CN100556980C - A kind of efficient thick-oil emulsified adhesive-reducing agent - Google Patents
A kind of efficient thick-oil emulsified adhesive-reducing agent Download PDFInfo
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- CN100556980C CN100556980C CNB2007100722440A CN200710072244A CN100556980C CN 100556980 C CN100556980 C CN 100556980C CN B2007100722440 A CNB2007100722440 A CN B2007100722440A CN 200710072244 A CN200710072244 A CN 200710072244A CN 100556980 C CN100556980 C CN 100556980C
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Abstract
Efficient thick-oil emulsified adhesive-reducing agent of the present invention is to be the synthetic tensio-active agent that contains sulfo group, two kinds of hydrophilic radicals of carboxyl of host by containing the polycyclic aromatic hydrocarbons organism, be equipped with polyethers nonionogenic tenside, long-chain alcohol analog assistant again, synthetic finished product effective content is 20%～60%.Its preparation method, be under 60 ℃～90 ℃ conditions, after polycyclic aromatic hydrocarbons organism, thiazolinyl carboxylicesters adding reaction, carry out sulfonation again and obtain a kind of novel surfactant, add polyethers nonionogenic tenside, long-chain alcohol analog assistant once more, make efficient thick-oil emulsified adhesive-reducing agent of the present invention after the reaction.Its advantage is: improved viscosity reducing effect, viscosity of thickened oil is reduced, crude oil is easy to peel off from rock surface, improves the purpose of recovery ratio.
Description
Technical field
The present invention relates to viscosity-depression agent, particularly relate to a kind of efficient thick-oil emulsified adhesive-reducing agent that can form low viscosity milk sap.
Background technology
Viscous crude is meant that the viscosity of gas-free oil under reservoir temperature surpasses the crude oil of 100mPas.Colloid, bituminous matter and paraffinicity are higher in the viscous crude, and viscosity is very big, and be mobile poor, thus its exploitation and collection to fail difficulty very big, need heat or dilution process.Use conventional thermal recovery technique effect poor separately, the cost height must take some physics or chemical process that viscous crude is carried out upgrading or modification is handled, and reduces viscosity, and raising is mobile, can adopt rate and recovery ratio thereby improve.Industrial used viscous crude modification viscosity reduction technology comprises and mixes the water phase surfactant mixture reducing viscosity by emulsifying, mixes rare reducing crude oil viscosity, is mixed with the machine solvent (gasoline, diesel oil, lighter hydrocarbons, mix benzene etc.) viscosity reduction, mix oil dissolubility viscosity-depression agent viscosity reduction and compound viscosity-depression agent viscosity reduction etc., and what wherein tool Technological Economy was worth is water soluble emulsifier viscosity reduction and oil-soluble viscosity reducer viscosity reduction.In traditional emulsifying and viscosity-reducing agent for condensed oil, each component tensio-active agent hydrophilic group is single group, and its salt resistance or temperature tolerance or viscosity reduction efficient are undesirable, therefore needs assembly to use.
Summary of the invention
The present invention is intended to overcome the deficiency of existing technology, has developed a kind of efficient thick-oil emulsified adhesive-reducing agent.
Efficient thick-oil emulsified adhesive-reducing agent of the present invention is to be the synthetic tensio-active agent that contains sulfo group, two kinds of hydrophilic radicals of carboxyl of host by containing the polycyclic aromatic hydrocarbons organism, be equipped with polyethers nonionogenic tenside, long-chain alcohol analog assistant again, the effective content of synthetic product is 20%～60%.
