CN115785441A - Amphoteric flocculant for oily sewage of oil field and preparation method thereof - Google Patents
Amphoteric flocculant for oily sewage of oil field and preparation method thereof Download PDFInfo
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- 239000010865 sewage Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 90
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 84
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229920000768 polyamine Polymers 0.000 claims abstract description 20
- 150000004985 diamines Chemical class 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 239000012153 distilled water Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 22
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- 229960001124 trientine Drugs 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 229920006317 cationic polymer Polymers 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000006845 Michael addition reaction Methods 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 34
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 14
- 239000008346 aqueous phase Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 7
- 239000008394 flocculating agent Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- WEAQXVDSAUMZHI-UHFFFAOYSA-M 2-methylprop-2-enamide;trimethyl(propyl)azanium;chloride Chemical compound [Cl-].CC(=C)C(N)=O.CCC[N+](C)(C)C WEAQXVDSAUMZHI-UHFFFAOYSA-M 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical group [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- HMHFERXOZSZRML-UHFFFAOYSA-M trimethyl-(3-methyloxiran-2-yl)azanium;chloride Chemical compound [Cl-].CC1OC1[N+](C)(C)C HMHFERXOZSZRML-UHFFFAOYSA-M 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 1
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses an amphoteric flocculant for oily sewage of an oil field and a preparation method thereof, belonging to the technical field of petroleum industry. The method comprises the steps of taking methyl acrylate, polyamine or diamine, a quaternary ammonium salt monomer, carbon disulfide and strong base as raw materials, firstly carrying out a reaction of the methyl acrylate and the polyamine or the diamine to generate polyamide-amine, then carrying out a substitution reaction or a Michael addition reaction of the polyamide-amine and the quaternary ammonium salt monomer to generate a hyperbranched cationic polymer, and finally adding alkali liquor and dropwise adding the carbon disulfide into an obtained polymer solution to prepare the amphoteric flocculant for treating the oily sewage of the oil field. The amphoteric flocculant has a good treatment effect when used for treating oily sewage generated by an oil field.
Description
Technical Field
The invention relates to the technical field of petroleum industry, in particular to an amphoteric flocculant for oily sewage in an oil field and a preparation method thereof.
Background
At present, flocculants developed for O/W type emulsions at home and abroad mainly comprise three categories of low molecular electrolytes, alcohols, surfactants and high molecular polymers. The high molecular polymer flocculant is used in many cases, and can be classified into cationic, anionic and nonionic flocculants according to the charge property of the flocculant. The exploitation of offshore oil fields gradually enters a high water-cut period, the retention time of oily sewage in a flow is shorter and shorter due to the limitation of space and equipment treatment capacity, and the conventional polymer flocculant cannot meet the equipment treatment requirement. With amine, naOH and CS 2 The bisthiocarbamate synthesized as the raw material has the common functions of demulsification, oil removal, sterilization, scale prevention and the like, and is a common flocculant. The flocculant has the advantages of low dosage, high oil removal speed, small molecular weight, dispersed flocculated product and easy blockage of the hydrocyclone. In order to improve the treatment effect of the medicament, the structural performance of the product needs to be improved from the design of a molecular structure, and an anionic group is introduced into a cationic polymer, so that the problems of space mismatching and steric hindrance existing in both micromolecules of a multifunctional group and a polymeric flocculant can be solved. Therefore, the development of an amphoteric flocculant capable of effectively treating oily sewage of a high-water-content oil field is important for oil field productionThe significance of production.
Disclosure of Invention
The invention aims to solve the technical problems and provides an amphoteric flocculant for oily sewage of an oil field and a preparation method thereof.
In a first aspect, the application provides a preparation method of an amphoteric flocculant for oily sewage in an oil field, which is realized by adopting the following technical scheme.
