CN112794945A - Reducible and degradable water clarifier and preparation method and application thereof - Google Patents
Reducible and degradable water clarifier and preparation method and application thereof Download PDFInfo
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- CN112794945A CN112794945A CN202110149266.2A CN202110149266A CN112794945A CN 112794945 A CN112794945 A CN 112794945A CN 202110149266 A CN202110149266 A CN 202110149266A CN 112794945 A CN112794945 A CN 112794945A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a reducible and degradable water clarifier and a preparation method and application thereof. The preparation method of the reducible and degradable water clarifier comprises the following steps: (1) in an inert atmosphere, in the presence of an initiator, carrying out polymerization reaction on polymerizable tertiary amine and cationic comonomer and polymerizable primary amine and/or polymerizable secondary amine to obtain an oligomer; (2) adding a reducible and degradable chain extender into the oligomer for chain extension reaction to obtain the polymer; the polymerizable tertiary amine is at least one of N, N-dimethylacrylamide, N- (3-dimethylaminopropyl) methacrylamide and dimethylaminoethyl methacrylate; the cationic comonomer is diallyl dimethyl ammonium chloride and/or acryloyloxyethyl trimethyl ammonium chloride; the polymerizable secondary amine is diallylamine; the polymerizable primary amine is an allylic primary amine. The degradable clear water agent can be degraded in hot water, the treated polymer flooding produced water has good oil removal rate, and the formed polymer-containing floc has self-digestion property.
Description
Technical Field
The invention relates to a reducible and degradable water clarifier and a preparation method and application thereof, belonging to the technical field of petroleum industry.
Background
The polymer flooding produced liquid has high stability and great treatment difficulty, and the produced liquid is usually produced by combining a chemical agent and physical oil removal. Common chemical agents include nonionic demulsifiers, reverse demulsifiers, and cationic flocculants, reverse demulsifiers. Cationic agents have quick and good effects, but can cause serious oil sludge problem; the nonionic medicament does not generate electrostatic neutralization with the returned anionic polyacrylamide to generate oil sludge, but has slow effect and poor effect. In the actual production, a treating agent which has quick response, good effect and no oil sludge is needed.
Disclosure of Invention
The invention aims to provide a reducible and disintegrable water clarifier for polymer flooding produced water, which can be degraded in hot water (self-reducing substances in oily sewage, such as olefins, ferrous ions and the like), has good water clarifying effect when used for treating the polymer flooding produced water, and has self-digestion performance of formed polymer-containing flocs.
The preparation method of the reducible and degradable water clarifier provided by the invention comprises the following steps:
(1) in an inert atmosphere, in the presence of an initiator, carrying out polymerization reaction on polymerizable tertiary amine and cationic comonomer and polymerizable primary amine and/or polymerizable secondary amine to obtain an oligomer;
(2) and adding a reducible and degradable chain extender into the oligomer for chain extension reaction to obtain the polymer.
In the above preparation method, the polymerizable tertiary amine is at least one of N, N-dimethylacrylamide, N- (3-dimethylaminopropyl) methacrylamide and dimethylaminoethyl methacrylate;
the cationic comonomer is diallyl dimethyl ammonium chloride and/or acryloyloxyethyl trimethyl ammonium chloride;
the polymerizable secondary amine is diallylamine;
the polymerizable primary amine is an allylic primary amine.
In the preparation method, in the step (1), the total mass of the polymerizable tertiary amine, the cationic comonomer and the polymerizable primary amine and/or polymerizable secondary amine is 10-70%, preferably 60-70%, 60% or 70% of the mass of the polymerization reaction system;
the mass ratio of the polymerizable tertiary amine to the polymerizable primary amine and/or polymerizable secondary amine is (51-59): 1-9, preferably 54-57: 2-3, 54: 2 or 57: 3;
the mass ratio of the cationic comonomer to the polymerizable primary amine and/or polymerizable secondary amine is 30-40: 1-3, preferably 30: 1-3, 30: 1 or 30: 3;
the amount of the initiator added is 0.3 to 0.8%, preferably 0.3 to 0.5%, 0.3% or 0.5% of the total mass of the polymerizable tertiary amine, the cationic comonomer and the polymerizable primary amine and/or polymerizable secondary amine.
In the above production method, in the step (1), the polymerization reaction is carried out in a polar organic solvent;
the polar organic solvent is methanol, ethanol, n-propanol, pyridine or acetone.
In the above preparation method, in the step (1), the initiator is an oxidation-reduction initiation system or an azo initiation system;
the temperature of the polymerization reaction is 0-65 ℃, and the time is 2-12 h.
In the preparation method, in the step (2), the reducible and degradable chain extender is N, N' -bis (acryloyl) cystamine and/or cystamine derivative;
the cystamine derivative is obtained by reacting cystamine with water-soluble isocyanate, wherein the molar ratio of the cystamine to the water-soluble isocyanate is 1: 2.
in the preparation method, in the step (2), the molar ratio of the reducible chain extender to the secondary amine groups in the oligomer is in a range of 0.05-0.3: 1;
the temperature of the chain extension reaction is 50-75 ℃, and the time is 2-24 hours.
