CN1506385A - Initiator system for preparing polyacrylamide - Google Patents
Initiator system for preparing polyacrylamide Download PDFInfo
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- CN1506385A CN1506385A CNA021359679A CN02135967A CN1506385A CN 1506385 A CN1506385 A CN 1506385A CN A021359679 A CNA021359679 A CN A021359679A CN 02135967 A CN02135967 A CN 02135967A CN 1506385 A CN1506385 A CN 1506385A
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- Prior art keywords
- initiator system
- agent
- molecular weight
- polyacrylamide
- persulphate
- Prior art date
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 35
- 239000003999 initiator Substances 0.000 title claims abstract description 25
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 tertiary amine compound Chemical class 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 41
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 9
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 7
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 7
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 7
- 150000003926 acrylamides Chemical class 0.000 claims description 7
- 239000012986 chain transfer agent Substances 0.000 claims description 7
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 7
- 229910052722 tritium Inorganic materials 0.000 claims description 7
- 239000004159 Potassium persulphate Substances 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 235000019394 potassium persulphate Nutrition 0.000 claims description 6
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 6
- 235000019252 potassium sulphite Nutrition 0.000 claims description 6
- 239000004160 Ammonium persulphate Substances 0.000 claims description 5
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 5
- MTPJEFOSTIKRSS-UHFFFAOYSA-N 3-(dimethylamino)propanenitrile Chemical compound CN(C)CCC#N MTPJEFOSTIKRSS-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000006184 cosolvent Substances 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 abstract 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 235000017550 sodium carbonate Nutrition 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 239000003513 alkali Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000004153 Potassium bromate Substances 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 235000019396 potassium bromate Nutrition 0.000 description 1
- 229940094037 potassium bromate Drugs 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Abstract
The initiator system for initiating the polymerization of acrylamide to obtain polymer polyacrylamide consists of co-solvent including ammonia water and urea or thiourea; molecular weight regulator tertiary amine compound or aliphatic amine compound; complexing agent complexone III; efficient chain transferring agent tertiary amine compound; oxidant persulfate; and reductant sulfite or acid sulfite. The polyacrylamide obtained in the presence of the initiator system has high molecular weight, high apparent viscosity, high dissolubility and small filtration ratio and may be used as oil replacing agent.
Description
Technical field
The present invention relates to a kind of new initiator system, specifically be used for the polymerizing acrylamide triggered initiator system that obtains high molecular polymer-polyacrylamide.
Background technology
The intermediate concentration aqueous solution polymerization of acrylamide is the conventional means of industrial production polyacrylamide, and the method for acrylamide initiated polymerization is a lot, and most widely used is that chemistry causes, and initiator system was a key factor during chemistry caused.Initiator system can make the acrylamide initiated polymerization, thereby obtains polyacrylamide, but not all polyacrylamide all has commodity value (or use value).In order to obtain the polyacrylamide of some characteristic, make and itself satisfy certain technical indicator, must carry out compatibility to numerous initiators and integrate, form and use effective initiator system within the specific limits.
The initiator system of the preparation polyacrylamide of bibliographical information mainly contains: Potassium Persulphate/S-WAT, ammonium persulphate/S-WAT/azo-compound, ammonium persulphate/formolation Sodium Thiosulfate/azo-compound, hydrogen peroxide/amine, t-butyl peroxide/S-WAT, Potassium Persulphate/carbamyl ethyl or mercaptoethanol, urea, xitix or oxyacetic acid, potassium permanganate/lactic acid, quadrivalent cerium ion/mercaptan, thiophosphoric acid, citric acid, methyl ethyl diketone/azanol, pentavalent vanadium ion/pimelinketone, potassium bromate/Thiovanic acid etc.The characteristics of these initiator systems are that reactive behavior is good, be suitable for polymerized at normal temperature, but molecular weight of product are lower.
In the oil recovery industry,, require to possess as the polyacrylamide that the displacement of reservoir oil is used: higher molecular weight (M 〉=1,800 ten thousand), instant, the moderate hydrolysis, acidproof, heatproof and good salt resistance, apparent viscosity 〉=11.5mpa.s, its leading indicator such as following table:
| Project | Index |
| Molecular weight (ten thousand) | ≥1800 |
| Apparent viscosity (mpa.s) | ≥11.5 |
| Filtration ratio | ＜1.5 |
| Degree of hydrolysis (%) | 20～25 |
| Dissolution rate (h) | ≤2 |
| Water-insoluble (%) | ≤0.2 |
The polyacrylamide that the initiator system that adopts existing document to provide obtains is difficult to reach the index request of the displacement of reservoir oil with super high molecular weight polyacrylamide.