A preparation method of an amphoteric flocculant for oily sewage in an oil field comprises the following steps:
s1. Preparation of Polyamide-amine
a. Uniformly mixing polyamine or diamine, methanol and distilled water, dropwise adding methyl acrylate at a preset temperature, and reacting for 12-24 hours after dropwise adding is finished to obtain a polymer A;
b. keeping the same reaction conditions, continuously dropwise adding polyamine or diamine into the polymer A, and reacting for 12-24 h after dropwise adding is finished to obtain a polymer B;
c. keeping the same reaction condition, continuously dropwise adding methyl acrylate into the polymer B, and reacting for 12-24 h after dropwise adding is finished to obtain a polymer C;
d. keeping the same reaction condition, continuously dropwise adding polyamine or diamine into the polymer C, reacting for 12-24 h after dropwise adding is finished, and then raising the temperature to 120 ℃ in a gradient manner to obtain polyamide-amine;
s2. Preparation of intermediate polymer
Mixing the polyamide-amine prepared in the step S1 with distilled water, dropwise adding a quaternary ammonium salt monomer at the temperature of 60 ℃, and continuously reacting for 4-6 hours after dropwise adding is finished to obtain an intermediate polymer;
s3, preparation of amphoteric flocculant
And (3) adding a strong base solution into the intermediate polymer prepared in the step (S2) under the stirring condition, slowly dropwise adding carbon disulfide at a preset temperature, and reacting for 4-6 h after dropwise adding is finished to obtain the amphoteric flocculant for the oily sewage of the oil field.
Further, in step S1, the diamine is ethylenediamine, hexamethylenediamine or polyetheramine D230, preferably ethylenediamine; the polyamine is selected from diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethylene polyamine and polyether amine T-403, preferably diethylenetriamine.
Further, in step S1a, the mass ratio of the polyamine or diamine to the methyl acrylate is (1-7): 1, the mass ratio of the methanol to the water is (0.1-10): 1, and the total mass of the polyamine or diamine to the methyl acrylate is M 1 The total mass of methanol and water is M 2 ，M 1 :M 2 1 is calculated from (0.1-4).
Further, in step S1b, the ratio of the amount of the polyamine or diamine to the amount of the substance of the polymer A is (1-7): 1.
Further, in step S1c, the ratio of the amount of methyl acrylate to the amount of polymer B is (1-42): 1.
Further, in step S1d, the ratio of the amount of polyamine or diamine to the amount of polymer C is (1-42): 1.
Further, in step S1, the reaction temperature before the temperature is raised in steps is 40 to 60 ℃.
Furthermore, in the step S1, the temperature rise process is carried out for 4 to 8 hours at 80 ℃, for 4 to 8 hours at 100 ℃ and for 4 to 8 hours at 120 ℃.
Further, in step S1, the dropping rate of the dropping reaction is 2 to 6kg/min.
Further, in step S2, the mass ratio of the quaternary ammonium salt monomer to the polyamide-amine obtained in step S1 is (0.1-2.5): 1. Preferably, the mass ratio of the quaternary ammonium salt monomer to the polyamide-amine prepared in step S1 is 1.
Further, in step S2, the quaternary ammonium salt monomer is selected from 2, 3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, (3-acrylamidopropyl) trimethylammonium chloride, or methacrylamidopropyltrimethylammonium chloride.
Further, in step S2, the dropping speed of the quaternary ammonium salt monomer is 1-6 kg/min.
Further, in step S3, the reaction temperature is 0 to 40 ℃, preferably 25 ℃.
Further, in step S3, the strong alkaline solution is an aqueous solution of sodium hydroxide or potassium hydroxide.
Further, in step S3, the mass ratio of the carbon disulfide to the strong base is (1.5-1.9): 1, and preferably 1.8).
Further, in step S3, the mass ratio of the carbon disulfide to the intermediate polymer obtained in step S2 is (0.1-1): 1.
Further, in the step S3, the dropping speed of the carbon disulfide is 1 to 3kg/min.
In a second aspect, the application provides an amphoteric flocculant for oily sewage in an oil field, which is realized by adopting the following technical scheme.
An amphoteric flocculant prepared by the preparation method of the amphoteric flocculant for the oily sewage of the oil field.
The present application has the following advantageous effects.
