CN1022417C - Preparation of fast-dissolving anion type polyacrylamide - Google Patents
Preparation of fast-dissolving anion type polyacrylamide Download PDFInfo
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- CN1022417C CN1022417C CN 90104113 CN90104113A CN1022417C CN 1022417 C CN1022417 C CN 1022417C CN 90104113 CN90104113 CN 90104113 CN 90104113 A CN90104113 A CN 90104113A CN 1022417 C CN1022417 C CN 1022417C
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- fast
- high molecular
- alkali
- molecular weight
- polyacrylamide
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Abstract
The present invention relates to a preparing method for fast-dissolving high molecular weight anion type polyacrylamide, which belongs to water soluble high molecular synthesis. Persulphate, beta-dimethylaminopropionitrile and an NH3 three-element initiation system are utilized to initiate acrylamide aqueous solution to be homogeneously polymerized to obtain polyacrylamide colloidal matters; alkali, urea, formate and a JFC non-ionic surface active agent are added after the polyacrylamide colloidal matters are kneaded by a kneader; then the procedures of hydrolyzing, baking and crushing are carried out. Thereby, the fast-dissolving high molecular weight anion type polyacrylamide which is fast dissolved in six minutes, wherein the molecular weight reaches 8000000 to 15000000; the product is used for tertiary oil recovery, ore dressing and sewage treatment and has good service performance.
Description
The present invention is the preparation method of instant high molecular anion type polycrylamide, belongs to the synthetic class of water-soluble polymer.
As tertiary oil recovery and ore dressing, the powdery anion-polyacrylamide (HPAM) that coal washing water treatment and various sewage purification are used, its optimum weight scope is between 800-1500 ten thousand, and wish that it does not have or seldom have crosslinked insolubles existence after being dissolved in water, The faster the better for dissolution rate, the content of unreacted poisonous monomer acrylamide (AM) is few as far as possible, and product cost is low as far as possible.For the final product that obtains to satisfy this several respects index request, people do a lot of work from different perspectives.The Japan clear 55-2209 of special permission communique has reported with (NH
4)
2S
2O
8And Na
2SO
3Make initiator, Ba Dousuan and sodium salt etc. thereof is made extraordinary admixture, and the method that adopts AM and sodium acrylate aqueous solution copolymerization to close synthesizes high molecular HPAM.The shortcoming of this method is that material purity requires height, and product contains insolubles, and dissolution rate is slower.The clear 50-149739 of day disclosure special permission communique discloses HPAM colloidal drying means.Adopt K
2S
2O
8With dimethylaminopropionitrile as initiator, cause AM and N-(2-propanesulfonic acid salt) the acrylamide solution copolymerization, synthesize sulphonate-base anionic high molecular weight polyacrylamide colloid, with kneader with Na
3PO
4, K
3PO
4Or the HCOONa admixture is mediated in the polymeric colloid oven dry, pulverizing acquisition powdery product equably.Product is crosslinked when preventing to dry that effect is arranged for the post-treatment condition of this method, but unusual effect is just arranged must add a large amount of admixture the time.Add the effective solid content that a large amount of admixtures greatly reduce product, improved cost.Even so also be difficult to obtain consoluet product, more do not reach instant.Because the shearing action of kneader, molecular weight product has sizable decline.
The objective of the invention is to set up the synthetic and production method of new instant high molecular HPAM, make the HPAM product satisfy tertiary oil recovery better, ore dressing, the requirement of coal washing water treatment and various sewage purifications.
