CN103570862A - Demulsifying agent, and preparation method and applications thereof - Google Patents
Demulsifying agent, and preparation method and applications thereof Download PDFInfo
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- CN103570862A CN103570862A CN201210252673.7A CN201210252673A CN103570862A CN 103570862 A CN103570862 A CN 103570862A CN 201210252673 A CN201210252673 A CN 201210252673A CN 103570862 A CN103570862 A CN 103570862A
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- polyether
- carboxylic acid
- unsaturated carboxylic
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000570 polyether Polymers 0.000 claims abstract description 55
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 carboxylic acid methyl ester Chemical class 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 239000003112 inhibitor Substances 0.000 claims abstract 4
- 230000018044 dehydration Effects 0.000 claims abstract 3
- 238000006297 dehydration reaction Methods 0.000 claims abstract 3
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract 2
- 239000000839 emulsion Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000010779 crude oil Substances 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005809 transesterification reaction Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 6
- 239000007870 radical polymerization initiator Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000005684 electric field Effects 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 229920003046 tetrablock copolymer Polymers 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 2
- 239000005011 phenolic resin Substances 0.000 claims 2
- 229920001568 phenolic resin Polymers 0.000 claims 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims 1
- 229920001400 block copolymer Polymers 0.000 claims 1
- 229920000359 diblock copolymer Polymers 0.000 claims 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims 1
- 229920000428 triblock copolymer Polymers 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000009884 interesterification Methods 0.000 abstract 2
- 239000003505 polymerization initiator Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000032050 esterification Effects 0.000 description 13
- 238000005886 esterification reaction Methods 0.000 description 13
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000004160 Ammonium persulphate Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 235000019395 ammonium persulphate Nutrition 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 101100388126 Caenorhabditis elegans dpy-2 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
The invention relates to a demulsifying agent, and a preparation method and applications thereof. The preparation method comprises following steps: (1) in the presence of a interesterification catalyst and a polymerization inhibitor, a polyether and an unsaturated carboxylic acid methyl ester and/or an unsaturated carboxylic acid ethyl ester are subjected to interesterification; (2) methanol and/or ethanol is separated via reduced pressure distillation; and (3) an unsaturated carboxylic acid, water and an free polymerization initiator are added for free radical polymerization. The demulsifying agent prepared by the preparation method is suitable for demulsification and dehydration of thickened oil.
Description
Technical field
The present invention relates to a kind of emulsion splitter and its preparation method and application.
Background technology
Viscous crude is a kind of unconventional petroleum resources, and along with the minimizing day by day of conventional thin oil reserves, viscous crude resource is taken over one of energy by becoming the important strategy of China.In China, viscous crude refers to that viscosity under reservoir temperature is greater than the crude oil of 50mPa.s, according to viscosity, can be common heavy oil (50～10000mPa.s), special viscous crude (10000～50000mPa.s), super viscous crude (more than 50000mPa.s) by viscous crude Further Division.Viscous crude has that density is high, viscosity is large, bituminous matter and the high feature of gum level, if the asphalt content of Tahe Crude Oil is up to 11%.Bituminous matter and colloid are natural water-in-oil emulsifiers, can form skin shape film in water droplet surface adsorption, hinder the coalescent of water droplet, thereby the breakdown of emulsion of high bituminous matter viscous crude are puzzlement people's difficult problems always.
From the twenties in 20th century, bring into use and developed so far three generations's water-in-oil-type emulsion splitter.There is 20～thirties of 20th century first-generation emulsion splitter, it is mainly low-molecular-weight, anionic type tensio-active agent, comprising carboxylic acid type, sulfuric acid type and sulfonate type three major types, the advantage of this class emulsion splitter is low price, shortcoming be consumption large (1000mg/L), efficiency low, be subject to Influence of Electrolyte etc.; Developed 40～fifties of 20th century s-generation emulsion splitter, mainly low molecule nonionogenic tenside, as OP type, Tween type tensio-active agent, though acidproof, alkaline-resisting, the salt tolerant of this class emulsion splitter energy, but emulsion splitter consumption is large (300～500mg/L) still, and demulsification is also not ideal enough; So far developed the third generation emulsion splitter sixties in 20th century, is mainly polymer nonionic surface active agent, and as the segmented copolymer of polyoxyethylene and polyoxypropylene, its advantage is consumption few (5～100mg/L), and shortcoming is that specificity is strong.
