阅读说明：本技术 一种聚驱产出液处理用絮凝剂及其制备方法 (Flocculant for treating polymer flooding output liquid and preparation method thereof ) 是由 张国欣 程艳 崔广振 魏强 张颖 郭海军 王永军 胡廷 于 2020-05-19 设计创作，主要内容包括：本发明提供一种聚驱产出液处理用絮凝剂及其制备方法,将二乙烯三胺与交联剂混合,向上述混合物中加入蒸馏水,搅拌均匀得到反应液,向上述反应液中通入氮气以去除反应容器内空气,将上述反应液搅拌条件下,升温至25-55℃,向上述反应液中滴加环氧氯丙烷,滴加时间1-4h,反应温度为45-85℃,滴加完成后,在氮气保护下,保持45-85℃温度下继续反应4-8h后,得到产物A；将聚二甲基二烯丙基氯化铵水溶液与步骤1制备得到的产物A混合,室温条件下,搅拌均匀后,即得到聚驱产出液处理用絮凝剂。该絮凝剂的制备方法简单、易于操作、可控性强、除油率高、净水效果好、油珠大、上浮速度快、产品粘度低,具有普遍适用性。(The invention provides a flocculant for treating polymer flooding output liquid and a preparation method thereof, which comprises the steps of mixing diethylenetriamine and a cross-linking agent, adding distilled water into the mixture, uniformly stirring to obtain a reaction liquid, introducing nitrogen into the reaction liquid to remove air in a reaction container, heating the reaction liquid to 25-55 ℃ under the stirring condition, dropwise adding epoxy chloropropane into the reaction liquid for 1-4 hours at the reaction temperature of 45-85 ℃, keeping the temperature of 45-85 ℃ for continuous reaction for 4-8 hours under the protection of nitrogen after dropwise adding is completed, and obtaining a product A; and (3) mixing the poly dimethyl diallyl ammonium chloride aqueous solution with the product A prepared in the step (1), and stirring uniformly at room temperature to obtain the flocculant for treating the polymer flooding output liquid. The preparation method of the flocculant is simple, easy to operate, strong in controllability, high in oil removal rate, good in water purification effect, large in oil drop, high in floating speed, low in product viscosity and universal in applicability.)

1. The flocculant for treating polymer flooding output liquid is characterized by comprising the following components in parts by weight: the method comprises the following steps:

step 1, mixing diethylenetriamine and a cross-linking agent, adding distilled water into the mixture, uniformly stirring to obtain a reaction liquid, introducing nitrogen into the reaction liquid to remove air in a reaction container, heating the reaction liquid to 25-55 ℃ under the stirring condition, dropwise adding epoxy chloropropane into the reaction liquid for 1-4h, wherein the reaction temperature is 45-85 ℃, after the dropwise adding is completed, under the protection of nitrogen, keeping the temperature of 45-85 ℃ to continue reacting for 4-8h to obtain a product A, wherein the mass ratio of the diethylenetriamine to the crosslinking agent is 12:1-3:1, the addition amount of the distilled water is 0.5-2.5 times of the total mass of the diethylenetriamine, the crosslinking agent and the epichlorohydrin, and the mass ratio of the diethylenetriamine to the epichlorohydrin is 1:2-6: 7;

and 2, mixing the poly-dimethyldiallylammonium chloride aqueous solution with the product A prepared in the step 1, and stirring uniformly at room temperature (20-25 ℃) to obtain the flocculant for treating the polymer flooding output liquid, wherein the amount of the poly-dimethyldiallylammonium chloride aqueous solution contained in the poly-dimethyldiallylammonium chloride aqueous solution is 0.3-2.0 times of the mass of the product A.

2. The flocculant for treating a polymer flooding production fluid according to claim 1, characterized in that: in the step 1, the mass ratio of the diethylenetriamine to the cross-linking agent is 10:1-4:1, the mass ratio of the diethylenetriamine to the epichlorohydrin is 2:3-5:6, the addition amount of the distilled water is 0.7-2 times of the total mass of the diethylenetriamine, the cross-linking agent and the epichlorohydrin, and the cross-linking agent is ethylenediamine or 1, 6-hexanediamine.

