CN102372806B - Initiator composition used for synthesizing polyacrylamide capable of displacing oil - Google Patents
Initiator composition used for synthesizing polyacrylamide capable of displacing oil Download PDFInfo
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 39
- 239000003999 initiator Substances 0.000 title abstract description 16
- 239000000203 mixture Substances 0.000 title abstract description 14
- 230000002194 synthesizing Effects 0.000 title abstract description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N edta Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N Thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000007864 aqueous solution Substances 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 238000006460 hydrolysis reaction Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000004090 dissolution Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000033558 biomineral tissue development Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 150000001408 amides Chemical class 0.000 claims description 9
- 238000004458 analytical method Methods 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 230000001105 regulatory Effects 0.000 claims description 9
- 238000005070 sampling Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L Sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 18
- 239000004202 carbamide Substances 0.000 abstract description 9
- 125000000217 alkyl group Chemical group 0.000 abstract description 8
- 238000006073 displacement reaction Methods 0.000 abstract description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 4
- 229940027983 antiseptics and disinfectants Quaternary ammonium compounds Drugs 0.000 abstract description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 abstract description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N Diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 125000005270 trialkylamine group Chemical group 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 14
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 9
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L disodium;2-[2-[carboxylatomethyl(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BHZRJJOHZFYXTO-UHFFFAOYSA-L Potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000977 initiatory Effects 0.000 description 4
- 230000000379 polymerizing Effects 0.000 description 4
- 235000019252 potassium sulphite Nutrition 0.000 description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 3
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 229940001607 sodium bisulfite Drugs 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- 230000001960 triggered Effects 0.000 description 3
- MTPJEFOSTIKRSS-UHFFFAOYSA-N 3-(dimethylamino)propanenitrile Chemical compound CN(C)CCC#N MTPJEFOSTIKRSS-UHFFFAOYSA-N 0.000 description 2
- 241000406668 Loxodonta cyclotis Species 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N 1-[2-[bis(2-hydroxypropyl)amino]ethyl-(2-hydroxypropyl)amino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M Potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L Potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Abstract
The invention relates to an initiator composition used for synthesizing polyacrylamide capable of displacing oil, which mainly solves the problems of low polyacrylamide molecular weight, poor heat resistance and salt resistance performances and difficult satisfaction for technical requirement of tertiary oil extraction. The initiator composition used for synthesizing polyacrylamide capable of displacing oil comprises the following ingredients by weight percentage: (a) 0.5-20% of persulfate; (b) 0.1-40% of sulfite or acid sulfite; (c) 0.5-20% of NR1R2R3-represented trialkylamine compounds or N<+>R4R5R6R7-represented quaternary ammonium compounds or NH2R8-represented aliphatic amine compounds, wherein R1-R7 in the formula are selected from C1-C14 straight chain or branched chain alkyl or alkyl derivatives, R8 is selected from straight chain or branched chain alkyl or alkyl derivatives; (d) 10-80% of urea, thiourea or ammonia liquor; (e) 5-60% of ethylenediaminetetraacetic acid. The technical scheme of the invention better solves the problems and can be used in industrial production of oil displacement.
Description
Technical field
The present invention relates to a kind of initiator composition for the synthesis of Polyacrylamides For Enhanced Oil Recoveries.
Background technology
Polyacrylamide (PAM) is homopolymer and the multipolymer of acrylamide and derivative thereof, is a kind of linear high molecular weight water soluble polymer.Polyacrylamide has multiple good performance, such as flocculence, tackifying, thickening property, surfactivity, filtrate-loss control, the characteristics such as frictional resistance are fallen, therefore, in industrial application, occupy most important status, be widely used in the fields such as drilling well, oil recovery, water blockoff, profile control, acidifying, pressure break, water treatment.At present, domestic each elephant through once, secondary oil recovery, crude oil water content constantly increases, the part elephant successively enters tertiary phase.Polymer flooding is the main technique methods of tertiary oil recovery, and oil-displacement mechanism is clear, and technique is relatively simple, and technology reaches its maturity, and is one and effectively improves the recovery efficiency technique measure.The oil-displacement mechanism of polymkeric substance mainly is the viscosity of utilizing the water-soluble polyacrylamide molecular chain, improves the mobility ratio of displacing fluid, improves efficiency of displacement and swept volume, thereby reaches the purpose that improves recovery ratio.Polyacrylamide is used to stabilize and increase crude production rate as the displacement of reservoir oil host of tertiary oil recovery.The PAM molecular mass is higher, and apparent viscosity is larger, and water-soluble better, oil displacement efficiency is better.Show that according to data super high molecular weight polyacrylamide is compared with common polyacrylamide can improve recovery ratio 2～8%.
