006698 induction Effects 0.000 description 7
- 239000012086 standard solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 238000013480 data collection Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000012956 testing procedure Methods 0.000 description 5
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006065 biodegradation reaction Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 230000015556 catabolic process Effects 0.000 description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 230000003111 delayed effect Effects 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- LNQCJIZJBYZCME-UHFFFAOYSA-N iron(2+);1,10-phenanthroline Chemical compound [Fe+2].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 LNQCJIZJBYZCME-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
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- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 108010059820 Polygalacturonase Proteins 0.000 description 1
- YUVLVONHNMXKBW-UHFFFAOYSA-L [Ag+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Ag+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O YUVLVONHNMXKBW-UHFFFAOYSA-L 0.000 description 1
- 241001148470 aerobic bacillus Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000011013 aquamarine Substances 0.000 description 1
- 231100000209 biodegradability test Toxicity 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 108010093305 exopolygalacturonase Proteins 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/34—Hydrogen distribution
Abstract
The invention discloses a green natural type hydrate inhibitor and a preparation method thereof. The green natural type hydrate inhibitor is a natural composite polysaccharide high-molecular compound, and can be extracted from various types of fruit pulp and pomace. According to the use conditions of the hydrate inhibitor, pressure ranges from 1.0 MPa to 30 MPa; temperature ranges from -20 DEG C to 25 DEG C; and the volume percentage of system water can change between 100% and 50 wt%. The inhibitor is injected into produced or conveyed petroleum fluid at low concentration, the inhibitor can decrease the hydrate nucleation and growth speeds under the harsh condition such as the high supercooling degree, and the aim of preventing and controlling hydrate is achieved. In addition, the natural type hydrate inhibitor has the beneficial effects of being good in biological degradability, easy to obtain, and good in economy and environmental protection property, can meet the requirements of offshore and onshore oilfields and pipeline additives for chemicals, and is wide in application range.
Description
Technical field
The present invention relates to technical field of oil-gas hydrate, be specifically related to a kind of green natural type hydrate inhibitor and preparation method thereof.
Technical background
In the transfer line of rock gas and petroleum fluids, various low boiling point hydrocarbon as methane, ethane, propane and carbon dioxide, hydrogen sulfide etc. under certain temperature, pressure condition and water effect generate the ice-like crystal of a class cage structure, it is a kind of non-stoichiometry type solid compounds.In oil and gas industry, the generation of gas hydrate can cause the blocking of oil gas delivering pipe, even causes line burst, brings many potential safety hazards and huge economic loss to the exploitation of petroleum and natural gas and transport.In addition, for offshore oil and gas field exploitation and territory, deep-sea Cemented filling, hydrate problems is also particularly outstanding, because the temperature and pressure condition in seabed is conducive to the generation of hydrate.Such as when pressure is 3MPa, ethane just can generate hydrate at lower than the temperature of 14 DEG C.And this type of temperature, pressure condition are very common in the oil-gas mining, pipe conveying procedure of reality, how to prevent hydrate from being the Important Problems that oil and gas industry is paid close attention to always.
Conventional hydrate prevention and controls, mainly by dewatering, heating, reduce pressure and add thermodynamic inhibitor, makes system not possess the thermodynamic condition generating hydrate, or one or several methods is joined together.Traditional thermomechanics suppresses method, normally by adding some alcohol ethers and salt makes the formation condition of hydrate move dynamic to lower temperature or higher pressure span, to reach the object suppressing hydrate to generate.But the shortcomings such as the alcohols being representative with methyl alcohol, ethylene glycol has consumption large (being generally the 40wt% ~ 60wt% of solution), cost is high, recovery is difficult, methyl alcohol is especially because its toxicity is large, contaminativity is eliminated by force and gradually.Be and for example that the salt of representative belongs to the electrolytes corrosive action larger to pipeline with sodium chloride, the economy that this type of electrolyte corrosion brings to industrial quarters and environmental issue also start to be subject to the concern of people.
At present, focus in developing the minimum hydrate inhibitor of consumption, be that is to say low dosage hydrate inhibitor by domestic and international researcher.Low dosage hydrate inhibitor comprises kinetic inhibitor and anti polymerizer.This kind of inhibitor does not affect the thermodynamic condition that hydrate generates, but reaches the object of water prevention compound generation by the growth or gathering suppressing hydrate.By postponing nucleation and the crystal growth time of hydrate, and there is not Hydrate Plugging phenomenon in such as kinetic inhibitor; Anti polymerizer is then by adding the very low surface active agent of some concentration or polymer, preventing the coalescent of hydrate crystal grain, ensures safe fluid conveying.But be with the N-vinyl caprolactam kinetic inhibitor that is representative or with the quaternary quaternary ammonium salt anti polymerizer that is representative all because biological degradability is poor, synthesis cost high, inhibit activities is not high, the problems such as applicable elements is narrow and cannot on a large scale commercialization practicality.
Summary of the invention
The object of the invention is to overcome prior art shortcoming, a kind of green natural type hydrate inhibitor and preparation method thereof is provided, inhibitor of the present invention can obtain from the fruit of cheapness or pomace, has the advantage that cost of production is low, biological degradability good, the feature of environmental protection is strong.More outstanding feature is the Subcoold temperature that inhibitor of the present invention can break through more than 15 DEG C under the condition of low dosage, good inhibition can not only be played can also play effect preferably in containing oil-water-gas heterogeneous system in absolutely moisture content system, having very wide usage range, is a kind of environmental protection, economy, efficiently hydrate inhibitor.
Objects of the present invention are achieved through the following technical solutions:
A kind of green natural type hydrate inhibitor, described hydrate inhibitor is a kind of pectic acid and derivative of esterification;
Described pectic acid is the straight-chain polysaccharide that D-galactopyranosyluronic couples together with ɑ-Isosorbide-5-Nitrae glycosidic bond;
Described methyl esters turns to hydrogen atom on straight-chain polysaccharide carboxyl by methyl substituted;
Acetylation or amidation process can be there is in the hydroxyl on described straight-chain polysaccharide;
Described straight-chain polysaccharide chain also comprises side chain, and side chain comprises D-galactose, Arabinose, D-wood sugar, D-sorbose, L-fucose, L-glucuronic acid, L-rhamnose or sweet mellow wine;
The methyl-esterification degree of described pectic acid and derivative thereof is 8% ~ 70%, and the content of galactopyranosyluronic is greater than 65wt%.Methyl-esterification degree is the galacturonic acidic group of esterification to the ratio of total galacturonic acidic group.