The amphoteric flocculant prepared by the method disclosed by the invention is low in dosage, high in oil removal speed, concentrated in flocculation product, not easy to block a hydrocyclone, and capable of overcoming the problems of space mismatching and steric hindrance. The preparation method of the amphoteric flocculant is simple, and when the amphoteric flocculant is used for treating oily sewage generated by an oil field, the treatment effect is good, and the amphoteric flocculant has a wide industrial application prospect.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of an amphoteric flocculant for oily sewage in an oil field comprises the following steps:
(1) Uniformly mixing 6g of ethylenediamine, 112.6g of methanol and 112.6g of distilled water, adding the mixture into a four-neck flask, then placing the flask into a water bath kettle, simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with 34.4g of methyl acrylate with the stirrer, starting stirring after the water bath is heated to 40 ℃, dropwise adding the methyl acrylate into the aqueous phase solution, and reacting the system for 12 hours after the dropwise adding is finished to generate a polymer A; under the same reaction condition, continuously dropwise adding 24g of ethylenediamine, and reacting the system for 12 hours after dropwise adding to generate a polymer B; continuously dropwise adding 68.8g of methyl acrylate under the same reaction condition, and reacting the system for 12 hours after dropwise adding to generate a polymer C; keeping the same reaction condition, continuously dropwise adding 48g of ethylenediamine, reacting the system for 12h after dropwise adding is finished, and reacting for 4h at 80 ℃,100 ℃ and 120 ℃ respectively to generate polyamide-amine;
(2) Pouring the prepared polyamide-amine and distilled water into a four-neck flask, after the temperature is raised to 60 ℃, slowly dropwise adding 41g of (3-acrylamidopropyl) trimethyl ammonium chloride into the four-neck flask, continuing to react for 4 hours after the dropwise adding is finished, and cooling to 25 ℃ to obtain an intermediate polymer;
(3) Placing the four-neck flask filled with the intermediate polymer solution in the step (2) into a water bath kettle, and simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with carbon disulfide with the four-neck flask; stirring is started, 26.4g of sodium hydroxide is dissolved by distilled water and then added into a four-neck flask, after the temperature is rapidly controlled to 25 ℃, 45.6g of carbon disulfide is slowly dripped into the intermediate polymer solution; after the dropwise addition is finished, the system reacts for 5 hours again to obtain the amphoteric flocculant 1 for treating the oily sewage of the oil field.
Example 2
A preparation method of an amphoteric flocculant for oily sewage in an oil field comprises the following steps:
(1) Uniformly mixing 6g of ethylenediamine, 137.1g of methanol and 137.1g of distilled water, adding the mixture into a four-neck flask, then placing the flask into a water bath kettle, simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with 34.4g of methyl acrylate, starting stirring after the water bath is heated to 40 ℃, dropwise adding the methyl acrylate into the aqueous phase solution, and reacting the system for 12 hours after the dropwise addition is finished to generate a polymer A; continuing to dropwise add 41.3g of diethylenetriamine under the same reaction condition, and reacting the system for 12 hours after dropwise adding to generate a polymer B; continuously dropwise adding 68.8g of methyl acrylate under the same reaction condition, and reacting the system for 12 hours after dropwise adding to generate a polymer C; under the same reaction condition, continuously dropwise adding 82.6g of diethylenetriamine, after the dropwise adding is finished, reacting the system for 12 hours, and then reacting for 4 hours at 80 ℃,100 ℃ and 120 ℃ respectively to generate polyamide-amine;
(2) Pouring the prepared polyamide-amine and distilled water into a four-neck flask, after the temperature is raised to 60 ℃, slowly dropwise adding 41g of (3-acrylamidopropyl) trimethyl ammonium chloride into the four-neck flask, continuing to react for 4 hours after the dropwise adding is finished, and cooling to 25 ℃ to obtain an intermediate polymer;
(3) Placing the four-neck flask filled with the intermediate polymer solution in the step (2) into a water bath kettle, and simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with carbon disulfide with the four-neck flask; starting stirring, dissolving 26.4g of sodium hydroxide by using distilled water, adding the solution into a four-neck flask, quickly controlling the temperature to be 25 ℃, and then slowly dropwise adding 45.6g of carbon disulfide into the intermediate polymer solution; after the dropwise addition is finished, the system reacts for 5 hours again to obtain the amphoteric flocculant 2 for treating the oily sewage of the oil field.