Efficient thick-oil emulsified adhesive-reducing agent of the present invention is that polycyclic aromatic hydrocarbons, thiazolinyl carboxylicesters, S-WAT or sodium bisulfite, ethanol, octodecyl alcohol polyoxyethylene polyethenoxy ether and the long-chain alcohol with parts by weight reacts under catalyst action and make:
A, 5～12 parts of polycyclic aromatic hydrocarbonss, 1～5 part of thiazolinyl carboxylicesters, catalyzer are mixed for 0.08～1 part mutually, under 60 ℃～90 ℃ conditions, reacted 1～3 hour;
B, add S-WAT or 1～5 part of sodium bisulfite, 0.5～3 part of ethanol in the reaction solution of a step, reaction down 1～4 hour refluxes;
C, in the material of b step, add 1～5 part of octodecyl alcohol polyoxyethylene polyethenoxy ether, 0.5～4 part of long-chain alcohol again, refluxed 0.5～2 hour, promptly synthesize effective content and be 20%～60% efficient thick-oil emulsified adhesive-reducing agent;
Described polycyclic aromatic hydrocarbons organism is alkylnaphthalene, alkyl rosin, alkyl rosin Amine D, alkyl sylvic acid;
Described thiazolinyl carboxylicesters: be selected from methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, dimethyl maleate, ethyl maleate, maleic acid propyl ester or maleic acid isopropyl ester;
Described catalyzer is a metal oxide, is selected from calcium oxide, potassium oxide, sodium oxide, magnesium oxide or aluminum oxide.
Described long-chain alcohol: octanol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol.
The application of efficient thick-oil emulsified adhesive-reducing agent of the present invention is sewage to be injected in the oil field of this reagent and 20 ℃～60 ℃ be made into 0.01%～1% solution, injects the back and forms low viscous oil-in-water emulsion.
Colloid and asphalt content height are the major causes that causes viscosity of thickened oil high in the viscous crude.Some effective viscous oil recovery technology have been researched and developed out both at home and abroad.In order further to increase substantially the recovery ratio of viscous crude, the reducing viscosity by emulsifying method is a kind of method of new heavy crude producing.This method is that water phase surfactant mixture is annotated the down-hole, makes full-bodied water-in-oil (W/O) type viscous crude change the extraction of low viscous oil-in-water (O/W) type viscous oil emulsion into.Inject tensio-active agent in oil reservoir or oil well, (1) has reduced the interfacial tension between crude oil and the formation rock, makes crude oil be easy to flow, thereby oil droplet is easily from being discharged the hole of water-wet; (2) after oil reservoir emulsification of crude oil, crude oil changed O/W type milk sap into from W/O, reduced the adsorptive power of oil the rock stratum, and oil is got off by displacement easily; (3) wettability of change rock stratum increases the rock layer surface wetting ability, and it is favourable to displacement crude oil that more water enters the rock stratum.It all is that emulsified viscous oil is formed O/W milk sap that viscosity reducing and chemistry are handled up, thus the reoovery method that viscosity is descended significantly.
The invention discloses a kind of efficient thick-oil emulsified adhesive-reducing agent, belong to the synthetic class viscosity-depression agent of tensio-active agent; Prepared a class novel surfactant, polycyclic aromatic hydrocarbons skeleton structure, polyoxyethylene ester fragment, sulfonic acid group and hydroxy-acid group have been comprised in its molecule, obtained the performance and the function of kinds of surface promoting agent, making with this tensio-active agent is that the emulsifying pour depressor of main body preparation has reached the reducing viscosity by emulsifying ability of viscous crude and needs the composite degree that just may reach of multi-agent; This emulsifying pour depressor according to structure design with high sticking low coagulate on the viscous crude structure close and adaptability hydrophilic group is wide, hydrophilic group contains sulfonic acid, carboxylate anion and polyethers non-ionic hydrophilic group simultaneously in the surfactant molecule, oleophilic group contains the polycyclic aromatic hydrocarbons skeleton structure, good with the sticking low close intermiscibility of heavy oil asphalt matter core texture that coagulates of height, so this product has very strong thick-oil emulsified adhesive-reducing function; The synthetic route of tensio-active agent is simple, the control condition gentleness.
Efficient thick-oil emulsified adhesive-reducing agent of the present invention is a class novel surfactant, comprised the polycyclic aromatic hydrocarbons skeleton structure in its molecule, the polyoxyethylene ester fragment, sulfonic acid group and hydroxy-acid group, the performance and the function of kinds of surface promoting agent have been obtained, with the polymerization of a few class hydrophilic radical in same molecule, adopt many rings or condensed ring oleophilic group as emulsifying pour depressor, such tensio-active agent has possessed the advantage of all kinds of hydrophilic radicals simultaneously, viscosity-depression agent molecule lipophilic group easily enters in the bituminous matter aggregate, improved viscosity reducing effect, viscosity of thickened oil is reduced, crude oil is easy to peel off from rock surface, reaches the purpose that improves recovery ratio.