Preferably, the pectic acid of described esterification and the typical structure of derivative are shown below:
Wherein, R
1for acetyl group, D-galactose, the one in Arabinose, D-wood sugar, D-sorbose, L-fucose, L-glucuronic acid, L-rhamnose or sweet mellow wine, R
2for amino.
Preferably, described hydrate inhibitor weight average molecular weight is 50kDa ~ 700kDa, can extract the product of certain molecular weight size as required from dissimilar pericarp pomace.
Preferably, hydrate inhibitor service condition is: pressure is at 1.0 ~ 30MPa, and temperature is at-25 ~ 25 DEG C, and the volumn concentration of system water can change between 100% to 50wt%.
Preferably, in the system of a hundred per cent moisture content, the weight ratio of this hydrate inhibitor and water is 0.1 ~ 10.0%, is preferably 0.5% ~ 2.0%.
Preferably, be greater than 50 percent at moisture content and be less than absolutely in oil gas water heterogeneous system, the weight ratio of this hydrate inhibitor and water is 0.1 ~ 20%, preferably 1.0% ~ 3.0%.
A preparation method for green natural type hydrate inhibitor, is characterized in that, comprises the steps: that (1) is by the thing to be extracted containing pectic acid, chopping, 5 ~ 10min is boiled, by the fruit after boiling or pomace rinsing 3 ~ 4 times, until solution is colourless in 90 DEG C ~ 95 DEG C hot water;
(2) configuring the solution of pH=2.0, is 1:5 ~ 1:15 at the feed liquid mass ratio of shaddock ped and solution, and temperature is extract 45 ~ 60min under the condition of 95 DEG C ~ 100 DEG C;
(3) while hot under the condition of 50 DEG C ~ 55 DEG C with the solution that filtered on buchner funnel step (2) obtains, obtain filtrate;
(4) alcohol of 95% is added in the filtrate that step (3) obtains, tentatively obtains the pectic acid of thick esterification; The volume ratio of described alcohol and filtrate is 2;
(5) pectic acid of the thick esterification obtained by absolute ethanol washing step (4), obtains the wet pectin that purity is higher after suction filtration;
(6) at 45 ~ 50 DEG C, under the vacuum degree condition of-0.08 ~-0.1MPa, be dried to constant weight, obtain dry fruit glue, be i.e. green natural type hydrate inhibitor.
In said method, described pectic acid thing to be extracted is Rutaceae, the rose family, Passifloraceae, Sonneratiaceae, extract in Cactaceae or Dioscoreaceae plant, be preferably oranges and tangerines (skin), obtain in the product that shaddock (skin), Peel of Navel Orange, apple (slag), sunflower plate or potato residues etc. are cheap and easy to get.
The advantage that the present invention has relative to prior art and beneficial effect:
(1) pollution-free: this green natural type hydrate inhibitor has the biological degradability up to more than 90%, meet the requirement of marine chemical product biological degradability completely, minimum to the contaminativity of environment, breach existing hydrate inhibitor because of the strong and disabled restriction of the large contaminativity of its toxicity.
(2) cost is low: from the pericarp pomace of cheap even waste gas, extract this natural product product, process units is simple, raw material reusable edible, cost of production is very low, well below the cost of existing commercial inhibitor, breach hydrate inhibitor synthesis cost high-leveled and difficult with the difficult problem used on a large scale.
(3) high efficiency: this natural type hydrate inhibitor is while breakthrough Economy ensures environment friendly, also there is very high inhibit activities, under Subcoold temperature is greater than the harsh environmental conditions of 15 DEG C, well can suppresses the generation of hydrate, there is higher inhibit activities.
Embodiment
Do specifically to describe in detail further to the present invention below in conjunction with specific embodiment, but embodiments of the present invention are not limited thereto, for the process parameter do not indicated especially, can refer to routine techniques and carry out.
First be the preparation of green natural type hydrate inhibitor of the present invention, specific experiment protocol see Example 1.
The extraction of pectin in embodiment 1 shaddock ped
Step 1: the shatian pomelo of fresh Growth in Meizhou City, Guangdong is removed the peel, obtains the fresh shaddock ped of 130g.Fresh for 130g shaddock ped is rubbed the blockage to 0.5cm × 0.5cm × 0.5cm, the fritter shaddock ped handled well is inserted in 500ml a bite flask.In 92 DEG C of hot water, boil 8min makes the pectinase in shaddock ped lose efficacy.By the shaddock ped rinsing after boiling 3 ~ 4 times, until solution is colourless, to ensure to remove the pigment in shaddock ped.
Step 2: the solution of configuration PH=2.0, be 1:10 at the solid-liquid ratio (mass ratio) of shaddock ped and solution, temperature is extract 50min under the condition of 95 DEG C.
Step 3: the solution obtained by filtered on buchner funnel step 2 under the condition of 50 DEG C while hot, obtains filtrate.
Step 4: be added to by the alcohol of 95% in the filtrate that step 3 obtains, along with adding gradually (volume ratio of alcohol and filtrate is 2 times) of alcohol, in filtrate, adularescent floccule Precipitation, tentatively obtains the pectic acid of thick esterification.
Step 5: the pectic acid of the thick esterification obtained by absolute ethanol washing step 4, obtains the wet pectin that purity is higher, about 40.0g after suction filtration.
Step 6: at 50 DEG C, is dried to constant weight under the vacuum degree condition of-0.08MPa, obtains the flaxen dry fruit glue of 4.0g, i.e. green natural type hydrate inhibitor, its methyl-esterification degree is 55%, and the content of galactopyranosyluronic is 70%, and weight average molecular weight is 26.3KDa.
Product used by following examples is the green natural type hydrate inhibitor of embodiment 1 gained.
The biological degradability of hydrate inhibitor evaluation test system and product of the present invention is tested experiment porch used and is described as follows:
The present invention's experiment porch used comprises hydrate inhibitor evaluation test system and biological degradability test system.