In the last few years, the technology of synthetic polyacrylamide mainly contained both at home and abroad: the methods such as aqueous solution polymerization, letex polymerization, radio polymerization, micellar copolymerization.Wherein, topmost method is aqueous solution polymerization.Initiator system is generally used Potassium Persulphate-sodium bisulfite redox initiation system, employing ammonium persulfate-sodium bisulfite-azo-compound, the ammonium persulphate-rongalite-composite initiation systems such as azo-compound are also arranged, and the initiator system of the compositions such as hydrogen peroxide-amine, Potassium Persulphate-thiocarbamide or urea.In recent years, more and more to the research of the novel initiation system of acrylamide copolymer.CN1865298A discloses a kind of trisegment composite initiator for the synthesis of super high molecular weight polyacrylamide, at the polyacrylamide more than 2,500 ten thousand, but need to cause at a lower temperature (below 10 ℃) for the synthesis of molecular weight, and the reaction times is longer; Although the polymkeric substance molecular weight higher (〉=2,000 ten thousand) that adopts the described initiator of CN1506385A to obtain, the solution apparent viscosity is not high, and according to inventor's test determination, its viscosity only is 12.5mPas (salt solution total mineralization 19334mgL
-1, Ca
2++ Mg
2+: 514mgL
-1); Need not protection of inert gas in the disclosed post-transition metal-sodium hydrogen sulfite system building-up process of CN1397571A; need not to stir, reaction can be carried out at normal temperatures, but molecular weight only has 71～3,770,000; and according to test determination, its viscosity only is 2.8mPas (salt solution total mineralization 19334mgL
-1, Ca
2++ Mg
2+: 514mgL
-1), all be difficult to reach the technical indicator of used for tertiary oil recovery acrylamide copolymer.
Summary of the invention
The Molecular Weight for Polyacrylamide that technical problem to be solved by this invention is in the prior art and is synthesized is on the low side, the temperature resistant antisalt poor performance, be difficult to satisfy the problem of the technical requirements of used for tertiary oil recovery polymkeric substance, a kind of new initiator composition for the synthesis of Polyacrylamides For Enhanced Oil Recoveries is provided.The polymkeric substance that adopts this initiator composition to obtain has the molecular weight height, and the advantage that the apparent viscosity in salt solution is large meets the index request of Polyacrylamides For Enhanced Oil Recoveries.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of initiator composition for the synthesis of Polyacrylamides For Enhanced Oil Recoveries and preparation method thereof comprises following component: (a) 0.5～20% persulphate by weight percentage; (b) 0.1～40% sulphite or bisul-phite; (c) 0.5～20% by NR
1R
2R
3The representative tertiary amine compounds or by N
+R
4R
5R
6R
7The representative quaternary ammonium compounds or by NH
2R
8The fat amine compound of representative, R in the formula
1～R
7All be selected from C
1～C
14Straight or branched alkyl or alkyl derivative, R
8Be selected from C
1～C
18Straight or branched alkyl or alkyl derivative; (d) 10～80% urea, thiocarbamide or ammoniacal liquor; (e) 5～60% disodium ethylene diamine tetraacetate.
In the technique scheme, the persulphate preferred version is selected from Potassium Persulphate, Sodium Persulfate or ammonium persulphate, and by weight percentage, add-on is 0.5～20%, and preferable range is 5～15%.The sulphite preferred version is selected from S-WAT or potassium sulfite, and the bisul-phite preferred version is selected from sodium bisulfite or Potassium hydrogen sulfite, and add-on is 0.1～40%, and preferable range is 3～25%.The tertiary amine compounds preferred version is selected from methacrylic acid N, N-dimethylaminoethyl or β-dimethylaminopropionitrile; The quaternary ammonium compounds preferred version is selected from N, the N-dimethyl diallyl ammonium chloride; The fat amine compound preferred version is selected from methylamine or quadrol; Above-mentioned aminated compounds can use separately or several common use, and add-on is 0.5～20%, and preferable range is 5～15%.In addition, urea, thiocarbamide or ammoniacal liquor, the employing of also can choosing any one kind of them, perhaps several simultaneously employings, add-on is 10～80%, preferable range is 20～60%.The disodium ethylene diamine tetraacetate add-on is 5～60%, and preferable range is 15～40%.