The present invention is by fundamental research, discovery product in the polymerization of AM and last handling process crosslinked mechanism takes place is: reacting deuterogenic intermolecular tertiary carbon free radical coupling, to form carbon carbon crosslinked, and find to prevent the method that this kind is crosslinked, promptly add an amount of chain-transfer agent and can stop and prevent crosslinked; In polymerization system, AM can generate NH in hydrolysis under the alkaline condition
3, also can add an amount of NH
3, NH
3Further generate nitrogen three propionic acid amides with AM, it is a chain-transfer agent, is again the reductive agent of redox initiation system.Based on these conclusions, the present invention has adopted persulphate, β-dimethylaminopropionitrile and NH
3(type of giving birth to of diving reductive agent) ternary initiator system causes the AM aqueous solution polymerization and generates high molecular weight polyacrylamide (PAM) colloid that does not contain cross-linking agent, adopt urea, admixture when the formate and nonionic surface active agent Zhong Xin polyoxyethylenated alcohol (JFC) trinity add alkali and mediate with kneader as colloid PAM, thus produce when having avoided the colloid oven dry fully crosslinked again.Because the use of above-mentioned two ternary systems has obtained instant high molecular HPAM powder-like product.
The used acrylamide monomer of the present invention is the 32% industrial AM aqueous solution by skeleton copper catalytic hydration acrylonitrile process, the smart monomer that obtains through ion-exchange again, and this kind AM aqueous solution contains Cu, and Fe is all between 0.3-0.6ppm.And without the industrial crude monomer of ion exchange resin exchange, its 30% aqueous solution contains Cu12ppm, contains Fe4ppm.The monomer concentration scope of polymerization system is 10-50%, preferably 15-30%.
Persulphate in the used ternary initiator system of the present invention, β-dimethylaminopropionitrile and NH
3, be all SILVER REAGENT, wherein NH
3Be to add with the ammoniacal liquor form, persulphate comprises K
2S
2O
8, (NH
4)
2S
2O
8And Na
2S
2O
8
The used hydrolytic reagent alkali of the present invention is sodium hydroxide, potassium and yellow soda ash, potassium, adds by the degree of hydrolysis of polymkeric substance.Kneading admixture urea, formate, Zhong Xin polyoxyethylenated alcohol are all technical pure.
The instant high molecular anion type polycrylamide manufacturing process of the present invention is as follows:
Pure system-the polymerization of monomer-Jia alkali kneading-hydrolysis-granulation-drying-pulverizing
Initiator in the polymerization procedure of the present invention and admixture are as follows with respect to monomeric weight percent:
100 parts of monomers
Disodium ethylene diamine tetraacetate 0.02-4.0% is 0.05-1.0% persulphate 0.01-10% 0.03-1.0% preferably preferably
Ammoniacal liquor 0.05-5.0% is 0.1-1.0% preferably
β-dimethylaminopropionitrile 0.001-2.0%, preferably 0.01～1.0%
Other conditions are:
Polymerization temperature is 20-50 ℃.
Monomer concentration in 10～50% scopes, 15-30% preferably.
Polymerization time 2-10 hour.
The present invention adds alkali and mediates in the posthydrolysis technology, and admixture and hydrolytic reagent to the weight percent of straight polymer in the colloid are:
Polymer weight is 100 parts in the polymeric colloid
Urea 2-10%
Formate 0.5-5%
JFC 0.5-3%
Na
2CO
3Exist with the ratio of NaOH addition
Between 2: 10～10: 2
Other conditions are:
Mediate 60-130 ℃ of temperature
0.5-6 hour kneading time
Hydrolysis temperature 70-100 ℃
Hydrolysis time 20-5 hour
Granulation after drying temperature is 90-120 ℃.
Characteristics of the present invention be two Trinitarian ternary systems in polymerization and kneading, the use in the posthydrolysis process.Be that polyreaction adds NH
3, persulphate and β-dimethylaminopropionitrile constitutes ternary initiator system, NH
3As the type of the giving birth to reductive agent of diving, in kneading and posthydrolysis process, adopt urea, formate and the nonionic surface active agent JFC trinity as admixture.
Unusual effect of the present invention and advantage are:
1, adopts the ternary initiator system to reduce the initiated polymerization temperature, and can obtain the not crosslinked PAM colloid of high molecular; Add the above-mentioned ternary admixture that adds when alkali is mediated, slowed down the degraded of PAM when mediating, the degraded of HPAM when having slowed down hydrolysis and oven dry, HPAM's is crosslinked when having prevented oven dry, has promoted the dissolution rate of HPAM in water.Above-mentioned two ternary systems are cores of the present invention, and the temperature and time of kneading and hydrolysis is assurance of the present invention.