Hydrate reaction system comprises three large typical hydrate inhibitor evaluating device, and three large typical hydrate inhibitor evaluating device are respectively air bath six still hydrate and suppress evaluating device, visual chuck circulating high pressure stirred autoclave and many autoclaves all-transparent to wave experimental setup.Above three large representative device all include reaction under high pressure system, temperature and pressure sensor, low-temperature control system, vacuumize and data acquistion system, maximum difference is that the mode of the disturbance aqueous solution is different, can from the action effect of different aspect qualitative evaluation hydrate inhibitors.Evaluating device is suppressed by air bath six still hydrate, can rise time of Fast Measurement hydrate, hydration temperature, with the hydration induction time of the mensuration hydrate inhibitor of precise and high efficiency and applicable Subcoold temperature; By visual chuck circulating high pressure reactor, the method of the hydrate crystal Developing restraint method (CGI) adopting Univ Heriot Watt RossAnderson to propose, the Developing restraint speed that test water compound inhibitors grows hydrate crystal in multiple cooling warming cycle, the crystal Developing restraint speed hydrate quantity that water in system per hour changes into represents.The crystal Developing restraint region of hydrate inhibitor is marked off with this standard, these regions comprise complete inhibition zone (0% water changes into hydrate), slowly vitellarium (0.01wt% ~ 5wt% water changes into hydrate), rapid failure district (5wt% ~ 10wt% water changes into hydrate) and slow resolver (in this region, the decomposition rate of hydrate is 1/10th of blank system), specify that the region of hydrate inhibitor useful effect to practical application without being suspected to have very crucial directive function; The time by the trapping timing Hydrate Plugging pipeline of bead in monitoring transparent pipe in experimental setup is waved, with the time of reaction water compound inhibitors total failure at many autoclaves all-transparent.The action effect of inhibitor of the present invention can according to the rise time of hydrate, and crystal Developing restraint speed and the trapping time of hydrate inhibitor judge.The inhibition that the hydrate rise time generates hydrate in order to reaction suppressor, the hydrate rise time is longer, and inhibition is better; The Developing restraint speed of hydrate crystal growth is less, and the useful effect of hydrate inhibitor is stronger; The trapping time is longer that is to say that the time of the complete blocking pipe of hydrate is longer, and the possibility of hydrate inhibitor total failure is less, more can play the effect suppressing hydration.
The method that biological degradability test system adopts chemical oxygen demand (COD) (COD) and BOD (BOD) to combine.Chemical oxygen demand (COD) (COD) reflects in water by the degree that reducing substances pollutes.Chemical oxygen demand (COD) refers under certain condition, calculates the amount by the reducing substances institute oxygen consumed agent in strong oxidizer oxidize water, and represents by the mg/litre (mg/L) of oxygen; Biochemical oxygen demand (BOD), refers under given conditions, by breeding and the respiration of aerobic bacteria in water, consumes or required dissolved oxygen content in decomposition water during organic substance.
The step that chemical oxygen demand (COD) (COD) is tested is:
(1) pipette the 5.00mL water sample being dissolved with this inhibitor with pipette in the special counteracting tank of COD, accurately add 5.00mL potash bichromate standard solution, slowly add 5.00mLH
2sO
4/ AgSO
4solution, puts inner cap safety disc and tightens enclosing cover, and complete sealed digestion tank, puts into microwave oven after shaking up symmetrically.Setting microwave time (2+n) min (n is the number putting into microwave oven counteracting tank), selects 100% firepower, starts microwave oven, after clearing up end, puts on Cotton glove and takes out counteracting tank, naturally cooling or flowing water cooling.
(2) to outward winding enclosing cover, carefully open inner cap, test solution is proceeded in the triangular flask of 300mL, rinse the inner side of inner cap with a small amount of water, and washing lotion is transferred in triangular flask, add water approximately to 30mL.
(3) after solution is chilled to room temperature again, add ferroin indicator 2 ~ 3, with the titration of 0.1moL/L iron ammonium sulfate titer, solution colour fades to bronzing by yellow through blueness and is terminal.
(4) while making sample, get 5.00mL distilled water, do blank assay by same step.
(5) COD (O is calculated
2, mg/L) and=(V
0-V
1) × C × 8 × 1000/V; In formula: the concentration of C=iron ammonium sulfate standard solution, mol/L; V
0iron ammonium sulfate standard solution consumption when=titration is blank, mL; V
1iron ammonium sulfate standard solution consumption during=Titration Water Sample, mL; The volume of V=water sample, mL; 8 is the molal weight of oxygen (1/2O), g/mol.
COD
bd=COD
0-COD
1; Biodegradation ratio Biodegradation=COD
bd/ COD
0;
Wherein COD
bdfor the chemical oxygen demand (COD) of hydrate inhibitor solution; COD
0for containing hydrate inhibitor solution degradation before COD value, COD
1for containing hydrate inhibitor solution degradation after COD value.
BOD testing procedure is as follows:
(1) prepare dilution water, measure 2000mL distilled water with graduated cylinder and pour in 2000mL beaker, in beaker, then add 2mL tetra-kinds of inorganic salt solutions.
(2) dilution water prepared is poured out about 200mL and be used for dissolving 300mg grape sugar and 300mg glutamic acid (standard sample) or a certain amount of hydrate inhibitor, pouring into after dissolving fills in the beaker of dilution water again, afterwards beaker to be placed in incubator constant temperature on main frame and to stir 2.5h.
(3) get fresh domestic sewage as inoculation liquid with 1000mL beaker, beaker is placed on the main frame in incubator with standard sample simultaneously constant temperature 2.5h.
(4) after standard sample all dissolves, by 10% inoculation, 200mL is poured out with graduated cylinder.And then get 200mL domestic sewage with graduated cylinder and pour in standard sample, postvaccinal standard sample to be still placed in incubator constant temperature on stirrer and to stir 2h.
(5) blake bottle of band stirrer is placed on main frame relevant position, a certain amount of test water sample is stirred, until TWS stablizes 1.5h within the scope of 20 ± 1 DEG C.
