CN1137247C - Polymer-type efficient demulsifier for emulsion of crude oil and its synthesizing process - Google Patents
Polymer-type efficient demulsifier for emulsion of crude oil and its synthesizing process Download PDFInfo
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- CN1137247C CN1137247C CNB011135433A CN01113543A CN1137247C CN 1137247 C CN1137247 C CN 1137247C CN B011135433 A CNB011135433 A CN B011135433A CN 01113543 A CN01113543 A CN 01113543A CN 1137247 C CN1137247 C CN 1137247C
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Abstract
The present invention relates to a high efficiency polymer-type demulsifier for crude oil emulsion and a synthesizing method thereof. The polymer-type demulsifier has the advantages of less consumption, wide range of use, favourable effect, quick water discharge speed and clear color of the dehydrated water. The demulsifier is synthesized from raw materials with the weight proportion: 50 to 90% of polyether, 5 to 40% of functional monomer which contains functional groups including -OH, -COOH and -NH2 and has double bonds, 0.3 to 8% of initiating agent, 0.3 to 3.0% of esterifying catalyst and the balance of benzene or an alcohol solvent. The synthesizing method comprises the steps that the polyether and the functional monomer, which contains functional groups including -OH, -COOH and -NH2 and has double bonds, react at the temperature of 90 to 160 DEG C under the functions of the esterifying catalyst; the functional monomer, which contains functional groups including -OH, -COOH and -NH2 and has double bonds, is led onto the polyether molecules, and then generate radical polymerization under the functions of the initiating agent at the temperature of 80 to 100 DEG C.
Description
The present invention is a kind of demulsifier for emulsion of crude oil and manufacture method, particularly a kind of polymer-type efficient demulsifier for emulsion of crude oil and synthetic method.
Before the crude oil transmission, the water in the emulsion of crude oil must be separated reducing to acceptable concentration, usually, this is undertaken by adding emulsion splitter.The composition of emulsion of crude oil depends on its source to a great extent, therefore, a large amount of different crude oils demulsifier for emulsion is widely used and obtains best demulsification, the emulsion splitter of domestic present use is simple polyoxyethylene poly-oxygen propylene aether emulsion splitter basically, or with cross-linking modified polyethers emulsion splitters such as isocyanic ester and phosphorus oxychloride, it is the kind difference of initiator, the emulsion splitter adaptability of this structure is relatively poor, the net effect of breakdown of emulsion is poor, need a large amount of screening operations, simultaneously composite its major issue that also becomes.As: what Chinese patent CN1037094A (1989), CN1074925A (1993) and CN1100735A (1995) were reported all is emulsion splitters of this type.Although Chinese patent CN1186710A (1998) report is the emulsion splitter of complete polymer form, amount, the price of acrylate is higher, so its cost is inevitable higher.Simultaneously, investigate according to us, its effect is very restricted, and is very big with breakdown of emulsion system relation.
Purpose of the present invention just provide a kind ofly have that consumption is few, use range is wide, effective, go out water speed is fast, deviate from water and the clear characteristics of water colour polymer-type efficient demulsifier for emulsion of crude oil and synthetic method thereof.
Polymer-type efficient demulsifier for emulsion of crude oil of the present invention, the raw material weight component of synthetic this emulsion splitter is a polyethers 50～90%, contain functional groups-OH ,-COOH and-NH
2And functional monomer 5-30%, initiator 0.3-5%, the esterifying catalyst 0.3-2.0% of two keys are arranged, and surplus is benzene class or alcoholic solvent.Described functional monomer is the mixture of vinylformic acid or acrylamide or acrylate or maleic anhydride or above 4 kinds of materials.Esterifying catalyst is hydrochloric acid or sulfuric acid or the phosphoric acid in the mineral acid.Perhaps be Witco 1298 Soft Acid or acidic anionic and the resin in the organic acid.Initiator is azo class or peroxide initiator, is azo two isonitrile and waits peroxide oil-soluble demulsifier and water soluble starters such as Potassium Persulphate and Ammonium Persulfate 98.5 such as azo class and benzoyl peroxide.
