CN103232570A - Method for preparing temperature-resistant, salt-resistant and shearing-resistant cationic polyacrylamide - Google Patents
Method for preparing temperature-resistant, salt-resistant and shearing-resistant cationic polyacrylamide Download PDFInfo
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- CN103232570A CN103232570A CN2013101525820A CN201310152582A CN103232570A CN 103232570 A CN103232570 A CN 103232570A CN 2013101525820 A CN2013101525820 A CN 2013101525820A CN 201310152582 A CN201310152582 A CN 201310152582A CN 103232570 A CN103232570 A CN 103232570A
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Abstract
The invention discloses a method for preparing temperature-resistant, salt-resistant and shearing-resistant cationic polyacrylamide, and the method comprises the following steps of: adding 90-110 parts by weight of acrylamide monomer, 30-60 parts by weight of cationic monomer and 0.04-0.08 part by weight of sodium formate into 100-400 parts by weight of long-chain alkyl double-bond quaternary ammonium salt micelle water system with the weight ratio of 0.5-3.0%, and then dissolving and mixing uniformly; removing dissolved oxygen by blowing nitrogen at 0-30 DEG C; decreasing the temperature to 0-10 DEG C, adding 0.04-0.08 parts by weight of initiator, mixing uniformly, and polymerizing to generate a transparent rubber block; and granulating, drying and crushing to obtain finished cationic polyacrylamide. The molecular weight of the cationic polyacrylamide prepared by the invention can be above 30 million; the cationic polyacrylamide has general temperature-resistant, salt-resistant and shearing-resistant properties; and furthermore, due to hydrophobic association, the viscosity is increased by above three times.
Description
Technical field
The present invention relates to macromolecular organic compound Preparation of Polyacrylamide technical field, particularly the preparation method of a kind of temperature resistance, anti-salt, shear-stable cationic polyacrylamide.
Background technology
Common cationic polyacrylamide, be that two key quaternary ammonium salt copolymerization by acrylamide monomer (AM) and short chain forms, this cationoid monomer comprises methylacryoyloxyethyl trimethyl ammonium chloride (DAM), dimethyl diallyl ammonium chloride (DAAC), acrylyl oxy-ethyl-trimethyl salmiac (DMC) etc.Though possess the numerous characteristics of cationic polyacrylamide in normal conditions, under a lot of abominable situations, its performance can obviously reduce.Be in particular in that molecular weight (perhaps apparent viscosity) reduces greatly.As everyone knows, when molecular structure was identical, the more high result of use of molecular weight was more good.Therefore, wishing under any circumstance can both keep its molecular weight, is the problem that people pay much attention to.In order to address this problem, having analyzed and researched influences three principal elements of its performance: 1. higher use temperature.2. use and handle object saltiness height.3. the mechanical shearing that causes of dissolution process high-speed stirring.These three kinds of environments for use make common cation polyacrylamide molecular chain rupture, and cause molecular weight obviously to reduce.
Summary of the invention
The invention provides the preparation method of a kind of temperature resistance, anti-salt, shear-stable cationic polyacrylamide, solve the existing cationic polyacrylamide problem that molecular chain easily ruptures under the environment of high temperature, saltiness height and high-speed stirring.
Technical scheme of the present invention is achieved in that the preparation method of a kind of temperature resistance, anti-salt, shear-stable cationic polyacrylamide, may further comprise the steps:
(1) weight ratio that cationic monomer and 0.04～0.08 weight part sodium formiate of the acrylamide monomer of 90～110 weight parts, 30～60 weight parts added 100～400 weight parts is in 0.5～3.0% the two key quaternary ammonium salt micella aqueous systems of chain alkyl, dissolves and mixes;
(2) remove dissolved oxygen 0～30 ℃ of nitrogen blowing;
(3) be cooled to 0～10 ℃, add the initiator of 0.04～0.08 weight part, mix, polymerization generates transparent blob of viscose;
(4) through granulation, oven dry, pulverizing, namely get the cationic polyacrylamide finished product.
