CN102504109B - Cyclodextrin supported hydrogel and preparation method thereof - Google Patents
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Abstract
The invention relates to a cyclodextrin supported hydrogel for oilfield wastewater processing and a preparation method thereof. The hydrogel can process heavy metal ions in oilfield wastewater and effectively adsorb Fe<3+>, Cr<3+>, Cu<2+> or Pb<2+>. According to the technical scheme of the hydrogel, raw materials of the hydrogel comprise the following components, by mass, 9-13 parts of maleic anhydride monoesterified-beta-cyclodextrin, 9-13 parts of acrylamide, 1-3 parts of sodium allylsulfonate, an initiator which comprises potassium persulfate and sodium sulfite and has a mass accounting for 0.5% of the total monomer mass, a crosslinking agent which is N,N-methylenebisacrylamide and has a mass accounting for 1% of the total monomer mass, a pH conditioning agent which is a 1% NaOH solution, and a solvent purified water. Cyclodextrin in the cyclodextrin supported hydrogel provided in the invention has a special structure that the external cavity is hydrophilic and the internal cavity is lyophobic, so cyclodextrin can adsorb certain amounts of lipophilic substances and heavy metal ions. The preparation method of the invention has the advantages of simple step and mild condition, and the product of the preparation method, which is a hydrogel adsorbent, is used to process the oilfield wastewater.
Description
Technical field
The present invention relates to a kind of cyclodextrin supported hydrogel of processing for the petroleum industry oil field waste and preparation method thereof.
Background technology
Along with China increases day by day to the demand of oil, Sweet natural gas, in the situation that oilfield exploitation intensity is increasing, the oil field waste amount also constantly increases.Contain a large amount of heavy metal ion in these waste water, as Fe
3+, Cr
3+, Cu
2+Or Pb
2+Deng.These heavy metal ion cause farm crop, agricultural-food and groundwater pollution by the sedimentation in soil, even by food chain harm humans life and health.
Recent domestic has carried out large quantity research to oil field waste and water treatment, has proposed various new sorbent materials and preparation method thereof.Chinese patent CN1387942 discloses " preparation method of titanium silicate adsorbent with high adsorption performance and application thereof ", CN1388070 discloses " preparation method who is used for the flocculation agent of water treatment ", CN101864034A discloses " application of acrylic acid cyclodextrin polymer in dying industrial wastewater is processed ", CN102199245A discloses " a kind of polyalcohol hydrogel, preparation method and the application in water treatment thereof ", CN101633712 discloses " temperature that can click/pH-sensibility microgel ", CN101344648 discloses " a kind of medicine-carrying contact lens and preparation method thereof ", CN101092471 discloses " preparation method of a kind of temperature sensitive hydrogel with supramolecular structure " etc., these patented technologies respectively have characteristics and application direction.But owing to still containing a small amount of oily matter in oil field waste, make prior art and method also can not adapt to the needs that oil field waste is processed far away, develop a kind of new adsorbent that can adsorb a small amount of lipophilicity substance and be still the task of top priority.
Summary of the invention
The objective of the invention is: contain a large amount of heavy metal ion in oil field waste in order to process, can active adsorption Fe
3+, Cr
3+, Cu
2+Or Pb
2+Ion, the spy provides a kind of cyclodextrin supported hydrogel and preparation method thereof.
