CN104479731A - Superheavy oil crude oil reverse-phase demulsifier preparation method - Google Patents

Superheavy oil crude oil reverse-phase demulsifier preparation method Download PDF

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Publication number
CN104479731A
CN104479731A CN201410649367.6A CN201410649367A CN104479731A CN 104479731 A CN104479731 A CN 104479731A CN 201410649367 A CN201410649367 A CN 201410649367A CN 104479731 A CN104479731 A CN 104479731A
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China
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preparation
reverse
crude oil
polyquaternium
pamams
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Pending
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CN201410649367.6A
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Chinese (zh)
Inventor
胡玉国
梁海臣
李靖
张冠洲
张有强
张凤跃
肖劲松
孙红桃
李东
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TIANJIN DAGANG OILFIELD BINGANG GROUP BOHONG PETROLEUM CHEMICAL CO Ltd
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TIANJIN DAGANG OILFIELD BINGANG GROUP BOHONG PETROLEUM CHEMICAL CO Ltd
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Priority to CN201410649367.6A priority Critical patent/CN104479731A/en
Publication of CN104479731A publication Critical patent/CN104479731A/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00Dewatering or demulsification of hydrocarbon oils
    • C10G33/04Dewatering or demulsification of hydrocarbon oils with chemical means

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

The invention provides a superheavy oil crude oil reverse-phase demulsifier preparation method characterized in that: epoxy chloropropane, glycerol and trimethylamine and the like are used as raw materials for preparation of multi segment poly quaternary ammonium salt, methyl acrylate and ethylenediamine are used as raw materials for preparation of 3.0 generation polyamidoamine-amine, and a water-soluble solution, namely a composite type reverse-phase demulsifier is prepared from the poly quaternary ammonium salt, the 3.0 generation polyamidoamine-amine, polymeric aluminium and a solvent according to the mass fraction ratio of (10-30): (10-40): (1-20): (100-500). The reverse-phase demulsifier prepared by the method has good demulsification effect on crude oil exploited from an oil field, and is a reverse-phase demulsifier suitable for chemical flooding produced liquid, and the preparation method provided by the invention has the advantages of simple operation, low requirement on equipment, wide application range and reduces the cost of crude oil exploitation.