2, use technology gained powder polyacrylamide molecular weight product height of the present invention, 800-1500 ten thousand; Dissolution rate is fast in water, and 6 minutes with interior instant, no insolubles.Its main performance index has reached the best service requirements of tertiary oil recovery and sewage purification etc. fully, is better than similar products at home and abroad.Under the 1-6 that tabulates, listed with the HPAM of the inventive method preparation and similar products at home and abroad at molecular weight dissolution rate, the coal washing water purifying effect, coal washing water flocculation sedimentation, tertiary oil recovery, converter dedusting water purifies, the performance comparison data of converter dedusting water flocculating settling etc.HPAM various aspects of performance with present method preparation is better than similar products at home and abroad as can be seen from the table.(table is seen the literary composition back)
3, AM content has reached the food grade purity requirement less than 0.05% in the product.
4, owing to adopted posthydrolysis technology, greatly reduce requirement to material purity, product cost reduces, as uses the crude monomer polymerization without ion-exchange, can produce molecular weight equally greater than 1,100 ten thousand instant polyacrylamide amine product.
Embodiment 1:
Have outside in the polyethylene plastic bag of iron sheet box (thickness is 3cm) moulding, add 80 gram AM, 0.08 gram disodium ethylene diamine tetraacetate, 0.92 gram strong aqua, 0.08 gram Sodium Persulfate and 0.016 gram β-dimethylaminopropionitrile, adding water to gross weight is 400 grams.Seal behind the letting nitrogen in and deoxidizing,, obtain molecular weight and be 1,172 ten thousand PAM colloid 30 ℃ of following polymerizations 4 hours.
Above-mentioned colloid is placed in the kneader, add the weight percent of 10%(to straight polymer, down with) urea, 0.5% sodium formiate, 0.5% JFC, 15.36% yellow soda ash and 14.64% sodium hydroxide were mediated 3 hours down at 80 ℃, 90 ℃ of hydrolysis 13 hours, granulation, 90 ℃ then～100 ℃ following warm air dryings obtain in 5.7 minutes complete moltenly again through pulverizing, molecular weight is 1,455 ten thousand HPAM powder-product.
Embodiment 2:
Except that adding 88 gram AM, 2.01 restrain strong aquas, 0.088 gram Potassium Persulphate, and outside 0.0196 gram β-dimethylaminopropionitrile, other are with embodiment 1.The result has obtained in 6 minutes molten entirely, and molecular weight is 1,200 ten thousand HPAM powder-product.
Embodiment 3:
In polymerization, add 0.08 gram ammonium persulphate, add 3.5% urea in the kneading process, 1.4% ammonium formiate, 1% JFC, 70 ℃ of hydrolysis 6 hours, all the other are with embodiment 1.Molten entirely in obtain 5.5 minutes, molecular weight is 1,134 ten thousand HPAM powder-product.
Embodiment 4:
Add potassium formiate 3% in kneading process, all the other are with embodiment 3.Obtain in 5.5 minutes moltenly entirely, molecular weight is 1,300 ten thousand HPAM powder-product.
Embodiment 5:
In polymerization process, add 96 gram AM, 0.096 gram disodium ethylene diamine tetraacetate,
0.0576 the gram Potassium Persulphate, 0.0096 gram β-dimethylaminopropionitrile, 30 ℃ of following polymerizations 88 hours, the result obtained the PAM colloid, and this colloid contains micro-cross-linking agent.
Embodiment 6:
Except that not adding in polymerization process the ammoniacal liquor, other is with embodiment 2, and the result has obtained containing the HPAM powder-product of crosslinked insolubles.
