CN105348509B - A kind of preparation method of the water cleaning agent of water quality containing polymer high - Google Patents

A kind of preparation method of the water cleaning agent of water quality containing polymer high Download PDF

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CN105348509B
CN105348509B CN201510717698.3A CN201510717698A CN105348509B CN 105348509 B CN105348509 B CN 105348509B CN 201510717698 A CN201510717698 A CN 201510717698A CN 105348509 B CN105348509 B CN 105348509B
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amino
polyether
water quality
cleaning agent
containing polymer
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CN105348509A (en
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唐勇
王吉
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Tianjin E Tech Energy Technology Development Co Ltd
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Tianjin E Tech Energy Technology Development Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32Polymers modified by chemical after-treatment
    • C08G65/329Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C08G65/33306Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • B01J20/265Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267Cross-linked polymers
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/285Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32Polymers modified by chemical after-treatment
    • C08G65/329Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331Polymers modified by chemical after-treatment with organic compounds containing oxygen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The present invention relates to a kind of preparation method of the water cleaning agent of water quality containing polymer high.The invention belongs to petroleum industry technical field of oilfield chemistry.A kind of preparation method of the water cleaning agent of water quality containing polymer high, comprises the following steps that:1) synthesis of amino-polyether:The initiator of amino-polyether is pentaethylene hexamine, with oxirane, the mixture addition reaction of expoxy propane, is made amino atactic polyether;125 DEG C~140 DEG C of addition reaction temperature, pressure 0.15MPa~0.3MPa;2) it is amino-polyether modified:The hydroxyl on amino-polyether side chain and dimethylamino-ethanol hydroxyl are carried out condensation reaction with crosslinking agent glutaraldehyde, the terminal hydroxy group of amino-polyether is changed into dimethylamino group;Reactant molar ratio is amino-polyether:Glutaraldehyde:Dimethylamino-ethanol=1:6:6;75 DEG C~90 DEG C of reaction temperature, 4~6h of time;The product that reaction is obtained is the water cleaning agent of water quality containing polymer high.The present invention has process is simple, and construction investment is few, and energy-saving, product is profitable, the advantages of application prospect is wide.