(6) get the seal cup cleaning up also drying, put into 0.01gNaOH or KOH particle in cup, blake bottle is placed on main frame corresponding position, treat that solution starts to stir screw on gently water column lid and cultivation bottle cap.Stablize 45min, tighten and cultivate bottle cap and water column lid, then unclamp the knob of fixation pressure meter calibrated scale, and regulate calibrated scale, 0 scale is just in time overlapped with the upper horizontal of mercury column, then again tightens knob.
After (7) 0 scales just in time overlap with the upper horizontal of mercury column and no longer change in 2h, start reading until experiment terminates, each sample BOD-t curve can be drawn on graph paper.
BOD and COD is two water quality index conventional in biological wastewater treatment process, this research is changed containing the COD before and after the aqueous solution biodegradation of hydrate inhibitor by research, determine the Changing Pattern of hydrate inhibitor in BOD degradation process, obtain the data of hydrate inhibitor biodegradation aspect, the biodegradability evaluating waste water by BOD/COD value is the most easy method of one extensively adopted.Generally, BOD/COD value is larger, waste water bio-treatment Feasibility is described better.During BOD/COD>0.45, represent that biodegradability is good; When BOD/COD is between 0.3 ~ 0.45, its biochemical is better; When BOD/COD is between 0.2 ~ 0.3, represent comparatively difficult for biological degradation; If BOD/COD<0.2, represent that the material in waste water should not adopt biodegradable way process.
Air bath six still hydrate suppresses to evaluate:
Embodiment 2
Reaction starts front deionized water and is cleaned up by reactor, and add 60g deionized water (gas liquid ratio 2:3), question response temperature in the kettle is stabilized in 30 DEG C, passes into the simulation rock gas (CH of 9.2MPa
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%) (mole fraction), opens magnetic agitation (700rpm).After gas reactor dissolution equilibrium pressure stability (being stabilized in 9.0MPa), start cooling, spin manifold temperature 0.5 DEG C is set.After 2h, the temperature of 6 autoclaves is all stabilized in about 2.0 DEG C.Occur at 1.8h, 1.9h, 2.0h, 1.85h, 1.75h, 1.94h the phenomenon that the unexpected unlifting pressure of temperature obviously declines respectively by temperature and pressure signal discovery 6 stills of data acquiring and recording, this illustrates in 6 stills and all generates hydrate (generation of hydrate is a heat release and consumes the process of gas) in the above-mentioned time.The average hydration induction time of blank assay is 1.87h.
Comparative example 1
Add the 60g solution containing 0.2wt% green natural type hydrate inhibitor in a kettle., question response temperature in the kettle is stabilized in about 30 DEG C, passes into the simulation rock gas (CH of 9.2MPa
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), magnetic agitation (700rpm) is opened.After gas reactor dissolution equilibrium pressure stability (being stabilized in 9.0MPa), start cooling, spin manifold temperature 0.5 DEG C is set.After 2h, the temperature of 6 autoclaves is all stabilized in about 2.0 DEG C.Occur at 32.1h, 34.4h, 29.7h, 30.1h, 31.5h, 33.4h the phenomenon that the unexpected unlifting pressure of temperature declines respectively by temperature and pressure signal discovery 6 stills of data acquiring and recording, this illustrates in 6 stills and all generates hydrate (generation of hydrate is a heat release and consumes the process of gas) in the above-mentioned time.The average hydration induction time adding this suppression product of 0.5wt% is 31.8h, illustrates that this inhibitor has the effect significantly suppressing hydration.
Comparative example 2
Add the 60g solution containing 0.8wt% green natural type hydrate inhibitor in a kettle., question response temperature in the kettle is stabilized in about 30 DEG C, passes into the simulation rock gas (CH of 9.2MPa
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), magnetic agitation (700rpm) is opened.After gas reactor dissolution equilibrium pressure stability (being stabilized in 9.0MPa), start cooling, spin manifold temperature 0.5 DEG C is set.After 2h, the temperature of 6 autoclaves is all stabilized in about 2.0 DEG C.The temperature phenomenon that declines a little of unlifting pressure is a little there is at 72.0h, 72.5h, 75.5h, 73.3h, 74.8h, 72.9h respectively by temperature and pressure signal discovery 6 stills of data acquiring and recording, this illustrates in 6 stills and all generates hydrate (generation of hydrate is a heat release and consumes the process of gas) in the above-mentioned time, the average hydration induction time adding this suppression product of 1.0wt% is 73.5h, illustrates that this inhibitor has the effect significantly suppressing hydration.
Embodiment 3
Reaction starts front deionized water and is cleaned up by reactor, and add 48g deionized water and 12g crude oil sample (moisture content of system is 80%), question response temperature in the kettle is stabilized in 30 DEG C, passes into the simulation rock gas (CH of 9.2MPa
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), magnetic agitation (700rpm) is opened.After gas reactor dissolution equilibrium pressure stability (being stabilized in 9.0MPa), start cooling, spin manifold temperature 0.5 DEG C is set.After 2h, the temperature of 6 autoclaves is all stabilized in about 2.0 DEG C.There is at 2.2h, 2.1h, 2.3h, 1.95h, 2.05h, 1.98h the phenomenon that the unexpected unlifting pressure of temperature obviously declines respectively by temperature and pressure signal discovery 6 stills of data acquiring and recording, this illustrates in 6 stills and all generates hydrate (generation of hydrate is a heat release and consumes the process of gas) in the above-mentioned time, and stop when being stirred in 3h, illustrate that the hydrate quantity generated is larger, the average hydration induction time of this blank assay is 2.09h.
Comparative example 3
Add 48g deionized water and 12g crude oil sample (moisture content of system is 80wt%) and 0.24g green natural type hydrate inhibitor in a kettle., question response temperature in the kettle is stabilized in 30 DEG C, passes into the simulation rock gas (CH of 9.2MPa
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), magnetic agitation (700rpm) is opened.After gas reactor dissolution equilibrium pressure stability (being stabilized in 9.0MPa), start cooling, spin manifold temperature 0.5 DEG C is set.After 2h, the temperature of 6 autoclaves is all stabilized in about 2.0 DEG C.By temperature and pressure signal discovery 6 stills of data acquiring and recording respectively at 65.2h, 64.8h, 64.3h, 63.8h, 65.1h, there is the temperature phenomenon that declines a little of unlifting pressure a little in 63.9h, this illustrates in 6 stills and all generates hydrate (generation of hydrate is a heat release and consumes the process of gas) in the above-mentioned time, but stir in the 80h of whole experiment and all do not stop because of the hydrate generated, illustrate that the hydrate quantity generated is smaller, in oil-water-gas heterogeneous system, the average hydration induction time of this suppression product is 64.5h, compare the rise time that this suppression product of blank sample is obviously delayed hydrate, there is preferably effect.