The external high-quality HPAM of table 1 and the properties of product table of comparisons of the present invention
Company's sample model ionic nature dissolution time under the sample, fractionated molecule amount, ten thousand remarks
Cloudy 20 583 is entirely molten among the U.S. DOW AP-30
Cloudy 120 1030 is not more among the U.S. DOW AP-273
Molten thing
Cloudy 27 1045 is entirely molten among the Mitsui cyanamide AP125
It is cloudy 40 1234 entirely molten that SANYO GS changes among the AH-180P
Cloudy 29 1222 is entirely molten among the Japan day eastern chemical AP-2200
Cloudy 26 1453 is entirely molten among the Japan day eastern chemical PDA-1020
Cloudy 16 943 is entirely molten among the Japan AT-430
Cloudy 2.0 990 is entirely molten among the T-23 of the present invention
Cloudy 5.7 1387 is entirely molten among the T-26 of the present invention
Cloudy 4.7 1031 is entirely molten among the 85-2 of the present invention
Cloudy 4.2 1114 is entirely molten among the 85-4 of the present invention
Cloudy 5.9 1180 is entirely molten among the 87-4 of the present invention
Cloudy 5.5 1300 is entirely molten among the 87-5 of the present invention
Cloudy 5.5 1455 is entirely molten among the T-29 of the present invention
Table 2 coal washing water purifying effect＊Contrast
Compile medicament model chemical feeding quantity settling ratio removal efficiency
Number (mg/l) (%) (g/l) (%)
1 same moral-1 4 37 2.522 90.1
(with Dehua factory) 3 47 3.949 84.5
2 65 7.515 70.5
1 81 11.795 53.7
4 15 0.433 98.3
2 AP-2802 3 21 2.165 91.5
(Japan) 2 42 3.770 85.2
1 66 7.006 72.5
3 T-106 4 14 0.357 98.6
(the present invention) 3 19 1.758 93.1
2 40 3.388 86.7
1 61 6.293 75.3
* by the measuring of Anshan environmental protection institute
Table 3 coal washing water flocculation settling test result
Compile medicament model height of sampling removal efficiency
Number (mm) be (%) (g/l)
1 same moral-1 500 8.376 67.1
(with Dehua factory) 400 9.044 64.5
300 10.082 60.4
200 11.823 53.2
2 AP-2802 500 1.749 93.1
(Japan) 400 2.420 90.5
300 4.025 84.2
200 5.579 78.1
3 T-106(the present invention) 500 1.638 93.6
400 2.293 91.0
300 3.439 86.5
200 5.013 80.3
* by the measuring of Anshan environmental protection institute
Table 4 is the various test result * * of used for tertiary oil recovery sample relatively
Sample [η] η M
LS ωThe dissolving of SEC monomer
The V W content * time
Numbering dl/g cps * 10
-6Ml 0/00 minute
AT-430 13.33 20.32 6.44±1.08 21.8 16 ～7.2 16
T-26 13.13 19.21 6.07±1.07 21.4 16 ～0.48 5.7
T-106 17.36 24.00 8.94 ± 0.07 21.3 16 does not detect 4.5
Illustrate: * is with respect to the percentage composition of polymer weight.
* AT-430 is that Japan produces used for tertiary oil recovery HPAM sample: T-26, T-106
Be sample of the present invention.Measure by changing institute Polymer Physics research department.
Table 5 converter dust-removing water purifying effect
*Contrast
Compile medicament model dosing amount suspended substance removal rate
Number (mg/l) be (%) (mg/l)
1 same moral-1 1.5 285 96.0
(with Dehua factory) 1.3 419 94.1
1.0 669 90.6
0.8 1324 81.4
2 AP-2802 1.5 85 98.8
(Japan) 1.3 121 98.3
1.0 327 95.4
0.8 704 90.1
3 T-106(the present invention) 1.5 57 99.2
1.3 100 98.6
1.0 270 96.3
0.8 569 92.0
* by the measuring of Anshan environmental protection institute
Table 6 converter dedusting water flocculating settling experimental result
Compile medicament model height of sampling suspension content clearance
Number (mm) be (%) (mg/l)
1 same moral-1 500 711 90.0
(with Dehua factory) 400 783 89.0
300 897 87.4
200 996 86.0
2 AP-2802 500 327 95.4
(Japan) 400 377 94.7
300 420 94.1
200 512 92.8
3 T-106(the present invention) 500 256 96.4
400 285 96.0
300 334 95.3
200 480 93.2
Annotate: test is under identical condition of water quality, and adding dose is 1.0mg/l.
