阅读说明：本技术 一种阳离子型聚丙烯酰胺高分子絮凝剂的制备方法 (Preparation method of cationic polyacrylamide polymeric flocculant ) 是由 王柱 刘海生 陈洋 张宇翔 李兴华 梁建文 许桂红 刘成扬 于 2021-10-27 设计创作，主要内容包括：本发明属于聚丙烯酰胺絮凝剂技术领域,特别涉及一种阳离子型聚丙烯酰胺高分子絮凝剂的制备方法,包括以下步骤：S1.将白油、乳化剂,混合均匀,得油相；S2.将丙烯酰胺与功能性单体按照质量比为0.2～2混合,并加入交联剂混合均匀,得水相；S3.将水相加入到油相中混合,然后将乳液均质；S4.向步骤S3得到的W/O型乳液中通入氮气除氧,加入引发剂反应,得到反相乳液；S5.在步骤S4得到的反相乳液中加入相反转剂,搅拌均匀,即得。本发明采用Span-80、Tween-20、聚苯乙烯微球、油酸、醚TX-3为复合乳化剂,更有利于聚合物和乳化剂以及油相形成疏水缔合作用,形成本发明方法获得的絮凝剂稳定性好,长时间方式不会存在分层的现象。(The invention belongs to the technical field of polyacrylamide flocculating agents, and particularly relates to a preparation method of a cationic polyacrylamide polymeric flocculating agent, which comprises the following steps: s1, uniformly mixing white oil and an emulsifier to obtain an oil phase; s2, mixing acrylamide and a functional monomer according to a mass ratio of 0.2-2, adding a cross-linking agent, and uniformly mixing to obtain a water phase; s3, adding the water phase into the oil phase, mixing, and homogenizing the emulsion; s4, introducing nitrogen into the W/O type emulsion obtained in the step S3 to remove oxygen, and adding an initiator to react to obtain an inverse emulsion; and S5, adding a phase inversion agent into the inverse emulsion obtained in the step S4, and uniformly stirring to obtain the emulsion. The invention adopts Span-80, Tween-20, polystyrene microspheres, oleic acid and ether TX-3 as composite emulsifiers, is more beneficial to the formation of hydrophobic association action of polymers, emulsifiers and oil phase, and the flocculant obtained by the method has good stability and cannot have the phenomenon of layering in a long-time mode.)

1. A preparation method of a cationic polyacrylamide polymeric flocculant is characterized by comprising the following steps:

s1, uniformly mixing white oil and an emulsifier at a rotating speed of 400-500 rpm to obtain an oil phase;

s2, mixing acrylamide and a functional monomer according to a mass ratio of 0.2-2, adding a cross-linking agent and deionized water, and uniformly mixing to obtain a water phase;

s3, adding the water phase into the oil phase, stirring at the rotating speed of 450-550 rpm for 20-40 min to obtain W/O type emulsion, and homogenizing the emulsion for 10-30 min;

s4, introducing nitrogen into the W/O type emulsion obtained in the step S3 to remove oxygen, controlling the temperature to be 60-90 ℃, and adding an initiator to react to obtain an inverse emulsion;

s5, adding a phase inversion agent into the inverse emulsion obtained in the step S4, and uniformly stirring to obtain the emulsion;

in the step S3, the dropping speed of the water phase added into the oil phase is 10-15 mL/min.

2. The method for preparing the cationic polyacrylamide polymeric flocculant of claim 1, wherein the emulsifier in step S1 is a mixture of Span-80, Tween-20, polystyrene microspheres, oleic acid, and ether TX-3 in a mass ratio of (3-20): 3-5): 1-3): 5-9): 3-5.

3. The preparation method of the cationic polyacrylamide polymeric flocculant according to claim 2, wherein the emulsifier is prepared by mixing Span-80, Tween-20, polystyrene microspheres, oleic acid and ether TX-3 according to a mass ratio of 15:4:2:7: 4.

4. The method for preparing the cationic polyacrylamide polymeric flocculant according to claim 2 or 3, wherein the amount of the emulsifier is 35-65% of the total mass of the acrylamide and the functional monomer.

