CN103086472A - High-temperature sewage treatment reverse demulsifier of ultra-heavy oil - Google Patents
High-temperature sewage treatment reverse demulsifier of ultra-heavy oil Download PDFInfo
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- CN103086472A CN103086472A CN2012105910343A CN201210591034A CN103086472A CN 103086472 A CN103086472 A CN 103086472A CN 2012105910343 A CN2012105910343 A CN 2012105910343A CN 201210591034 A CN201210591034 A CN 201210591034A CN 103086472 A CN103086472 A CN 103086472A
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- polyamide
- amide
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- polyether
- phase emulsifier
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- 239000010865 sewage Substances 0.000 title claims abstract description 21
- 239000000295 fuel oil Substances 0.000 title claims abstract description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 39
- 229920000570 polyether Polymers 0.000 claims abstract description 33
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 20
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 150000001768 cations Chemical class 0.000 claims description 14
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229940059260 amidate Drugs 0.000 claims description 7
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 claims description 7
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- -1 polyoxyethylene propylene oxide Polymers 0.000 claims description 6
- 241000555268 Dendroides Species 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 abstract 4
- 229910015900 BF3 Inorganic materials 0.000 abstract 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract 1
- 238000007112 amidation reaction Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 239000000412 dendrimer Substances 0.000 abstract 1
- 229920000736 dendritic polymer Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920000289 Polyquaternium Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000019600 saltiness Nutrition 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
本发明的一种超稠油高温污水处理反相破乳剂，先以丙三醇、环氧氯丙烷为原料，三氟化硼乙醚液为引发剂制得氯代聚醚，并将氯代聚醚和三甲胺水溶液在高压反应釜中制得阳离子聚醚；再以甲醇作为溶剂，三氟化硼乙醚为引发剂，乙二胺、丙烯酸甲酯等重复交替进行Michael加成反应和酰胺化反应，制备得到3.0代树枝状大分子聚酰胺-胺；然后以聚乙二醇和聚丙二醇为原料，氢氧化钾粉末为催化剂，当聚乙二醇反应一段时间后加入聚丙二醇制得非离子聚醚；最后以3.0代聚酰胺-胺为交联剂，阳离子聚醚与非离子聚醚复合得到改性复合型--聚酰胺-胺-聚醚型的超稠油高温污水处理反相破乳剂。A kind of anti-phase demulsifier for ultra-heavy oil high-temperature sewage treatment of the present invention first uses glycerol and epichlorohydrin as raw materials, boron trifluoride ether solution as initiator to prepare chlorinated polyether, and chlorinated polyether Ether and trimethylamine aqueous solution are prepared in a high-pressure reactor to prepare cationic polyether; then methanol is used as a solvent, boron trifluoride ether is used as an initiator, and ethylenediamine, methyl acrylate, etc. are repeatedly and alternately carried out Michael addition reaction and amidation reaction , to prepare 3.0 generation dendrimer polyamide-amine; then polyethylene glycol and polypropylene glycol are used as raw materials, potassium hydroxide powder is used as catalyst, and polypropylene glycol is added after polyethylene glycol reacts for a period of time to obtain nonionic polyether ; Finally, the 3.0 generation polyamide-amine is used as the cross-linking agent, and the cationic polyether is compounded with the non-ionic polyether to obtain a modified composite type - polyamide-amine-polyether type super heavy oil high temperature sewage treatment reverse demulsifier.
Description
Technical field
The present invention relates to the technical field of petroleum chemistry treatment agent, the reverse-phase emulsifier that provides is particularly useful for the processing of super Heavy Oil High Temperature sewage.
