CN1290714A - High hydroscopicity resin specially for oil field and agriculture - Google Patents
High hydroscopicity resin specially for oil field and agriculture Download PDFInfo
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- CN1290714A CN1290714A CN 00132217 CN00132217A CN1290714A CN 1290714 A CN1290714 A CN 1290714A CN 00132217 CN00132217 CN 00132217 CN 00132217 A CN00132217 A CN 00132217A CN 1290714 A CN1290714 A CN 1290714A
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Abstract
The resin is prepared with acrylic acid or acrylate; the second monomer selected from methyl acrylate, ethyl acrylate, butyl acrylate, ethyoxyl acrylate, hydroxypropy acrylate, hydroxybutyl acrylate, acrylamide, polyvinyl alcohol, maleic anhydride and vinyl sulfonic acid; the third monomer selected from starch, cellulose, soybean protein, pectin and wheat bran; crosslinking agent and primer and through crosslinking, grafting and copolymerizing reactions. The resin of the present invention has proper hydroscopicity, excellent volume expansion coefficient, excellent pressure strength, high heat stability, slow degradation, and no harm to crop, and is especially suitable for use as hydroscopic resin in oil field and agriculture.
Description
The present invention relates to a kind of absorbent resin, refer to the super absorbent resin by vinylformic acid, acrylate and other two kinds of monomer-grafted copolymerization of a kind of oil field, agriculture usefulness especially.
Water-absorbing resin is to be engaged in economizing northern Research Institute success by U.S.'s farming the earliest, after this various water-absorbing resins have been developed in the U.S., Japan, Europe in succession, as Japanese Patent CN1098727A, United States Patent (USP) No. 3980663, No. 4093776, european patent application disclose No. 467073, No. 478150 etc.The disclosed resin of these patents, the overwhelming majority all are used for aspects such as health field, medicine, agricultural gardening, fresh keeping product, daily-use chemical industry.Application on oil field, agricultural is less, almost is blank.Said resin characteristics is water absorbent rate height (500～700 times) in these patents, but inhales the ability of salt solution, salt tolerant, and generally inhaling physiological saline (0.9%) is 50～70 times; Bad mechanical strength, the suction back becomes pasty state, is subjected to easily to decompose after the uviolizing; Absorption speed very fast (being generally 20～30 seconds), this is unfavorable for field use, and also will increase cost through complicated aftertreatment technology.In view of this, the inventor sets about research and development, and has invented oil field of the present invention, agriculture tailored version very-high performance water-absorbing resin.
The purpose of this invention is to provide a kind ofly have that suitable water absorbent rate, preferable volumetric expansion size, compressive strength are good, Heat stability is good, degradation speed are slow, farm crop are not had the oil field of injury, agriculture tailored version very-high performance water-absorbing resin.
The object of the present invention is achieved like this: a kind of oil field, agriculture dedicated high performance water-absorbing resin is characterized in that it is one or more the functional monomer that by vinylformic acid, acrylate and (A) is selected from methyl acrylate, ethyl propenoate, butyl acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, acrylamide, polyvinyl alcohol, maleic anhydride, the vinyl sulfonic acid; (B) be selected from one or more the 3rd monomer in starch, Mierocrystalline cellulose, soybean protein, pectin, the wheat bran, add linking agent, the resin that initiator carries out is crosslinked, grafting, copolyreaction are made.
Acrylate described in the present invention is to add neutralizing agent by vinylformic acid to make, and is the aqueous solution and the neutralizing agent reaction that vinylformic acid is mixed with 80-90 weight % during reaction, and degree of neutralization is 70-85%, and all monomer total amounts account for 38～60 weight % in the reaction solution.
Neutralizing agent described in the present invention is sodium hydroxide or potassium hydroxide.
The 3rd monomeric amount described in the present invention is 0.5%～45 weight % of vinylformic acid consumption.