5. The method for preparing the cationic polyacrylamide polymeric flocculant according to claim 1, wherein the functional monomers in step S2 include: one or more of methacryloyloxyethyltrimethyl ammonium chloride, dimethyldipropyl ammonium chloride and dimethylaminoethyl methacrylate.

6. The method for preparing the cationic polyacrylamide polymeric flocculant of claim 1, wherein the cross-linking agent in step S2 is one or more of methylene bisacrylamide, N-methylolacrylamide, and allyl sucrose ether.

7. The method for preparing the cationic polyacrylamide polymeric flocculant according to claim 6, wherein the amount of the cross-linking agent is 0.2-0.4% of the total mass of acrylamide and the functional monomer.

8. The method for preparing the cationic polyacrylamide polymeric flocculant according to claim 1, wherein in step S4, the initiator comprises: one or two of potassium persulfate and ammonium persulfate.

9. The method for preparing the cationic polyacrylamide polymeric flocculant according to claim 8, wherein the amount of the initiator is 0.1-0.3% of the total mass of acrylamide and the functional monomer.

10. The method for preparing the cationic polyacrylamide polymeric flocculant according to claim 1, wherein in step S5, the phase inversion agent is hypivert 3110, and the amount of the phase inversion agent is 10% to 14% of the total mass of the acrylamide and the functional monomer.

Technical Field

The invention belongs to the technical field of polyacrylamide flocculating agents, and particularly relates to a preparation method of a cationic polyacrylamide polymeric flocculating agent.

Background

The water-in-oil, i.e. inverse emulsion polymerization method is adopted to overcome the problem of excessive heat release in the polymerization reaction process of the acrylamide and the derivative monomers thereof, and simultaneously improve the molecular weight and the polymerization speed of the acrylamide and the derivative monomers. The polyacrylamide polymer prepared by the method is widely applied to the fields of petroleum drilling and production, water treatment, papermaking, daily chemicals and the like. However, in general, products obtained by inverse emulsion polymerization have a problem that the polymer is settled and separated from the oil phase after the emulsion is left for a long time, i.e., the emulsion has poor storage stability.

Disclosure of Invention

In order to overcome the problem of high organic chlorine content in the existing PAE, the invention provides a preparation method of an environment-friendly wet strength agent.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a preparation method of a cationic polyacrylamide polymeric flocculant comprises the following steps:

s1, uniformly mixing white oil and an emulsifier at a rotating speed of 400-500 rpm to obtain an oil phase;

s2, mixing acrylamide and a functional monomer according to a mass ratio of 0.2-2, adding a cross-linking agent and deionized water, and uniformly mixing to obtain a water phase;

s3, adding the water phase into the oil phase, stirring at the rotating speed of 450-550 rpm for 20-40 min to obtain W/O type emulsion, and homogenizing the emulsion for 10-30 min;

s4, introducing nitrogen into the W/O type emulsion obtained in the step S3 to remove oxygen, controlling the temperature to be 60-90 ℃, and adding an initiator to react to obtain an inverse emulsion;

s5, adding a phase inversion agent into the inverse emulsion obtained in the step S4, and uniformly stirring to obtain the emulsion;

in the step S3, the dropping speed of the water phase added into the oil phase is 10-15 mL/min.

Preferably, the white oil is one or a mixture of 10# white oil and 26# white oil. The amount of the white oil is 25-50% of the total mass of the acrylamide and the functional monomer.

Preferably, in the step S1, the emulsifier is mixture of Span-80, Tween-20, polystyrene microspheres, oleic acid and ether TX-3 according to the mass ratio of (3-20), (3-5), (1-3), (5-9) and (3-5).

Preferably, the emulsifier is prepared by mixing Span-80, Tween-20, polystyrene microspheres, oleic acid and ether TX-3 according to the mass ratio of 15:4:2:7: 4.

The composite emulsifier obtained by compounding different types of emulsifiers has great influence on the stability of the finally obtained flocculating agent.

Preferably, the amount of the emulsifier is 35-65% of the total mass of the acrylamide and the functional monomer.