Description

A kind of preparation method of the water cleaning agent of water quality containing polymer high
Technical field
The invention belongs to petroleum industry technical field of oilfield chemistry, more particularly to a kind of height water cleaning agent of water quality containing polymer Preparation method.
Background technology
At present, oil field major part has subsequently entered the High water cut productive life, around raising oil recovery factor, tertiary oil recovery skill Art have developed rapidly.Stratum residual oil that can effectively after displacement water drive with chemical agent oil removing, improves oil recovery factor, to oil field Stable yields is significant.But the application of these technology of reservoir sweep makes the emulsification degree of crude oil increasingly severe, profit is caused to sink Drop separates more difficult.Polymer displacement of reservoir oil has been carried out in part oil field in succession, finds, because polymer content is high in Produced Liquid, to cause Crude oil is dehydrated and sewage oil removing is difficult, increased processing cost, notes poly- Produced Liquid water-oil separating problem and fails to obtain preferably always Solve, have impact on the normal production in oil field.With the expansion of poly- scale and the extension of time of showwing loving care for, in Produced Liquid polymer content by Cumulative many, extraction liquid measure increases year by year, and its intractability is also being continuously increased.Seen according to the condition of production that current scene is fed back, Conventional crude oil is dehydrated and sewage disposal technology has been difficult in adapt to, and a large amount of Produced Liquids containing polymer cause existing equipment treatment effeciency The problems such as reduction, service life shorten.
The content of the invention
The present invention provides a kind of water cleaning agent of water quality containing polymer high to solve technical problem present in known technology Preparation method.
Existing more oil field uses the poly- displacement of reservoir oil of note, with the expansion of poly- scale and the extension of time of showwing loving care for, in Produced Liquid Polymer content gradually increases, and extraction liquid measure increases year by year, and its intractability is also being continuously increased.The clear water of research and development department of the present invention Agent, being directed to the treatment containing note polywater high has preferable effect, solves oil produced water difficult treatment, and re-injection/row sea does not reach The problems such as mark.
Easy to operate it is an object of the invention to provide a kind of process is simple, product stabilization is directed to the place containing note polywater high The preparation method of high water quality containing the polymer water cleaning agent of the features such as reason has preferable effect.
The preparation method of the height water cleaning agent of water quality containing polymer of the invention, being directed to for synthesis is high containing the clear water for noting polywater matter Agent, main component is cross-linking modified amino-polyether, and the core of modified polyether is a polyamino group, and eight branch end of the chain tails are two Methylamine group, the lone pair electrons on total N atoms are all charged groups.With good adsorption capacity.It is a kind of difference In cationic and the new water cleaning agent of polymer-type.
The preparation method of the height water cleaning agent of water quality containing polymer of the invention is adopted the technical scheme that:
A kind of preparation method of the water cleaning agent of water quality containing polymer high, is characterized in:The system of the water cleaning agent of water quality containing polymer high Comprised the following steps that for process,
1) synthesis of amino-polyether:
The initiator of amino-polyether is pentaethylene hexamine, with oxirane, the mixture addition reaction of expoxy propane, is made Amino atactic polyether;Pentaethylene hexamine has eight active hydrogens, connects eight side chains, is polyoxypropylene, polyoxy second on each side chain The mixed group of alkene, end group is hydroxyl;125 DEG C~140 DEG C of addition reaction temperature, pressure 0.15MPa~0.3MPa;
2) it is amino-polyether modified:
The hydroxyl on amino-polyether side chain and dimethylamino-ethanol hydroxyl are carried out condensation reaction, ammonia with crosslinking agent glutaraldehyde The terminal hydroxy group of base polyethers is changed into dimethylamino group;Reactant molar ratio is amino-polyether:Glutaraldehyde:Dimethylamino-ethanol=1: 6:6;75 DEG C~90 DEG C of reaction temperature, 4~6h of time;The product that reaction is obtained is the water cleaning agent of water quality containing polymer high.
The preparation method of the height water cleaning agent of water quality containing polymer of the invention can also be adopted the following technical scheme that:
The preparation method of described high water quality containing polymer water cleaning agent, is characterized in:During the synthesis of amino-polyether, five ethene Hexamine obtains amino atactic polyether with m oxirane and n expoxy propane addition reaction;M+n=24~32.
The preparation method of described high water quality containing polymer water cleaning agent, is characterized in:During the synthesis of amino-polyether, initiator It is potassium hydroxide, weight concentration is 0.2-0.5%.
The present invention has the advantages and positive effects that:
The preparation method of the water cleaning agent of water quality containing polymer high as a result of brand-new technical scheme of the invention, with existing skill Art is compared, and the present invention is the development in adaptation oil field, for a kind of efficient water cleaning agent of the research and development containing polymer produced liquid, makes sewage Re-injection up to standard or row sea, and can reduce to a certain extent construction investment, it is energy-saving, facilitate production management, with wide Application prospect, preferable economy and environmental benefit.
Specific embodiment
For the content of the invention of the invention, feature and effect can be further appreciated that, following examples are hereby enumerated, and describe in detail It is as follows:
Embodiment 1
The preparation method of the water cleaning agent of water quality containing polymer high, the height that is directed to of synthesis contains the water cleaning agent for noting polywater matter, mainly Composition is cross-linking modified amino-polyether, and the core of modified polyether is a polyamino group, and eight branch end of the chain tails are dimethylamino Group, the lone pair electrons on total N atoms are all charged groups.With good adsorption capacity.The clear water of water quality containing polymer high The preparation process of agent is comprised the following steps that:
1) synthesis of amino-polyether:
The initiator of amino-polyether is pentaethylene hexamine, with oxirane, the mixture addition reaction of expoxy propane, is made Amino atactic polyether.Pentaethylene hexamine has eight active hydrogens, can connect eight side chains, is polyoxypropylene on each side chain, gathers The mixed group of oxygen ethene, end group is hydroxyl.
Reaction equation:Pentaethylene hexamine+m oxirane+n expoxy propane
=amino atactic polyether m+n=(24~32)
Reaction condition:130 DEG C of temperature, pressure 0.2MPa.
Initiator:Potassium hydroxide 0.3%.
2) it is amino-polyether modified
The hydroxyl on amino-polyether side chain and dimethylamino-ethanol hydroxyl are carried out condensation reaction, ammonia with crosslinking agent glutaraldehyde The terminal hydroxy group of base polyethers is changed into dimethylamino group.
Reactant molar ratio:Amino-polyether:Glutaraldehyde:Dimethylamino-ethanol=1:6:6.
Reaction condition:80 DEG C of temperature, normal pressure, time 5h.
The product as water cleaning agent that reaction is obtained.
Comparative example 2
Water sample used mutually exports water quality (not plus water cleaning agent), experiment for Bohai Sea upstream platform primary separator water in experiment Temperature is 60 degree, and experiment water cleaning agent species used has several medicaments and implementation in live water cleaning agent, our company's medicament storehouse The water cleaning agent ELWC-02 of the synthesis of example 1.
Water quality quality is evaluated and is from getting well to differing from:A+/A/A-/B+/B/B-/C/D
First group of experiment, medicament filling concentration is 240ppm.
Live medicament Water quality is yellow, and effect is slightly good B+
WC-80 Water quality is turned to be yellow, and has a small amount of wall built-up, and effect is general B-
WC-82 Water quality is turned to be yellow, and has a small amount of wall built-up, and effect is general B-
WC-85 Water quality is dark yellow, and effect is poor C
ELWC-02 Water quality is yellowish, there is a small amount of wall built-up, and effect is preferable B+
WC-87 Water quality blacks, and effect is poor D
WC-91 Water quality blacks, and effect is poor D
WC-92 Water quality is dark yellow, and effect is poor C
Second group of experiment:Medicament filling concentration is 400ppm.
WC81 Water quality is turned to be yellow, and generation floc particle is larger, and ascent rate is general B
WC82 Water quality blacks, and effect is poor D
WC79 Water quality is turned to be yellow, and generation floc particle is tiny, and ascent rate is very slow B-
WC88 Water quality is turned to be yellow, and produces flocculation structure loose, and ascent rate is fast B+
Live medicament Water quality is yellowish, produces flocculation structure loose, and ascent rate is fast B+
WC80 Water quality blacks, and effect is poor D
WC59 Water quality is yellowish, and generation flco viscosity is larger, and wall built-up is serious B
ELWC-02 Water quality is clear, and generation floc particle is small, and ascent rate is fast A
The present embodiment has described process is simple, easy to operate, product stabilization, and being directed to the polywater containing note high has preferably The features such as treatment effect.