Background technology
The key character that super viscous crude is different from other class petroleum resources is that its bituminous matter, gum level are very high, cause that its viscosity is high, density is large, super heavy oil recovery adopts the steam thermal recovery more, high-temperature produced liquid have a following characteristic: (1) super viscous crude density is high, because resin and asphalt content is high, cause the density variation of crude oil and water little, the mean density of viscous crude is 900kg/m
3, the density of special super viscous crude is at 990kg/m
3Above; (2) super viscous crude Produced Liquid has more impurity, and oil-contg and solid suspension content be up to more than 10000mg/L, and contains the Multiple components such as petroleum-type, suspended solid, dispersed oil and oil slick, oil in water emulsion and chemical agent; (3) have natural emulsified character due to colloid and pitch, the oil droplet cohesion is added to the difficulties, and adds to the difficulties for the breakdown of emulsion of super viscous crude Produced Liquid, and emulsification is serious; (4) have larger viscosity, particularly more remarkable when water temperature is low; (5) water temperature is high, often temperature will be brought up to more than 90 ℃ in order to reduce viscosity of crude on stream; (6) contain a large amount of positively charged ion (Na in super viscous crude Produced Liquid
+, Ca
2+Deng) and negatively charged ion (Cl
-, SO
4 2-Deng), they can affect surge capability, saltiness and the fouling tendency of viscous crude Produced Liquid; In addition, during sedimentation, the chemical agents such as the emulsion splitter that uses can remain in sewage super viscous crude Produced Liquid in a large number in dehydration, and the emulsion's stability that makes sewage form is extremely strong, are one of the most unmanageable oil extraction waste waters.
Patent for reverse-phase emulsifier discloses: the U.S. has announced a kind of quaternary ammonium salt reverse-phase emulsifier (US387017); The U.S. has announced a kind of allylic reverse-phase emulsifier (US4614593); European publication a kind of amine macromolecular compound emulsion splitter (EP0331323A2) that is applicable to crude oil development; China has announced a kind of reverse-phase emulsifier and preparation method thereof (CN102559246A), namely gets described reverse-phase emulsifier for cationic polyamide-amine, Hydrin quaternary ammonium salt, polyacrylamide oxy-ethyl-trimethyl salmiac and water mix.China has announced a kind of preparation method (CN101357992) of stellate poly quaternary ammonium salt high efficient reverse-phase emulsifier, first make linear polyquaternium with the organic amine such as secondary amine, tertiary amine and epoxy chloropropane ring-opening polymerization, take polyamide-amide as linking agent, finally make the stellate poly quaternary ammonium salt reverse-phase emulsifier again.China has also announced a kind of highly efficient anti-phase emulsion breaker for thick oil pollution water processing (CN1966138), with propylene glycol as initiator, under the effect of catalyzer, carry out propoxylation reaction, then carry out addition polymerization with oxyethane, with nonyl phenol as initiator, under the effect of catalyzer, generate nonyl phenol ethoxylate with reacting ethylene oxide, then carry out addition polymerization with propylene oxide, generate alkylphenol polyoxyethylene; Mixture and the vinylformic acid of propylene glycol polyethers and alkylphenol polyoxyethylene are carried out esterification under acidic conditions, carry out radical polymerization under the effect of initiator, generate carboxylate; Carry out esterification with toxilic acid more partially end-blocked, generate acrylic acid modified high molecular weight demulsifier.
The reverse-phase emulsifier kind is more at present, has stronger specific aim, mainly contain mineral-type macromolecular compound and organic cationic polymers, but when being applied to the rp demulsification of super viscous crude Produced Liquid, effect is undesirable, complexity day by day along with super Heavy Oil High Temperature sewage quality, high temperature sewage changes O/W type or W/O/W type into by the w/o type of initial stage of development, oil-water emulsion stability is extremely strong, therefore traditional reverse-phase emulsifier has been difficult to meet the demands, and the exploitation of the super Heavy Oil High Temperature Produced Liquid reverse-phase emulsifier of high temperature resistant, excellent performance seems particularly urgent.