Preferably, the functional monomers in step S2 include: one or more of methacryloyloxyethyltrimethyl ammonium chloride, dimethyldipropyl ammonium chloride and dimethylaminoethyl methacrylate.

Preferably, the cross-linking agent in step S2 is one or more of methylene bisacrylamide, N-methylol acrylamide, and allyl sucrose ether.

Preferably, the amount of the cross-linking agent is 0.2-0.4% of the total mass of the acrylamide and the functional monomer.

Preferably, in step S4, the initiator includes: one or two of potassium persulfate and ammonium persulfate.

Preferably, the amount of the initiator is 0.1-0.3% of the total mass of the acrylamide and the functional monomer.

Preferably, in step S5, the phase inversion agent is hypivert 3110, and the amount of the phase inversion agent is 10% to 14% of the total mass of the acrylamide and the functional monomer.

Compared with the prior art, the invention has the following technical effects:

the cationic polyacrylamide polymeric flocculant disclosed by the invention adopts Span-80, Tween-20, polystyrene microspheres, oleic acid and ether TX-3 as composite emulsifiers, so that a hydrophobic association effect is formed among a polymer, the emulsifiers and an oil phase, and the flocculant obtained by the method disclosed by the invention is good in stability and free from layering in a long-time mode.

Detailed Description

The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

The test methods used in the following experimental examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.

Example 1

A preparation method of a cationic polyacrylamide polymeric flocculant comprises the following steps:

s1, weighing 120g of No. 10 white oil and 6g of composite emulsifier, and uniformly mixing at the rotating speed of 450rpm to obtain an oil phase.

S2, weighing 60g of acrylamide, 80g of methacryloyloxyethyl trimethyl ammonium chloride, 0.42g of cross-linking agent methylene bisacrylamide and deionized water, and mixing to obtain a water phase.

S3, adding the water phase into the oil phase, stirring at the rotating speed of 500rpm for 30min to obtain a W/O type emulsion, and homogenizing for 20 min.

S4, introducing nitrogen into the W/O type emulsion obtained in the step S3 to remove oxygen, controlling the temperature at 80 ℃, and adding 0.28g of initiator potassium persulfate to react.

S5, adding 16.8g of phase inversion agent Hypinvert 3110 into the inverse emulsion of Deao in the step S4, and uniformly stirring to obtain cationic polyacrylamide flocculant emulsion;

in the step S3, the dropping rate of the aqueous phase into the oil phase was 12 mL/min.

The composite emulsifier comprises Span-80, Tween-20, polystyrene microspheres, oleic acid and ether TX-3 which are mixed according to the mass ratio of 15:4:2:7: 4.

Example 2

A preparation method of a cationic polyacrylamide polymeric flocculant comprises the following steps:

s1, weighing 120g of No. 10 white oil and 6g of composite emulsifier, and uniformly mixing at the rotating speed of 450rpm to obtain an oil phase.

S2, weighing 60g of acrylamide, 80g of methacryloyloxyethyl trimethyl ammonium chloride, 0.42g of cross-linking agent methylene bisacrylamide and deionized water, and mixing to obtain a water phase.

S3, adding the water phase into the oil phase, stirring at the rotating speed of 500rpm for 30min to obtain a W/O type emulsion, and homogenizing for 20 min.

S4, introducing nitrogen into the W/O type emulsion obtained in the step S3 to remove oxygen, controlling the temperature at 80 ℃, and adding 0.28g of initiator potassium persulfate to react.

S5, adding 16.8g of phase inversion agent Hypinvert 3110 into the inverse emulsion of Deao in the step S4, and uniformly stirring to obtain cationic polyacrylamide flocculant emulsion;

in the step S3, the dropping rate of the aqueous phase into the oil phase was 15 mL/min.

The composite emulsifier comprises Span-80, Tween-20, polystyrene microspheres, oleic acid and ether TX-3 which are mixed according to the mass ratio of 20:3:1:5: 3.

Example 3

A preparation method of a cationic polyacrylamide polymeric flocculant comprises the following steps:

s1, weighing 120g of No. 10 white oil and 6g of composite emulsifier, and uniformly mixing at the rotating speed of 450rpm to obtain an oil phase.