Along with the increase of viscous oil recovery amount, its breakdown of emulsion problem is more and more outstanding, impels people constantly to find better effects if, the emulsion splitter that universality is stronger.People find in practice, and molecular weight is high, and the emulsion splitter effect of racemosus wooden fork is better.The method that improves emulsion splitter molecular weight mainly contains 3 kinds: (1) adopts new catalyst, as chainextenders (3) such as triisobutyl aluminium-methyl ethyl diketone-water or triisobutyl aluminium-methyl ethyl diketone-water-oil of mirbane system (2) use tolylene diisocyanates (TDI), on pfpe molecule, introduce the polymerisable monomers such as vinylformic acid, by polymerization, pfpe molecule amount is increased.The third method has overcome first two method catalyzer or chainextender is expensive, poisonous, product dissolves the shortcomings such as difficulty.
Patent reports more both domestic and external to polyethers, introduce the method for polymerisable monomer, as USP4,678,599 have reported and have introduced the allyl polyether of vinyl carbinol and the multipolymer of vinyl acetate or methyl methacrylate.USP5,661,220 have reported the acrylic acid polyethers of introducing and acrylic acid multipolymer.Domestic also have a similar report, as CN1137247.These inventions adopt esterification that unsaturated carboxylic acid polymer is connected with polyethers, and esterification need to be made band aqua with toluene, to separate the water of generation, make to react completely, but toluene is poisonous on the one hand, and while using toluene on the other hand, the polyether of generation can be separated out.In prior art, seldom adopt aqueous solution polymerization to prepare the method for polyether, although CN1966138 has reported a kind of preparation method of aqueous polymer polyethers, and as viscous crude reverse-phase emulsifier, but its direct polymerization and esterification in the aqueous solution, effect can not be satisfactory.
Summary of the invention
The invention provides a kind of preparation method of emulsion splitter, the emulsion splitter that adopts the present invention to prepare not only has good breaking emulsion and dewatering performance to high bituminous matter viscous crude, and has good storage stability.
A preparation method for emulsion splitter, comprising:
(1) under the existence of transesterification catalyst and stopper, the ethyl ester of the methyl esters of polyethers and unsaturated carboxylic acid and/or unsaturated carboxylic acid is carried out to transesterification reaction, described polyethers is-CH
2cH
2o-and-CH
2cH (CH
3) segmented copolymer that O-forms, it has an end group at least is hydroxyl, number-average molecular weight is 500～30000, in polyethers-CH
2cH
2o-and-CH
2cH (CH
3) mass ratio of O-is 0.1～10:1;
(2) methyl alcohol and/or ethanol are isolated in underpressure distillation;
(3) mix with unsaturated carboxylic acid, water and free crowd initiator, carry out Raolical polymerizable; The quality of polyethers raw material of step (1) of take is 1, and the consumption of unsaturated carboxylic acid is 0.01～1;
In step (1) and (3), described unsaturated carboxylic acid can be identical or different, is all selected from one or more in vinylformic acid, methacrylic acid, maleic anhydride, toxilic acid and fumaric acid.
The temperature of reaction of step (1) is 100～120 ℃, preferably 105～110 ℃.
The reaction times of step (1) is 1～24 hour, preferably 2～6 hours.
Transesterification catalyst comprises basic catalyst, an acidic catalyst, biological enzyme agent etc.In the present invention, described transesterification catalyst is preferably sulfuric acid, phosphoric acid or tosic acid.When transesterification catalyst is tosic acid, it is 0.1%～8% of polyethers raw material and esters of unsaturated carboxylic acids total mass for consumption, is preferably 0.4%～1.5%.
In step (1), described stopper is preferably Resorcinol or MEHQ, and consumption is 0.1%～1% of esters of unsaturated carboxylic acids quality, is preferably 0.2%～0.6%.
In step (1), the mass ratio of polyethers and esters of unsaturated carboxylic acids is 1～200:1, is preferably 10～130:1
The temperature of reaction of step (3) is 65～95 ℃, preferably 80～90 ℃.
The reaction times of step (3) is 1～24 hour, preferably 2～5 hours.
The quality of polyethers raw material of step (1) of take is 1, and in step (3), the consumption of unsaturated carboxylic acid is 0.025～0.15.
Described radical polymerization initiator comprises azo-compound initiator, peroxide initiator and redox initiator.In step (3), described radical polymerization initiator is preferably persulphate, hydrogen peroxide or water-soluble azo initiator.In step (3), described radical polymerization initiator is ammonium persulphate more preferably, and consumption is 2%～45% of unsaturated carboxylic acid total mass in polyethers raw material, esters of unsaturated carboxylic acids and the step (3) in step (1), is preferably 10%～20%.
The quality of the polyethers raw material in step (1) of take is 1, and in step (3), the consumption of water is 0.5～2, is preferably 0.9～1.5.
In step (1), the number-average molecular weight of described polyethers is preferably 800～25000.