Embodiment
A kind of efficient thick-oil emulsified adhesive-reducing agent of the present invention is to be made by following operation steps in weight part by polycyclic aromatic hydrocarbons organism, thiazolinyl carboxylicesters, catalyzer, S-WAT or sodium bisulfite, ethanol, octodecyl alcohol polyoxyethylene polyethenoxy ether and long-chain alcohol:
A, 5～12 parts of polycyclic aromatic hydrocarbonss, 1～5 part of thiazolinyl carboxylicesters, catalyzer are mixed for 0.08～1 part mutually, under 60 ℃～90 ℃ conditions, reacted 1～3 hour;
B, add S-WAT or 1～5 part of sodium bisulfite, 0.5～3 part of ethanol in the reaction solution of a step, reaction down 1～4 hour refluxes;
C, in the material of b step, add 1～5 part of octodecyl alcohol polyoxyethylene polyethenoxy ether, 0.5～4 part of long-chain alcohol again, refluxed 0.5～2 hour, promptly synthesize effective content and be 20%～60% efficient thick-oil emulsified adhesive-reducing agent;
Described polycyclic aromatic hydrocarbons is alkylnaphthalene, alkyl rosin, alkyl rosin Amine D, alkyl sylvic acid;
Described thiazolinyl carboxylicesters: be selected from methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, dimethyl maleate, ethyl maleate, maleic acid propyl ester or maleic acid isopropyl ester;
Described catalyzer is a metal oxide, is selected from calcium oxide, potassium oxide, sodium oxide, magnesium oxide or aluminum oxide;
Described long-chain alcohol: octanol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol.
Following table is the viscosity-depression agent that efficient thick-oil emulsified adhesive-reducing agent of the present invention prepares with different components as stated above:
To injecting the efficient thick-oil emulsified adhesive-reducing agent 0.3% that sewage adds example 1～7 preparation, to 190mPas, viscosity break ratio reaches 88.6% to the viscous crude of 0.05% couple of initial viscosity 1.6Pas of alkali add-on (25 ℃) at 7: 3 o'clock emulsion viscosity drop of profit volume ratio.
The product performance synopsis
| Name of product | Viscosity break ratio |
| Efficient thick-oil emulsified adhesive-reducing agent of the present invention | 88.6％ |
| Daqing oil field eight factories of recovering the oil now use the sample of viscosity-depression agent | 52％ |
Claims (3)
1, a kind of efficient thick-oil emulsified adhesive-reducing agent is that polycyclic aromatic hydrocarbons, thiazolinyl carboxylicesters, S-WAT or sodium bisulfite, ethanol, octodecyl alcohol polyoxyethylene polyethenoxy ether and long-chain alcohol with parts by weight reacts under catalyst action and make:
A, 5～12 parts of polycyclic aromatic hydrocarbonss, 1～5 part of thiazolinyl carboxylicesters, catalyzer are mixed for 0.08～1 part mutually, under 60 ℃～90 ℃ conditions, reacted 1～3 hour;
B, add S-WAT or 1～5 part of sodium bisulfite, 0.5～3 part of ethanol in the reaction solution of a step, reaction down 1～4 hour refluxes;
C, in the material of b step, add 1～5 part of octodecyl alcohol polyoxyethylene polyethenoxy ether, 0.5～4 part of long-chain alcohol again, refluxed 0.5～2 hour, promptly synthesize effective content and be 20%～60% efficient thick-oil emulsified adhesive-reducing agent;
Described polycyclic aromatic hydrocarbons is alkylnaphthalene, alkyl rosin, alkyl rosin Amine D, alkyl sylvic acid;
Described thiazolinyl carboxylicesters: be selected from methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, dimethyl maleate, ethyl maleate, maleic acid propyl ester or maleic acid isopropyl ester;
Described catalyzer is a metal oxide, is selected from calcium oxide, potassium oxide, sodium oxide, magnesium oxide or aluminum oxide;
Described long-chain alcohol: octanol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol.