Example 3
A preparation method of an amphoteric flocculant for oily sewage in an oil field comprises the following steps:
(1) Uniformly mixing 6g of ethylenediamine, 142.2g of methanol and 142.2g of distilled water, adding the mixture into a four-neck flask, then placing the flask into a water bath kettle, simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with 34.4g of methyl acrylate with the stirrer, starting stirring after the water bath is heated to 40 ℃, dropwise adding the methyl acrylate into the aqueous phase solution, and reacting the system for 12 hours after the dropwise adding is finished to generate a polymer A; under the same reaction condition, continuously dropwise adding 58.4g of triethylene tetramine, and after dropwise adding is finished, reacting the system for 12 hours to generate a polymer B; continuously dropwise adding 68.8g of methyl acrylate under the same reaction condition, and reacting the system for 12 hours after dropwise adding is finished to generate a polymer C; under the same reaction condition, continuously dropwise adding 116.8g of triethylene tetramine, after dropwise adding, reacting the system for 12 hours, and then reacting at 80 ℃,100 ℃ and 120 ℃ for 4 hours to generate polyamide-amine;
(2) Pouring the prepared polyamide-amine and distilled water into a four-neck flask, after the temperature is raised to 60 ℃, slowly dropwise adding 41g of (3-acrylamidopropyl) trimethyl ammonium chloride into the four-neck flask, continuing to react for 4 hours after dropwise adding is finished, and cooling to 25 ℃ to obtain an intermediate polymer;
(3) Placing the four-neck flask filled with the intermediate polymer solution in the step (2) into a water bath kettle, and simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with carbon disulfide with the four-neck flask; starting stirring, dissolving 26.4g of sodium hydroxide by using distilled water, adding the solution into a four-neck flask, quickly controlling the temperature to be 25 ℃, and then slowly dropwise adding 45.6g of carbon disulfide into the intermediate polymer solution; after the dropwise addition is finished, the system reacts for 5 hours to obtain the amphoteric flocculant 3 for treating the oily sewage of the oil field.
Example 4
A preparation method of an amphoteric flocculant for oily sewage in an oil field comprises the following steps:
(1) Uniformly mixing 6g of ethylenediamine, 168.1g of methanol and 168.1g of distilled water, adding the mixture into a four-neck flask, then placing the flask into a water bath kettle, simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with 34.4g of methyl acrylate with the stirrer, starting stirring after the water bath is heated to 40 ℃, dropwise adding the methyl acrylate into the aqueous phase solution, and reacting the system for 12 hours after the dropwise adding is finished to generate a polymer A; continuously dropwise adding 75.7g of tetraethylenepentamine under the same reaction condition, and reacting the system for 12 hours after dropwise adding to generate a polymer B; continuously dropwise adding 68.8g of methyl acrylate under the same reaction condition, and reacting the system for 12 hours after dropwise adding is finished to generate a polymer C; under the same reaction condition, continuously dropwise adding 151.4g of tetraethylenepentamine, reacting the system for 12 hours after dropwise adding is finished, and then reacting for 4 hours at 80 ℃,100 ℃ and 120 ℃ respectively to generate polyamide-amine;
(2) Pouring the prepared polyamide-amine and distilled water into a four-neck flask, after the temperature is raised to 60 ℃, slowly dropwise adding 41g of (3-acrylamidopropyl) trimethyl ammonium chloride into the four-neck flask, continuing to react for 4 hours after the dropwise adding is finished, and cooling to 25 ℃ to obtain an intermediate polymer;
(3) Placing the four-neck flask filled with the intermediate polymer solution in the step (2) into a water bath kettle, and simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with carbon disulfide with the four-neck flask; starting stirring, dissolving 26.4g of sodium hydroxide by using distilled water, adding the solution into a four-neck flask, quickly controlling the temperature to be 25 ℃, and then slowly dropwise adding 45.6g of carbon disulfide into the intermediate polymer solution; after the dropwise addition is finished, the system reacts for 5 hours to obtain the amphoteric flocculant 4 for treating the oily sewage of the oil field.