It is as follows to use the present composition to carry out polymerizing acrylamide triggered process: the acrylamide with metering is dissolved in the deionized water first, be mixed with the monomer solution of 25% mass concentration, add sodium hydroxide, the pH value is adjusted to 8, after being cooled to 15 ℃, passed into high pure nitrogen 30 minutes, then add successively urea, thiocarbamide or ammoniacal liquor, disodium ethylene diamine tetraacetate, aminated compounds, persulphate, sulphite or bisul-phite, be warming up to 40 ℃ after 1 hour and continue reaction, namely got the gel polymerisate in 4 hours, add the sodium hydroxide of 10% mass concentration in 90 ℃ of hydrolysis 2 hours, then drying after cutting glue, pulverize to get powdered sample.
The present composition is owing to adopted the lower redox initiator of activation energy, can reduce the polymerization kick off temperature, the control polymerization rate, the amine initiator that activation energy is higher then makes the polyreaction middle and later periods, is guaranteeing that polyreaction is completely under the prerequisite, even polymeric reaction temperature is higher, still can effectively reduce polymerization rate, so reacting balance, it is even to be conducive to chainpropagation, obtains the higher product of molecular weight.Wherein double bond containing aminated compounds also can be participated in polyreaction directly, may make the more special structure of polymer formation, so that it has preferably temperature resistant antisalt performance simultaneously.The adding of solubility promoter urea etc. can improve structure adaptability, and the adding of complexing agent disodium ethylene diamine tetraacetate then can effectively be removed metal ion to the impact of polyreaction.When using composition of the present invention polymerizing acrylamide triggered, under 15 ℃ of initiations, 40 ℃ of polymerizing conditions, the polymericular weight that obtains 〉=2,000 ten thousand, (the salt solution total mineralization 20000mgL of the apparent viscosity 〉=20mPas in salt solution
-1About, Ca
2++ Mg
2+〉=500mgL
-1), be suitable for the displacement of reservoir oil, obtained preferably technique effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
First 125g acrylamide (AM) is added in the 352g deionized water, after stirring and dissolving is even, NaOH solution with 5% mass concentration is regulated pH value to 8, and water-bath is cooled to 15 ℃, then begin to pass into high pure nitrogen, behind the logical nitrogen 30min, add successively 1.25% aqueous solution of urea 10g, 0.9% disodium ethylene diamine tetraacetate (EDTA-disodium) aqueous solution 10g, 1.25% methacrylic acid N, N-dimethylaminoethyl (DMAEMA) aqueous solution 1g, 1.25% persulfate aqueous solution 1g, 1% aqueous solution of sodium bisulfite 1g rose to 40 ℃ gradually with temperature of reaction after 1 hour, reacted to obtain the gel polymerisate after 4 hours, add 10%NaOH aqueous solution 140g after cutting glue, 90 ℃ of hydrolysis reaction 2 hours, then at 75 ℃ of lower vacuum-drying 6h, smash sampling analysis after the screening with pulverizer.
Testing solid content by GB/T12005.2-89 polyacrylamide determination of solid content method is 90.5%, press GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test dissolution time≤90min, testing degree of hydrolysis by GB/T12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method is 20.6%, press the GB/T12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is that 3,250 ten thousand, 1500mg/L polymer concentration solution are at 65 ℃, 7.34s
-1Under apparent viscosity be 26.5mPas (salt solution total mineralization 19334mgL
-1, Ca
2++ Mg
2+: 514mgL
-1).
[embodiment 2]
First 125g acrylamide (AM) is added in the 370g deionized water, after stirring and dissolving is even, NaOH solution with 5% mass concentration is regulated pH value to 8, and water-bath is cooled to 15 ℃, then begin to pass into high pure nitrogen, behind the logical nitrogen 30min, add successively 1.25% thiourea solution 1g, 0.81% disodium ethylene diamine tetraacetate (EDTA-disodium) aqueous solution 1g, 1.25% β-dimethylaminopropionitrile aqueous solution 1g, 1.25% sodium persulfate aqueous solution 1g, 1.69% potassium sulfite aqueous solution 1g, after 1 hour temperature of reaction is risen to 40 ℃ gradually, react and obtain the gel polymerisate after 4 hours, add 10%NaOH aqueous solution 140g after cutting glue, 90 ℃ of hydrolysis reaction 2 hours, then at 75 ℃ of lower vacuum-drying 6h, smash the rear sampling analysis of screening with pulverizer.