Wherein, preferably, described cationic monomer is the two key quaternary ammonium salt monomers of short chain.
Wherein, preferably, the two key quaternary ammonium salt monomers of described short chain are any one of dimethyl diallyl ammonium chloride, methylacryoyloxyethyl trimethyl ammonium chloride, acrylyl oxy-ethyl Bian Ji alkyl dimethyl ammonium chloride.
Wherein, preferably, have the two key quaternary ammonium salts of surface-active chain alkyl, be 12～octadecyl allyl dimethyl ammonium chloride or be 12～octadecyl allyl dimethyl base brometo de amonio any one.
Wherein, preferably, described initiator is any one or a few of benzoyl peroxide, Potassium Persulphate, ferrous sulfate.
Wherein, preferably, in step 2, residual oxygen is 0.1～0.3mg/L after the deoxygenation.
The problem that the present invention need solve provides a kind of novel cation polyacrylamide preparation method, testing sieve has been selected the two key quaternary ammonium salts of chain alkyl, as hydrophobic reactive monomer, this monomer not only has the activity double key that can carry out copolymerization, and itself also is a kind of tensio-active agent.Therefore when preparation micellar system, need not to add in addition tensio-active agent.Evidence, the add-on that this monomer is suitable.It is feasible selecting the copolymerizable hydrophobic monomer of 12～octadecyl allyl dimethyl base ammonium halide one class for use.Less than dodecyl, its performance is not obvious, greater than octadecyl, and its solvability variation, even lose the use meaning.
The present invention is when the two key quaternary ammonium salt monomer copolymerization of acrylamide monomer (AM) and short chain, introduces a kind of chain alkyl pair key quaternary ammonium salts, carries out terpolymer, and its molecular weight can reach more than 3,000 ten thousand.Because the structure of this long chain alkyl ammonium salt has stronger hydrophobicity, so its multipolymer should have the hydrophobic association performance.Theory according to the hydrophobic association of polyacrylamide.It should have temperature resistance, anti-salt, shear-stable general property.And the hydrophobic association interaction energy makes viscosity increase more than three times, even higher.This characteristics make the product consumption reduce greatly, thereby have reduced use cost.
The product of the present invention's preparation is white powdery solid, and water soluble forms hydrogel.Mainly comparatively use under the condition of severe in condition, for example recover the oil in the oil field, under the stratum of last km, construct possibly, its temperature may be more than 150 ℃, and the regional saltiness that has is very high, and common cationic polyacrylamide does not reach effect at all, in addition, the oil extraction waste water saltiness is very high, and at the high-salt wastewater that other production produce, uses this product will reach good effect.
In handled common industry and urban domestic wastewater, the characteristics of demonstration were that consumption is few, and particularly the physical strength height of flocs unit is difficult for wearing filter, and the filter residue water ratio can be less than 50%, and common cationic polyacrylamide can only make it reach 70%.
Description of drawings
Fig. 1 is temperature resistance of the present invention, anti-salt, shear-stable cationic polyacrylamide preparation method's process flow sheet.
Embodiment
To the technical scheme in the embodiment of the invention be clearly and completely described below, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
As shown in Figure 1, the invention provides the preparation method of a kind of temperature resistance, anti-salt, shear-stable cationic polyacrylamide, may further comprise the steps:
(1) weight ratio that the sodium formiate of the cationic monomer of the acrylamide monomer of 90～110 weight parts, 30～60 weight parts and 0.04～0.08 weight part is added 100～400 weight parts is in 0.5～3.0% the two key quaternary ammonium salt micella aqueous systems of chain alkyl, dissolves and mixes;
(2) remove dissolved oxygen 0～30 ℃ of nitrogen blowing;
(3) be cooled to 0～10 ℃, add the initiator of 0.04～0.08 weight part, mix, polymerization generates transparent blob of viscose;
(4) through granulation, oven dry, pulverizing, namely get the cationic polyacrylamide finished product.