Comparative example 4
Add 48g deionized water and 12g crude oil sample (moisture content of system is 80%) and 0.48g green natural type hydrate inhibitor in a kettle., question response temperature in the kettle is stabilized in 30 DEG C, passes into the simulation rock gas (CH of 9.2MPa
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), magnetic agitation (700rpm) is opened.After gas reactor dissolution equilibrium pressure stability (being stabilized in 9.0MPa), start cooling, spin manifold temperature 0.5 DEG C is set.After 2h, the temperature of 6 autoclaves is all stabilized in about 2.0 DEG C.By temperature and pressure signal discovery 6 stills of data acquiring and recording respectively at 78.2h, 76.5h, 75.8h, 77.8h, 77.1h, there is the temperature phenomenon that declines a little of unlifting pressure a little in 75.7h, this illustrates in 6 stills and all generates hydrate (generation of hydrate is a heat release and consumes the process of gas) in the above-mentioned time, but stir in the 80h of whole experiment and all do not stop because generating hydrate, illustrate that the hydrate quantity generated is smaller, in oil-water-gas heterogeneous system, the average hydration induction time of this suppression product is 76.8h, compare the rise time that this suppression product of blank sample is obviously delayed hydrate, this hydrate inhibitor has preferably effect.
Visual chuck circulating high pressure reactor measures the crystal Developing restraint speed of hydrate inhibitor:
Embodiment 4
Add the 210g solution (gas liquid ratio 2:3) containing this suppression of 0.42g product in a kettle., at the temperature of 30 DEG C, be filled with the simulation rock gas (CH of 9.2MPa to reactor
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), ensure that temperature, pressure is outside hydrate phase balance region.After the temperature, pressure in still is stable, opens and stir (700rpm), the hydrate crystal Developing restraint method (CGI) next adopting Univ Heriot Watt RossAnderson to propose tests the crystal Developing restraint region of this inhibitor.Testing procedure is as follows: 1. drop to high supercooling degree district (lower than actual Phase Equilibrium Temperature more than 10 DEG C) fast to induce the generation of hydrate with the cooling rate of 20 DEG C/h; 2. after a large amount of generation of hydrate first time, progressively heat (rate of heat addition is 5 DEG C/h) to system and make most of decomposition of hydrate until only have very little a part of hydrate undecomposed (water being normally less than 0.5wt% changes into hydrate) in system, in this decomposition process, can be observed decomposition region unusual in the presence of the inhibitors, in this region, decomposition of hydrate speed is less than 1/10th for blank system decomposition rate usually; 3. the cooling of whole reaction system is given with the constant rate of speed of 1 DEG C/h again, so that the speed of hydrate crystal growth under can offering an explanation out each Subcoold temperature; 4. the experimental implementation more than 3 times of 2-3 step is repeated, to ensure the reliability of experimental result.5. last, then step 2, only having (water being less than 0.5wt% in usual system changes into hydrate) under a small amount of hydrate existent condition to adopt the mode of substep cooling to determine, complete inhibition zone and hydrate start the separation slowly grown.Experimental result shows: under this inflation pressure, the complete inhibition zone of this suppression of 0.5wt% product is Δ T=0 DEG C ~-7.4 DEG C, slowly growth district be Δ T=-7.4 DEG C ~-10.3 DEG C, Δ T=-9.3 ~-12.6, rapid failure district DEG C, slowly resolver Δ T=0 DEG C ~ 4.6 DEG C.
Embodiment 5
Add the 210g solution (gas liquid ratio 2:3) containing 1.05g green natural type hydrate inhibitor in a kettle., at the temperature of 30 DEG C, be filled with the simulation rock gas (CH of 9.2MPa to reactor
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), ensure that temperature, pressure is outside hydrate phase balance region.After the temperature, pressure in still is stable, opens and stir (700rpm), the hydrate crystal Developing restraint method (CGI) next adopting Univ Heriot Watt RossAnderson to propose tests the crystal Developing restraint region of this inhibitor.Testing procedure is as follows: 1. drop to high supercooling degree district (lower than actual Phase Equilibrium Temperature more than 10 DEG C) fast to induce the generation of hydrate with the cooling rate of 20 DEG C/h; 2. after a large amount of generation of hydrate first time, progressively heat (rate of heat addition is 5 DEG C/h) to system and make most of decomposition of hydrate until only have very little a part of hydrate undecomposed (water being normally less than 0.5wt% changes into hydrate) in system, in this decomposition process, can be observed decomposition region unusual in the presence of the inhibitors, in this region, decomposition of hydrate speed is less than 1/10th for blank system decomposition rate usually; 3. the cooling of whole reaction system is given with the constant rate of speed of 1 DEG C/h again, so that the speed of hydrate crystal growth under can offering an explanation out each Subcoold temperature; 4. the experimental implementation more than 3 times of 2-3 step is repeated, to ensure the reliability of experimental result.5. last, then step 2, only having (water being less than 0.5wt% in usual system changes into hydrate) under a small amount of hydrate existent condition to adopt the mode of substep cooling to determine, complete inhibition zone and hydrate start the separation slowly grown.Experimental result shows: under this inflation pressure, the complete inhibition zone of this suppression of 1.0wt% product is Δ T=0 DEG C ~-8.9 DEG C, slowly growth district be Δ T=-8.9 DEG C ~-11.8 DEG C, Δ T=-11.8 ~-13.5, rapid failure district DEG C, slowly resolver Δ T=0 DEG C ~ 5.2 DEG C.