3. The flocculant for treating a polymer flooding production fluid according to claim 1, characterized in that: in the step 1, the mixing and stirring temperature of the diethylenetriamine, the cross-linking agent and the distilled water is 30-50 ℃, and the reaction temperature is 50-80 ℃ when the epichlorohydrin is dripped into the reaction liquid and after the epichlorohydrin is dripped.

4. The flocculant for treating a polymer flooding production fluid according to claim 1, characterized in that: in the step 2, the amount of the aqueous solution of the poly-dimethyldiallylammonium chloride contained in the aqueous solution of the poly-dimethyldiallylammonium chloride is 0.5 to 1.5 times of the mass of the product A, the number average molecular weight of the poly-dimethyldiallylammonium chloride in the aqueous solution of the poly-dimethyldiallylammonium chloride is 30 to 200 ten thousand, and the mass concentration of the poly-dimethyldiallylammonium chloride in the aqueous solution of the poly-dimethyldiallylammonium chloride is 20 to 40 percent.

5. A preparation method of a flocculant for treating polymer flooding output liquid is characterized by comprising the following steps: the method comprises the following steps:

step 1, mixing diethylenetriamine and a cross-linking agent, adding distilled water into the mixture, uniformly stirring to obtain a reaction liquid, introducing nitrogen into the reaction liquid to remove air in a reaction container, heating the reaction liquid to 25-55 ℃ under the stirring condition, dropwise adding epoxy chloropropane into the reaction liquid for 1-4h, wherein the reaction temperature is 45-85 ℃, after the dropwise adding is completed, under the protection of nitrogen, keeping the temperature of 45-85 ℃ to continue reacting for 4-8h to obtain a product A, wherein the mass ratio of the diethylenetriamine to the crosslinking agent is 12:1-3:1, the addition amount of the distilled water is 0.5-2.5 times of the total mass of the diethylenetriamine, the crosslinking agent and the epichlorohydrin, and the mass ratio of the diethylenetriamine to the epichlorohydrin is 1:2-6: 7;

and 2, mixing the poly-dimethyldiallylammonium chloride aqueous solution with the product A prepared in the step 1, and stirring uniformly at room temperature (20-25 ℃) to obtain the flocculant for treating the polymer flooding output liquid, wherein the amount of the poly-dimethyldiallylammonium chloride aqueous solution contained in the poly-dimethyldiallylammonium chloride aqueous solution is 0.3-2.0 times of the mass of the product A.

6. The method for preparing the flocculant for treating polymer flooding output liquid according to claim 5, characterized by comprising the following steps: in the step 1, the mass ratio of the diethylenetriamine to the cross-linking agent is 10:1-4:1, the mass ratio of the diethylenetriamine to the epichlorohydrin is 2:3-5:6, the addition amount of the distilled water is 0.7-2 times of the total mass of the diethylenetriamine, the cross-linking agent and the epichlorohydrin, and the cross-linking agent is ethylenediamine or 1, 6-hexanediamine.

7. The method for preparing the flocculant for treating polymer flooding output liquid according to claim 5, characterized by comprising the following steps: in the step 1, the mixing and stirring temperature of the diethylenetriamine, the cross-linking agent and the distilled water is 30-50 ℃, and the reaction temperature is 50-80 ℃ when the epichlorohydrin is dripped into the reaction liquid and after the epichlorohydrin is dripped.

8. The method for preparing the flocculant for treating polymer flooding output liquid according to claim 5, characterized by comprising the following steps: in the step 2, the amount of the aqueous solution of the poly-dimethyldiallylammonium chloride contained in the aqueous solution of the poly-dimethyldiallylammonium chloride is 0.5 to 1.5 times of the mass of the product A, the number average molecular weight of the poly-dimethyldiallylammonium chloride in the aqueous solution of the poly-dimethyldiallylammonium chloride is 30 to 200 ten thousand, and the mass concentration of the poly-dimethyldiallylammonium chloride in the aqueous solution of the poly-dimethyldiallylammonium chloride is 20 to 40 percent.