By the measuring of Anshan environmental protection institute
Claims (1)
1, the preparation method of instant high molecular anion type polycrylamide, by the pure system of monomer, polymerization, add steps such as alkali kneading, hydrolysis, granulation, drying and pulverizing and form, feature of the present invention is to add alkali to mediate and the posthydrolysis step ternary admixture trinity, and polymer weight ratio is in the relative polymeric colloid of its each component:
Urea 2-10%;
Formate 0.5-5%.
Zhong Xin polyoxyethylenated alcohol 0.5-3%.
Hydrolytic reagent alkali is alkali-metal sodium hydroxide and carbonate, Na
2CO
3And the ratio of NaOH addition was mediated 60-130 ℃ of temperature between 2: 10 to 10: 2, mediated time 0.5-6 hour, hydrolysis temperature 70-100 ℃, and hydrolysis time 5-20 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90104113 CN1022417C (en) | 1990-06-04 | 1990-06-04 | Preparation of fast-dissolving anion type polyacrylamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90104113 CN1022417C (en) | 1990-06-04 | 1990-06-04 | Preparation of fast-dissolving anion type polyacrylamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1057057A CN1057057A (en) | 1991-12-18 |
| CN1022417C true CN1022417C (en) | 1993-10-13 |
Family
ID=4878400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90104113 Expired - Fee Related CN1022417C (en) | 1990-06-04 | 1990-06-04 | Preparation of fast-dissolving anion type polyacrylamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1022417C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074990C (en) * | 1995-01-26 | 2001-11-21 | 芬格拉弗股份有限公司 | Method for production of printing mould plate and apparatus thereof |
| CN1108925C (en) * | 1995-10-13 | 2003-05-21 | 库夫曼模板技术股份公司 | Method of producing stencil, especially for printing paper or textiles |
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|---|---|---|---|---|
| CN1323942C (en) * | 2005-04-04 | 2007-07-04 | 崔凤才 | Deposition and purification method for borax ore |
| US8785573B2 (en) | 2012-09-12 | 2014-07-22 | Ecolab Usa Inc | Process for preparing water soluble polymers with no insoluble gels and low levels of residual monomers |
| CN103304714A (en) * | 2013-06-26 | 2013-09-18 | 上海宇昂水性新材料科技股份有限公司 | Preparation method of instant ultra-high molecular weight polyacrylamide dry powder |
| CN104558322B (en) * | 2013-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Method for polymerizing acrylamide by ultrasonic technology |
| CN104262517B (en) * | 2014-10-23 | 2016-12-07 | 山东宝莫生物化工股份有限公司 | Method for hydrolysis after a kind of polyacrylamide serialization |
| CN105542068B (en) * | 2014-10-24 | 2017-11-21 | 中国石油化工股份有限公司 | Hydrophobically associated polyacrylamide class fracturing fluid thickener and its preparation method and application |
| CN107445272A (en) * | 2017-07-21 | 2017-12-08 | 扬州科宇化工有限公司 | A kind of desalinization high polymer coagulant |
| CN113861314A (en) * | 2021-09-24 | 2021-12-31 | 宁波锋成先进能源材料研究院有限公司 | Polyacrylamide hydrolytic agent and preparation method and application thereof |
-
1990
- 1990-06-04 CN CN 90104113 patent/CN1022417C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074990C (en) * | 1995-01-26 | 2001-11-21 | 芬格拉弗股份有限公司 | Method for production of printing mould plate and apparatus thereof |
| CN1108925C (en) * | 1995-10-13 | 2003-05-21 | 库夫曼模板技术股份公司 | Method of producing stencil, especially for printing paper or textiles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1057057A (en) | 1991-12-18 |
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