Embodiment 1
Present embodiment provides the preparation method of a kind of temperature resistance, anti-salt, shear-stable cationic polyacrylamide, and its process flow sheet as shown in Figure 1.
In one 500 liters stainless steel polymeric kettle, add the 135Kg deionized water, take by weighing 1.3Kg tetradecyl allyl dimethyl ammonium chloride, be added to the water, high-speed stirring 20 minutes, make weight ratio and be 0.96% tetradecyl allyl dimethyl ammonium chloride micella aqueous systems, 46Kg acrylamide monomer, 18Kg methylacryoyloxyethyl trimethyl ammonium chloride 0.0227Kg sodium formiate are added in the above-mentioned tetradecyl allyl dimethyl ammonium chloride micella aqueous systems, dissolve and stir.25 ℃ of nitrogen blowing deoxygenations 30 minutes, residual oxygen is 0.2mg/L after the deoxygenation.Be cooled to 5 ℃, add benzoyl peroxide 0.02Kg, Potassium Persulphate 0.005Kg, ferrous sulfate 0.004Kg mixes, and static polymerization 4 hours generates transparent blob of viscose.With the blob of viscose granulation, place on 70 ℃ the oven dry bed, dry to solid content 90%, be crushed to below 20 orders, be finished product.The sample examination result, molecular weight is 3,069 ten thousand, 80 minutes water-soluble time.The cationic polyacrylamide temperature resistance of making, anti-salt, anti-shear performance are as shown in table 1.
Embodiment 2
Present embodiment provides the preparation method of a kind of temperature resistance, anti-salt, shear-stable cationic polyacrylamide, and its process flow sheet as shown in Figure 1.
In one 500 liters stainless steel polymeric kettle, add the 70Kg deionized water, take by weighing 0.95Kg hexadecyl allyl dimethyl ammonium chloride, be added to the water, high-speed stirring 20 minutes, make weight ratio and be 1.37 tetradecyl allyl dimethyl ammonium chloride micella aqueous systems, 41.5Kg acrylamide monomer, 26.7Kg dimethyl diallyl ammonium chloride, 0.0202Kg sodium formiate are added in the above-mentioned tetradecyl allyl dimethyl ammonium chloride micella aqueous systems, dissolve and stir.15 ℃ of nitrogen blowing deoxygenations 30 minutes, residual oxygen is 0.1mg/L after the deoxygenation.Be cooled to 5 ℃, add benzoyl peroxide 0.01Kg, Potassium Persulphate 0.005Kg, ferrous sulfate 0.0038Kg mixes, and static polymerization 4 hours generates transparent blob of viscose.With the blob of viscose granulation, place on 75 ℃ the oven dry bed, dry to solid content 90%, be crushed to below 20 orders, be finished product.The sample examination result, molecular weight is 3,102 ten thousand, 75 minutes water-soluble time.The cationic polyacrylamide temperature resistance of making, anti-salt, anti-shear performance are as shown in table 1.
Embodiment 3
Present embodiment provides the preparation method of a kind of temperature resistance, anti-salt, shear-stable cationic polyacrylamide, and its process flow sheet as shown in Figure 1.