In step (1), described polyethers is preferably two blocks, three blocks or Tetrablock copolymer.
In step (1), described polyethers is preferably one or more with alcohol, amine, phenol, carboxylic acid, acid amides, resol, phenol-amine resin or polyethylene polyamine initiator gained polyethers.
In step (1), the preparation method of described polyethers raw material comprises: under the existence of catalyzer and initiator, and proceed step by step anionoid polymerization, every step polymerization is used alternatingly oxyethane or propylene oxide as polymerization single polymerization monomer.Described being used alternatingly refers to that continuous two-stage polymerization is used respectively different polymerization single polymerization monomers.
In the preparation method of polyethers, preferably in two steps, three steps or four steps carry out polyreaction, every step polymerization is used alternatingly oxidative ethane or propylene oxide as polymerization single polymerization monomer.
Described initiator is preferably one or more that use in alcohol, amine, phenol, carboxylic acid, acid amides, resol, phenol-amine resin and polyethylene polyamine.
Oxyethane, the general available following catalyst system of propylene oxide carry out polymerization.The anionoid polymerization of base catalysis, this class catalyzer has Na, K, Li, KOH, NaOH, and with the most use in production is KOH and NaOH; The cationoid polymerisation of lewis acid catalysis, this class catalyzer has BF
3, AlCl
3deng; Coordinated cationic polymerization, catalyzer is metal oxygen key compound and alkaline earth metal compound etc.The present invention can adopt above-mentioned three class catalyzer, is preferably alkali catalyst, alkali metal hydroxide more preferably, and more preferably KOH and/or NaOH, its consumption is 0.1～2% of oxyethane and propylene oxide total mass.
The emulsion splitter that the present invention also provides aforesaid method to prepare.
A breaking dehydrating method for crude oil, comprising: crude oil, water filling and above-mentioned emulsion splitter mixed, and breaking emulsion and dewatering under the effect of heat and/or electric field, the quality of crude oil of take is benchmark, emulsion splitter consumption is that 20～100ppm, water injection rate are crude quality 2～50%.
Emulsion splitter of the present invention can be used for the breaking emulsion and dewatering of hydrocarbon ils, is applicable to the breaking emulsion and dewatering of viscous crude, is specially adapted to the breaking emulsion and dewatering of high bituminous matter viscous crude.Emulsion splitter of the present invention can be used in the electric desalting process of crude oil.
Embodiment
Embodiment 1
In autoclave, add 10g methyl alcohol and 1g potassium hydroxide, logical nitrogen deoxygenation, is warming up to 130 ℃, drip 100g propylene oxide, when reaction pressure no longer reduces, be cooled to 110 ℃, drip 200 grams of oxyethane, insulation, until pressure no longer reduces, obtains two block polyether D1A.
In autoclave, add 15g nonylphenolic resin (molecular weight is 1090) and 0.9g potassium hydroxide, drip 36.2g propylene oxide, when reaction pressure no longer reduces, then drip 65.8g oxyethane, control 130 ℃ of temperature of reaction, pressure 2.3kg/cm
2, treat that reacting ethylene oxide is complete, at this temperature, add 72.5g propylene oxide, obtain block polyether D1B.
In autoclave, add 5g tetraethylene pentamine, 2.4g potassium hydroxide and 400g propylene oxide, nitrogen replacement 2～3 times, is warming up to 115 ℃, keep temperature until pressure is 0, continue to react after half an hour, be warming up to 130 ℃, drip 200g oxyethane, until pressure no longer reduces, obtain block polyether D1C.
Embodiment 2
In there-necked flask, once add D1A polyethers 100g, tosic acid 0.62g, Resorcinol 0.012g, stirring is warmed up to 105 ℃, slowly drips methyl methacrylate 5.8g, dropwises, in 105 ℃ of insulation reaction 4h, methyl alcohol is removed in underpressure distillation, obtains esterification products D2A solution.
In there-necked flask, add above-mentioned D2A esterification products 29.4g, deionized water 20ml, toxilic acid 2.6g, stirs and heats up.Ammonium persulphate 4.6g is dissolved in 15ml deionized water, respectively 1.6g vinylformic acid and ammonium persulfate aqueous solution is placed in to separating funnel, treat that still liquid is warmed up to 85 ℃, starts to drip vinylformic acid and initiator.Dropwise at 85～90 ℃ of insulation reaction 3h, obtain polymerisate D3A.
Embodiment 3
In there-necked flask, once add D1B polyethers 100g, tosic acid 0.9g, Resorcinol 0.0034g, stirring is warmed up to 105 ℃, slowly drips methyl methacrylate 1.18g, dropwises, in 105 ℃ of insulation reaction 4h, methyl alcohol is removed in underpressure distillation, obtains esterification products D2B solution.