The present invention carries out copolymerization with polyamide-amide and polyethers and non-ionic polyalcohol and obtains new modified reverse-phase emulsifier, belong to water miscible polymkeric substance, water external emulsion to super Heavy Oil High Temperature sewage has excellent demulsification, with performances such as electrical neutralization, absorption, bridge formations, add 10-30ppm and can effectively remove the pollutents such as oil in high oily(waste)water, suspended substance.
Summary of the invention
The object of the invention is to: the super Heavy Oil High Temperature sewage disposal high efficient reverse-phase emulsifier that provides, can efficiently process super Heavy Oil High Temperature sewage, have oily water separation speed fast, the beneficial effect of the universality of raising product and the economic benefit of product.
The object of the present invention is achieved like this: a kind of super Heavy Oil High Temperature sewage disposal reverse-phase emulsifier, the modified composite reverse-phase emulsifier that obtains is take cation polyether and nonionic polyoxyalkylene as raw material, take 3.0G dendroid polyamide-amide as linking agent, and implementation step is as follows:
Wherein cation polyether is synthetic:
The glycerol that adds 0.020-0.030mol in the four-hole boiling flask that agitator, prolong, thermometer are housed, then add the 2.10-2.17g boron trifluoride diethyl etherate, under agitation temperature control 45-55 ℃, slowly drip again epoxy chloropropane 38-42g, time for adding 4-6min dropwises, and is warming up to 75 ℃, reaction 5-7h gets the thick terminal hydroxy group chloro polyethers of brown; With 90-110g terminal hydroxy group chloro polyethers and 182-202g trimethylamine aqueous solution, be placed in clean reactor, pass into the nitrogen excluding air, temperature control 70-80 ℃, reaction 4-6h continues to be warming up to 120-130 ℃, reaction 6-8h gets the water miscible cation polyether of brown; Wherein the ratio of quality and the number of copies of epoxy chloropropane, glycerol, Trimethylamine 99 is 40-60:1:40-60, and the consumption of initiator boron trifluoride diethyl etherate liquid is 1% of epoxy chloropropane;
Wherein 3.0G PAMAM's is synthetic:
1) the 0.5G polyamide-amide is synthetic: under the protection of nitrogen, add quadrol 30.6g, methyl alcohol 96.2g in the four-hole boiling flask that stirring rod, thermometer, prolong are housed, after being cooled to 0 ℃ with ice-water bath, slowly drip methyl acrylate 174.0g, stir lower temperature control 22-27 ℃, continue reaction 22-26h, the weak yellow liquid that obtains, carry out underpressure distillation under 45 ℃ of conditions, obtain flaxen 0.5G polyamide-amide product;
2) the 1.0G polyamide-amide is synthetic: with methyl alcohol 120g dissolving 1.0G polyamide-amide 270g, join in four-hole boiling flask, after ice-water bath is cooled to 0 ℃, slowly drip quadrol, stir lower temperature control 23-28 ℃, time for adding 1-1.5h, dropwise and continue reaction 24h, the weak yellow liquid that obtains carries out underpressure distillation under 70 ℃ of conditions, obtain faint yellow 1.0G polyamide-amide product;
3) reverse-phase emulsifier: proceed the Michael addition reaction with above-mentioned 1.0G polyamide-amide, namely get the 1.5G polyamide-amide, then carry out amidate action, namely get the 2.0G polyamide-amide, carry out successively Michael addition reaction and amidate action, namely obtain the polyamide-amide of corresponding algebraically;
Wherein nonionic polyoxyalkylene is synthetic:
Add 90-110g potassium hydroxide powder and 900-1100ml methylene dichloride in there-necked flask, mix and blend under room temperature, then drip 600-polyoxyethylene glycol 230-270g, the potassium hydroxide powder that adds respectively 4-6g when 1.0h, 2.0h, 3.0h, wherein add the 20g polypropylene glycol in the centre that adds the potassium hydroxide powder, continue to obtain crude product after reaction 20h, after methylene dichloride is evaporated completely, toluene 400-500ml dissolving with heating, get the potassium hydroxide precipitation after standing, toluene 400-500ml with heating dissolves once again, obtains the polyoxyethylene propylene oxide;
Wherein the modified composite reverse-phase emulsifier is synthetic: be in the aqueous solution of 800-1200g in gross weight, add successively the dendroid polyamide-amide 150-400g in cation polyether 100-250g, 3.0 generations, nonionic polyoxyalkylene 50-100g; Stir 2-3h under 35-45 ℃, get the modified composite reverse-phase emulsifier, be super Heavy Oil High Temperature sewage disposal reverse-phase emulsifier.