Summary of the invention
The object of the present invention is to provide a kind of polymerizing acrylamide triggered initiator system, adopt the polyacrylamide of this initiator system, possess the index request of the displacement of reservoir oil with polyacrylamide in the high molecular (M 〉=1,800 ten thousand) that keeps obtaining under the high rate of polymerization.
For achieving the above object, the present invention adopts following scheme:
The preparation polyacrylamide initiator system, be by
(1) solubility promoter: content is 25～28% ammoniacal liquor, urea or thiocarbamide;
(2) molecular weight mediator agent: by the tertiary amine compounds of following general formula representative
R in the formula
1, R
2, R
3Represent C separately
1～C
14Straight or branched alkyl or alkyl derivative
Or by the fat amine compound of following general formula representative
R’-NH
2
R ' represents C
1～C
18Straight or branched alkyl or alkyl derivative;
(3) complexing agent: disodium ethylene diamine tetraacetate;
(4) efficient chain-transfer agent: by the tertiary amine compounds of following general formula representative
R ' in the formula
1, R '
2, R '
3Represent C
1～C
18The derivative that contains carbonyl;
(5) oxygenant: persulphate;
(6) reductive agent: sulphite or bisul-phite are formed,
The per-cent that the consumption of solubility promoter, molecular weight mediator agent, complexing agent, efficient chain-transfer agent, Oxidizing and Reducing Agents accounts for acrylamide weight is respectively 0.21～4.5%, 0.01～0.5%, 0.015～0.065%, 0.013～0.36%, 0.003～0.1%, 0.003～0.1%.
Tertiary amine compounds in the molecular weight regulator, preferably β-dimethylaminopropionitrile or N-N '-Tetramethyl Ethylene Diamine, the fat amine compound in the molecular weight regulator, preferably methylamine or quadrol.Efficient chain-transfer agent is nitrogen tritium three acrylamides preferably.What oxygenant was preferable is Potassium Persulphate, Sodium Persulfate or ammonium persulphate.Sulphite in the reductive agent, preferable is S-WAT or potassium sulfite, the bisul-phite in the reductive agent, preferable is sodium acid sulfite or acidic potassium sulfite.
In addition, in this initiator system, for ammoniacal liquor, urea or the thiocarbamide as solubility promoter, the three can choose one wantonly and adopt, but also optional the two employing of three, but also the three adopts jointly.For tertiary amine compounds or the fat amine compound as molecular weight regulator, the two can be chosen one wantonly and adopt, but also the two common employing.
Allot the aqueous solution of the acrylamide of intermediate concentration earlier, in molten alkali still, make soda ash solution with de-salted water, then with the two uniform mixing and be cooled to 5～20 ℃, with mixing solutions with pump delivery to polymeric kettle, add solubility promoter successively, molecular weight regulator, and feeding nitrogen, in the process of logical nitrogen, add complexing agent successively, efficient chain-transfer agent, oxygenant and reductive agent, seal airtight then, after reaction finishes, with pressurized air polymeric colloid is extruded from polymeric kettle, through granulation, oven dry, pulverize, screening, obtain the polyacrylamide finished product after the packing.
Show by test-results, cause the polyacrylamide that obtains by initiator system provided by the invention, its molecular weight height, apparent viscosity height, solvability is good, filtration ratio is little, meets the every index of the displacement of reservoir oil with super high molecular weight polyacrylamide fully.
Embodiment
The present invention is further described below in conjunction with several specific embodiments.