The synthetic method of polymer-type efficient demulsifier for emulsion of crude oil of the present invention be by polyethers and contain functional groups-OH ,-COOH and-NH
2And the functional monomer that two keys are arranged reacts in 90 ℃-160 ℃ under the esterifying catalyst effect, will contain-OH ,-COOH and-NH
2And the functional monomer that two keys are arranged is incorporated on the pfpe molecule, carries out Raolical polymerizable in 80 ℃-100 ℃ then under the initiator effect.
The invention has the advantages that the above-mentioned shortcoming that solves prior art, adopt polyethers and the substance reaction that contains two or more function group, carry out condensation polymerization or/and Raolical polymerizable then, obtain having the emulsion splitter kind that certain crosslinking structure molecular weight significantly increases, it is few that this emulsion splitter has a consumption, and use range is wide, effective, it is fast to go out water speed, deviates from advantages such as the water colour of water is clear, belongs to the demulsifier for emulsion of crude oil kind of a new generation.
Be exactly that the screening result of use of emulsion splitter in the different oil fields of China of utilizing the technology of the present invention to produce contrasts below.
Use 1: emulsion of crude oil source: Central Plains three factories: breakdown of emulsion temperature: 40 ℃: Water in oil amount: 20%; Sample volume: 50ml; Dosage 35PPM.The result is as follows: time (min) 5 10 15 30 45 60 remarks examples, 1 sample is deviate from the clear AP-221. of volume of water (ml) 6.0 8.0 8.5 9.0 9.0 9.0 water colour and is deviate from volume of water (ml) 0.5 1.0 1.5 1.5 2.0 2.0 sticking walls, and water colour is clear
Use 2: emulsion of crude oil source: Shengli Oil Field; Breakdown of emulsion temperature: 55 ℃; Water in oil amount: 30%; Sample volume: 50ml, dosage 50PPM.The result is as follows: time (min) 5 10 15 30 45 60 remarks examples, 1 sample is deviate from the clear AE-69-52 of volume of water (ml) 10.5 12.0 13.0 13.5 14.0 14.5 water colour and is deviate from volume of water (ml) 1.5 4.0 7.5 8.5 9.0 9.0 sticking walls, and water is muddy slightly
Use 3: emulsion of crude oil source: oil field, Nanyang: breakdown of emulsion temperature: 55 ℃; Water in oil amount: 80%; Sample volume: 50ml, dosage 15PPM.The result is as follows: time (min) 5 10 15 30 45 60 remarks examples, 1 sample is deviate from the clear TA-1031/SP169 of volume of water (ml) 32.0 35.0 39.0 39.5 39.5 39.5 water colour, and to deviate from volume of water (ml) 30.0 34.0 37.5 38.5 39.0 39.0 water muddy slightly
Embodiment of the present invention are as follows:
The used polyethers of the present invention can be existing polyether demulsification agent, as: do initiator with phenol amine and phenolic aldehyde and under the basic catalyst effect, carry out PO and poly-TA type, PFA type and the F type emulsion splitter that obtains of EO negatively charged ion open loop, be that initiator carries out two blocks and three block AE types and the AP type emulsion splitter that PO and EO anionic ring-opening polymerization obtain with the polyamines polyene under the basic catalyst effect, comprise simultaneously with propylene glycol, ethylene glycol, imidazoles, two shrink propylene glycol, stearyl alcohol and 2-amino-2-methylol-propylene glycol etc. contain-OH ,-NH
2Under the basic catalyst effect, carry out diblock or the multi-block polyether that PO and EO anionic ring-opening polymerization obtain with the initiator of-functional monomers such as COOH.The double-functional group that the present invention is used or the material of more function group comprise and containing-OH ,-NH
2With in-the functional monomers such as COOH one or several or and contain the material of unsaturated double-bond, they comprise: maleic anhydride, vinylcarbinol, vinylformic acid, acrylamide, Tetra hydro Phthalic anhydride and pyromellitic dianhydride etc., also comprise simultaneously some materials that can carry out transesterify, as: vinyl esters materials such as acrylate and vinyl-acetic ester.Used basic catalyst comprises basic metal and alkaline earth metal hydroxides such as KOH, NaOH, used an acidic catalyst comprises: mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, also comprise that simultaneously organic acids such as Witco 1298 Soft Acid, acidic anionic resin, used initiator comprise water soluble starters such as oil-soluble initiator such as Diisopropyl azodicarboxylate and Ammonium Persulfate 98.5.