9. Use of a flocculant according to any one of claims 1 to 4 for polymer flooding production fluid treatment.

10. Use according to claim 9, characterized in that: the flocculant for treating the polymer flooding output liquid has the oil removal rate of 99.2-99.7 percent to the polymer flooding output liquid.

Technical Field

The invention relates to the technical field of oil-gas-water treatment, in particular to a flocculant for treating polymer flooding output liquid and a preparation method thereof.

Background

Petroleum resources are very important strategic resources and play an important role in national economic development and improvement of the living standard of people. However, as the exploration and development degree is deepened, the exploitation difficulty is gradually increased, so that the improvement of the oil recovery rate is not only a problem generally concerned by the oil industry but also a problem generally concerned by the whole society.

Polymer flooding is one of important technical measures of tertiary oil recovery, and also becomes one of important technologies of increasing storage and increasing production and stabilizing oil and controlling water in an oil field, field tests and application prove the technical reliability and economic effectiveness of the polymer flooding, taking a Bohai sea oil field as an example, the technology is applied in a large scale from 2003, and the oil fields applying the technology in the Bohai sea area have the following steps: the method comprises the steps of accumulating 44 wells in a SZ36-1 oil field, a JZ9-3 oil field, an LD10-1 oil field and other major oil fields, and preliminarily building a chemical flooding efficient development demonstration base for the offshore heavy oil field on the basis of the implementation scale of 179 benefited oil wells.

With the continuous expansion of the scale of polymer flooding, the concentration of the produced polymer in the produced liquid of the Bohai sea chemical flooding oilfield rises continuously, the polymer is subjected to long-time action of various factors on the stratum, such as shearing action, thermal action, bacterial action, hydrolysis action, salt action and the like, compared with the injection, the structure and the property of the produced liquid are greatly changed, the treatment difficulty of the produced liquid is increased continuously, the treatment of the produced liquid under a platform condition is seriously influenced, the popularization of the chemical flooding under an offshore condition is seriously restricted, and the treatment of the produced liquid of the oilfield is compelled to be very demanding.

Disclosure of Invention

The invention overcomes the defects in the prior art, the polymer is acted by various factors for a long time in the stratum, and compared with the polymer injected, the structure and the property of the polymer are greatly changed, so that the treatment difficulty of the produced liquid is increased, and the treatment of the platform produced liquid is seriously influenced.

The purpose of the invention is realized by the following technical scheme.

A flocculant for treating polymer flooding output liquid and a preparation method thereof are carried out according to the following steps:

step 1, mixing diethylenetriamine and a cross-linking agent, adding distilled water into the mixture, uniformly stirring to obtain a reaction liquid, introducing nitrogen into the reaction liquid to remove air in a reaction container, heating the reaction liquid to 25-55 ℃ under the stirring condition, dropwise adding epoxy chloropropane into the reaction liquid for 1-4h, wherein the reaction temperature is 45-85 ℃, after the dropwise adding is completed, under the protection of nitrogen, keeping the temperature of 45-85 ℃ to continue reacting for 4-8h to obtain a product A, wherein the mass ratio of the diethylenetriamine to the crosslinking agent is 12:1-3:1, the addition amount of the distilled water is 0.5-2.5 times of the total mass of the diethylenetriamine, the crosslinking agent and the epichlorohydrin, and the mass ratio of the diethylenetriamine to the epichlorohydrin is 1:2-6: 7;

and 2, mixing the poly-dimethyldiallylammonium chloride aqueous solution with the product A prepared in the step 1, and stirring uniformly at room temperature (20-25 ℃) to obtain the flocculant for treating the polymer flooding output liquid, wherein the amount of the poly-dimethyldiallylammonium chloride aqueous solution contained in the poly-dimethyldiallylammonium chloride aqueous solution is 0.3-2.0 times of the mass of the product A.