Testing solid content by GB/T12005.2-89 polyacrylamide determination of solid content method is 89.9%, press GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test dissolution time≤120min, testing degree of hydrolysis by GB/T12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method is 22.1%, press the GB/T12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is that 2,215 ten thousand, 1500mg/L polymer concentration solution are at 65 ℃, 7.34s
-1Under apparent viscosity be 21.8mPas (salt solution total mineralization 19334mgL
-1, Ca
2++ Mg
2+: 514mgL
-1).
[embodiment 3]
First 125g acrylamide (AM) is added in the 370g deionized water, after stirring and dissolving is even, NaOH solution with 5% mass concentration is regulated pH value to 8, and water-bath is cooled to 15 ℃, then begin to pass into high pure nitrogen, behind the logical nitrogen 30min, add successively 1.38% aqueous solution of urea 1g, 0.33% disodium ethylene diamine tetraacetate (EDTA-disodium) aqueous solution 1g, 0.99%N, N-dimethyl diallyl ammonium chloride aqueous solution 1g, 1.25% ammonium persulfate aqueous solution 1g, 2.63% potassium sulfite aqueous solution 1g rose to 40 ℃ gradually with temperature of reaction after 1 hour, reacted to obtain the gel polymerisate after 4 hours, add 10%NaOH aqueous solution 140g after cutting glue, 90 ℃ of hydrolysis reaction 2 hours, then at 75 ℃ of lower vacuum-drying 6h, smash sampling analysis after the screening with pulverizer.
Testing solid content by GB/T12005.2-89 polyacrylamide determination of solid content method is 89.8%, press GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test dissolution time≤90min, testing degree of hydrolysis by GB/T12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method is 19.6%, press the GB/T12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is that 2,053 ten thousand, 1500mg/L polymer concentration solution are at 65 ℃, 7.34s
-1Under apparent viscosity be 20.7mPas (salt solution total mineralization 19334mgL
-1, Ca
2++ Mg
2+: 514mgL
-1).
[embodiment 4]
First 125g acrylamide (AM) is added in the 369g deionized water, after stirring and dissolving is even, NaOH solution with 5% mass concentration is regulated pH value to 8, and water-bath is cooled to 15 ℃, then begin to pass into high pure nitrogen, behind the logical nitrogen 30min, add successively 3.13% thiourea solution 1g, 1.04% ammonia soln 1g, 2.5% disodium ethylene diamine tetraacetate (EDTA-disodium) aqueous solution 1g, 1.56% methacrylic acid N, N-dimethylaminoethyl (DMAEMA) aqueous solution 1g, 1.25% ammonium persulfate aqueous solution 1g, 0.94% sodium sulfite aqueous solution 1g, after 1 hour temperature of reaction is risen to 40 ℃ gradually, react and obtain the gel polymerisate after 4 hours, add 10%NaOH aqueous solution 140g after cutting glue, 90 ℃ of hydrolysis reaction 2 hours, then at 75 ℃ of lower vacuum-drying 6h, smash the rear sampling analysis of screening with pulverizer.
Testing solid content by GB/T12005.2-89 polyacrylamide determination of solid content method is 89.8%, press GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test dissolution time≤90min, testing degree of hydrolysis by GB/T12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method is 21.4%, press the GB/T12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is that 2,835 ten thousand, 1500mg/L polymer concentration solution are at 65 ℃, 7.34s
-1Under apparent viscosity be 25.2mPas (salt solution total mineralization 19334mgL
-1, Ca
2++ Mg
2+: 514mgL
-1).
[embodiment 5～8]
Each Step By Condition according to embodiment 1 is polymerizing acrylamide triggered, obtains polyacrylamide, just changes component and the content of initiator composition, and the polymkeric substance result that it obtains lists in table 1.