Linking agent described in the present invention is to be selected from: glycol ether, Triethylene glycol, polyoxyethylene glycol, Polyglycerine, polyvinyl alcohol, Malaya's acid, FUMARIC ACID TECH GRADE, N, N-methylene-bisacrylamide, diallyl p phthalate, dosage of crosslinking agent are 0.05 weight %-5 weight % of described monomer total amount
Initiator described in the present invention is two kinds of oxygenant, reductive agents, they can be selected from: Potassium Persulphate, ammonium persulphate, Sodium Persulfate, hydrogen peroxide, S-WAT, sodium bisulfite, ferrous sulfate, Sulfothiorine, the oxygenant consumption is 0.02 weight %-0.5 weight % of monomer total amount, and reductive agent is 0.02 weight %-0.6 weight %.
Most important in dosage of crosslinking agent described in the invention and kind.Dosage of crosslinking agent is too little, and then polymkeric substance can not form tridimensional network, and product facile hydrolysis, water absorbent rate are not high; On the contrary, dosage of crosslinking agent is too big, and cross-linking set increases in the polymer ions web frame, and cross-linking density is excessive, causes that micropore diminishes in the network structure, so water absorbent rate also can descend.Therefore dosage of crosslinking agent should be selected suitable amount according to practical situation;
Described initiator amount is also very important.When consumption too hour, sluggish, not exclusively, residual monomer is many; When consumption is too high, can produces implode and cause danger, and influence quality product;
In above-mentioned reaction, polymerization temperature should be controlled between 50-70 ℃, and the reactive polymeric time is 10-60 minute, and be 3-5 hour time of drying, and drying temperature is 130-160 ℃;
Described product cut size size should be decided according to customer need, but particle diameter is too little, and intensity can descend during as (100-150 order).
Concrete technology of the present invention is: vinylformic acid is mixed with the certain density aqueous solution, and dissolution of sodium hydroxide in water, is made into certain density solution, adds acrylic acid solution then, neutralizes with sodium hydroxide.In above-mentioned neutralizer, add the 3rd monomer and functional monomer, add linking agent, feed nitrogen, warming while stirring after reaching certain temperature, adds initiator and carries out crosslinked, grafting, copolyreaction, reaction finishes, and the blob of viscose granulation is put into the drying baker oven dry, pulverized, and obtains desired product.
Characteristics, advantage that the present invention compares with other orthophthalic type resin
1. water absorbent rate: coventional type water-absorbing resin, water absorbent rate all are controlled at 400-600 doubly, and the present invention is controlled at 300-400 doubly with water absorbent rate, and purpose is in order to increase its compressive strength.Because what really work below oil well is not that water absorbent rate is high more good more, but the perfect adaptation of the composite factor of the several aspects of needs, and the present invention has just in time satisfied this requirement;
2. volumetric expansion: in the coventional type water-absorbing resin, do not have this notion of volumetric expansion, and the strict just expanded size of having controlled the resin volume of the present invention has played the effects such as water-content of water blockoff, leak stopping, profile control, reduction oil-water common-layer well on the oil field;
3. compressive strength: the technology of most critical of the present invention is exactly a compressive strength of having strengthened water-absorbing resin greatly, the impact capacity of oil resistant water;
4. thermostability: the resin that the present invention produced after 100-180 ℃ of water-swelling, can not be affected good stability under certain pressure;
5. the performance of the water of anti-the subterranean strata is good: the resin that the present invention produced, and the outlet capacity of anti-subterranean strata extra-heavy is inhaled subterranean strata water more than 100 times, is 1-2 times of orthophthalic type resin;
6. degradation speed is slow, and sticking power is good: the resin that the present invention produced, and degradation speed is slow, keeps do not change half a year basically; Strong adhesion can be adsorbed in the fine gap of rock well, withstand profit impact, scrub.Resin of the present invention because above advantage and characteristics are arranged, so the effect on the oil field is quite obvious, can improve tar productivity widely.Utilization is extremely successful in four purposes of water-content of water blockoff, leak stopping, profile control, reduction oil-water common-layer well.The application of water-absorbing resin on agricultural that the present invention produced simultaneously is also quite extensive, as water conservation drought resisting, desert afforestation, afforestation, seed pelleting or the like.
