CN102373077B - Functional demulsifier for extra-thick oil and preparation and application thereof - Google Patents
Functional demulsifier for extra-thick oil and preparation and application thereof Download PDFInfo
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- CN102373077B CN102373077B CN201010262276.9A CN201010262276A CN102373077B CN 102373077 B CN102373077 B CN 102373077B CN 201010262276 A CN201010262276 A CN 201010262276A CN 102373077 B CN102373077 B CN 102373077B
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Abstract
The invention relates to a functional demulsifier for extra-thick oil, a preparation method and an application thereof; the composite material comprises the following components in percentage by mass: polyethylene polyamine polyoxypropylene polyoxyethylene ether: 10-15%; phenol resin polyoxypropylene polyoxyethylene ether: 30-40%; clear water type demulsifier: 10-15%; organic small molecular auxiliary agent: 5-10%; solid particle surface modifier: 5-10%; solvent: the balance; the invention utilizes the synergistic action among the demulsifiers to crosslink and compound various demulsifiers, and adds the functional auxiliary agent, thereby effectively improving the dehydration effect of the extra-thick oil, reducing the oil content of the dehydrated sewage and achieving the output standard.
Description
Technical field
The present invention relates to a kind of oily water separation emulsion splitter containing Saudi Arabia viscous crude formula and preparation and the application of viscosity more than 10000mPa.s that be applicable to.
Background technology
Emulsion splitter is the larger a kind of chemical of usage quantity in petroleum industry, is mainly used in oil field surface production and the defeated process of collection.Special viscous crude has the features such as high-density, high viscosity, high bituminous matter and gum level, and bituminous matter and colloid are the natural emulsifying agents of crude oil, are the stable major reasons of crude oil emulsion; Meanwhile, in viscous oil recovery process, various oil recovery auxiliary agents, profit are processed chemical agent Circulation in whole system of use, and the oil-water emulsion characteristic of Produced Liquid is increasingly sophisticated, and chemical property also has a very large change.From Produced Liquid, watch, be by two types of the O/W milk sap of a small amount of W/O milk sap and deep yellow substantially and deposit or more complicated multiple emulsion, in Produced Liquid, profit middle layer obviously increases.All of these factors taken together has caused viscous crude Produced Liquid stability strong, oily water separation difficulty, and in the crude oil water containing after separation and sewage, oil-containing is not up to standard, to field produces, brings great effect.Because viscous crude water-content exceeds standard, cause in crude oil salts contg and metal content also not up to standard, bring very large difficulty to refinery crude oil upgrading.Therefore, the special viscous oil emulsion high oily(waste)water problem that breaking emulsion and dewatering problem and oil water separation process produce under high aqueous conditions becomes each oil field and a refinery difficult problem urgently to be resolved hurrily.
At present, thick oil emulsion breaking is mainly adopted to thermo-chemical demulsification and two kinds of methods of electrochemistry breakdown of emulsion both at home and abroad.Thermo-chemical demulsification is in crude oil emulsion, to add a certain amount of emulsion splitter, in order to change the interfacial property of milk sap, reaches the object of oily water separation.But because viscous crude density is large, active component content high, viscous oil emulsion is very stable.Cause the velocity of diffusion of emulsion splitter slow, water droplet coalescence difficulty.Make de-emulsification speed slow, emulsion splitter usage quantity is large, breakdown of emulsion temperature is high, demulsification is poor.Viscous crude water ratio after oily water separation is high.Electrochemistry breakdown of emulsion is to carry out breaking emulsion and dewatering under the acting in conjunction of electric field and a small amount of emulsion splitter.The method has advantages of that breakdown of emulsion efficiency is high, but equipment investment is high, water must be dropped to a certain degree to (being generally first to carry out thermo-chemical demulsification), otherwise cannot obtain stable electric field before stock oil access arrangement.Therefore, emulsion splitter has very consequence in viscous oil emulsion breakdown of emulsion process.