Description

A kind of preparation method of super―heavy oil crude oil reverse-phase emulsifier
Technical field
The present invention relates to petrochemical industry, particularly relate to a kind of preparation method of super―heavy oil crude oil reverse-phase emulsifier.
Background technology
Oil and gas pipes collection is defeated is an important step in oil and gas industry oilfield exploitation procedure, for solving produced problem in oil-gas gathering and transportation process, a large amount of chemical agents must be used, chemical used in oil-gas gathering and transportation process is called oil-gas gathering and transportation chemical, and it mainly contains emulsion splitter, inhibiter, flow improver, emulsifying agent etc.The chemical agent that emulsification crude oil demulsification can be made to dewater is super crude oil demulsifier spy.Because Viscosity of Heavy Crude Oil is high, density is large, be difficult to exploit by ordinary method, at present, the thermal recovery processes such as steam stimulation and steam flood is topmost exploitation side, but, due to the reason such as rising year by year and steam injection exploitation of water content in crude oil, along with the high temperature oily(waste)water that a large amount of emulsification is serious in super heavy oil recovery process, become a great problem that field produces faces.Exploitation has the reverse-phase emulsifier of efficient demulsification performance, significant to reclaim crude oil to purification separation height oily(waste)water.At present, the reverse-phase emulsifier being used as O/W type emulsion breakdown both at home and abroad comprises low molecule ionogen, alcohols, tensio-active agent and polymkeric substance, because polyquarternium-type emulsion splitter possesses the advantages such as good water solubility, velocity of diffusion be fast, therefore instead of polyethers emulsion splitter gradually.Positively charged ion polyquaternary amine salt is the synergy and the synergistic effect that utilize surfactant component, is formed by multiple nonionic surface active agent and other additive compound.There is superpower surfactivity, wettability, flocculation and agglutinating power, can disperse rapidly in crude oil, replace, neutralize originally at the emulsifying agent of water-oil interface, form unstable adsorption film and change the wettability of particulate matter, make the water molecule energy that coupled together by tensio-active agent coalescent fast, thus reach the object of breakdown of emulsion.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the crude oil demulsifier that a kind of crude oil adaptability is good, de-emulsification speed is fast, dewatering efficiency is high is provided.For achieving the above object, technical scheme provided by the present invention is:
The invention provides a kind of preparation method of super―heavy oil crude oil reverse-phase emulsifier, its concrete operation steps is:
(1) synthesis of multichain section polyquaternium
Initiator glycerol and catalyzer boron trifluoride diethyl etherate liquid are added in the there-necked flask that driven stirring rod, prolong and dropping funnel are housed, open driven stirring rod, temperature control 50 DEG C, dropwise add epoxy chloropropane, be warming up to 70 DEG C of insulation reaction 3 ~ 5 hours after dripping, namely obtain brown multichain section chloro polyethers; In autoclave, add chloro polyethers and triethylamine aqueous solution, ensure chlorine and amino equivalent, pass into nitrogen, raised temperature to 70 DEG C, stir lower insulation reaction 2 ~ 4 hours, be finally warming up to 120 ~ 130 DEG C and continue reaction, namely obtain sorrel multichain section positively charged ion polyquaternium.
(2) synthesis of dendritic interphase
Under the protection of nitrogen, in the four-hole boiling flask that stirring rod, thermometer, prolong be housed, add 1,2-propylene diamine, methyl alcohol, after being cooled to 0 DEG C with ice-water bath, slowly drip methyl acrylate, stir lower temperature control 25 DEG C, continue reaction 24h.Under 45 DEG C of conditions, carry out underpressure distillation, obtain the light yellow product of 0.5 PAMAM.With above-mentioned 0.5 PAMAM separated of dissolve with methanol, join in four-hole boiling flask, after ice-water bath is cooled to 0 DEG C, slowly drip 1,2-propylene diamine of different equivalent respectively, stir lower temperature control 25 DEG C, continue reaction 24h.The weak yellow liquid obtained carries out underpressure distillation under 70 DEG C of conditions, namely obtains the yellowish chromaticity of 1.0 PAMAMs, reaction repeated process, obtains the yellowish chromaticity of 2.0 generations and 3.0 PAMAMs respectively.
(3) preparation of composite demulsifying agent
Polyquaternium, 3.0 PAMAMs, polymerize aluminum chloride and solvent are mixed with water-soluble solution according to suitable proportion, namely obtain compound reverse-phase emulsifier.The wherein massfraction ratio (10 ~ 30) of polyquaternium, 3.0 PAMAMs, polymerize aluminum chloride and solvent: (10 ~ 40): (1 ~ 20): (100 ~ 500).Wherein solvent for use be in methyl alcohol, ethanol or water any one.
Advantage of the present invention is: the reverse-phase emulsifier of preparation has good demulsification to oil field produced crude oil, it is a kind of reverse-phase emulsifier of applicable chemical flooding Produced Liquid, simultaneously preparation method provided by the invention has simple to operate, low for equipment requirements, applied range and reduce the cost of Oil extraction.
Embodiment
The invention will be further described for Application Example below.
Embodiment 1: a kind of preparation of compound reverse-phase emulsifier, concrete operation steps is:
1. the synthesis of multichain section polyquaternium: initiator glycerol and catalyzer boron trifluoride diethyl etherate liquid are added in the there-necked flask that driven stirring rod, prolong and dropping funnel are housed, open driven stirring rod, temperature control 50 DEG C, dropwise add epoxy chloropropane, be warming up to 70 DEG C of insulation reaction 4 hours after dripping, namely obtain brown multichain section chloro polyethers; In autoclave, add chloro polyethers and triethylamine aqueous solution, ensure chlorine and amino equivalent, pass into nitrogen, raised temperature to 70 DEG C, stir lower insulation reaction 3 hours, be finally warming up to 125 DEG C and continue reaction, namely obtain sorrel multichain section positively charged ion polyquaternium.
2. the synthesis of dendritic interphase: under the protection of nitrogen; in the four-hole boiling flask that stirring rod, thermometer, prolong be housed, add 1,2-propylene diamine, methyl alcohol, after being cooled to 0 DEG C with ice-water bath, slowly drip methyl acrylate; stir lower temperature control 25 DEG C, continue reaction 24h.Under 45 DEG C of conditions, carry out underpressure distillation, obtain the light yellow product of 0.5 PAMAM.With above-mentioned 0.5 PAMAM separated of dissolve with methanol, join in four-hole boiling flask, after ice-water bath is cooled to 0 DEG C, slowly drip 1,2-propylene diamine of different equivalent respectively, stir lower temperature control 25 DEG C, continue reaction 24h.The weak yellow liquid obtained carries out underpressure distillation under 70 DEG C of conditions, namely obtains the yellowish chromaticity of 1.0 PAMAMs, reaction repeated process, obtains the yellowish chromaticity of 2.0 generations and 3.0 PAMAMs respectively.
3. the preparation of composite demulsifying agent: being mixed with water-soluble solution by synthesizing the polyquaternium, 3.0 PAMAMs, polymerize aluminum chloride and the methyl alcohol that obtain according to suitable proportion, namely obtaining compound reverse-phase emulsifier.Wherein the massfraction ratio of polyquaternium, 3.0 PAMAMs, polymerize aluminum chloride and solvent is 20: 30: 10: 100.
Embodiment 2: a kind of preparation of compound reverse-phase emulsifier, concrete operation steps is:
1. the synthesis of multichain section polyquaternium is with embodiment 1.
2. the synthesis of dendritic interphase is with embodiment 1.
3. the preparation of composite demulsifying agent: being mixed with water-soluble solution by synthesizing the polyquaternium, 3.0 PAMAMs, polymerize aluminum chloride and the ethanol that obtain according to suitable proportion, namely obtaining compound reverse-phase emulsifier.Wherein the massfraction ratio of polyquaternium, 3.0 PAMAMs, polymerize aluminum chloride and solvent is 15: 15: 10: 300.
The embodiment of the above is only the preferred embodiment of the present invention, not limits practical range of the present invention with this, therefore the change that all shapes according to the present invention, principle are done, all should be encompassed in protection scope of the present invention.