Described reverse-phase emulsifier adopts the super Heavy Oil High Temperature sewage of this product treatment, and its oleaginousness drops to below 10mg/L from 6250mg/L.
Effect of the present invention and mechanism: the synthesis mechanism of multichain section cation polyether-glycerol chloro polyethers: as initiator, boron trifluoride diethyl etherate liquid is initiator with glycerol, causes epoxy chloropropane and carries out the positively charged ion ring-opening polymerization, generates terminal hydroxy group chloro polyethers; Active chlorine atom in terminal hydroxy group chloro polyethers and Trimethylamine 99 carry out the alkylated reaction of amine, generate the polycation polyethers with positive charge.The synthesis mechanism of polyamide-amide: hocket Michael addition and amidate action can obtain for 1.5 generations, 2.0 generations, 2.5 generations, 3.0 generation PAMAM.
The method of the reverse-phase emulsifier of the present invention preparation comprises the synthetic of cation polyether, 3.0 PAMAMs synthetic, nonionic polyoxyalkylene synthetic, polyamide-amide-polyether-type--modified composite reverse-phase emulsifier synthetic, its technological line is simple, reaction conditions is gentle, dewatering speed is fast, and breakdown of emulsion efficient is high, produces practical function splendid, the product innovation that provides, reduce production cost, also made demonstration for enterprise energy-saving and cost-reducing, shown technical progress.
Embodiment
The present invention is described further in conjunction with the embodiments.
Embodiment
1) cation polyether is synthetic:
Be equipped with agitator, prolong, thermometer four-hole boiling flask in add the glycerol of 0.025mol as initiator, then add 2.13g (being about 1%) boron trifluoride diethyl etherate liquid, temperature control is 50 ℃ under agitation condition, slowly drip epoxy chloropropane, time for adding 5min, be warming up to 75 ℃ of reaction 6h after complete, obtain the thick terminal hydroxy group chloro polyethers of brown; 100g terminal hydroxy group chloro polyethers and 191.3g trimethylamine aqueous solution (amino and chlorine atom equivalent) are placed in clean reactor, pass into the nitrogen excluding air, 75 ℃ of temperature controls, reaction 5h, continue to be warmed up to 125 ℃, reaction 7h obtains the water miscible cation polyether of brown; Wherein the ratio of quality and the number of copies of epoxy chloropropane, glycerol, Trimethylamine 99 is 40:1:40 or 60:1:60, epoxy chloropropane and Trimethylamine 99 equivalent, and take boron trifluoride diethyl etherate liquid as initiator, its consumption is 1% of epoxy chloropropane.
2) 3.0GPAMAM's is synthetic
(1) the 0.5G polyamide-amide is synthetic: under the protection of nitrogen; add quadrol 30.6g, methyl alcohol 96.2g in the four-hole boiling flask with stirring rod, thermometer, prolong; be cooled to 0 ℃ with ice-water bath; slowly drip methyl acrylate; stir 25 ℃ of lower temperature controls, the complete continuation reaction of time for adding 1h 24h, the weak yellow liquid that obtains; carry out underpressure distillation under 45 ℃ of conditions, namely obtain the light yellow product of 0.5G polyamide-amide.