Embodiment 6
Add in a kettle. containing 1.68g green natural type hydrate inhibitor and 168g deionized water and 42g crude oil (system moisture content is 80wt%), at the temperature of 30 DEG C, be filled with the simulation rock gas (CH of 9.2MPa to reactor
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), ensure that temperature, pressure is outside hydrate phase balance region.After the temperature, pressure in still is stable, opens and stir (700rpm), the hydrate crystal Developing restraint method (CGI) next adopting Univ Heriot Watt RossAnderson to propose tests the crystal Developing restraint region of this inhibitor.Testing procedure is as follows: 1. drop to high supercooling degree district (lower than actual Phase Equilibrium Temperature more than 10 DEG C) fast to induce the generation of hydrate with the cooling rate of 20 DEG C/h; 2. after a large amount of generation of hydrate first time, progressively heat (rate of heat addition is 5 DEG C/h) to system and make most of decomposition of hydrate until only have very little a part of hydrate undecomposed (water being normally less than 0.5wt% changes into hydrate) in system, in this decomposition process, can be observed decomposition region unusual in the presence of the inhibitors, in this region, decomposition of hydrate speed is less than 1/10th for blank system decomposition rate usually; 3. the cooling of whole reaction system is given with the constant rate of speed of 1 DEG C/h again, so that the speed of hydrate crystal growth under can offering an explanation out each Subcoold temperature; 4. the experimental implementation more than 3 times of 2-3 step is repeated, to ensure the reliability of experimental result.5. last, then step 2, only having (water being less than 0.5wt% in usual system changes into hydrate) under a small amount of hydrate existent condition to adopt the mode of substep cooling to determine, complete inhibition zone and hydrate start the separation slowly grown.Experimental result shows: under this inflation pressure, the complete inhibition zone of this suppression of 1.0wt% product is Δ T=0 DEG C ~-7.9 DEG C, slowly growth district be Δ T=-7.9 DEG C ~-10.7 DEG C, Δ T=-10.7 ~-11.9, rapid failure district DEG C, slowly resolver Δ T=0 DEG C ~ 4.2 DEG C.
Embodiment 7
Add in a kettle. containing 3.36g green natural type hydrate inhibitor and 168g deionized water and 42g crude oil (system moisture content is 80wt%), at the temperature of 30 DEG C, be filled with the simulation rock gas (CH of 9.2MPa to reactor
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), ensure that temperature, pressure is outside hydrate phase balance region.After the temperature, pressure in still is stable, opens and stir (700rpm), the hydrate crystal Developing restraint method (CGI) next adopting Univ Heriot Watt RossAnderson to propose tests the crystal Developing restraint region of this inhibitor.Testing procedure is as follows: 1. drop to high supercooling degree district (lower than actual Phase Equilibrium Temperature more than 10 DEG C) fast to induce the generation of hydrate with the cooling rate of 20 DEG C/h; 2. after a large amount of generation of hydrate first time, progressively heat (rate of heat addition is 5 DEG C/h) to system and make most of decomposition of hydrate until only have very little a part of hydrate undecomposed (water being normally less than 0.5wt% changes into hydrate) in system, in this decomposition process, can be observed decomposition region unusual in the presence of the inhibitors, in this region, decomposition of hydrate speed is less than 1/10th for blank system decomposition rate usually; 3. the cooling of whole reaction system is given with the constant rate of speed of 1 DEG C/h again, so that the speed of hydrate crystal growth under can offering an explanation out each Subcoold temperature; 4. the experimental implementation more than 3 times of 2-3 step is repeated, to ensure the reliability of experimental result.5. last, then step 2, only having (water being less than 0.5wt% in usual system changes into hydrate) under a small amount of hydrate existent condition to adopt the mode of substep cooling to determine, complete inhibition zone and hydrate start the separation slowly grown.Experimental result shows: under this inflation pressure, the complete inhibition zone of this suppression of 2.0wt% product is Δ T=0 DEG C ~-9.2 DEG C, slowly growth district be Δ T=-9.2 DEG C ~-12.5 DEG C, Δ T=-12.5 ~-13.5, rapid failure district DEG C, slowly resolver Δ T=0 DEG C ~ 6.2 DEG C.
Many autoclaves all-transparent waves the trapping time that experimental setup measures hydrate inhibitor:
Embodiment 8
Many autoclaves all-transparent is utilized to wave the experimental procedure of experimental setup test inhibitor trapping time as follows: 1. in 6 clean transparent straight pipe reactors, to add 30g deionized water; 2. impurity gas is wherein got rid of by vacuum pump, injects simulation rock gas (CH afterwards
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), until pressure reaches 9.2MPa; 3. swing with the speed of 20r/min, the Angle ambiguity waved is at about 30 °; 4. 2 DEG C are dropped to the speed of 1 DEG C/h from 21 DEG C (Phase Equilibrium Temperatures corresponding to 9.5MPa), and at 2 DEG C of stable at least 24h; 5. turn-on data collection, the hydration time in record experimentation, hydration temperature and trapping time.Experimental result shows: in 6 stills, the trapping time of hydrate is respectively 6.20h, 5.98h, 6.12h, 6.16h, 6.05h, 6.04h, starts hydration temperature and is respectively 17.2 DEG C, 17.4 DEG C, 17.2 DEG C, 17.2 DEG C, 17.3 DEG C, 17.3 DEG C.
Comparative example 5
Many autoclaves all-transparent is utilized to wave the experimental procedure of experimental setup test inhibitor trapping time as follows: in 6 clean transparent straight pipe reactors, 1. add the 30g deionized water containing 0.15g green natural type hydrate inhibitor; 2. impurity gas is wherein got rid of by vacuum pump, injects simulation rock gas (CH afterwards
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), until pressure reaches 9.2MPa; 3. swing with the speed of 20r/min, the Angle ambiguity waved is at about 30 °; 4. drop to 2 DEG C with the speed of 1 DEG C/h from 21 DEG C (Phase Equilibrium Temperatures corresponding to 9.5MPa) and be stabilized in 2 DEG C of at least 24h; 5. turn-on data collection, the hydration time in record experimentation, hydration temperature and trapping time.Experimental result shows: in 6 stills, the trapping time of hydrate is respectively 24.20h, 24.50h, 24.30h, 24.4h, 24.5h, 24.3h, starts hydration temperature and is respectively 12.1 DEG C, 12.2 DEG C, 11.9 DEG C, 12.1 DEG C, 11.9 DEG C, 12.2 DEG C.Compared to blank sample, this suppression product of 0.5wt% has the effect well suppressing hydration.