In the step 1, the mass ratio of the diethylenetriamine to the crosslinking agent is 10:1-4:1, the mass ratio of the diethylenetriamine to the epichlorohydrin is 2:3-5:6, and the addition amount of the distilled water is 0.7-2 times of the total mass of the diethylenetriamine, the crosslinking agent and the epichlorohydrin.

In the step 1, the mixing and stirring temperature of the diethylenetriamine, the cross-linking agent and the distilled water is 30-50 ℃, and the reaction temperature is 50-80 ℃ when the epichlorohydrin is dripped into the reaction liquid and after the epichlorohydrin is dripped.

In step 1, ethylene diamine or 1, 6-hexamethylene diamine is used as a crosslinking agent.

In the step 2, the amount of the aqueous solution of the poly-dimethyldiallylammonium chloride contained in the aqueous solution of the poly-dimethyldiallylammonium chloride is 0.5 to 1.5 times of the mass of the product A, the number average molecular weight of the poly-dimethyldiallylammonium chloride in the aqueous solution of the poly-dimethyldiallylammonium chloride is 30 to 200 ten thousand, and the mass concentration of the poly-dimethyldiallylammonium chloride in the aqueous solution of the poly-dimethyldiallylammonium chloride is 20 to 40 percent.

The invention has the beneficial effects that: the flocculant obtained by the method solves the problem of difficult sewage treatment caused by polymer flooding output liquid, and overcomes the defects of large consumption, poor effect and large transportation amount of the flocculant used in the process; compared with the traditional flocculating agent, the flocculating agent prepared by the invention has the characteristics of high oil removal rate, good water purification effect, large oil droplets, high floating speed, low product viscosity, wide molecular weight distribution and high cationic degree in chemical components, can be practically adjusted according to the characteristics of on-site polymer flooding output liquid, has high effective content, simple method and process, is easy to operate, is convenient to control reaction temperature, is convenient to fill on site, and has universal applicability.

Detailed Description

The technical solution of the present invention is further illustrated by the following specific examples.

Example 1

(1) Firstly, mixing 103g of diethylenetriamine, 11.6g of 1, 6-hexanediamine (wherein the mass ratio of the diethylenetriamine to the 1, 6-hexanediamine is 10:1) and 157.9g of distilled water, uniformly stirring, introducing nitrogen to remove air in a reaction vessel, and heating to 30 ℃;

(2) slowly dripping 111g of epoxy chloropropane (wherein the mass ratio of the diethylenetriamine to the epoxy chloropropane is 5:6) into the reaction liquid, controlling the reaction temperature at 50 ℃ and dripping for 3 hours;

(3) after the epoxy chloropropane is dripped, reacting for 5 hours under the protection of nitrogen to obtain a product A;

(4) and (3) mixing the aqueous solution of the poly dimethyl diallyl ammonium chloride which is 1.5 times of the mass of the product A with the product A, and uniformly stirring to obtain the flocculant.

Example 2

(1) Mixing 82.5g of diethylenetriamine, 12g of ethylenediamine (wherein the mass ratio of the diethylenetriamine to the ethylenediamine is 4:1) and 411g of distilled water, stirring uniformly, introducing nitrogen to remove air in a reaction vessel, and heating to 50 ℃;

(2) slowly dripping 111g of epoxy chloropropane (wherein the mass ratio of the diethylenetriamine to the epoxy chloropropane is 2:3) into the reaction liquid, controlling the reaction temperature at 80 ℃, and dripping for 2 hours;

(3) after the epoxy chloropropane is dripped, reacting for 7 hours under the protection of nitrogen to obtain a product A;

(4) and (3) mixing the aqueous solution of the poly dimethyl diallyl ammonium chloride which is 1.5 times of the mass of the product A with the product A, and uniformly stirring to obtain the flocculant.