The degradable clear water agent can be degraded in hot water, the treated polymer flooding produced water has good oil removal rate, and the formed polymer-containing floc has self-digestion property.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the following examples, the oil removal rate, the hot water degradability of the degradable clear water agent and the self-digestion of the flocs-containing material were measured by the following methods, respectively:
(1) determination of oil removal Rate
The oilfield sewage is taken from a certain polymer injection oilfield in China, the oil content of the produced water is 8210mg/L, and the concentration of the produced polymer is 105 mg/L. The evaluation test of the water scavenger is as follows: pouring 100ml of polymer flooding produced water into a beaker, preserving heat at 60 ℃ for 10min, adding 350ppm of a water clarifier, stirring for 1min, standing for 5min, and then measuring the oil content in the water by using a lower-layer water sample. And calculating the oil removal rate.
Oil removal rate is (initial oil content-oil content after treatment)/initial oil content × 100%.
(2) Determination of floc disappearance time
The main reason for the formation of polymer-containing oil sludge is that clear water interacts with a polymer for displacement of reservoir oil (HPAM) to form water-insoluble polyelectrolyte complex flocs, and if the flocs can be self-digested, the polymer-containing oil sludge can be self-digested. Preparing an oil displacement polymer (HPAM) water solution with the concentration of 500mg/L, adding a degradable water clarifier (500mg/L) into the water solution to form polyelectrolyte complex flocs, heating to 65 ℃, and recording the disappearance time of the flocs.
Example 1 preparation of reducible and degradable clear water agent for Polymer flooding produced Water treatment
Firstly, 57g of N, N-dimethylacrylamide, 3g of diallylamine, 30g of methacryloyloxyethyl trimethyl ammonium chloride and 40g of ethanol are weighed and added into a reactor, the temperature is raised to 55 ℃, nitrogen is introduced for 30min, and then 0.3g of initiator azobisisobutyronitrile is added for reaction for 8h to obtain an ethanol solution of N, N-dimethylacrylamide and diallyl amine oligomer; then 1.24g N, N' -bis (acryloyl) cystamine is added to react for 2h at 70 ℃, and the thermally degradable water clarifier 1 is obtained.
Example 2 preparation of reducible and degradable clear water agent for Polymer flooding produced Water treatment
Firstly, 57g of N- (3-dimethylaminopropyl) methacrylamide, 3g of diallylamine, 30g of methacryloyloxyethyl trimethyl ammonium chloride and 40g of ethanol are weighed and added into a reactor, the temperature is raised to 55 ℃, nitrogen is introduced for 30min, and then 0.3g of initiator tert-butyl hydroperoxide is added for reaction for 8h, so as to obtain an N- (3-dimethylaminopropyl) methacrylamide and diallylamine oligomer ethanol solution; then 1.24g of N, N' -bis (acryloyl) cystamine is added to react for 2h at 70 ℃ to obtain the thermally degradable water clarifier 2.
Example 3 preparation of reducible and degradable Water aqua clarifier for Polymer flooding produced Water treatment
Firstly, 57g of dimethylaminoethyl methacrylate, 3g of diallylamine, 30g of diallyldimethylammonium chloride and 40g of ethanol are weighed and added into a reactor, the temperature is raised to 55 ℃, nitrogen is introduced for 30min, and then 0.3g of initiator azobisisobutyronitrile is added for reaction for 8h to obtain an ethanol solution of dimethylaminoethyl methacrylate and diallylamine oligomer; then 1.24g N, N' -bis (acryloyl) cystamine is added to react for 2h at 70 ℃, and the thermally degradable water clarifier 3 is obtained.
Example 4 preparation of reducible and degradable Water aqua clarifier for Polymer flooding produced Water treatment
Firstly, 27g N- (3-dimethylaminopropyl) methacrylamide, 30 diallyl dimethyl ammonium chloride, 1g allyl amine and 40g ethanol are weighed and added into a reactor, the temperature is raised to 55 ℃, nitrogen is introduced for 30min, and then 0.3g initiator azobisisobutyronitrile is added for reaction for 8h to obtain an ethanol solution of N- (3-dimethylaminopropyl) methacrylamide and diallyl amine oligomer; then, 2.41g of telechelic derivative generated by cystamine and water-soluble isocyanate (the telechelic derivative generated by the molar ratio of the cystamine to the water-soluble isocyanate is 1: 2) is added and reacted for 2 hours at 50 ℃, so as to obtain the degradable water clarifier 4.
The performance evaluation results of the water-clearing agents prepared in examples 1 to 4 are shown in Table 1.