Example 5
A preparation method of an amphoteric flocculant for oily sewage in an oil field comprises the following steps:
(1) Uniformly mixing 6g of ethylenediamine, 137.1g of methanol and 137.1g of distilled water, adding the mixture into a four-neck flask, then placing the flask into a water bath kettle, simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with 34.4g of methyl acrylate with the stirrer, starting stirring after the water bath is heated to 40 ℃, dropwise adding the methyl acrylate into the aqueous phase solution, and reacting the system for 12 hours after the dropwise adding is finished to generate a polymer A; continuing to dropwise add 41.3g of diethylenetriamine under the same reaction condition, and reacting the system for 12 hours after dropwise adding to generate a polymer B; continuously dropwise adding 68.8g of methyl acrylate under the same reaction condition, and reacting the system for 12 hours after dropwise adding to generate a polymer C; under the same reaction condition, continuously dropwise adding 82.6g of diethylenetriamine, after the dropwise adding is finished, reacting the system for 12 hours, and then reacting for 4 hours at 80 ℃,100 ℃ and 120 ℃ respectively to generate polyamide-amine;
(2) Pouring the prepared polyamide-amine and distilled water into a four-neck flask, after the temperature is raised to 60 ℃, slowly dropwise adding 23.2g of 2, 3-epoxypropyltrimethylammonium chloride into the four-neck flask, continuing to react for 4 hours after the dropwise adding is finished, and cooling to 25 ℃ to obtain an intermediate polymer;
(3) Placing the four-neck flask filled with the intermediate polymer solution in the step (2) into a water bath kettle, and simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with carbon disulfide with the four-neck flask; stirring is started, 26.4g of sodium hydroxide is dissolved by distilled water and then added into a four-neck flask, after the temperature is rapidly controlled to 25 ℃, 45.6g of carbon disulfide is slowly dripped into the intermediate polymer solution; after the dropwise addition is finished, the system reacts for 5 hours to obtain the amphoteric flocculant 5 for treating the oily sewage of the oil field.
Example 6
A preparation method of an amphoteric flocculant for oily sewage in an oil field comprises the following steps:
(1) Uniformly mixing 6g of ethylenediamine, 137.1g of methanol and 137.1g of distilled water, adding the mixture into a four-neck flask, then placing the flask into a water bath kettle, simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with 34.4g of methyl acrylate with the stirrer, starting stirring after the water bath is heated to 40 ℃, dropwise adding the methyl acrylate into the aqueous phase solution, and reacting the system for 12 hours after the dropwise adding is finished to generate a polymer A; continuing to dropwise add 41.3g of diethylenetriamine under the same reaction condition, and reacting the system for 12 hours after dropwise adding to generate a polymer B; continuously dropwise adding 68.8g of methyl acrylate under the same reaction condition, and reacting the system for 12 hours after dropwise adding to generate a polymer C; under the same reaction condition, continuously dropwise adding 82.6g of diethylenetriamine, after dropwise adding, reacting the system for 12 hours, and then reacting for 4 hours at 80 ℃,100 ℃ and 120 ℃ respectively to generate polyamide-amine;
(2) Pouring the prepared polyamide-amine and distilled water into a four-neck flask, after the temperature is raised to 60 ℃, slowly dropwise adding 44g of methacrylamide propyl trimethyl ammonium chloride into the four-neck flask, continuing to react for 4 hours after the dropwise adding is finished, and cooling to 25 ℃ to obtain an intermediate polymer;
(3) Placing the four-neck flask filled with the intermediate polymer solution in the step (2) into a water bath kettle, and simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with carbon disulfide with the four-neck flask; starting stirring, dissolving 26.4g of sodium hydroxide by using distilled water, adding the solution into a four-neck flask, quickly controlling the temperature to be 25 ℃, and then slowly dropwise adding 45.6g of carbon disulfide into the intermediate polymer solution; after the dropwise addition is finished, the system reacts for 5 hours again to obtain the amphoteric flocculant 6 for treating the oily sewage of the oil field.
Example 7
A preparation method of an amphoteric flocculant for oily sewage in an oil field comprises the following steps:
(1) Uniformly mixing 10.3g of diethylenetriamine, 113.5g of methanol and 113.5g of distilled water, adding the mixture into a four-neck flask, then placing the flask into a water bath kettle, simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with 34.4g of methyl acrylate, starting stirring after the water bath is heated to 40 ℃, dropwise adding the methyl acrylate into the aqueous phase solution, and reacting the system for 12 hours after the dropwise addition is finished to generate a polymer A; under the same reaction condition, continuously dropwise adding 24g of ethylenediamine, and reacting the system for 12 hours after dropwise adding to generate a polymer B; continuously dropwise adding 68.8g of methyl acrylate under the same reaction condition, and reacting the system for 12 hours after dropwise adding to generate a polymer C; keeping the same reaction condition, continuously dropwise adding 48g of ethylenediamine, reacting the system for 12h after dropwise adding is finished, and then reacting for 4h at 80 ℃,100 ℃ and 120 ℃ respectively to generate polyamide-amine;
(2) Pouring the prepared polyamide-amine and distilled water into a four-neck flask, after the temperature is raised to 60 ℃, slowly dropwise adding 41g of (3-acrylamidopropyl) trimethyl ammonium chloride into the four-neck flask, continuing to react for 4 hours after the dropwise adding is finished, and cooling to 25 ℃ to obtain an intermediate polymer;
(3) Placing the four-neck flask filled with the intermediate polymer solution in the step (2) into a water bath kettle, and simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with carbon disulfide with the four-neck flask; starting stirring, adding 26.4g of sodium hydroxide solution dissolved by distilled water into a four-neck flask, quickly controlling the temperature to 25 ℃, and then slowly dropwise adding 45.6g of carbon disulfide into the intermediate polymer solution; after the dropwise addition is finished, the system reacts for 5 hours again to obtain the amphoteric flocculant 7 for treating the oily sewage of the oil field.