Summary of the invention
The object of this invention is to provide the functional emulsion splitter of a kind of special viscous crude (viscosity is more than 10000mPa.s) and preparation and application.This functional emulsion splitter utilizes the synergy between emulsion splitter, multiple emulsion splitter is cross-linked composite, and adds functional aid, effectively raises the dehydrating effect of Gao Han Saudi Arabia viscous crude, has reduced the oil-contg of deviating from sewage.
The technical scheme that the functional emulsion splitter of a kind of special viscous crude of the present invention is taked is:
This functional emulsion splitter is comprised of following ingredients by mass percentage:
Polyethylene polyamine polyoxyethylene polyoxypropylene ether (industrial goods): 10～15%;
Resol polyoxyethylene polyoxypropylene ether (industrial goods): 30～40%;
Clear water type emulsion splitter (industrial goods): 10～15%;
Organic molecule auxiliary agent (industrial goods): 5～10%;
Solid particles surface properties-correcting agent (self-control): 5～10%;
Solvent (industrial goods): surplus.
Described organic molecule auxiliary agent is methyl alcohol, ethanol or Diethylene Glycol butyl ether.
Described solvent is benzene, toluene, ethanol, methyl alcohol or water.
Described clear water type emulsion splitter is for using the Soxylat A 25-7 (production of Binzhou chemical plant) that glycerol (glycerine) is initiator.
Described solid particles surface properties-correcting agent is cationic Gemini surfactants or is a kind of anionic type Gemini surface active agent.The preparation method of cationic Gemini surfactants: at 40～45 ℃, distilled water and aqueous hydrochloric acid to adding in ground three-necked bottle, then drip alkyl N, N-dimethyl tertiary amine, preparation Amine from Tertiary Amine Hydrochloride.By three-necked bottle heating, make a bottle interior mixture boiling reflux.In said mixture, add n-propyl alcohol.In said mixture, drip epoxy chloropropane, maintain boiling.In said mixture, drip alkyl N, N-dimethyl tertiary amine, reaction 6h.Crude product is carried out to the dry desciccate of reduced vacuum.
The preparation method of anionic type Gemini surface active agent: nonyl phenol is placed in to the four-hole boiling flask that mechanical stirring and reflux condensing tube and thermometer are housed, add cetyl trimethylammonium bromide and sodium hydroxide solution, stirring and be heated to 70 ℃, again by 1,4-dibromobutane adds reaction system, continue to be heated to 90 ℃, reaction 2h, stopped reaction.System is cooling, with ether, extract, after wash with water, then use anhydrous magnesium sulfate drying, filter, then be spin-dried for solvent with Rotary Evaporators, obtain bis ether.Bis ether is placed in to the there-necked flask that hydrogen chloride absorption device is housed, and adds anhydrous methylene chloride, magnetic agitation.Chlorsulfonic acid is dissolved in to anhydrous methylene chloride, at room temperature in 1h, splashes into reaction system, continue reaction 4h, stopped reaction.Ethanolic soln neutralization with sodium hydroxide, is spin-dried for solvent, with dehydrated alcohol, it is carried out to recrystallization, obtains white solid and is product.
The production method of this functional special thick oil demulsifier is:
A, major equipment: the enamel reaction still with the 2000L of stirring, heating, cooling and vacuum system;
B, production method: first, polyethylene polyamine polyoxyethylene polyoxypropylene ether, resol polyoxyethylene polyoxypropylene ether, three kinds of emulsion splitters of clear water type emulsion splitter are joined to enamel reaction still in proportion, slowly be warming up to 50～80 ℃, stir on intensification limit, limit, add benzene, methyl alcohol simultaneously, continue to stir after 30～60 minutes, stop heating, cooling while stirring, add in proportion solid particles surface properties-correcting agent and water, be cooled to room temperature (25 ℃), stir 30 minutes, discharging, obtains functional thick oil demulsifier.