In one 500 liters stainless steel polymeric kettle, add the 160Kg deionized water, take by weighing 2.5Kg octadecyl allyl dimethyl ammonium chloride, be added to the water, high-speed stirring 20 minutes is made weight ratio and is 0.71% tetradecyl allyl dimethyl ammonium chloride micella aqueous systems, with 50Kg acrylamide monomer, 20.7Kg acrylyl oxy-ethyl Bian Ji alkyl dimethyl ammonium chloride, 0.0350Kg sodium formiate adds in the above-mentioned tetradecyl allyl dimethyl ammonium chloride micella aqueous systems, dissolves and stirs.10 ℃ of nitrogen blowing deoxygenations 30 minutes, residual oxygen is 0.3mg/L after the deoxygenation.Be cooled to 5 ℃, add benzoyl peroxide 0.02Kg, Potassium Persulphate 0,015Kg mix, and static polymerization 5 hours generates transparent blob of viscose.With the blob of viscose granulation, place on 72 ℃ the oven dry bed, dry to solid content 90%, be crushed to below 20 orders, be finished product.The sample examination result, molecular weight is 3,100 ten thousand, 85 minutes water-soluble time.The cationic polyacrylamide temperature resistance of making, anti-salt, anti-shear performance are as shown in table 1.
Table 1 cationic polyacrylamide temperature resistance, anti-salt, anti-shear performance
By above data as can be known, adopt the cationic polyacrylamide of production method preparation of the present invention, molecular weight can reach three times of usual production, aspect high temperature resistance, anti-salt and anti-mechanical shearing, has very remarkable advantages.
Claims (6)
1. the preparation method of a temperature resistance, anti-salt, shear-stable cationic polyacrylamide may further comprise the steps:
(1) weight ratio that cationic monomer and 0.04～0.08 weight part sodium formiate of the acrylamide monomer of 90～110 weight parts, 30～60 weight parts added 100～400 weight parts is in 0.5～3.0% the two key quaternary ammonium salt micella aqueous systems of chain alkyl, dissolves and mixes;
(2) remove dissolved oxygen 0～30 ℃ of nitrogen blowing;
(3) be cooled to 0～10 ℃, add the initiator of 0.04～0.08 weight part, mix, polymerization generates transparent blob of viscose;
(4) through granulation, oven dry, pulverizing, namely get the cationic polyacrylamide finished product.
2. the preparation method of a kind of temperature resistance according to claim 1, anti-salt, shear-stable cationic polyacrylamide is characterized in that: described cationic monomer is the two key quaternary ammonium salt monomers of short chain.
3. the preparation method of a kind of temperature resistance according to claim 2, anti-salt, shear-stable cationic polyacrylamide is characterized in that: the two key quaternary ammonium salt monomers of described short chain are any one of dimethyl diallyl ammonium chloride, methylacryoyloxyethyl trimethyl ammonium chloride, acrylyl oxy-ethyl Bian Ji alkyl dimethyl ammonium chloride.
4. the preparation method of a kind of temperature resistance according to claim 1, anti-salt, shear-stable cationic polyacrylamide is characterized in that: the two key quaternary ammonium salts of chain alkyl be 12～octadecyl allyl dimethyl ammonium chloride, 12～octadecyl allyl dimethyl base brometo de amonio any one.
5. the preparation method of a kind of temperature resistance according to claim 1, anti-salt, shear-stable cationic polyacrylamide is characterized in that: described initiator is any one or a few of benzoyl peroxide, Potassium Persulphate, ferrous sulfate.
6. the preparation method of a kind of temperature resistance according to claim 1, anti-salt, shear-stable cationic polyacrylamide, it is characterized in that: in step 2, residual oxygen is 0.1～0.3mg/L after the deoxygenation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108250081A (en) * | 2018-01-16 | 2018-07-06 | 重庆科技学院 | A kind of allyl dimethyl base isooctane base ammonium bromide and preparation method thereof |
| CN114380946A (en) * | 2020-10-22 | 2022-04-22 | 中国石油天然气股份有限公司 | Self-tackifying steering acid liquid thickener and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250081A (en) * | 2018-01-16 | 2018-07-06 | 重庆科技学院 | A kind of allyl dimethyl base isooctane base ammonium bromide and preparation method thereof |
| CN114380946A (en) * | 2020-10-22 | 2022-04-22 | 中国石油天然气股份有限公司 | Self-tackifying steering acid liquid thickener and preparation method and application thereof |
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