(2) the 1.0G polyamide-amide is synthetic: the 1.0G polyamide-amide of separating with dissolve with methanol, join in four-hole boiling flask, ice-water bath is cooled to 0 ℃, slowly drip quadrol, stir 25 ℃ of lower temperature controls, time for adding 1-1.5h continues reaction 24h, the weak yellow liquid that obtains, carry out underpressure distillation under 70 ℃ of conditions, namely obtain the light yellow product of 1.0G polyamide-amide.
Reverse-phase emulsifier (3) is proceeded the Michael addition reaction with 1.0G polyamide-amide obtained above, namely can obtain the 1.5G polyamide-amide, then carry out amidate action, namely obtain the 2.0G polyamide-amide, carry out successively Michael addition reaction and amidate action, namely obtain the polyamide-amide of corresponding algebraically.
3) nonionic polyoxyalkylene is synthetic
Add 100g potassium hydroxide powder and 1000ml methylene dichloride in there-necked flask, mix and blend under room temperature, then drip 250g polyoxyethylene glycol-600, the potassium hydroxide powder that adds respectively 5g when being 1.0h, 2.0h, 3.0h, and drip the 20g polypropylene glycol when 2.0h, continue to obtain crude product after reaction 20h, after methylene dichloride is evaporated completely, toluene 400-500ml dissolving with heat, the standing unreacted potassium hydroxide precipitation of removing, the toluene 400-500ml dissolution precipitation of reusable heat once obtains the product of polyoxyethylene propylene oxide.
4) the modified composite reverse-phase emulsifier is synthetic
Cation polyether is mixed with nonionic polyoxyalkylene, 3.0G polyamide-amide is linking agent, be in the aqueous solution of 1000g in gross weight, cation polyether be 100 or 250g, the dendroid polyamide-amide in 3.0 generations be 150 or 400g, nonionic polyoxyalkylene is 50 or 100g; Stir 2h under 40 ℃, obtain final product modified composite reverse-phase emulsifier, be i.e. super Heavy Oil High Temperature sewage disposal reverse-phase emulsifier.
Reverse-phase emulsifier of the present invention is the synthesis type medicament, and at 85 ℃, pH:7.0 or 8.0, dosage are under the condition of 30mg/L, the oleaginousness that surpasses Heavy Oil High Temperature sewage can be dropped to below 10mg/L from 6249.3mg/L, and evaluation result sees the following form:
Reverse-phase emulsifier of the present invention possesses very strong close electric charge ability, is enough to the negative charge that the balance emulsifying agent forms; Very strong surfactivity is arranged, can destroy the interfacial energy of milk sap, oil removal rate is greater than 98%; This reverse-phase emulsifier is not stratified, without caking, machinery-free impurity, good water solubility, have oily water separation speed soon, low characteristics of oleaginousness in water.
The present invention obtains the modified composite reverse-phase emulsifier, and namely super Heavy Oil High Temperature sewage disposal reverse-phase emulsifier product meets company standard.
The manufacturer of the glycerol that the present invention selects is Shanghai auspicious Chemicals of the present company limited; Boron trifluoride diethyl etherate manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group; Epoxy chloropropane manufacturer is Qilu Petrochemical Company; Terminal hydroxy group chloro polyethers is self-control; Trimethylamine 99 manufacturer is the poly-Feng Huagong of Changzhou company limited; Potassium hydroxide powder production producer is the Jinan vast and boundless chemical industry of gold company limited; The manufacturer of polypropylene glycol is Jiangsu Hai'an Petrochemical Plant.