[comparative example 1]
First 125g acrylamide (AM) is added in the 373g deionized water, after stirring and dissolving is even, NaOH solution with 5% mass concentration is regulated pH value to 8, and water-bath is cooled to 15 ℃, then begin to pass into high pure nitrogen, behind the logical nitrogen 30min, add successively 1.25% persulfate aqueous solution 1g, 1% aqueous solution of sodium bisulfite 1g rose to 40 ℃ gradually with temperature of reaction after 1 hour, reacted to obtain the gel polymerisate after 4 hours, add 10%NaOH aqueous solution 140g after cutting glue, 90 ℃ of hydrolysis reaction 2 hours, then at 75 ℃ of lower vacuum-drying 6h, smash sampling analysis after the screening with pulverizer.
Testing solid content by GB/T12005.2-89 polyacrylamide determination of solid content method is 89.5%, press GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test dissolution time≤120min, testing degree of hydrolysis by GB/T12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method is 21.4%, press the GB/T12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is that 1,238 ten thousand, 1500mg/L polymer concentration solution are at 65 ℃, 7.34s
-1Under apparent viscosity be 12.6mPas (salt solution total mineralization 19334mgL
-1, Ca
2++ Mg
2+: 514mgL
-1).
[comparative example 2]
First 125g acrylamide (AM) is added in the 373g deionized water, after stirring and dissolving is even, NaOH solution with 5% mass concentration is regulated pH value to 8, and water-bath is cooled to 15 ℃, then begin to pass into high pure nitrogen, behind the logical nitrogen 30min, add successively 1.25% methacrylic acid N, N-dimethylaminoethyl (DMAEMA) aqueous solution 1g, 1.25% persulfate aqueous solution 1g, after 1 hour temperature of reaction is risen to 40 ℃ gradually, react and obtain the gel polymerisate after 4 hours, add 10%NaOH aqueous solution 140g after cutting glue, 90 ℃ of hydrolysis reaction 2 hours, then at 75 ℃ of lower vacuum-drying 6h, smash the rear sampling analysis of screening with pulverizer.
Testing solid content by GB/T12005.2-89 polyacrylamide determination of solid content method is 89.6%, press GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test dissolution time≤180min, testing degree of hydrolysis by GB/T12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method is 20.9%, press the GB/T12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is that 1,465 ten thousand, 1500mg/L polymer concentration solution are at 65 ℃, 7.34s
-1Under apparent viscosity be 15.6mPas (salt solution total mineralization 19334mgL
-1, Ca
2++ Mg
2+: 514mgL
-1).
[comparative example 3]
First 125g acrylamide (AM) is added in the 372g deionized water, after stirring and dissolving is even, NaOH solution with 5% mass concentration is regulated pH value to 8, and water-bath is cooled to 15 ℃, then begin to pass into high pure nitrogen, behind the logical nitrogen 30min, add successively 1.04% ammonia soln 1g, 1.25% ammonium persulfate aqueous solution 1g, 0.94% sodium sulfite aqueous solution 1g, after 1 hour temperature of reaction is risen to 40 ℃ gradually, react and obtain the gel polymerisate after 4 hours, add 10%NaOH aqueous solution 140g after cutting glue, 90 ℃ of hydrolysis reaction 2 hours, then at 75 ℃ of lower vacuum-drying 6h, smash the rear sampling analysis of screening with pulverizer.
Testing solid content by GB/T12005.2-89 polyacrylamide determination of solid content method is 90.3%, press GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test dissolution time≤120min, testing degree of hydrolysis by GB/T12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method is 19.8%, press the GB/T12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is that 1,156 ten thousand, 1500mg/L polymer concentration solution are at 65 ℃, 7.34s
-1Under apparent viscosity be 11.9mPas (salt solution total mineralization 19334mgL
-1, Ca
2++ Mg
2+: 514mgL
-1).
[comparative example 4]
First 125g acrylamide (AM) is added in the 353g deionized water, after stirring and dissolving is even, NaOH solution with 5% mass concentration is regulated pH value to 8, and water-bath is cooled to 15 ℃, then begin to pass into high pure nitrogen, behind the logical nitrogen 30min, add successively 1.25% aqueous solution of urea 10g, 0.9% disodium ethylene diamine tetraacetate (EDTA-disodium) aqueous solution 10g, 1.25% sodium persulfate aqueous solution 1g, 0.47% potassium sulfite aqueous solution 1g rose to 40 ℃ gradually with temperature of reaction after 1 hour, reacted to obtain the gel polymerisate after 4 hours, add 10%NaOH aqueous solution 140g after cutting glue, 90 ℃ of hydrolysis reaction 2 hours, then at 75 ℃ of lower vacuum-drying 6h, smash sampling analysis after the screening with pulverizer.