Further specify the present invention below in conjunction with embodiment:
1. manufacturing oil field, agriculture specificity water-absorbing resin are filled a prescription as following table:
| Mierocrystalline cellulose (g) | 100.0 | 80.0 | 60.0 |
| (methyl) Hydroxyethyl acrylate (g) | 5.0 | 6.0 | 2.0 |
| Logical nitrogen (min) | 15 | 15 | 15 |
| Polyoxyethylene glycol (g) | 0.65 | 0.60 | 0.55 |
| Potassium Persulphate (g) | 0.5 | 0.5 | 0.5 |
| S-WAT (g) | 0.6 | 0.6 | 0.6 |
| Temperature of reaction (℃) | 65 | 65 | 68 |
Above raw material reacted in open containers 60 minutes, carried out granulation then.Under 140 ℃ of temperature dry 3-4 hour, pulverize and obtain resin particle.
2. water-absorbing resin performance test such as following table:
| Model | Inhale deionized water (g/g) | Inhale subterranean strata water (g/g) | Gel-strength | Water-retaining capacity (%) |
| Ⅰ | 300 | 90 | 500g/cm 2 | 85 |
| Ⅱ | 380 | 110 | 460g/cm 2 | 80 |
| Ⅲ | 500 | 80 | 350g/cm 2 | 75 |
Wherein I, II type are special products such as Water in Water Shutoff in Oil Field, leak stopping, profile control, and the III type is tailored version products such as coping with agriculture drought, water conservation.
Annotate: (1) surveys the water absorbent rate filtration method; It is in having the 1000ml beaker of rotor, adds deionized water 800ml, and temperature is controlled at 25 ℃, and precision weighing 1.00g sample also adds in the beaker, stirs 1 hour, be filled into gel and no longer drip, and the weight of weighing gelinite then,
The peak pressure that gel can bear when (2) gel-strength was saturated suction state;
(3) water-retaining capacity is after resin is inhaled subterranean strata water, under preserving behind the high speed dewatering and mass percent former saturated suction physiological saline.
Claims (6)
1, a kind of oil field, agriculture dedicated high performance water-absorbing resin is characterized in that it is one or more the functional monomer that by vinylformic acid, acrylate and (A) is selected from methyl acrylate, ethyl propenoate, butyl acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, acrylamide, polyvinyl alcohol, maleic anhydride, the vinyl sulfonic acid; (B) be selected from one or more the 3rd monomer in starch, Mierocrystalline cellulose, soybean protein, pectin, the wheat bran, add linking agent, the resin that initiator carries out is crosslinked, grafting, copolyreaction are made.
2, oil field according to claim 1, agriculture dedicated high performance water-absorbing resin, it is characterized in that wherein acrylate is to add neutralizing agent by vinylformic acid to make, during reaction the aqueous solution and the neutralizing agent reaction that vinylformic acid is mixed with 80-90 weight %, degree of neutralization is 70-85%, and all monomer total amounts account for 38～60 weight % in the reaction solution.
3, oil field according to claim 1, agriculture dedicated high performance water-absorbing resin is characterized in that described neutralizing agent is sodium hydroxide or potassium hydroxide.
4, oil field according to claim 1, agriculture dedicated high performance water-absorbing resin, the described the 3rd monomeric amount that it is characterized in that are 0.5%～45 weight % of vinylformic acid consumption.
5, oil field according to claim 1, agriculture dedicated high performance water-absorbing resin, it is characterized in that described linking agent is to be selected from: glycol ether, Triethylene glycol, polyoxyethylene glycol, Polyglycerine, polyvinyl alcohol, Malaya's acid, FUMARIC ACID TECH GRADE, N, N-methylene-bisacrylamide, diallyl p phthalate, dosage of crosslinking agent are 0.05 weight %-5 weight % of described monomer total amount.