Beneficial effect of the present invention and advantage are:
1, functional emulsion splitter of the present invention utilizes the synergy between emulsion splitter, multiple emulsion splitter is cross-linked composite, and add functional aid, effectively raise the dehydrating effect of Gao Han Saudi Arabia viscous crude, reduce the oil-contg of deviating from sewage, be specially adapted to the breaking emulsion and dewatering of Gao Han Saudi Arabia viscous crude Produced Liquid.
2, in the present invention, take the polyethers emulsion splitter that polyamines is initiator, there is the features such as dewatering speed is fast, breakdown of emulsion temperature is low; The emulsion splitter that the resol of take is initiator, has stronger dissolving, diffusion, infiltration, viscosity reduction texts; Clear water type emulsion splitter has very strong clear water effect, can effectively reduce the oil-contg of deviating from water; By these three kinds of emulsion splitters composite being implemented in dehydrating of crude oil proportionally, there is the advantages such as consumption is few, breakdown of emulsion temperature is low.
3, fluorescence probe auxiliary agent has played certain effect in special thick oil emulsion breaking process.Many organic solvent small molecules itself have certain polarity or have unsaturated cyclic structure or gum asphalt is had to very strong dissolving power, they can effectively change interfacial phase aromaticity or polarity environment, bituminous matter micelle is had to solublization, demulsification to special viscous crude improves, and can improve 20～30% breakdown of emulsion ability.
4, solid particles surface properties-correcting agent of the present invention can effectively change the surface properties of solid particulate in viscous crude, thereby changes the wettability of solid particulate, reduces solid particulate solublization in water to crude oil, thereby reduces the oil-contg of deviating from water.
5, the functional emulsion splitter of special viscous crude that adopts the present invention to prepare, be applicable to the Gao Han Saudi Arabia viscous crude of viscosity more than 10000mPa.s, breakdown of emulsion temperature is 70～90 ℃, consumption is within the scope of 50～150ppm of special viscous crude quality, moisture lower than 0.8% after special heavy oil dehydration, sewage with oil is lower than 1500ppm.
Embodiment
The component of functional emulsion splitter of the present invention and massfraction are:
A, polyethylene polyamine polyoxyethylene polyoxypropylene ether (industrial goods): 10～15%; (mixture of the material that a kind of molecular weight of initiator is different, BinHua Group Co., Ltd produces)
B, resol polyoxyethylene polyoxypropylene ether (industrial goods): 30～40%; (mixture of the material that a kind of molecular weight of initiator is different, BinHua Group Co., Ltd produces)
C, clear water type emulsion splitter (industrial goods): 10～15%; The Soxylat A 25-7 that glycerol (glycerine) is initiator (production of Binzhou chemical plant)
D, organic molecule auxiliary agent (industrial goods): 5～10%;
E, solid particles surface properties-correcting agent (self-control): 5～10%;
F: solvent (industrial goods): surplus.
Described organic molecule auxiliary agent is methyl alcohol or ethanol or Diethylene Glycol butyl ether.
Described solvent is benzene or toluene or ethanol or methyl alcohol or water.
Described solid particles surface properties-correcting agent is cationic Gemini surfactants or is a kind of anionic type Gemini surface active agent.
Embodiment 1
The component of this functional emulsion splitter and massfraction are:
A, polyethylene polyamine polyoxyethylene polyoxypropylene ether (industrial goods): 10%;
B, resol polyoxyethylene polyoxypropylene ether (industrial goods): 40%;
C, clear water type emulsion splitter (industrial goods): 10%;
D, Diethylene Glycol butyl ether (industrial goods): 5%;
E, solid particles surface properties-correcting agent: 5%;
F: benzene (industrial goods): 30%.
This functional emulsion splitter sees the following form to the demulsification of the special viscous crude of difference:
Embodiment 2
The component of this functional emulsion splitter and massfraction are:
A, polyethylene polyamine polyoxyethylene polyoxypropylene ether (industrial goods): 10%;
B, resol polyoxyethylene polyoxypropylene ether (industrial goods): 35%;
C, clear water type emulsion splitter (industrial goods): 5%;
D, ethanol (industrial goods): 5%;
E, solid particles surface properties-correcting agent (self-control): 10%;
F: methyl alcohol (industrial goods): 35%.