Comparative example 6
Many autoclaves all-transparent is utilized to wave the experimental procedure of experimental setup test inhibitor trapping time as follows: in 6 clean transparent straight pipe reactors, 1. add the 30g deionized water containing 0.30g green natural type hydrate inhibitor; 2. impurity gas is wherein got rid of by vacuum pump, injects simulation rock gas (CH afterwards
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), until pressure reaches 9.2MPa; 3. swing with the speed of 20r/min, the Angle ambiguity waved is at about 30 °; 4. drop to 2 DEG C with the speed of 1 DEG C/h from 21 DEG C (Phase Equilibrium Temperatures corresponding to 9.5MPa) and be stabilized in 2 DEG C of at least 24h; 5. turn-on data collection, the hydration time in record experimentation, hydration temperature and trapping time.Experimental result shows: wherein in 4 stills the trapping time of hydrate be respectively 41.20,42.50,41.8h, 42.0h, and other 2 stills are testing all non-stop motion of bead in 43 hours that carry out.Start hydration temperature and be respectively 9.9 DEG C, 10.1 DEG C, 10.2 DEG C, 9.8 DEG C, 9.9 DEG C, 10.0 DEG C.As can be seen here, this suppression product of 1.0wt% has the effect well suppressing hydration.
Embodiment 9
Many autoclaves all-transparent is utilized to wave the experimental procedure of experimental setup test trapping time as follows: 1. in 6 clean transparent straight pipe reactors, to add 24g deionized water and 6g crude oil; 2. impurity gas is wherein got rid of by vacuum pump, injects simulation rock gas (CH afterwards
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), until pressure reaches 9.2MPa; 3. swing with the speed of 20r/min, the Angle ambiguity waved is at about 30 °; 4. 2 DEG C are dropped to the speed of 1 DEG C/h from 21 DEG C (Phase Equilibrium Temperatures corresponding to 9.5MPa), and at 2 DEG C of stable at least 24h; 5. turn-on data collection, the hydration time in record experimentation, hydration temperature and trapping time.Experimental result shows: in 6 stills, the trapping time of hydrate is respectively 7.20h, 7.18h, 7.10h, 7.25h, 7.09h, 7.15h, starts hydration temperature and is respectively 16.2 DEG C, 16.4 DEG C, 16.2 DEG C, 16.2 DEG C, 16.3 DEG C, 16.3 DEG C.
Comparative example 7
Many autoclaves all-transparent is utilized to wave the experimental procedure of experimental setup test inhibitor trapping time as follows: 1. in 6 clean transparent straight pipe reactors, to add 0.24g green natural type hydrate inhibitor, 24g deionized water and 6g crude oil; 2. impurity gas is wherein got rid of by vacuum pump, injects simulation rock gas (CH afterwards
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), until pressure reaches 9.2MPa; 3. swing with the speed of 20r/min, the Angle ambiguity waved is at about 30 °; 4. 2 DEG C are dropped to the speed of 1 DEG C/h from 21 DEG C (Phase Equilibrium Temperatures corresponding to 9.5MPa), and at 2 DEG C of stable at least 24h; 5. turn-on data collection, the hydration time in record experimentation, hydration temperature and trapping time.Experimental result shows: in 6 stills, the trapping time of hydrate is respectively 29.20h, 28.8h, 28.9h, 29.6h, 30.1h, 30.2h, starts hydration temperature and is respectively 11.2 DEG C, 11.1 DEG C, 10.9 DEG C, 11.1 DEG C, 10.9 DEG C, 11.2 DEG C.
Comparative example 8
Many autoclaves all-transparent is utilized to wave the experimental procedure of experimental setup test inhibitor trapping time as follows: 1. in 6 clean transparent straight pipe reactors, to add 0.48g green natural type hydrate inhibitor, 24g deionized water and 6g crude oil; 2. impurity gas is wherein got rid of by vacuum pump, injects simulation rock gas (CH afterwards
487.16%, C
2h
63.60%, C
3h
81.43%, i-C
4h
100.29%, n-C
4h
100.30%, i-C
5h
120.10%, n-C
5h
120.03%, C
6h
140.95%, CO
25.73%, N
20.41%), until pressure reaches 9.2MPa; 3. swing with the speed of 20r/min, the Angle ambiguity waved is at about 30 °; 4. 2 DEG C are dropped to the speed of 1 DEG C/h from 21 DEG C (Phase Equilibrium Temperatures corresponding to 9.5MPa), and at 2 DEG C of stable at least 24h; 5. turn-on data collection, the hydration time in record experimentation, hydration temperature and trapping time.Experimental result shows: in 6 stills, the trapping time of hydrate is respectively 42.5h, 42.1h, 41.9h, 41.5h, 42.0h, 40.9h, starts hydration temperature and is respectively 9.8 DEG C, 9.5 DEG C, 10.1 DEG C, 9.6 DEG C, 9.7 DEG C, 9.6 DEG C.
Biodegradability test is tested:
Embodiment 10
COD test instrument: power is the microwave oven one of 900W; Special COD counteracting tank (internal volume 100mL, maximum working pressure 1MPa); 300ml triangular flask is some; One, 50mL burette.
BOD test instrument: flask; Conical flask; Measuring flask; Glass rod; BOD tester.
It is as follows that COD tests the reagent used:
(1) digestion solution: 0.2000mol/L potash bichromate standard solution;
(2) 0.042mol/L iron ammonium sulfate standard solution;
Calibration process: pipette pipettes 5.00ml potash bichromate standard solution in 150mL conical flask, be diluted with water to about 30ml, slowly add the 5mL concentrated sulphuric scid, mixing, after cooling, add 2 ferroins (about 0.1mL) and use l ferrous ammonium sulfate solution titration, solution colour is terminal through aquamarine blue to bronzing by yellow.Ferrous ammonium sulfate concentration c=0.2000*5/V marks (mol/L)
(3) ferroin indicator;
(4) sulfuric acid-silver sulfate catalyzer;
(5) the kinetic inhibition agent solution of degraded is that the inhibitor of 300 ~ 500mg to add in distilled water in measuring flask constant volume to 250ml.