Example 8
A preparation method of an amphoteric flocculant for oily sewage in an oil field comprises the following steps:
(1) Uniformly mixing 10.3g of diethylenetriamine, 121g of methanol and 121g of distilled water, adding the mixture into a four-neck flask, then placing the flask into a water bath kettle, simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with 34.4g of methyl acrylate, starting stirring after the water bath is heated to 40 ℃, dropwise adding the methyl acrylate into the aqueous phase solution, and reacting the system for 12 hours after the dropwise adding is finished to generate a polymer A; under the same reaction condition, continuously dropwise adding 24g of ethylenediamine, and reacting the system for 12 hours after dropwise adding is finished to generate a polymer B; continuously dropwise adding 68.8g of methyl acrylate under the same reaction condition, and reacting the system for 12 hours after dropwise adding to generate a polymer C; under the same reaction condition, continuously dropwise adding 82.4g of diethylenetriamine, after the dropwise adding is finished, reacting the system for 12 hours, and then reacting for 4 hours at 80 ℃,100 ℃ and 120 ℃ respectively to generate polyamide-amine;
(2) Pouring the prepared polyamide-amine and distilled water into a four-neck flask, after the temperature is raised to 60 ℃, slowly dropwise adding 22.2g2, 3-epoxypropyltrimethylammonium chloride into the four-neck flask, continuing to react for 4 hours after dropwise adding is finished, and cooling to 25 ℃ to obtain an intermediate polymer;
(3) Placing the four-neck flask filled with the intermediate polymer solution in the step (2) into a water bath kettle, and simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with carbon disulfide with the four-neck flask; starting stirring, dissolving 26.4g of sodium hydroxide by using distilled water, adding the solution into a four-neck flask, quickly controlling the temperature to be 25 ℃, and then slowly dropwise adding 45.6g of carbon disulfide into the intermediate polymer solution; after the dropwise addition is finished, the system reacts for 5 hours again to obtain the amphoteric flocculant 8 for treating the oily sewage of the oil field.
Example 9
A preparation method of an amphoteric flocculant for oily sewage in an oil field comprises the following steps:
(1) Uniformly mixing 10.3g of diethylenetriamine, 130.5g of methanol and 130.5g of distilled water, adding the mixture into a four-neck flask, then placing the flask into a water bath kettle, simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with 34.4g of methyl acrylate, starting stirring after the water bath is heated to 40 ℃, dropwise adding the methyl acrylate into the aqueous phase solution, and reacting the system for 12 hours after the dropwise adding is finished to generate a polymer A; under the same reaction condition, continuously dropwise adding 24g of ethylenediamine, and reacting the system for 12 hours after dropwise adding to generate a polymer B; continuously dropwise adding 68.8g of methyl acrylate under the same reaction condition, and reacting the system for 12 hours after dropwise adding is finished to generate a polymer C; under the same reaction condition, continuously dropwise adding 82.4g of diethylenetriamine, reacting the system for 12 hours after dropwise adding, and then reacting for 4 hours at 80 ℃,100 ℃ and 120 ℃ respectively to generate polyamide-amine;
(2) Pouring the prepared polyamide-amine and distilled water into a four-neck flask, after the temperature is raised to 60 ℃, slowly dropwise adding 41g of (3-acrylamidopropyl) trimethyl ammonium chloride into the four-neck flask, continuing to react for 4 hours after the dropwise adding is finished, and cooling to 25 ℃ to obtain an intermediate polymer;
(3) Placing the four-neck flask filled with the intermediate polymer solution in the step (2) into a water bath kettle, and simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with carbon disulfide with the four-neck flask; stirring is started, 26.4g of sodium hydroxide is dissolved by distilled water and then added into a four-neck flask, after the temperature is rapidly controlled to 25 ℃, 45.6g of carbon disulfide is slowly dripped into the intermediate polymer solution; after the dropwise addition is finished, the system reacts for 5 hours to obtain the amphoteric flocculant 9 for treating the oily sewage of the oil field.