Claims (3)

1. a preparation method for super―heavy oil crude oil reverse-phase emulsifier, is characterized in that, its concrete operation step is as follows:
(1) synthesis of multichain section polyquaternium: initiator glycerol and catalyzer boron trifluoride diethyl etherate liquid are added in the there-necked flask that driven stirring rod, prolong and dropping funnel are housed, open driven stirring rod, temperature control 50 DEG C, dropwise add epoxy chloropropane, be warming up to 70 DEG C of insulation reaction 3 ~ 5 hours after dripping, namely obtain brown multichain section chloro polyethers; In autoclave, add chloro polyethers and triethylamine aqueous solution, pass into nitrogen, raised temperature to 70 DEG C, stir lower insulation reaction 2 ~ 4 hours, be finally warming up to 120 ~ 130 DEG C and continue reaction, namely obtain sorrel multichain section positively charged ion polyquaternium;
(2) synthesis of dendritic interphase: under the protection of nitrogen, toward stirring rod is housed, thermometer, 1 is added in the four-hole boiling flask of prolong, 2-propylene diamine, methyl alcohol, slowly methyl acrylate is dripped after being cooled to 0 DEG C with ice-water bath, stir lower temperature control 25 DEG C, continue reaction 24h, underpressure distillation is carried out under 45 DEG C of conditions, obtain the light yellow product of 0.5 PAMAM, with above-mentioned 0.5 PAMAM separated of dissolve with methanol, join in four-hole boiling flask, slowly 1 of equivalent is dripped respectively after ice-water bath is cooled to 0 DEG C, 2-propylene diamine, stir lower temperature control 25 DEG C, continue reaction 24h, the weak yellow liquid obtained carries out underpressure distillation under 70 DEG C of conditions, namely the yellowish chromaticity of 1.0 PAMAMs is obtained, reaction repeated process, obtain the yellowish chromaticity of 2.0 generations and 3.0 PAMAMs respectively,
(3) preparation of composite demulsifying agent: polyquaternium, 3.0 PAMAMs, polymerize aluminum chloride and solvent are mixed with water-soluble solution according to suitable proportion, namely obtain compound reverse-phase emulsifier.
2. the preparation method of a kind of super―heavy oil crude oil reverse-phase emulsifier according to claim 1, it is characterized in that, the massfraction ratio (10 ~ 30) of polyquaternium, 3.0 PAMAMs, polymerize aluminum chloride and solvent in step (3): (10 ~ 40): (1 ~ 20): (100 ~ 500).
3. the preparation method of a kind of super―heavy oil crude oil reverse-phase emulsifier according to claim 1 and 2, is characterized in that, the solvent described in step (3) be in methyl alcohol, ethanol or water any one.
CN201410649367.6A 2014-11-14 2014-11-14 Superheavy oil crude oil reverse-phase demulsifier preparation method Pending CN104479731A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104774646A (en) * 2015-04-22 2015-07-15 孙豫庆 Comb type polyether emulsion breaker taking multi-amino polyether as initiator and preparation method of comb type polyether emulsion breaker
CN106866954A (en) * 2017-04-01 2017-06-20 大庆市富杰化工有限公司 A kind of cation polyether reverse-phase emulsifier and preparation method thereof
CN106957673A (en) * 2017-05-02 2017-07-18 东营黄蓝知识产权运营管理有限公司 A kind of demulsifier and breaking method for thick oil emulsion breaking dehydration
CN107057754A (en) * 2017-05-26 2017-08-18 天津正达科技有限责任公司 A kind of demulsifier of suitable high-moisture percentage heavy crude emulsion
CN107699213A (en) * 2017-11-06 2018-02-16 中国石油集团川庆钻探工程有限公司 Preparation method of polyamide inhibitor suitable for drilling fluid
CN108130122A (en) * 2017-12-12 2018-06-08 中海油天津化工研究设计院有限公司 A kind of more quaternary amine reverse-phase emulsifiers and preparation method thereof
CN109420364A (en) * 2017-08-30 2019-03-05 中国石油化工股份有限公司 Demulsifier and preparation method thereof and demulsification method for hydrocarbon oil
CN111908633A (en) * 2019-05-10 2020-11-10 中国石油天然气集团有限公司 Petroleum hydrocarbon polluted underground water treatment process
CN112877112A (en) * 2021-01-15 2021-06-01 宋子云 Efficient lubricating oil demulsifier and production method thereof
CN113429955A (en) * 2021-06-24 2021-09-24 中国矿业大学 Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier and application of load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment
CN114768309A (en) * 2022-05-12 2022-07-22 广东粤首新科技有限公司 Reverse demulsifier and preparation method thereof