Embodiment 1
In the 500ml wide-necked bottle, stir down with glass stick, 13 parts of (weight, down with) soda ash are joined lentamente in 280 part 30% the acrylamide solution, mix the back and be diluted to 400ml with de-salted water (electricity is led≤3 μ s/cm).In the acrylamide is the weight percent (down together) of benchmark, adds ammoniacal liquor (content is 25～28%) 0.3% and urea 2% earlier, adds β-dimethylaminopropionitrile 0.2% and quadrol 0.15% again.After the stirring thorough mixing is even, be cooled to 5～20 ℃, begin to feed high pure nitrogen (nitrogen gas purity 〉=99.99%) with the oxygen in the expeling system.In the process of logical nitrogen, every interval added disodium ethylene diamine tetraacetate 0.03%, nitrogen tritium three acrylamides 0.025%, Potassium Persulphate 0.08% and S-WAT 0.06% in 1～3 minute successively.When the system oxygen level is sealed less than 0.2% the time airtight.When reaction when no longer heating up, put into 75～95 ℃ water-bath heat tracing 4～6 hours.Insulation finishes the back and takes out colloid, pulverizes through oven for drying, pulverizer and obtains polyacrylamide.The detected result of polyacrylamide is as follows:
| Project | The result |
| Molecular weight (ten thousand) | 2285 |
| Apparent viscosity (mpa.s) | 13.1 |
| Filtration ratio | 0.46 |
| Degree of hydrolysis (%) | 24.25 |
| Dissolution rate (h) | ≤1.2 |
| Water-insoluble (%) | ≤0.15 |
Embodiment 2
In the 500ml wide-necked bottle, stir down with glass stick, 13 parts of soda ash are joined lentamente in 280 part 30% the acrylamide solution, mix the back and be diluted to 400ml with de-salted water (electricity is led≤3 μ s/cm).In the acrylamide is the weight percent (down together) of benchmark, adds ammoniacal liquor (content is 25～28%) 2.5% and thiocarbamide 1.8% earlier, adds N-N '-Tetramethyl Ethylene Diamine 0.15% and methylamine 0.1% again.After the stirring thorough mixing is even, be cooled to 5～20 ℃, begin to feed high pure nitrogen (nitrogen gas purity 〉=99.99%) with the oxygen in the expeling system.In the process of logical nitrogen, every interval added disodium ethylene diamine tetraacetate 0.03%, nitrogen tritium three acrylamides 0.02%, Sodium Persulfate 0.075% and potassium sulfite 0.062% in 1～3 minute successively.When the system oxygen level is sealed less than 0.2% the time airtight.When reaction when no longer heating up, put into 75～95 ℃ water-bath heat tracing 4～6 hours.Insulation finishes the back and takes out colloid, pulverizes through oven for drying, pulverizer and obtains polyacrylamide.The detected result of polyacrylamide is as follows:
| Project | The result |
| Molecular weight (ten thousand) | 2073 |
| Apparent viscosity (mpa.s) | 12.6 |
| Filtration ratio | 0.64 |
| Degree of hydrolysis (%) | 23.84 |
| Dissolution rate (h) | ≤1.2 |
| Water-insoluble (%) | ≤0.15 |
Embodiment 3
In the 150L reactor, under agitation 3575 parts of soda ash are joined lentamente in 77000 part 30% the acrylamide solution, mix the back and be diluted to 110L with de-salted water (electricity is led≤3 μ s/cm).In the acrylamide is the weight percent (down together) of benchmark, adds ammoniacal liquor (content is 25～28%) 1.8% and urea 2.5% earlier, adds N-N '-Tetramethyl Ethylene Diamine 0.3% and quadrol 0.2% again.After the stirring thorough mixing is even, be cooled to 5～20 ℃, begin to feed high pure nitrogen (nitrogen gas purity 〉=99.99%), with the oxygen in the expeling system.In the process of logical nitrogen, every interval added disodium ethylene diamine tetraacetate 0.04%, nitrogen tritium three acrylamides 0.02%, ammonium persulphate 0.07% and S-WAT 0.055% in 1～3 minute successively.When the system oxygen level is sealed sealing less than 0.2% the time.When reaction when no longer heating up, put into 75～95 ℃ water-bath heat tracing 4～6 hours.Insulation finishes the back and takes out colloid, pulverizes through oven for drying, pulverizer and obtains polyacrylamide.The detected result of polyacrylamide is as follows:
| Project | The result |
| Molecular weight (ten thousand) | 2219 |
| Apparent viscosity (mpa.s) | 12.9 |
| Filtration ratio | 0.51 |
| Degree of hydrolysis (%) | 24.65 |
| Dissolution rate (h) | ≤1.2 |
| Water-insoluble (%) | ≤0.15 |
Embodiment 4
The accurate acrylamide solution of 7700000 part 30% of metering in material-compound tank is imported it in material-compound tank after under stirring with a certain amount of de-salted water (electricity is led≤3 μ s/cm) in molten alkali still 357500 parts of soda ash being dissolved fully, mends de-salted water then to 11m
3It mixed and be cooled to 5～20 ℃ by external-cooling type circulation, with mixing solutions with pump delivery to polymeric kettle.In the acrylamide is the weight percent (down together) of benchmark, adds ammoniacal liquor (content is 25～28%) 0.55%, N-N '-Tetramethyl Ethylene Diamine 0.18%, methylamine 0.2% successively by charging opening.Feed nitrogen (flow 40～80Nm from the polymeric kettle bottom