Claims (1)

1. a kind of preparation method of the water cleaning agent of water quality containing polymer high, it is characterized in that:The preparation of the water cleaning agent of water quality containing polymer high Process comprises the following steps that,
1) synthesis of amino-polyether:
The initiator of amino-polyether is pentaethylene hexamine, with oxirane, the mixture addition reaction of expoxy propane, is made amino Atactic polyether;Pentaethylene hexamine has eight active hydrogens, connects eight side chains, is polyoxypropylene, polyoxyethylated on each side chain Mixed group, end group is hydroxyl;125 DEG C~140 DEG C of addition reaction temperature, pressure 0.15MPa~0.3MPa;
Reaction equation:Pentaethylene hexamine+m oxirane+n expoxy propane=amino atactic polyether, m+n=24~32;
2) it is amino-polyether modified:
The hydroxyl on amino-polyether side chain and dimethylamino-ethanol hydroxyl are carried out condensation reaction with crosslinking agent glutaraldehyde, amino gathers The terminal hydroxy group of ether is changed into dimethylamino group;Reactant molar ratio is amino-polyether:Glutaraldehyde:Dimethylamino-ethanol=1:6:6; 75 DEG C~90 DEG C of reaction temperature, 4~6h of time;The product that reaction is obtained is the water cleaning agent of water quality containing polymer high.
CN201510717698.3A 2015-10-28 2015-10-28 A kind of preparation method of the water cleaning agent of water quality containing polymer high Active CN105348509B (en)

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CN114989410A (en) * 2022-05-13 2022-09-02 中海油(天津)油田化工有限公司 Water clarifier for offshore oil field and preparation method thereof

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DE3049450A1 (en) * 1980-12-30 1982-07-29 Hoechst Ag, 6000 Frankfurt "OXALKYLATED ADDITION PRODUCTS FROM ETHYLENE-OXIDE-PROPYLENE-OXIDE BLOCK POLYMERS AND BIS-GLYCIDYL ETHERS AND THE USE THEREOF"
US5190683A (en) * 1990-06-19 1993-03-02 Baker Hughes Incorporated Water clarification composition containing a water clarifier component and a floc modifier component
CN101024153A (en) * 2007-01-12 2007-08-29 辽河石油勘探局 Compound-type demulsifying agent of thick-oil steam-driven dewatering type
CN102786982B (en) * 2011-05-20 2014-12-03 克拉玛依奥克化学有限公司 Preparation method for intermediate base-cycloalkyl crude oil emulsion de-emulsifier and product thereof
CN103642518B (en) * 2013-12-10 2015-08-19 天津亿利科能源科技发展股份有限公司 A kind of oil field High water cut thick oil demulsifier and preparation method thereof
CN103739837B (en) * 2013-12-20 2016-08-17 西南石油大学 A kind of Block polyether oilfield sewage treatment agent with N ' N-dimethylethanolamine as initiator and preparation method thereof
CN104497297A (en) * 2014-12-10 2015-04-08 辽宁石油化工大学 Novel broad-spectrum crude oil demulsifying agent and preparation method thereof
CN104774646B (en) * 2015-04-22 2016-05-11 孙豫庆 Comb-type polyether demulsifier and preparation method taking polyamino polyethers as initiator

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