6, oil field according to claim 1, agriculture dedicated high performance water-absorbing resin, it is characterized in that described initiator is two kinds of oxygenant, reductive agents, they can be selected from: Potassium Persulphate, ammonium persulphate, Sodium Persulfate, hydrogen peroxide, S-WAT, sodium bisulfite, ferrous sulfate, Sulfothiorine, the oxygenant consumption is 0.02 weight %-0.5 weight % of monomer total amount, and reductive agent is 0.02 weight %-0.6 weight %.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 00132217 CN1290714A (en) | 2000-11-09 | 2000-11-09 | High hydroscopicity resin specially for oil field and agriculture |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00132217 CN1290714A (en) | 2000-11-09 | 2000-11-09 | High hydroscopicity resin specially for oil field and agriculture |
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| CN1320002C (en) * | 2005-06-28 | 2007-06-06 | 苏州大学 | High water absorptive resin for sanitary material |
| CN100339458C (en) * | 2003-07-03 | 2007-09-26 | 广西贵糖（集团）股份有限公司 | Oil field filtering loss reducing agent using molasses alcohol waste liquid as raw material and its production method |
| CN100516097C (en) * | 2007-08-17 | 2009-07-22 | 广东工业大学 | Method for synthesizing completely biological degradable high-absorbent resin by solution polymerization process |
| CN100532411C (en) * | 2007-08-17 | 2009-08-26 | 广东工业大学 | Method for synthesizing completely biological degradable high-absorbent resin by anti-phase suspension polymerization |
| CN100575374C (en) * | 2008-02-29 | 2009-12-30 | 厦门大学 | A kind of preparation method of acrylic acid series semi-interpenetration network composite high water absorption resin |
| CN101531745B (en) * | 2009-04-13 | 2011-05-25 | 浙江大学 | Preparation of plural gel water absorbent material composed of silk fibroin/acrylic acid/acrylamide |
| CN102127191A (en) * | 2010-12-24 | 2011-07-20 | 江苏富淼科技股份有限公司 | Preparation method of graft copolymer for surface sizing |
| CN101597414B (en) * | 2009-07-10 | 2011-07-27 | 杨凌瑞丰环保科技有限公司 | Starch base degradable plastic |
| CN102153703A (en) * | 2011-03-23 | 2011-08-17 | 浙江理工大学 | Preparation method of cellulose-based high-water-absorption high-water-retention resin |
| CN101508895B (en) * | 2009-03-17 | 2012-07-04 | 北京鸿森鹏程生态农业科技股份有限公司 | Agricultural water-loss reducer and production process |
| CN103299803A (en) * | 2013-05-30 | 2013-09-18 | 曹世雄 | Method for planting trees or grass in rock cracks through packaged seeds |
| CN103897114A (en) * | 2012-12-27 | 2014-07-02 | 青岛鑫垚保水高新材料有限公司 | Method for preparing organic aquasorb-fertilizer from soybean meal |
| CN104140499A (en) * | 2014-02-26 | 2014-11-12 | 重庆文理学院 | Method for preparing super absorbent polymer (SAP) from carboxymethylcellulose (CMC) and maleic acid (MA) |
| CN105567200A (en) * | 2016-03-03 | 2016-05-11 | 仇颖超 | Method for preparing biological gel profile control agent |
| CN105884975A (en) * | 2014-09-15 | 2016-08-24 | 邹城市安德机械制修有限公司 | Preparation method of polymer water-absorbent resin |
| CN106008857A (en) * | 2016-05-09 | 2016-10-12 | 北京化工大学 | Synthesis and application of novel sand fixing dust inhibitor prepared from alkali corn stalk |
| CN106117982A (en) * | 2016-06-27 | 2016-11-16 | 梅庆波 | A kind of preparation method of hydrophilic polyester master batch |
| CN106146735A (en) * | 2015-03-09 | 2016-11-23 | 邹城市安德机械制修有限公司 | A kind of method of rice chaff synthesis hydroscopic high-molecular resin |
| CN106146762A (en) * | 2015-03-09 | 2016-11-23 | 邹城市安德机械制修有限公司 | A kind of method of rapeseed meal synthesis hydroscopic high-molecular resin |
| CN106146763A (en) * | 2015-03-09 | 2016-11-23 | 邹城市安德机械制修有限公司 | A kind of method of Fructus Gleditsia full powder synthesis hydroscopic high-molecular resin |
| CN106146736A (en) * | 2015-03-09 | 2016-11-23 | 邹城市安德机械制修有限公司 | A kind of method of Sorghum vulgare Pers. full powder synthesis hydroscopic high-molecular resin |