TABLE 1 Effect of degradable clear water agents 1-4
| Medicament | Degradable water clarifier 1 | Degradable water clarifier 2 | Degradable water clarifier 3 | Degradable water clarifier 4 |
| Oil removal Rate (%) | 91.5 | 89 | 93 | 99.5 |
| Disappearance of floc (min) | 200 | 270 | 250 | 320 |
The floc disappearance time is closely related to the content of the reducing substances in the oily sewage, the time is longer when the ferrous ions in the oily sewage are less than 1mg/L, the reducing substance tri (2-carbonyl ethyl) phosphate hydrochloride can be added, and no reagent is needed to be added to the sewage evaluated by the experiment.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a reducible and degradable water clarifier comprises the following steps:
(1) in an inert atmosphere, in the presence of an initiator, carrying out polymerization reaction on polymerizable tertiary amine and cationic comonomer and polymerizable primary amine and/or polymerizable secondary amine to obtain an oligomer;
(2) and adding a reducible and degradable chain extender into the oligomer for chain extension reaction to obtain the polymer.
2. The method of claim 1, wherein: the polymerizable tertiary amine is at least one of N, N-dimethylacrylamide, N- (3-dimethylaminopropyl) methacrylamide and dimethylaminoethyl methacrylate;
the cationic comonomer is diallyl dimethyl ammonium chloride and/or acryloyloxyethyl trimethyl ammonium chloride;
the polymerizable secondary amine is diallylamine;
the polymerizable primary amine is an allylic primary amine.
3. The production method according to claim 1 or 2, characterized in that: in the step (1), the total mass of the polymerizable tertiary amine, the cationic comonomer and the polymerizable primary amine and/or polymerizable secondary amine is 10-70% of the mass of a polymerization reaction system;
the mass ratio of the polymerizable tertiary amine to the polymerizable primary amine and/or polymerizable secondary amine is (51-59): 1-9;
the mass ratio of the cationic comonomer to the polymerizable primary amine and/or polymerizable secondary amine is 30-40: 1-3;
the addition amount of the initiator is 0.3-0.8% of the total mass of the polymerizable tertiary amine, the cationic comonomer and the polymerizable primary amine and/or polymerizable secondary amine.
4. The production method according to any one of claims 1 to 3, characterized in that: in the step (1), the polymerization reaction is carried out in a polar organic solvent;
the polar organic solvent is methanol, ethanol, n-propanol, pyridine or acetone.
5. The production method according to any one of claims 1 to 4, characterized in that: in the step (1), the initiator is an oxidation-reduction initiation system or an azo initiation system;
the temperature of the polymerization reaction is 0-65 ℃, and the time is 2-12 h.
6. The production method according to any one of claims 1 to 5, characterized in that: in the step (2), the reducible and degradable chain extender is N, N' -bis (acryloyl) cystamine and/or cystamine derivatives.
7. The method of claim 6, wherein: the cystamine derivative is obtained by reacting cystamine with water-soluble isocyanate.
8. The production method according to any one of claims 1 to 7, characterized in that: in the step (2), the molar ratio of the reducible chain extender to the secondary amine groups in the oligomer is in the range of 0.05-0.3: 1;
the temperature of the chain extension reaction is 50-75 ℃, and the time is 2-24 hours.
9. A reducible degradable water clarifier prepared by the process defined in any one of claims 1 to 8.
10. Use of the reducible and degradable water clarifier of claim 9 in the treatment of polymer flooding produced water.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SK280241B6 (en) * | 1988-12-19 | 1999-10-08 | Cytec Technology Corp. | Water-soluble, branched, cationic, polymeric flocculant, process for its preparation and its use |
| WO2004041884A1 (en) * | 2002-11-04 | 2004-05-21 | Ge Betz, Inc. | Modified polymeric flocculants with improved performance characteristics |
| CN101575132A (en) * | 2009-06-11 | 2009-11-11 | 吴江市恒茂电子科技有限公司 | Dication polyacrylamide flocculating agent and preparation method thereof |
| CN105314724A (en) * | 2015-11-25 | 2016-02-10 | 苏州书瑞环保科技有限公司 | Composite water treatment material and preparing method thereof |
| CN106317298A (en) * | 2015-06-16 | 2017-01-11 | 中石化石油工程技术服务有限公司 | Cationic coating flocculant and preparation method thereof |
-
2021
- 2021-02-03 CN CN202110149266.2A patent/CN112794945A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SK280241B6 (en) * | 1988-12-19 | 1999-10-08 | Cytec Technology Corp. | Water-soluble, branched, cationic, polymeric flocculant, process for its preparation and its use |
| WO2004041884A1 (en) * | 2002-11-04 | 2004-05-21 | Ge Betz, Inc. | Modified polymeric flocculants with improved performance characteristics |
| CN101575132A (en) * | 2009-06-11 | 2009-11-11 | 吴江市恒茂电子科技有限公司 | Dication polyacrylamide flocculating agent and preparation method thereof |
| CN106317298A (en) * | 2015-06-16 | 2017-01-11 | 中石化石油工程技术服务有限公司 | Cationic coating flocculant and preparation method thereof |
| CN105314724A (en) * | 2015-11-25 | 2016-02-10 | 苏州书瑞环保科技有限公司 | Composite water treatment material and preparing method thereof |
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Application publication date: 20210514 |