In there-necked flask, add above-mentioned D2B esterification products 14g, deionized water 10ml, methylene-succinic acid 1.44g, stirs and heats up.Ammonium persulphate 2.4g is dissolved in 9ml deionized water, respectively 0.8g vinylformic acid and ammonium persulfate aqueous solution is placed in to separating funnel, treat that still liquid is warmed up to 85 ℃, starts to drip vinylformic acid and initiator.Dropwise at 85～90 ℃ of insulation reaction 3h, obtain polymerisate D3B.
Embodiment 4
In there-necked flask, once add D1C polyethers 100g, tosic acid 0.5g, Resorcinol 0.0012g, stirring is warmed up to 105 ℃, slowly drips methyl methacrylate 0.83g, dropwises, in 105 ℃ of insulation reaction 4h, methyl alcohol is removed in underpressure distillation, obtains esterification products D2C solution.
In there-necked flask, add above-mentioned D2C esterification products 58.6g, deionized water 41ml, acrylamide 1.72g, stirs and heats up.Ammonium persulphate 9.0g is dissolved in 28ml deionized water, respectively 1.43g vinylformic acid and ammonium persulfate aqueous solution is placed in to separating funnel, treat that still liquid is warmed up to 85 ℃, starts to drip vinylformic acid and initiator.Dropwise at 85～90 ℃ of insulation reaction 3h, obtain polymerisate D3C.
Comparative example 1
In there-necked flask, once add vinylformic acid 4.2g, D1A polyethers 50g, tosic acid 0.62g, Resorcinol 0.012g, toluene 60ml, loads onto water trap, stirs and is warmed up to 125～130 ℃, and back flow reaction 8h, obtains esterification products solution.
Get above-mentioned esterification products solution, add vinylformic acid 9.3g, benzoyl peroxide 3.1g, toluene 50ml, at N
2at environment and 85 ℃, reaction 8h, steams solvent and obtains polymerisate D4.
Comparative example 2
In there-necked flask, once add vinylformic acid 0.85g, D1B polyethers 100g, tosic acid 0.9g, Resorcinol 0.0034g, toluene 173ml, loads onto water trap, and back flow reaction 8h obtains esterification products solution.
Get above-mentioned esterification products solution, add vinylformic acid 4.3g, maleic anhydride 4.3g, benzoyl peroxide 3.0g, at N
2at environment and 85 ℃, reaction 8h, steams solvent and obtains polymerisate D5.
Embodiment 5
The dehydrating effect of evaluating emulsion splitter with the outer oil transportation of Tahe, oil property is in Table 1.During experiment, by emulsion splitter (consumption is 50ppm), water filling be preheating to the stock oil of 90～100 ℃ and fully mix in mixing tank, pour in cone-shaped glass desalter, adopt DPY-2 emulsion splitter competition instrument (Jiangyan City, Jiangsu analytical instrument factory) to carry out oily water separation, electric-force gradient 2000v/cm, 80 ℃ of temperature, the water yield that time recording separates.The dehydrating effect of emulsion splitter is in Table 2.As can be seen from the table, block polyether is after acrylic acid modified, and with conventional emulsion splitter TA1031 ratio, demulsification is improved to some extent; The acrylic acid modified polyethers that emulsion splitter of the present invention is more simple, demulsification significantly improves.In addition, bad according to the package stability of the synthetic demulsifier product of comparative example, layering after placing, and emulsion splitter D3A, D3B, D3C in the embodiment of the present invention, excellent storage stability, not stratified after placing.
The outer oil transportation character of table 1 Tahe
| Analyze component | Analytical data |
| 20 ℃ of density, kg/m 3 | 946.9 |
| 80 ℃ of viscosity, mm 2/s | 203.2 |
| 10% carbon residue, % (w) | 15.9 |
| Moisture, % (w) | 0.25 |
| Total acid value, mgKOH/g | 0.14 |
| Stable hydrocarbon, % (w) | 29.8 |
| Aromatic hydrocarbons, % (w) | 26.8 |
| Colloid, %(w) | 28.9 |
| Bituminous matter, % (w) | 14.5 |
The dehydrating effect of table 2 emulsion splitter
TA1031: take the ethylene oxide-propylene oxide block copolymer of phenol-amine resin as initiator gained
The package stability of table 3 synthetic polymer polyethers
| Polyether | Package stability |
| D4 | Layering |
| D5 | Layering |
| D3A | Not stratified |
| D3B | Not stratified |
| D3C | Not stratified |
Note: sintetics is at room temperature placed and within 1 month, observed stability.
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