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104774646A (en) * 2015-04-22 2015-07-15 孙豫庆 Comb type polyether emulsion breaker taking multi-amino polyether as initiator and preparation method of comb type polyether emulsion breaker
CN106866954B (en) * 2017-04-01 2019-04-26 大庆市富杰化工有限公司 A kind of cation polyether reverse-phase emulsifier and preparation method thereof
CN106866954A (en) * 2017-04-01 2017-06-20 大庆市富杰化工有限公司 A kind of cation polyether reverse-phase emulsifier and preparation method thereof
CN106957673A (en) * 2017-05-02 2017-07-18 东营黄蓝知识产权运营管理有限公司 A kind of demulsifier and breaking method for thick oil emulsion breaking dehydration
CN106957673B (en) * 2017-05-02 2018-06-19 东营黄蓝知识产权运营管理有限公司 A kind of demulsifier and breaking method for thick oil emulsion breaking dehydration
CN107057754A (en) * 2017-05-26 2017-08-18 天津正达科技有限责任公司 A kind of demulsifier of suitable high-moisture percentage heavy crude emulsion
CN109420364B (en) * 2017-08-30 2020-11-13 中国石油化工股份有限公司 Demulsifier and preparation method thereof, and hydrocarbon oil demulsification method
CN109420364A (en) * 2017-08-30 2019-03-05 中国石油化工股份有限公司 Demulsifier and preparation method thereof and demulsification method for hydrocarbon oil
CN107699213A (en) * 2017-11-06 2018-02-16 中国石油集团川庆钻探工程有限公司 Preparation method of polyamide inhibitor suitable for drilling fluid
CN108130122B (en) * 2017-12-12 2020-08-21 中海油天津化工研究设计院有限公司 Multi-quaternary ammonium salt reverse demulsifier and preparation method thereof
CN108130122A (en) * 2017-12-12 2018-06-08 中海油天津化工研究设计院有限公司 A kind of more quaternary amine reverse-phase emulsifiers and preparation method thereof
CN111908633A (en) * 2019-05-10 2020-11-10 中国石油天然气集团有限公司 Petroleum hydrocarbon polluted underground water treatment process
CN112877112A (en) * 2021-01-15 2021-06-01 宋子云 Efficient lubricating oil demulsifier and production method thereof
CN113429955A (en) * 2021-06-24 2021-09-24 中国矿业大学 Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier and application of load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment
CN113429955B (en) * 2021-06-24 2022-03-11 中国矿业大学 Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier and application of load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment
CN114768309A (en) * 2022-05-12 2022-07-22 广东粤首新科技有限公司 Reverse demulsifier and preparation method thereof

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Application publication date: 20150401