In order to achieve the above object, the present invention by the following technical solutions, a kind of cyclodextrin supported hydrogel is comprised of MALEIC ANHYDRIDE mono-esterification-beta-cyclodextrin code name MAH-β-CD, acrylamide code name AM, sodium allylsulfonate code name SAS, initiator, linking agent, sodium hydroxide and water.each component concentration and partial properties that this hydrogel is raw materials used are, quality in grams, MAH-β-CD 9 ~ 13, be that 0.01mol beta-cyclodextrin and 9.8g are the N that the 0.1mol MALEIC ANHYDRIDE is dissolved in the 60ml drying with 11.36g, in the dinethylformamide solvent, 10h is reacted in the water bath with thermostatic control that is placed in temperature and is 80 ℃, reaction is cooled to room temperature with reactant after finishing, be settled out product with trichloromethane, with washing with acetone 2 ~ 3 times, drain, 80 ℃ of dryings of vacuum make product MAH-β-CD, take again dry MALEIC ANHYDRIDE mono-esterification-beta-cyclodextrin powder dissolution in pure water, be mixed with mass percentage concentration and be 25 ~ 30% MAH-β-CD water solution A, AM 9 ~ 13, take dry AM powder and are dissolved in pure water, are mixed with mass percentage concentration and are 20 ~ 22% AM aqueous solution B, SAS 1 ~ 3, takes dry SAS powder dissolution in pure water, is mixed with mass percentage concentration and is 10 ~ 15% SAS aqueous solution C, initiator is 0.5% of monomer total mass with Potassium Persulphate and S-WAT, consumption, takes respectively dry Potassium Persulphate, S-WAT, is dissolved in pure water, is mixed with mass percentage concentration and is 10% potassium persulfate solution D and 10% sodium sulfite solution E, the linking agent N,N methylene bis acrylamide, consumption is 1% of monomer total mass, takes dry N,N methylene bis acrylamide and is dissolved in pure water, is mixed with mass percentage concentration and is 10% cross-linking agent aqueous solution F, pH adjusting agent NaOH, being mixed with mass percentage concentration with pure water is 1% NaOH solution, water is pure water or deionized water, as solvent.
A kind of preparation method of cyclodextrin supported hydrogel is: first get the AM aqueous solution B of 30 ~ 36ml in beaker, add the SAS aqueous solution C of the MAH-β of 25 ~ 30ml-CD water solution A and 8 ~ 15ml, the mass ratio of its MAH-β-CD: AM:SAS is 9 ~ 13:9 ~ 13:1 ~ 3 again; Be to stir under 45 ~ 50 ℃ of conditions in temperature, after solution mixes, add linking agent: mass percentage concentration is 10% N, N-methylene-bisacrylamide aqueous solution F 1.6 ~ 2.2ml, and with 1% NaOH solution regulation system pH value to 7, add initiator at last in above-mentioned mixing solutions: concentration is 10% K
2S
2O
8Solution D 0.09 ~ 1.2ml and concentration are 10% Na
2SO
3Solution E 0.09 ~ 1.2ml, be slowly to stir under the condition of 45 ~ 50 ℃ in temperature, in reaction 30 ~ 40min, the polymkeric substance that reaction is made is cut into fritter of uniform size to be put into pure water and soaks 48h, change a water at interval of 12h, to remove the reaction monomers that there is no polymerization in product, pulling polymkeric substance out is that in the vacuum drying oven of 60 ℃, oven dry can make the cyclodextrin supported hydrogel product in temperature.
Beneficial effect of the present invention is: (1), this cyclodextrin supported hydrogel can be processed the heavy metal ion that contains in oil field waste, can effectively adsorb Fe
3+, Cr
3+, Cu
2+Or Pb
2+Ion; (2), preparation method's step of the present invention is easy, mild condition, product is the hydrogel sorbent material, can adsorb a small amount of lipophilicity substance, is used for oil field waste and processes.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
Prepare gel adsorber of the present invention according to following step:
(1) take dry MALEIC ANHYDRIDE mono-esterification-beta-cyclodextrin and be dissolved in pure water, be mixed with mass percentage concentration and be 25% MAH-β-CD water solution A; Take dry acrylamide pressed powder and be dissolved in pure water, be mixed with mass percentage concentration and be 21% AM aqueous solution B; Take dry sodium allylsulfonate dissolution of solid in pure water, be mixed with mass percentage concentration and be 12% SAS aqueous solution C; Take respectively dry Potassium Persulphate, S-WAT, be dissolved in pure water, be mixed with mass percentage concentration and be 10% potassium persulfate solution D and 10% sodium sulfite solution E; Take dry N,N methylene bis acrylamide and be dissolved in pure water, be mixed with mass percentage concentration and be 10% cross-linking agent aqueous solution F; PH adjusting agent is the NaOH solution of mass percentage concentration 1%.