Testing solid content by GB/T12005.2-89 polyacrylamide determination of solid content method is 90.5%, press GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test dissolution time≤90min, testing degree of hydrolysis by GB/T12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method is 20.8%, press the GB/T12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is that 1,385 ten thousand, 1500mg/L polymer concentration solution are at 65 ℃, 7.34s
-1Under apparent viscosity be 13.8mPas (salt solution total mineralization 19334mgL
-1, Ca
2++ Mg
2+: 514mgL
-1).
The different initiator compositions of table 1 are to the acrylamide polymerization test-results
Claims (1)
1. the preparation method of partially hydrolyzed polyacrylamide, step is:
First the 125g acrylamide is added in the 369g deionized water, after stirring and dissolving is even, NaOH solution with 5% mass concentration is regulated pH value to 8, and water-bath is cooled to 15 ℃, then begin to pass into high pure nitrogen, behind the logical nitrogen 30min, add successively 3.13% thiourea solution 1g, 1.04% ammonia soln 1g, 2.5% disodium ethylene diamine tetra-acetic acid aqueous solution 1g, 1.56% methacrylic acid N, N-dimethylaminoethyl aqueous solution 1g, 1.25% ammonium persulfate aqueous solution 1g, 0.94% sodium sulfite aqueous solution 1g, after 1 hour temperature of reaction is risen to 40 ℃ gradually, react and obtain the gel polymerisate after 4 hours, add 10%NaOH aqueous solution 140g after cutting glue, 90 ℃ of hydrolysis reaction 2 hours, then at 75 ℃ of lower vacuum-drying 6h, smash the rear sampling analysis of screening with pulverizer;
Testing solid content by GB/T12005.2-89 polyacrylamide determination of solid content method is 89.8%, press GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test dissolution time≤90min, testing degree of hydrolysis by GB/T12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method is 21.4%, press the GB/T12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is that 2,835 ten thousand, 1500mg/L polymer concentration solution are at 65 ℃, 7.34s
-1Under apparent viscosity be 25.2mPas; Salt solution total mineralization 19334mgL in the wherein said 1500mg/L polymer concentration solution
-1, Ca
2++ Mg
2+Be 514mgL
-1
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| CN104448127B (en) * | 2013-09-24 | 2017-07-14 | 中国石油化工股份有限公司 | Polymer mobility control agent suitable for special high salinity reservoirs and preparation method thereof |
| CN104449636B (en) * | 2013-09-24 | 2018-06-08 | 中国石油化工股份有限公司 | Oil displacement agent of recovery ratio and preparation method thereof is improved suitable for high temperature and high salt harshness oil reservoir |
| CN104448125B (en) * | 2013-09-24 | 2017-02-15 | 中国石油化工股份有限公司 | Amphoteric hydrophobically-associating polymer and preparation method thereof |
| CN104558402B (en) * | 2013-10-28 | 2017-01-04 | 中国石油化工股份有限公司 | Oil deposit deep part transfer drive polymer micro-emulsion |
| CN105504104B (en) * | 2014-09-24 | 2018-06-15 | 中国石油化工股份有限公司 | Photoinitiator composite and POLYACRYLAMIDE FLOODING polymer and its preparation method and application |
| CN105505364B (en) * | 2014-10-13 | 2018-10-23 | 中国石油化工股份有限公司 | LOW PERMEABILITY RESERVOIR improves the displacement composition and its preparation method and application of recovery ratio in high temperature and high salt |
| CN105566560B (en) * | 2014-10-15 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of structure directing type composite initiator system and acrylamide polymer and its preparation method and application |
| 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 |
| CN107987820B (en) * | 2018-01-05 | 2020-04-07 | 中海石油(中国)有限公司 | Temperature-resistant and salt-resistant oil displacement polymer and preparation method and application thereof |
| CN109134726B (en) * | 2018-04-18 | 2021-04-30 | 宁波大学 | Phthalocyanine dye high-molecular method |
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| CN101157741A (en) * | 2007-09-28 | 2008-04-09 | 东营顺通化工（集团）有限公司 | Synthesis technology of high molecular weight temperature-tolerant anti-salt polyacrylamide |
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