CN107474171B

CN107474171B - High-viscosity cationic polyelectrolyte dry powder and preparation method thereof

Info

Publication number: CN107474171B
Application number: CN201610403849.2A
Authority: CN
Inventors: 郭卫东; 张勇; 李留忠; 梁斌
Original assignee: China Petroleum and Chemical Corp
Current assignee: China Petroleum and Chemical Corp
Priority date: 2016-06-07
Filing date: 2016-06-07
Publication date: 2021-02-19
Anticipated expiration: 2036-06-07
Also published as: CN107474171A

Abstract

The invention relates to high-viscosity cationic polyelectrolyte dry powder and a preparation method thereof. Methacryloyloxyethyl trimethyl ammonium chloride (DMC) is used as a polymerization monomer, quaternary initiation is adopted, and the initiators are itaconic acid, an azo initiator, ammonium persulfate and sodium bisulfite. The polymerization concentration is 60 +/-2%, and the polymerization process adopts aqueous solution polymerization. The invention adopts the high-efficiency initiation of itaconic acid, and the cooperation of redox and azo initiators, and through the selection of an initiation system, the processes of the early stage, the middle stage and the later stage of polymerization are stable, and the defects of quick initiation of a single initiator and insufficient late-stage initiation are overcome, so that the high-viscosity cationic polyelectrolyte PDMC dry powder with the intrinsic viscosity of more than 15dL/g and less than 0.5 percent of monomer residue is prepared; can be used as an acidification thickener for oil extraction in oil fields, and can also be used in the industries of sewage treatment, papermaking, coal washing, mining and the like; the invention also provides a preparation method of the composition.

Description

High-viscosity cationic polyelectrolyte dry powder and preparation method thereof

Technical Field

The invention relates to high-viscosity cationic polyelectrolyte dry powder and a preparation method thereof.

Background

At present, there are many types of cationic polyelectrolytes on the market, most of which are copolymers, most of which are cationic polyacrylamides, and the application is wide, and the consumption is large especially in the oil field oil extraction, sewage treatment and paper making industries, but the manufacturing and the use of cationic homopolymers are few, and the mature technology is polydimethyldiallyl ammonium chloride (PDMDAAC), which has been described in detail in PDMDAAC synthesis process research progress by yaxu and shingyu, and the maximum viscosity of which is 7.7dL/g, while the research and the report of homopolymer PDMC of quaternary ammonium salt monomer, namely methacryloyloxyethyl trimethyl ammonium chloride (DMC) are in the initial stage. Two of these main reasons: on one hand, the use, research and development and manufacture of the PDMC are limited due to the high price of the PDMC, and on the other hand, the viscosity of the PDMC is not easy to increase, and most of homopolymers are colloids and aqueous solutions and are not beneficial to storage and transportation. As described in Zhangjun, Tangli et al 105017453A, the intrinsic viscosity of the colloidal polymer was increased to 14.7dL/g and the conversion to 99.2% using a peroxide initiator in a two-step temperature ramp. The viscosity value can be used in many aspects such as sewage treatment, papermaking, coal slime coal washing and the like, but a certain difference exists in the aspect of well drilling acidification thickening fluid, and the viscosity value has obvious effect only when reaching more than 15 dL/g.

The viscosity of homopolymerized PDMC cation product is generally lower than that of copolymerized cation product, and the price of homopolymer is higher, so that the application range of PDMC homopolymer is limited, but if the intrinsic viscosity of PDMC can be continuously improved, so that the performance of the product is greatly improved, the using amount can be reduced, the cost is reduced, the possibility of popularizing the product on a large scale is provided, after all, the product has unique performance, for example, in the aspect of acidizing thickening fluid of an oil field, the effect of other cation products is poor no matter the viscosity is high or low, only PDMC has obvious effect when the viscosity exceeds more than 15 dL/g. Therefore, the economic benefit of the experiment for improving the intrinsic viscosity of the PDMC is obvious after the experiment is successful.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide high-viscosity cationic polyelectrolyte dry powder, the intrinsic viscosity of which is more than 15dL/g, the monomer residue of which is less than 0.5 percent, and the high-viscosity cationic polyelectrolyte dry powder can be used as an acidification thickener for oil well oil extraction and industries of sewage treatment, papermaking, coal washing, mining and the like; the invention also provides a preparation method of the composition.

The high-viscosity cationic polyelectrolyte dry powder takes methacryloyloxyethyl trimethyl ammonium chloride (DMC) as a polymerization monomer, and adopts quaternary initiation, wherein the initiator is itaconic acid, an azo initiator, ammonium persulfate and sodium bisulfite.