Claims (3)
1. super Heavy Oil High Temperature sewage disposal reverse-phase emulsifier is characterized in that: the modified composite reverse-phase emulsifier that obtains is take cation polyether and nonionic polyoxyalkylene as raw material, take 3.0G dendroid polyamide-amide as linking agent, and implementation step is as follows:
Wherein cation polyether is synthetic:
The glycerol that adds 0.020-0.030mol in the four-hole boiling flask that agitator, prolong, thermometer are housed, then add 2.10-2.17 g boron trifluoride diethyl etherate, under agitation temperature control 45-55 ℃, slowly drip again epoxy chloropropane 38-42g, time for adding 4-6min dropwises, and is warming up to 75 ℃, reaction 5-7h gets the thick terminal hydroxy group chloro polyethers of brown; With 90-110g terminal hydroxy group chloro polyethers and 182-202g trimethylamine aqueous solution, be placed in clean reactor, pass into the nitrogen excluding air, temperature control 70-80 ℃, reaction 4-6h continues to be warming up to 120-130 ℃, reaction 6-8h gets the water miscible cation polyether of brown; Wherein the ratio of quality and the number of copies of epoxy chloropropane, glycerol, Trimethylamine 99 is 40-60:1:40-60, and the consumption of initiator boron trifluoride diethyl etherate liquid is 1% of epoxy chloropropane;
Wherein 3.0G PAMAM's is synthetic:
1) the 0.5G polyamide-amide is synthetic: under the protection of nitrogen, add quadrol 30.6g, methyl alcohol 96.2g in the four-hole boiling flask that stirring rod, thermometer, prolong are housed, after being cooled to 0 ℃ with ice-water bath, slowly drip methyl acrylate 174.0g, stir lower temperature control 22-27 ℃, continue reaction 22-26h, the weak yellow liquid that obtains, carry out underpressure distillation under 45 ℃ of conditions, obtain flaxen 0.5G polyamide-amide product;
2) the 1.0G polyamide-amide is synthetic: with methyl alcohol 120g dissolving 1.0G polyamide-amide 270g, join in four-hole boiling flask, after ice-water bath is cooled to 0 ℃, slowly drip quadrol, stir lower temperature control 23-28 ℃, time for adding 1-1.5h, dropwise and continue reaction 24h, the weak yellow liquid that obtains carries out underpressure distillation under 70 ℃ of conditions, obtain faint yellow 1.0G polyamide-amide product;
3) reverse-phase emulsifier: proceed the Michael addition reaction with above-mentioned 1.0G polyamide-amide, namely get the 1.5G polyamide-amide, then carry out amidate action, namely get the 2.0G polyamide-amide, carry out successively Michael addition reaction and amidate action, namely obtain the polyamide-amide of corresponding algebraically;
Wherein nonionic polyoxyalkylene is synthetic:
Add 90-110g potassium hydroxide powder and 900-1100ml methylene dichloride in there-necked flask, mix and blend under room temperature, then drip 600-polyoxyethylene glycol 230-270g, the potassium hydroxide powder that adds respectively 4-6g when 1.0h, 2.0h, 3.0h, wherein add the 20g polypropylene glycol in the centre that adds the potassium hydroxide powder, continue to obtain crude product after reaction 20h, after methylene dichloride is evaporated completely, toluene 400-500ml dissolving with heating, get the potassium hydroxide precipitation after standing, toluene 400-500ml with heating dissolves once again, obtains the polyoxyethylene propylene oxide;
Wherein the modified composite reverse-phase emulsifier is synthetic: be in the aqueous solution of 800-1200g in gross weight, add successively the dendroid polyamide-amide 150-400g in cation polyether 100-250g, 3.0 generations, nonionic polyoxyalkylene 50-100g; Stir 2-3h under 35-45 ℃, get the modified composite reverse-phase emulsifier, be super Heavy Oil High Temperature sewage disposal reverse-phase emulsifier.
2. according to the described reverse-phase emulsifier of right 1, it is characterized in that: adopt the super Heavy Oil High Temperature sewage of this product treatment, its oleaginousness drops to below 10mg/L from 6250mg/L.
3. according to the described reverse-phase emulsifier of right 1, it is characterized in that: the raw material of selecting is the commercially available prod.
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