2, a kind of efficient thick-oil emulsified adhesive-reducing agent as claimed in claim 1 is characterized in that making by the following method:
A, 7～10 parts of polycyclic aromatic hydrocarbonss, 2～4 parts of thiazolinyl carboxylicesterss, catalyzer are mixed for 0.1～0.8 part mutually, under 70 ℃～80 ℃ conditions, reacted 1～3 hour;
B, add S-WAT or 2～4 parts of sodium bisulfites, 1～2 part of ethanol in the reaction solution of a step, reaction down 2～3 hours refluxes;
C, in the material of b step, add 2～4 parts of octodecyl alcohol polyoxyethylene polyethenoxy ethers, 1～3 part of long-chain alcohol again, refluxed 1～1.5 hour, promptly synthesize effective content and be 20%～60% efficient thick-oil emulsified adhesive-reducing agent.
3, the application of efficient thick-oil emulsified adhesive-reducing agent as claimed in claim 1 or 2, the oil field that it is characterized in that this efficient thick-oil emulsified adhesive-reducing agent and 20 ℃～60 ℃ is injected sewage and is made into 0.01%～1% solution, injects the back and forms low viscous oil-in-water emulsion.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101875838B (en) * | 2009-04-30 | 2012-02-22 | 中国石油大学(北京) | Oil-soluble viscosity reducer and preparation method thereof |
| CN101851494B (en) * | 2009-08-14 | 2012-11-07 | 新疆德蓝股份有限公司 | Oil-soluble viscosity depressant |
| CN102019205B (en) * | 2009-09-15 | 2012-05-30 | 中国石油天然气股份有限公司 | Complex catalyst for viscosity reduction of thick oil through hydrothermal catalytic cracking and preparation and application thereof |
| CN102604621B (en) * | 2012-01-20 | 2013-03-13 | 中国石油大学(北京) | Novel high-efficiency composite viscosity reducer for super heavy oil |
| CN103540297B (en) * | 2012-07-12 | 2017-04-19 | 中国石油化工股份有限公司 | Composite oil-based emulsifier containing fatty alcohol polyoxyethylene polypropylene oxide ether carboxylate and preparation method thereof |
| CN103965850A (en) * | 2014-05-13 | 2014-08-06 | 新疆福利精细化工厂 | Viscosity reducer for crude oil and preparation method thereof |
| CN108117639B (en) * | 2016-11-30 | 2021-04-30 | 中国石油天然气股份有限公司 | Unsaturated fatty alcohol polyoxypropylene polyoxyethylene block copolymer, and preparation method and application thereof |
| CN107893648B (en) * | 2017-12-19 | 2019-06-18 | 北京百利时能源技术股份有限公司 | The cold mining method of heavy crude reservoir carbon dioxide accumulation of energy high pressure viscosity reduction |
| CN111217961B (en) * | 2020-04-07 | 2021-06-25 | 山东新港化工有限公司 | Water-soluble pour point depressant for crude oil and preparation method and application thereof |
| CN113549441A (en) * | 2020-04-23 | 2021-10-26 | 吉林省安和石油技术服务有限公司 | Preparation method of automatic-arrangement rapid-diffusion amphiphilic molecule viscosity reducer for oil extraction |
| CN112480894A (en) * | 2020-11-04 | 2021-03-12 | 东营东方化学工业有限公司 | Process for producing water-soluble viscosity-reducing composition for thick oil and viscosity-reducing composition obtained by the process |
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Assignee: Daqing Hualongxiang Chemical Co., Ltd. Assignor: Cai Jianhua Contract record no.: 2011230000177 Denomination of invention: Efficient thick-oil emulsified adhesive-reducing agent Granted publication date: 20091104 License type: Exclusive License Open date: 20071114 Record date: 20110815 |
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Owner name: DAQING HUAYING CHEMICAL INDUSTRY CO., LTD. Free format text: FORMER OWNER: CAI JIANHUA Effective date: 20150826 |
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Effective date of registration: 20150826 Address after: 163000 Heilongjiang high tech Zone in Daqing City, Grand Park Patentee after: Daqing Huaying Chemical Industry Co., Ltd. Address before: 163714 Heilongjiang province Daqing city Daqing high tech Zone Xinghua ethylene Park hualongxiang Chemical Co. Ltd. Patentee before: Cai Jianhua |