3/ h, nitrogen gas purity 〉=99.99%), in the process of logical nitrogen, every interval added disodium ethylene diamine tetraacetate 0.05%, nitrogen tritium three acrylamides 0.045%, persulfuric acid in 1～3 minute successively and receives 0.072% and acidic potassium sulfite 0.058%.When the system oxygen level is sealed less than 0.2% the time airtight.When reaction no longer heats up, feed 1kg steam insulation 4～8 hours.After the insulation end, with 0.5Mpa pressurized air polymeric colloid is extruded from polymeric kettle, blob of viscose obtains the polyacrylamide finished product again after vibrated fluidized bed oven dry, pulverizer are pulverized, sieve, packed after slightly granulation, thin granulation.The product detected result is as follows:
| Project | The result |
| Molecular weight (ten thousand) | 2168 |
| Apparent viscosity (mpa.s) | 12.8 |
| Filtration ratio | 0.55 |
| Degree of hydrolysis (%) | 24.29 |
| Dissolution rate (h) | ≤1.2 |
| Water-insoluble (%) | ≤0.15 |
Embodiment 5
The accurate acrylamide solution of 7700000 part 30% of metering in material-compound tank is imported it in material-compound tank after under stirring with a certain amount of de-salted water (electricity is led≤3 μ s/cm) in molten alkali still 357500 parts of soda ash being dissolved fully, mends de-salted water then to 11m
3It mixed and be cooled to 5～20 ℃ by external-cooling type circulation, with mixing solutions with pump delivery to polymeric kettle.In the acrylamide is the weight percent (down together) of benchmark, adds ammoniacal liquor (content is 25～28%) 0.35%, urea 1.6%, β-dimethylaminopropionitrile 0.22%, quadrol 0.12% successively by charging opening.Feed nitrogen (flow 40～80Nm from the polymeric kettle bottom
3/ h, nitrogen gas purity 〉=99.99%), in the process of logical nitrogen, every interval added disodium ethylene diamine tetraacetate 0.05%, nitrogen tritium three acrylamides 0.045%, Potassium Persulphate 0.072% and sodium acid sulfite 0.058% in 1～3 minute successively.When the system oxygen level is sealed less than 0.2% the time airtight.When reaction no longer heats up, feed 1kg steam insulation 4～8 hours.After the insulation end, with 0.5Mpa pressurized air polymeric colloid is extruded from polymeric kettle, blob of viscose obtains the polyacrylamide finished product again after vibrated fluidized bed oven dry, pulverizer are pulverized, sieve, packed after slightly granulation, thin granulation.The product detected result is as follows:
| Project | The result |
| Molecular weight (ten thousand) | 2113 |
| Apparent viscosity (mpa.s) | 12.7 |
| Filtration ratio | 0.54 |
| Degree of hydrolysis (%) | 24.06 |
| Dissolution rate (h) | ≤1.2 |
| Water-insoluble (%) | ≤0.15 |
By above several embodiment as can be seen, cause the polyacrylamide that obtains, its molecular weight, apparent viscosity, filter when index such as dissolution rate and all reach the requirement of the displacement of reservoir oil with polyacrylamide by initiator system provided by the invention.
Claims (6)
1, the preparation polyacrylamide initiator system, it is characterized in that by
(1) solubility promoter: content is 25～28% ammoniacal liquor, urea or thiocarbamide;
(2) molecular weight mediator agent: by the tertiary amine compounds of following general formula representative
R in the formula
1, R
2, R
3Represent C separately
1～C
14Straight or branched alkyl or alkyl derivative
Or by the fat amine compound of following general formula representative
R’-NH
2
R ' represents C
1～C
18Straight or branched alkyl or alkyl derivative;
(3) complexing agent: disodium ethylene diamine tetraacetate;
(4) efficient chain-transfer agent: by the tertiary amine compounds of following general formula representative
R ' in the formula
1, R '
2, R '
3Represent C
1～C
18The derivative that contains carbonyl;
(5) oxygenant: persulphate;
(6) reductive agent: sulphite or bisul-phite are formed,
The per-cent that the consumption of solubility promoter, molecular weight mediator agent, complexing agent, efficient chain-transfer agent, Oxidizing and Reducing Agents accounts for acrylamide weight is respectively 0.21～4.5%, 0.01～0.5%, 0.015～0.065%, 0.013～0.36%, 0.003～0.1%, 0.003～0.1%.
2, the initiator system of preparation polyacrylamide according to claim 1 is characterized in that, tertiary amine compounds is β-dimethylaminopropionitrile or N-N '-Tetramethyl Ethylene Diamine.
3, the initiator system of preparation polyacrylamide according to claim 1 is characterized in that, fat amine compound is methylamine or quadrol.
4, the initiator system of preparation polyacrylamide according to claim 1 is characterized in that, efficient chain-transfer agent is nitrogen tritium three acrylamides.
5, the initiator system of preparation polyacrylamide according to claim 1 is characterized in that, persulphate is Potassium Persulphate, Sodium Persulfate or ammonium persulphate.
6, the initiator system of preparation polyacrylamide according to claim 1 is characterized in that, sulphite is S-WAT or potassium sulfite, and bisul-phite is sodium acid sulfite or acidic potassium sulfite.
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