The present invention is described further below in conjunction with specific embodiments.
1. the preparation of polyoxyethylene poly-oxygen propylene aether
In the autoclave that electric mixer, thermometer are housed, add the aqueous solution that 1 mole of 2-amino-2-methylol-propylene glycol and 10g potassium hydroxide and less water are made into, be warming up to 80 ℃, vacuumize, lead to nitrogen replacement 3 times, solution moisture in still and oxygen content are under the concentration of regulation, as: hundreds of PPM, then 130 ± 10 ℃ of temperature, pressure 4atm feeds 50 moles PO and 25 moles EO down, being polymerized to the still internal pressure is to be warming up to 150 ℃ behind the normal pressure, reacted 1 hour, blowing promptly gets desired polyethers then again.
2. polymer-type efficient demulsifier for emulsion of crude oil is synthetic
Embodiment 1: with the polyethers 1000g that obtains previously, vinylformic acid 300g, phosphatase 11 0g and solvent xylene 500g join in the reactor, be heated to 140-160 ℃ while stirring, kept this thermotonus 6 hours, promptly obtain acrylic acid polyester ether, in order to stop polymerizing acrylic acid, can add a little to benzene diethylstilbestrol inhibitor solution in reactor.After reaction is set finishes, temperature of reaction kettle is adjusted to 80-85 ℃, adds benzoyl peroxide 30g in this scheme, polyreaction promptly obtained desired efficient gather qi together type demulsifier for emulsion of crude oil 1840g in 12 hours.
Embodiment 2: with the polyethers 1500g that obtains previously, vinylformic acid 200g, Witco 1298 Soft Acid 10.0g and solvent xylene 600g join in the reactor, be heated to 140-160 while stirring, kept this thermotonus 6 hours, promptly obtain acrylic acid polyester ether,, can add a little the benzene diethylstilbestrol is hindered the pump agent solution in reactor in order to stop polymerizing acrylic acid.After reaction is set finishes, temperature is adjusted to 90-100 ℃, adds Diisopropyl azodicarboxylate 40g and acrylamide 150g in this reactor, polyreaction promptly obtained desired polymer-type efficient demulsifier for emulsion of crude oil 2500g in 10 hours.
Claims (7)
1, a kind of polymer-type efficient demulsifier for emulsion of crude oil is characterized in that the raw material weight component of synthetic this emulsion splitter is polyethers 50-90%, contain functional groups-OH ,-COOH and-NH
2And functional monomer 5-40%, initiator 0.3-8%, the esterifying catalyst 0.3-30% of two keys are arranged, and surplus is a solvent.
2, polymer-type efficient demulsifier for emulsion of crude oil according to claim 1 is characterized in that described functional monomer is the mixture of vinylformic acid or acrylamide or acrylate or maleic anhydride or above 4 kinds of materials.
3, polymer-type efficient demulsifier for emulsion of crude oil according to claim 1 and 2 is characterized in that esterifying catalyst is hydrochloric acid or sulfuric acid or the phosphoric acid in the mineral acid.
4 polymer-type efficient demulsifier for emulsion of crude oil according to claim 1 and 2 is characterized in that esterifying catalyst is Witco 1298 Soft Acid or the acidic anionic resin in the organic acid;
5, polymer-type efficient demulsifier for emulsion of crude oil according to claim 1 and 2 is characterized in that initiator is azo class or peroxide initiator.