Wherein:

by weight, the proportion of methacryloyloxyethyl trimethyl ammonium chloride, itaconic acid, azo initiator, ammonium persulfate and sodium bisulfite is 300: 0.03 to 0.3: 0.03 to 0.3: 0.006-0.06: 0.006-0.06.

The azo initiator is preferably azo initiator v-50.

The high-viscosity cationic polyelectrolyte dry powder is a homopolymer, the polymerization concentration is 60 +/-2%, and the polymerization process adopts aqueous solution polymerization.

The preparation method of the high-viscosity cationic polyelectrolyte dry powder comprises the following steps: the method comprises the following steps:

mixing DMC monomers with deionized water, adjusting the pH value to 3-4, respectively adding itaconic acid, an azo initiator, ammonium persulfate and sodium bisulfite, carrying out nitrogen deoxidization reaction to obtain colloid, and granulating, drying, crushing and sieving the polymerized colloid to obtain a dry powder product.

As a preferred technical scheme, the preparation method of the high-viscosity cationic polyelectrolyte dry powder comprises the steps of mixing a DMC monomer with deionized water, adjusting the pH value to 3-4, adding itaconic acid, an azo initiator, ammonium persulfate and sodium bisulfite at 50-60 ℃, removing oxygen by nitrogen for 15-20 minutes, reacting for 3-4 hours to obtain a colloid, and granulating, drying, crushing and sieving the polymerized colloid to obtain a dry powder product.

Wherein:

the pH value is adjusted by hydrochloric acid.

In summary, the invention has the following advantages:

(1) the invention adopts the high-efficiency initiation of itaconic acid, and the cooperation of redox and azo initiators, and through the selection of an initiation system, the processes of the early stage, the middle stage and the later stage of polymerization are stable, and the defects of quick initiation of a single initiator and insufficient late-stage initiation are overcome, so that the high-viscosity cationic polyelectrolyte PDMC dry powder with the intrinsic viscosity of more than 15dL/g and less than 0.5 percent of monomer residue is prepared;

(2) the high-viscosity cationic polyelectrolyte dry powder is a polymethacryloxyethyl trimethyl ammonium chloride homopolymer, has high viscosity, can be used as an acidification thickener for oil extraction in oil fields, and can also be used in the industries of sewage treatment, papermaking, coal washing, mining industry and the like.

Detailed Description

The present invention will be further described with reference to the following examples.

Example 1

Adding 384g of 78% DMC monomer and 116g of deionized water into a reactor, shaking up, adjusting the pH value to 3 by using hydrochloric acid, then placing the reactor into a thermostatic water bath at 50 ℃, filling nitrogen into a donor system for 20 minutes, respectively adding 0.3g of itaconic acid, 0.3g v-50, 0.06g of ammonium persulfate and 0.06g of sodium bisulfite, starting polymerization after about 1 minute, stopping the nitrogen after 5 minutes, finishing the reaction for 4 hours to obtain colloid, granulating, drying, crushing and screening the colloid to obtain white PDMC dry powder particles, and performing a viscosity test on the sample (by using GB12005.1-89) to obtain the polymer with the intrinsic viscosity of 15.22dL/g, the residual monomer of 0.44% and the solid content of 90%.

Example 2

The same as in example 1, except that the pH was adjusted to 4, the resulting polymer had an intrinsic viscosity of 15.53dL/g, a residual monomer content of 0.42% and a solids content of 90%.

Example 3

The same as example 1 except that the polymerization temperature in example 3 was 55 ℃ C, the resulting polymer had an intrinsic viscosity of 15.82dL/g, a residual monomer content of 0.43% and a solid content of 90%.

Example 4

The same as in example 1 except that the reaction temperature in example 4 was 60 ℃ C, the resulting polymer had an intrinsic viscosity of 16.02dL/g, a residual monomer content of 0.44% and a solid content of 90%.

Example 5

The same as example 1 except that in example 5, the polymerization temperature was 55 ℃ and the pH was adjusted to 4, the resulting polymer had an intrinsic viscosity of 15.47dL/g, residual monomer content of 0.42% and solid content of 90%.

Example 6

The same as example 1 except that in example 6, the polymerization temperature was 60 ℃ and the pH was adjusted to 4, the resulting polymer had an intrinsic viscosity of 16.22dL/g, residual monomer content of 0.45% and solid content of 90%.