S2, weighing 60g of acrylamide, 80g of methacryloyloxyethyl trimethyl ammonium chloride, 0.42g of cross-linking agent methylene bisacrylamide and deionized water, and mixing to obtain a water phase.

S3, adding the water phase into the oil phase, stirring at the rotating speed of 500rpm for 30min to obtain a W/O type emulsion, and homogenizing for 20 min.

S4, introducing nitrogen into the W/O type emulsion obtained in the step S3 to remove oxygen, controlling the temperature at 80 ℃, and adding 0.28g of initiator potassium persulfate to react.

S5, adding 16.8g of phase inversion agent Hypinvert 3110 into the inverse emulsion of Deao in the step S4, and uniformly stirring to obtain cationic polyacrylamide flocculant emulsion;

in the step S3, the dropping rate of the aqueous phase into the oil phase was 10 mL/min.

The composite emulsifier comprises Span-80, Tween-20, polystyrene microspheres, oleic acid and ether TX-3 which are mixed according to the mass ratio of 3:5:3:9: 5.

Comparative example 1

Compared with the embodiment 1, the composite emulsifier adopted in the comparative example is formed by mixing Tween-20, polystyrene microspheres, oleic acid and ether TX-3 according to the mass ratio of 4:2:7:4, and other components and conditions are the same as those in the embodiment 1.

Comparative example 2

Compared with the embodiment 1, the composite emulsifier adopted by the comparative example is formed by mixing Span-80, polystyrene microspheres, oleic acid and ether TX-3 according to the mass ratio of 15:2:7:4, and other components and conditions are the same as those of the embodiment 1.

Comparative example 3

Compared with the embodiment 1, the composite emulsifier adopted in the comparative example is formed by mixing Span-80, Tween-20, oleic acid and ether TX-3 according to the mass ratio of 15:4:7:4, and other compositions and conditions are the same as those of the embodiment 1.

Comparative example 4

Compared with the example 1, the composite emulsifier adopted in the comparative example is formed by mixing Span-80, Tween-20, polystyrene microspheres and ether TX-3 according to the mass ratio of 15:4:2:4, and other components and conditions are the same as those of the example 1.

Comparative example 5

Compared with the embodiment 1, the composite emulsifier adopted in the comparative example is prepared by mixing Span-80, Tween-20, polystyrene microspheres and oleic acid according to the mass ratio of 20:3:1: 5.

Comparative example 6

Compared with the example 1, the water phase is added into the oil phase in a one-time dripping mode in the comparative example.

Comparative example 7

The drop acceleration of the aqueous phase into the oil phase in this comparative example was 20mL/min, compared to example 1.

Examples of the experiments

The flocculant obtained in the equivalent example and the comparative example is centrifuged for 20min at 9000rpm by using a centrifuge, the height of the upper oil phase of the centrifuge tube and whether precipitates exist at the bottom of the centrifuge tube are measured after centrifugation, and the results are shown in the following table:

group of	Height/mm of upper oil phase after centrifugation	Bottom sediment condition after centrifugation
			Example 1	0.6	Is free of
Example 2	1.6	Hardly any
			Example 3	1.3	Hardly any
Comparative example 1	4	Is provided with
			Comparative example 2	2	Hardly any
Comparative example 3	6	Is provided with
			Comparative example 4	10	Is provided with
Comparative example 5	5	Is provided with
			Comparative example 6	3.1	Is provided with
Comparative example 7	2.3	Hardly any

The less the oil phase on the upper layer of the centrifugal tube after centrifugation, the better the storage stability of the product, and as can be seen from the table above, the better the stability of the flocculant obtained in each group of examples. The comparative examples 3 and 4 are most obvious, and the composite emulsifier obtained by compounding different emulsifiers can obviously improve the stability of the flocculant. It can be seen from comparative examples 6 and 7 that the rate of addition of the aqueous phase to the oil phase also affects the stability of the flocculant. When the dropping speed is too fast, the stable phase is not favorable to be formed, and the formed flocculating agent is unstable.

The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.