This functional emulsion splitter sees the following form to the demulsification of the special viscous crude of difference:
Claims (3)
1. the functional emulsion splitter of special viscous crude, described special viscous crude be viscosity more than 10000mPa.s containing husky viscous crude, it is characterized in that: by following one-tenth, be grouped into by mass percentage:
Described solid particles surface properties-correcting agent is cationic Gemini surfactants or is a kind of anionic type Gemini surface active agent;
The functional emulsion splitter of described special viscous crude is for the Gao Han Saudi Arabia thick oil demulsifier of viscosity more than 10000mPa.s, and breakdown of emulsion temperature is 70～90 ℃, and consumption is 50～150ppm of special viscous crude quality;
Described organic molecule auxiliary agent is methyl alcohol, ethanol or Diethylene Glycol butyl ether;
The Soxylat A 25-7 that described clear water type emulsion splitter is is initiator by glycerol.
2. the functional emulsion splitter of special viscous crude according to claim 1, is characterized in that: described solvent is benzene, toluene, ethanol, methyl alcohol or water.
3. a preparation method for the functional emulsion splitter of special viscous crude claimed in claim 1, is characterized in that:
Equipment is the enamel reaction still with the 2000L of stirring, heating, cooling and vacuum system;
Production method: first, polyethylene polyamine polyoxyethylene polyoxypropylene ether, resol polyoxyethylene polyoxypropylene ether, clear water type emulsion splitter are joined to enamel reaction still in ratio claimed in claim 1, slowly be warming up to 50～80 ℃, stir on intensification limit, limit, in ratio claimed in claim 1, add benzene, methyl alcohol simultaneously, continue to stir after 30～60 minutes, stop heating, cooling while stirring, in ratio claimed in claim 1, add solid particles surface properties-correcting agent and water, be cooled to room temperature, stir 30 minutes, discharging, obtains the functional emulsion splitter of special viscous crude.
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| CN201010262276.9A CN102373077B (en) | 2010-08-25 | 2010-08-25 | Functional demulsifier for extra-thick oil and preparation and application thereof |
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| CN102373077B true CN102373077B (en) | 2014-01-15 |
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| CN104556624B (en) * | 2013-10-22 | 2016-02-10 | 中国石油化工股份有限公司 | A kind of greasy filth emulsion splitter and greasy filth advanced treatment process |
| CN104072683A (en) * | 2014-07-17 | 2014-10-01 | 天津亿利科能源科技发展股份有限公司 | Preparation method for crude oil demulsifying agent containing polymer |
| CN105062448A (en) * | 2015-07-28 | 2015-11-18 | 中国石油集团渤海钻探工程有限公司 | Water soluble ultra-thick crude oil emulsifying and viscosity-reducing agent and preparation method thereof |
| CN106701155A (en) * | 2016-12-20 | 2017-05-24 | 吴中区穹窿山福顺生物技术研究所 | Novel high-efficiency demulsifier |
| EP3574027A1 (en) * | 2017-01-25 | 2019-12-04 | SI Group, Inc. | Compositions and process for stabilizing phenolic resins containing calixarenes |
| CN110382576A (en) * | 2017-01-25 | 2019-10-25 | Si集团有限公司 | The alkoxylate calixarenes resin of solubilising |
| CN106947517A (en) * | 2017-04-21 | 2017-07-14 | 四川省广汉市阜康化工科技开发有限公司 | A kind of oil-soluble condensate demulsifier and preparation method thereof |
| CN109943360A (en) * | 2017-12-21 | 2019-06-28 | 中国石油化工股份有限公司 | A kind of Compositional type heavy oil low-temperature demulsifier |
| CN114736707A (en) * | 2021-01-07 | 2022-07-12 | 中国石油天然气集团有限公司 | Composite polyether type demulsifier and preparation method thereof |
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