Example 10
A preparation method of an amphoteric flocculant for oily sewage in an oil field comprises the following steps:
(1) Uniformly mixing 10.3g of diethylenetriamine, 132g of methanol and 132g of distilled water, adding the mixture into a four-neck flask, then placing the flask into a water bath kettle, simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with 34.4g of methyl acrylate with the stirrer, starting stirring after the water bath is heated to 40 ℃, dropwise adding the methyl acrylate into the aqueous phase solution, and reacting the system for 12 hours after the dropwise adding is finished to generate a polymer A; under the same reaction condition, continuously dropwise adding 24g of ethylenediamine, and reacting the system for 12 hours after dropwise adding to generate a polymer B; continuously dropwise adding 68.8g of methyl acrylate under the same reaction condition, and reacting the system for 12 hours after dropwise adding to generate a polymer C; under the same reaction condition, continuously dropwise adding 82.4g of diethylenetriamine, reacting the system for 12 hours after dropwise adding, and then reacting for 4 hours at 80 ℃,100 ℃ and 120 ℃ respectively to generate polyamide-amine;
(2) Pouring the prepared polyamide-amine and distilled water into a four-neck flask, after the temperature is raised to 60 ℃, slowly dropwise adding 44g of methacrylamide propyl trimethyl ammonium chloride into the four-neck flask, continuing to react for 4 hours after the dropwise adding is finished, and cooling to 25 ℃ to obtain an intermediate polymer;
(3) Placing the four-neck flask filled with the intermediate polymer solution in the step (2) into a water bath kettle, and simultaneously connecting a stirrer, a condenser pipe and a constant-pressure dropping funnel filled with carbon disulfide with the four-neck flask; stirring is started, 26.4g of sodium hydroxide is dissolved by distilled water and then added into a four-neck flask, after the temperature is rapidly controlled to 25 ℃, 45.6g of carbon disulfide is slowly dripped into the intermediate polymer solution; after the dropwise addition is finished, the system reacts for 5 hours again to obtain the amphoteric flocculant 10 for treating the oily sewage of the oil field.
Performance detection
1. Evaluation of performance of different flocculants in treating oily sewage
Firstly, 80ml of oily sewage (oil content 1860 mg/L) of a certain oil field is taken and poured into a 100ml water removing bottle, and the bottle is placed at 60 ℃ for heat preservation for 10min; then adding 50mg/L of flocculating agent, oscillating 100 times before and after, standing for 5min, taking a lower layer water sample to measure the oil content and calculating the oil removal rate. The results of the oil removal rates for the different flocculants are shown in table 1.
TABLE 1 oil removal rates of different agents for oily wastewater
2. Evaluation of performances of flocculants with different concentrations in treating oily sewage
Firstly, 80ml of oily sewage (oil content 1860 mg/L) of a certain oil field is taken and poured into a 400ml water removing bottle, and the bottle is placed at 60 ℃ for heat preservation for 10min; then adding amphoteric flocculant 4 with different concentrations, oscillating 100 times, standing for 5min, taking the lower layer water sample to determine the oil content and calculating the oil removal rate. The results of the oil removal rates for different concentrations of flocculant are shown in table 2.