BOD test material is as follows:
(1) phosphate buffer 21.75gK
2hPO
4, 8.5gKH
2pO
4, 33.4gNa
2hPO
47H
2o, 1.7gNH
4cl/1LH
2o;
(2) Adlerika 22.5gMgSO
47H
2o/1LH
2o;
(3) calcium chloride solution 27.5gCaCl
2/ 1LH
2o;
(4) liquor ferri trichloridi 0.25gFeCl
36H
2o/1LH
2o;
Concrete experimental procedure as described previously, COD
0=260mg/L, COD
1=24.5mg/L, COD
bd=(260-24.5)/260*100%=90.57%, the biological degradability of this inhibitor is fine as can be seen here; The BOD=300mg/L of this inhibitor, BOD/COD=300/260=1.15, illustrate that the biodegradability of the aqueous solution being added with this inhibitor product is good especially, can not cause delay in the aqueous solution, minimum to the contaminativity of environment.
Above-described embodiment illustrates that green natural type hydrate inhibitor provided by the present invention has very strong high efficiency; the specific methyl-esterification degree of product of the present invention; the content of galactopyranosyluronic and weight average molecular weight; this is played to vital effect; and inventor did associated verification; when these parameter values of product too high or too low (not in application claims protection domain), its effect reduces greatly.
The above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all mode of executions.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection domain that all should be included in the claims in the present invention.
Claims (10)
1. a green natural type hydrate inhibitor, is characterized in that, described hydrate inhibitor is a kind of pectic acid and derivative thereof of esterification;
Described pectic acid is the straight-chain polysaccharide that D-galactopyranosyluronic couples together with ɑ-Isosorbide-5-Nitrae glycosidic bond;
Described methyl esters turns to hydrogen atom on straight-chain polysaccharide carboxyl by methyl substituted;
Hydroxyl generation acetylation on described straight-chain polysaccharide or amidation process;
Described straight-chain polysaccharide chain also comprises side chain, and side chain comprises D-galactose, Arabinose, D-wood sugar, D-sorbose, L-fucose, L-glucuronic acid, L-rhamnose or sweet mellow wine;
The methyl-esterification degree of described pectic acid and derivative thereof is 8% ~ 70%, and the content of galactopyranosyluronic is greater than 65wt%.
2. green natural type hydrate inhibitor according to claim 1, is characterized in that, the pectic acid of described esterification and the typical structure of derivative are shown below:
Wherein, R
1for acetyl group, D-galactose, the one in Arabinose, D-wood sugar, D-sorbose, L-fucose, L-glucuronic acid, L-rhamnose or sweet mellow wine, R
2for amino.
3. green natural type hydrate inhibitor according to claim 1, is characterized in that, described hydrate inhibitor weight average molecular weight is 50kDa ~ 700kDa.
4. green natural type hydrate inhibitor according to claim 1, it is characterized in that, the service condition of described hydrate inhibitor is: pressure is at 1.0 ~ 30MPa, and temperature is at-25 ~ 25 DEG C, and the volumn concentration of system water changes between 100% to 50wt%.
5. green natural type hydrate inhibitor according to claim 1, is characterized in that, in the system of a hundred per cent moisture content, the weight ratio of this hydrate inhibitor and water is 0.1% ~ 10.0%.
6. green natural type hydrate inhibitor according to claim 1, is characterized in that, in the system of a hundred per cent moisture content, the weight ratio of this hydrate inhibitor and water is 0.5% ~ 2.0%.
7. green natural type hydrate inhibitor according to claim 1, is characterized in that, be greater than 50 percent at moisture content and be less than absolutely in oil gas water heterogeneous system, the weight ratio of this hydrate inhibitor and water is 0.1 ~ 20%.
8. green natural type hydrate inhibitor according to claim 1, is characterized in that, be greater than 50 percent at moisture content and be less than absolutely in oil gas water heterogeneous system, the weight ratio of this hydrate inhibitor and water is 1.0% ~ 3.0%.
9. the preparation method of green natural type hydrate inhibitor described in any one of claim 1-8, it is characterized in that, comprise the steps: that (1) is by the thing to be extracted containing pectic acid, chopping, 5 ~ 10min is boiled in 90 DEG C ~ 95 DEG C hot water, by the fruit after boiling or pomace rinsing 3 ~ 4 times, until solution is colourless;
(2) configuring the solution of pH=2.0, is 1:5 ~ 1:15 at the feed liquid mass ratio of shaddock ped and solution, and temperature is extract 45 ~ 60min under the condition of 95 DEG C ~ 100 DEG C;
(3) while hot under the condition of 50 DEG C ~ 55 DEG C with the solution that filtered on buchner funnel step (2) obtains, obtain filtrate;
(4) alcohol of 95% is added in the filtrate that step (3) obtains, tentatively obtains the pectic acid of thick esterification; The volume ratio of described alcohol and filtrate is 2;
(5) pectic acid of the thick esterification obtained by absolute ethanol washing step (4), obtains the wet pectin that purity is higher after suction filtration;
(6) at 45 ~ 50 DEG C, under the vacuum degree condition of-0.08 ~-0.1MPa, be dried to constant weight, obtain dry fruit glue, be i.e. green natural type hydrate inhibitor.
10. according to preparation method according to claim 7, it is characterized in that, described pectic acid thing to be extracted is Rutaceae, the rose family, Passifloraceae, Sonneratiaceae, extract in Cactaceae or Dioscoreaceae plant, comprises orange peel, pomelo peel, Peel of Navel Orange, pomace, sunflower plate or potato residues.
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| CN108446258A (en) * | 2018-04-10 | 2018-08-24 | 清华大学深圳研究生院 | A kind of hydrate inhibitor efficiency evaluation method and system |
| WO2023122947A1 (en) * | 2021-12-28 | 2023-07-06 | 大连理工大学 | Environmentally-friendly natural gas hydrate inhibitor and application |
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| CN108446258B (en) * | 2018-04-10 | 2021-12-31 | 清华大学深圳研究生院 | Hydrate inhibitor efficiency evaluation method and system |
| WO2023122947A1 (en) * | 2021-12-28 | 2023-07-06 | 大连理工大学 | Environmentally-friendly natural gas hydrate inhibitor and application |
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