| CN110760033A (en) * | 2019-11-06 | 2020-02-07 | 岭南师范学院 | Functional high-adsorption resin and simple preparation method and application thereof |
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| CN111225966A (en) * | 2017-08-28 | 2020-06-02 | 新加坡国立大学 | Production of nutritional gel materials from soybean waste |
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2000
- 2000-11-09 CN CN 00132217 patent/CN1290714A/en active Pending
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| CN100339458C (en) * | 2003-07-03 | 2007-09-26 | 广西贵糖（集团）股份有限公司 | Oil field filtering loss reducing agent using molasses alcohol waste liquid as raw material and its production method |
| CN1320002C (en) * | 2005-06-28 | 2007-06-06 | 苏州大学 | High water absorptive resin for sanitary material |
| CN100516097C (en) * | 2007-08-17 | 2009-07-22 | 广东工业大学 | Method for synthesizing completely biological degradable high-absorbent resin by solution polymerization process |
| CN100532411C (en) * | 2007-08-17 | 2009-08-26 | 广东工业大学 | Method for synthesizing completely biological degradable high-absorbent resin by anti-phase suspension polymerization |
| CN100575374C (en) * | 2008-02-29 | 2009-12-30 | 厦门大学 | A kind of preparation method of acrylic acid series semi-interpenetration network composite high water absorption resin |
| CN101508895B (en) * | 2009-03-17 | 2012-07-04 | 北京鸿森鹏程生态农业科技股份有限公司 | Agricultural water-loss reducer and production process |
| CN101531745B (en) * | 2009-04-13 | 2011-05-25 | 浙江大学 | Preparation of plural gel water absorbent material composed of silk fibroin/acrylic acid/acrylamide |
| CN101597414B (en) * | 2009-07-10 | 2011-07-27 | 杨凌瑞丰环保科技有限公司 | Starch base degradable plastic |
| CN102127191A (en) * | 2010-12-24 | 2011-07-20 | 江苏富淼科技股份有限公司 | Preparation method of graft copolymer for surface sizing |
| CN102127191B (en) * | 2010-12-24 | 2012-09-05 | 江苏富淼科技股份有限公司 | Preparation method of graft copolymer for surface sizing |
| CN102153703A (en) * | 2011-03-23 | 2011-08-17 | 浙江理工大学 | Preparation method of cellulose-based high-water-absorption high-water-retention resin |
| CN102153703B (en) * | 2011-03-23 | 2013-06-05 | 浙江理工大学 | Preparation method of cellulose-based high-water-absorption high-water-retention resin |
| CN103897114A (en) * | 2012-12-27 | 2014-07-02 | 青岛鑫垚保水高新材料有限公司 | Method for preparing organic aquasorb-fertilizer from soybean meal |
| CN103299803A (en) * | 2013-05-30 | 2013-09-18 | 曹世雄 | Method for planting trees or grass in rock cracks through packaged seeds |
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| CN105884975A (en) * | 2014-09-15 | 2016-08-24 | 邹城市安德机械制修有限公司 | Preparation method of polymer water-absorbent resin |
| CN106146762A (en) * | 2015-03-09 | 2016-11-23 | 邹城市安德机械制修有限公司 | A kind of method of rapeseed meal synthesis hydroscopic high-molecular resin |
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| CN105567200A (en) * | 2016-03-03 | 2016-05-11 | 仇颖超 | Method for preparing biological gel profile control agent |
| CN106008857A (en) * | 2016-05-09 | 2016-10-12 | 北京化工大学 | Synthesis and application of novel sand fixing dust inhibitor prepared from alkali corn stalk |
| CN106008857B (en) * | 2016-05-09 | 2018-10-30 | 北京化工大学 | A kind of synthesis and application of the novel dust suppressant that fixes the sand of alkali maize straw |
| CN106117982A (en) * | 2016-06-27 | 2016-11-16 | 梅庆波 | A kind of preparation method of hydrophilic polyester master batch |
| CN111225966A (en) * | 2017-08-28 | 2020-06-02 | 新加坡国立大学 | Production of nutritional gel materials from soybean waste |
| CN110760033A (en) * | 2019-11-06 | 2020-02-07 | 岭南师范学院 | Functional high-adsorption resin and simple preparation method and application thereof |
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| CN111138593A (en) * | 2020-01-10 | 2020-05-12 | 岭南师范学院 | Simple preparation method and application of composite high-adsorption resin |
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