TABLE 2 oil removal rates of different agents for oily wastewater
| Serial number | Name of medicament | Concentration of drug in mg/L | Oil removal rate% |
| 1 | Blank space | / | / |
| 2 | Amphoteric flocculant 4 | 20 | 42 |
| 3 | Amphoteric flocculant 4 | 30 | 79 |
| 4 | Amphoteric flocculant 4 | 40 | 88 |
| 5 | Amphoteric flocculant 4 | 50 | 92 |
| 6 | Amphoteric flocculant 4 | 60 | 94 |
| 7 | Amphoteric flocculant 4 | 70 | 90 |
| 8 | Amphoteric flocculant 4 | 80 | 81 |
As can be seen from Table 2, the water and oil removing effect is best when the addition amount of the amphoteric flocculant 4 is more than 60 mg/L.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (10)
1. A preparation method of an amphoteric flocculant for oily sewage in an oil field is characterized by comprising the following steps: the method comprises the following steps:
s1. Preparation of Polyamide-amine
a. Uniformly mixing polyamine or diamine, methanol and distilled water, dropwise adding methyl acrylate at a preset temperature, and reacting for 12-24 h after dropwise adding to obtain a polymer A;
b. keeping the same reaction conditions, continuously dropwise adding polyamine or diamine into the polymer A, and reacting for 12-24 h after dropwise adding to obtain a polymer B;
c. keeping the same reaction condition, continuously dropwise adding methyl acrylate into the polymer B, and reacting for 12-24 h after dropwise adding is finished to obtain a polymer C;
d. keeping the same reaction condition, continuously dropwise adding polyamine or diamine into the polymer C, reacting for 12-24 h after dropwise adding is finished, and then raising the temperature to 120 ℃ in a gradient manner to obtain polyamide-amine;
s2. Preparation of intermediate polymer
Mixing the polyamide-amine prepared in the step S1 with distilled water, dropwise adding a quaternary ammonium salt monomer at the temperature of 60 ℃, and continuously reacting for 4-6 hours after dropwise adding is finished to obtain an intermediate polymer;
s3, preparation of amphoteric flocculant
And (3) adding a strong base solution into the intermediate polymer prepared in the step (S2) under the stirring condition, slowly dropwise adding carbon disulfide at a preset temperature, and reacting for 4-6 h after dropwise adding is finished to obtain the amphoteric flocculant for the oily sewage of the oil field.
2. The preparation method of the amphoteric flocculant for oily sewage in oil fields according to claim 1, which is characterized by comprising the following steps: in the step S1, the diamine is ethylenediamine, hexamethylenediamine or polyether amine D230; the polyamine is selected from diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine and polyether amine T-403.
3. The preparation method of the amphoteric flocculant for oily sewage in oil fields according to claim 1, which is characterized by comprising the following steps: in the step S1a, the mass ratio of the polyamine or diamine to the methyl acrylate is (1-7) to 1, and the mass ratio of the methanol to the water is (0.1-10) to 1; the total mass of polyamine or diamine and methyl acrylate is M 1 The total mass of methanol and water is M 2 ，M 1 :M 2 1 is calculated from (0.1-4).
4. The preparation method of the amphoteric flocculant for oily sewage in oil fields according to claim 1, which is characterized by comprising the following steps: in step S1b, the ratio of the amount of polyamine or diamine to the amount of polymer A is (1-7): 1.
5. The preparation method of the amphoteric flocculant for oily sewage in oil fields according to claim 1, which is characterized by comprising the following steps: in step S1c, the ratio of the amount of methyl acrylate to the amount of polymer B is (1-42): 1.
6. The preparation method of the amphoteric flocculant for oily sewage of oil fields according to claim 1, which is characterized by comprising the following steps: in step S1d, the ratio of the amount of polyamine or diamine to the amount of polymer C is (1-42): 1.
7. The preparation method of the amphoteric flocculant for oily sewage of oil fields according to claim 1, which is characterized by comprising the following steps: in the step S1, the reaction temperature before the temperature rise in the echelon is 40-60 ℃; the gradient heating process is that the reaction is carried out for 4 to 8 hours at 80 ℃, for 4 to 8 hours at 100 ℃ and for 4 to 8 hours at 120 ℃.
8. The preparation method of the amphoteric flocculant for oily sewage of oil fields according to claim 1, which is characterized by comprising the following steps: in step S2, the mass ratio of the quaternary ammonium salt monomer to the polyamide-amine obtained in step S1 is (0.1-2.5): 1.
9. The preparation method of the amphoteric flocculant for oily sewage of oil fields according to claim 1, which is characterized by comprising the following steps: in the step S3, the mass ratio of the carbon disulfide to the intermediate polymer prepared in the step S2 is (0.1-1): 1.
10. An amphoteric flocculant prepared by the method for preparing an amphoteric flocculant for oily sewage of an oil field according to any one of claims 1 to 9.
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| CN114230788A (en) * | 2021-12-16 | 2022-03-25 | 中国石油大学(华东) | Novel multivalent polyanion oily sewage purifying agent and preparation method thereof |
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