6, polymer-type efficient demulsifier for emulsion of crude oil according to claim 5 is characterized in that initiator is Diisopropyl azodicarboxylate and benzoyl peroxide oil-soluble initiator and Potassium Persulphate and Ammonium Persulfate 98.5 water soluble starter.
7, a kind of synthetic method of polymer-type efficient demulsifier for emulsion of crude oil, it is characterized in that the synthetic method for by polyethers and contain functional groups-OH ,-COOH and-NH
2And the functional monomer that two keys are arranged reacts in 90 ℃-160 ℃ under the esterifying catalyst effect, will contain-OH ,-COOH and-NH
2And the functional monomer that two keys are arranged is incorporated on the pfpe molecule, carries out Raolical polymerizable in 80-100 ℃ then under the initiator effect.
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| CNB011135433A CN1137247C (en) | 2001-04-18 | 2001-04-18 | Polymer-type efficient demulsifier for emulsion of crude oil and its synthesizing process |
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| CNB011135433A CN1137247C (en) | 2001-04-18 | 2001-04-18 | Polymer-type efficient demulsifier for emulsion of crude oil and its synthesizing process |
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| CN1317544A CN1317544A (en) | 2001-10-17 |
| CN1137247C true CN1137247C (en) | 2004-02-04 |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382675A (en) * | 2011-08-03 | 2012-03-21 | 西安长庆化工集团有限公司 | Preparation method of polymer-containing emulsified crude oil emulsion breaker |
| CN103570862B (en) * | 2012-07-20 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of emulsion splitter and its preparation method and application |
| CN102786639A (en) * | 2012-08-27 | 2012-11-21 | 句容宁武高新技术发展有限公司 | Preparation method of high performance demulsifier |
| CN102796552A (en) * | 2012-08-31 | 2012-11-28 | 句容宁武高新技术发展有限公司 | Preparation method of high-performance emulsion breaker |
| CN103665273B (en) * | 2012-09-03 | 2016-03-23 | 中国石油化工股份有限公司 | A kind of emulsion splitter and its preparation method and application |
| CN103484149A (en) * | 2013-10-14 | 2014-01-01 | 江苏大学 | Self-crosslinking polyether demulsifier |
| CN103525455A (en) * | 2013-10-14 | 2014-01-22 | 江苏大学 | Cationic polymer modified crude oil demulsifying agent |
| CN103554512A (en) * | 2013-10-14 | 2014-02-05 | 句容宁武高新技术发展有限公司 | Preparation method of self-crosslinking polyether demulsifier |
| CN103484150B (en) * | 2013-10-14 | 2015-05-13 | 江苏大学 | Polyion-liquid-modified crude oil demulsifier |
| CN103554513A (en) * | 2013-10-14 | 2014-02-05 | 句容宁武高新技术发展有限公司 | Synthetic method of poly(ionic liquid) modified emulsifier for crude oil |
| CN103484151B (en) * | 2013-10-14 | 2015-05-13 | 句容宁武高新技术发展有限公司 | Synthesis method of cationic-polymer-modified crude oil demulsifier |
| CN104194822B (en) * | 2014-09-04 | 2015-11-18 | 中国海洋石油总公司 | A kind of cross-linking type nonionic polyoxyalkylene crude oil demulsifier and preparation method thereof |
| CN105238439B (en) * | 2015-11-09 | 2017-07-07 | 淄博德信联邦化学工业有限公司 | The preparation method of compound oil field demulsifier |
| CN107601797B (en) * | 2017-11-03 | 2020-12-25 | 北京博惠通科技发展有限公司 | Oil sludge treating agent and oil sludge treating method |
| CN111057577B (en) * | 2018-10-17 | 2021-09-21 | 中国石油化工股份有限公司 | Acrylate copolymer and preparation method thereof, water-in-oil emulsion demulsifier and application thereof |
| CN110628012A (en) * | 2019-09-24 | 2019-12-31 | 天津大学 | Novel demulsifier |
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