Example 3

(1) Firstly, mixing 72.3g of diethylenetriamine, 11.6g of 1, 6-hexanediamine (wherein the mass ratio of the diethylenetriamine to the 1, 6-hexanediamine is 7:1) and 230g of distilled water, uniformly stirring, introducing nitrogen to remove air in a reaction vessel, and heating to 40 ℃;

(2) slowly dripping 86.3g of epoxy chloropropane (wherein the mass ratio of the diethylenetriamine to the epoxy chloropropane is 3:4) into the reaction liquid, controlling the reaction temperature at 65 ℃ and dripping the epoxy chloropropane for 2.5 h;

(3) after the epoxy chloropropane is dripped, reacting for 6 hours under the protection of nitrogen to obtain a product A;

(4) and (3) mixing the aqueous solution of the poly dimethyl diallyl ammonium chloride which is 1 time of the mass of the product A with the product A, and uniformly stirring to obtain the flocculant.

Example 4

(1) Mixing 82.5g of diethylenetriamine, 6g of ethylenediamine (wherein the mass ratio of the diethylenetriamine to the ethylenediamine is 8:1) and 187.2g of distilled water, stirring uniformly, introducing nitrogen to remove air in a reaction vessel, and heating to 45 ℃;

(2) slowly dripping 98.7g of epoxy chloropropane (wherein the mass ratio of diethylenetriamine to the epoxy chloropropane is 3:4) into the reaction liquid, controlling the reaction temperature at 70 ℃, and dripping for 2.5 h;

(3) after the epoxy chloropropane is dripped, reacting for 5.5 hours under the protection of nitrogen to obtain a product A;

(4) and (3) mixing the aqueous solution of the poly dimethyl diallyl ammonium chloride which is 1.2 times of the mass of the product A with the product A, and uniformly stirring to obtain the flocculant.

Experimental example 1

Experiment raw materials: certain offshore oilfield polymer flooding effluent sewage 1 (8000 mg/L of sewage oil)

Experiment temperature: 68 deg.C

The concentration of the medicament: 200mg/L

Evaluation criteria: SY/T0530 spectrophotometry for measuring oil content in water produced from oil field

SY/T5797 demulsification usability evaluation method for oil-in-water emulsion

The evaluation method comprises the following steps: adding 200mg/L of flocculating agent into 80mL of sewage at the high oily sewage temperature of 68 ℃, oscillating and uniformly mixing, observing an oil-water interface, a floc state and water color, and measuring the oil content of the lower layer of sewage after 10 minutes.

Table 1 polymer flooding effluent sewage 1 test data

Remarking: water color: a-, A, A + -Qing B-, B, B + -general C-, C, C + -Difference

Interface: a-, A, A + -full B-, B, B + -generally C-, C, C + -full

Oil droplet floating speed: slow, normal, fast and fast

Experimental example 2

Experiment raw materials: certain offshore oilfield polymer flooding effluent sewage 2 (oil content in sewage 6300mg/L)

Experiment temperature: 65 deg.C

The concentration of the medicament: 150mg/L

Evaluation criteria: SY/T0530 spectrophotometry for measuring oil content in water produced from oil field

SY/T5797 demulsification usability evaluation method for oil-in-water emulsion

The evaluation method comprises the following steps: adding 150mg/L flocculant into 80mL of sewage at the temperature of 65 ℃ of the high-oil-content sewage, oscillating and uniformly mixing, observing an oil-water interface, a floc state and water color, and measuring the oil content of the lower-layer sewage after 10 minutes.

TABLE 2 Polymer flooding produced fluid Sewage 2 test data

Remarking: water color: a-, A, A + -Qing B-, B, B + -general C-, C, C + -Difference

Interface: a-, A, A + -full B-, B, B + -generally C-, C, C + -full

Oil droplet floating speed: slow, normal, fast and fast

The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.