Comparative example 1

Adding 384g of 78% DMC monomer and 116g of deionized water into a reactor, shaking up, adjusting the pH value to 3 by hydrochloric acid, then placing the reactor into a thermostatic water bath at 50 ℃, filling nitrogen into a donor system for 20 minutes, adding 0.3g v-50, 0.06g of ammonium persulfate and 0.06g of sodium bisulfite, starting polymerization after about 5 minutes, stopping the nitrogen after 5 minutes, finishing the reaction for 4 hours to obtain colloid, granulating, drying, crushing and screening the colloid to obtain white PDMC dry powder particles, and performing a viscosity test on the sample (by adopting GB12005.1-89) to obtain the polymer with the intrinsic viscosity of 13.45dL/g, the residual monomer of 0.64% and the solid content of 90%.

Comparative example 2

Similar to comparative example 1, except that comparative example 2 had a pH of 4, the resulting polymer had an intrinsic viscosity of 12.56dL/g, residual monomer 0.58%, and solids content 90%;

comparative example 3

The same as in comparative example 1 except that the polymerization temperature in comparative example 3 was 55 ℃ to give a polymer having an intrinsic viscosity of 13.34dL/g, 0.60% of residual monomer and 90% of solid content;

comparative example 4

The difference from comparative example 1 is that the polymerization temperature of comparative example 4 was 60 ℃ to give a polymer having an intrinsic viscosity of 14.01dL/g, residual monomer 0.65% and solids content 90%.

As can be seen from examples 1-6 and comparative examples 1-4, the absence of itaconic acid in the initiation system resulted in a polymer having an intrinsic viscosity of less than 15dL/g, which is a value that is less effective in drilling acidized viscosifiers.

Claims

1. A high-viscosity cationic polyelectrolyte dry powder is characterized in that: taking methacryloyloxyethyl trimethyl ammonium chloride as a polymerization monomer, and adopting quaternary initiation, wherein the initiators are itaconic acid, an azo initiator, ammonium persulfate and sodium bisulfite; by weight, the proportion of methacryloyloxyethyl trimethyl ammonium chloride, itaconic acid, azo initiator, ammonium persulfate and sodium bisulfite is 300: 0.03 to 0.3: 0.03 to 0.3: 0.006-0.06: 0.006-0.06;

the preparation method of the high-viscosity cationic polyelectrolyte dry powder comprises the steps of mixing a methacryloyloxyethyl trimethyl ammonium chloride polymerized monomer with deionized water, adjusting the pH value to 3-4, respectively adding itaconic acid, an azo initiator, ammonium persulfate and sodium bisulfite, carrying out nitrogen deoxidization reaction to obtain colloid, and granulating, drying, crushing and sieving the polymerized colloid to obtain the high-viscosity cationic polyelectrolyte dry powder with the intrinsic viscosity of more than 15dL/g and the monomer residue of less than 0.5%.

2. The high viscosity cationic polyelectrolyte dry powder according to claim 1, characterized in that: the azo initiator is azo initiator v-50.

3. The high viscosity cationic polyelectrolyte dry powder according to claim 1, characterized in that: the high-viscosity cationic polyelectrolyte dry powder is a homopolymer, the polymerization concentration is 60 +/-2%, and the polymerization process adopts aqueous solution polymerization.

4. A method for preparing the high viscosity cationic polyelectrolyte dry powder according to any one of claims 1 to 3, characterized in that: mixing a methacryloyloxyethyl trimethyl ammonium chloride polymerized monomer with deionized water, adjusting the pH value to 3-4, respectively adding itaconic acid, an azo initiator, ammonium persulfate and sodium bisulfite, carrying out nitrogen deoxidization reaction to obtain colloid, and granulating, drying, crushing and sieving the polymerized colloid to obtain the high-viscosity cation polyelectrolyte dry powder with the intrinsic viscosity of more than 15dL/g and the monomer residue of less than 0.5%.

5. The method for preparing high viscosity cationic polyelectrolyte dry powder according to claim 4, wherein: mixing a methacryloyloxyethyl trimethyl ammonium chloride polymerized monomer with deionized water, adjusting the pH value to 3-4, adding itaconic acid, an azo initiator, ammonium persulfate and sodium bisulfite at 50-60 ℃, deoxidizing for 15-20 minutes by nitrogen, reacting for 3-4 hours to obtain colloid, and granulating, drying, crushing and sieving the polymerized colloid to obtain a dry powder product.

6. The method for preparing high viscosity cationic polyelectrolyte dry powder according to claim 5, wherein: the pH value is adjusted by hydrochloric acid.