(2) measure 34.5ml aqueous solution B(and include the 9g acrylamide) in beaker, then according to the mass ratio of MAH-β-CD: AM:SAS=9.3:9:1.2, measure 28ml water solution A (include 9.3g MAH-β-CD) and 9mlSAS aqueous solution C(and include the 1.2g sodium allylsulfonate) and pour in the beaker that aqueous solution B is housed, stir under 50 ℃ of conditions.
(3) after mentioned solution mixes, according to linking agent: the mass ratio of reaction monomers total mass=1:100 adds 1.8ml cross-linking agent aqueous solution F(to include N in beaker, N-methylene-bisacrylamide quality 0.195g), and with 1% NaOH solution regulation system pH value to 7.
(4) after above-mentioned mixing solutions mixes, according to initiator: the mass ratio of reaction monomers total mass=0.5:100, and oxygenant equates with the quality of reductive agent, adds the potassium persulfate solution D(of 0.9ml to include Potassium Persulphate quality 0.0975g in mixed solution) and 0.9ml sodium sulfite solution E(include S-WAT quality 0.0975g).Slowly stir under the condition of 50 ℃, in reaction 30 ~ 40min, the polymkeric substance that reaction is made is cut into fritter of uniform size to be put into pure water and soaks 48h, changes a water at interval of 12h, pulling out, is that in the vacuum drying oven of 60 ℃, oven dry can make this cyclodextrin supported hydrogel in temperature.
The mensuration of cyclodextrin supported hydrogel to heavy metal ion adsorbed amount:
At first take 4 parts of cyclodextrin supported hydrogel desciccates, every part of quality is about 0.08g(± 0.0010g), be placed in respectively the 500ml beaker, then adds respectively 250ml4 * 10
-3The Fe of mol/L
3+, Cr
3+, Cu
2+, Pb
2+Single solution, beaker is placed in constant temperature oscillator, carry out constant temperature absorption 72h under the condition of 25 ℃, then get beaker at the middle and upper levels clear liquid measure its absorbancy in maximum adsorption wavelength place separately on atomic spectrophotometer, absorbancy by solution before and after processing is calculated the hydrogel adsorptive capacity, and result is by shown in table 1
Table 1
| The heavy metal ion type | Fe 3+ | Cr 3+ | Cu 2+ | Pb 2+ |
| Hydrogel adsorptive capacity (mg/g) | 36.6674 | 2.0324 | 2.1760 | 3.2067 |
Embodiment 2
Prepare gel adsorber of the present invention according to following step:
(1) take dry MALEIC ANHYDRIDE mono-esterification-beta-cyclodextrin and be dissolved in pure water, be mixed with mass percentage concentration and be 25% MAH-β-CD water solution A; Take dry acrylamide pressed powder and be dissolved in pure water, be mixed with mass percentage concentration and be 20% AM aqueous solution B; Take dry sodium allylsulfonate dissolution of solid in pure water, be mixed with mass percentage concentration and be 15% SAS aqueous solution C; Take respectively dry Potassium Persulphate, S-WAT, be dissolved in pure water, be mixed with mass percentage concentration and be 10% potassium persulfate solution D and 10% sodium sulfite solution E; Take dry N,N methylene bis acrylamide and be dissolved in pure water, be mixed with mass percentage concentration and be 10% cross-linking agent aqueous solution F; PH adjusting agent is the NaOH solution of mass percentage concentration 1%.
(2) measure 35ml aqueous solution B(and include acrylamide quality 8.5g) in beaker, then according to the mass ratio of MAH-β-CD:AM:SAS=9.2:8.5:2.3, measure 28ml water solution A (including MAH-β-CD quality 9.2g) and 13mlSAS aqueous solution C(and include sodium allylsulfonate quality 2.3g) pour in the beaker that aqueous solution B is housed, stir under 50 ℃ of conditions.
(3) after mentioned solution mixes, according to linking agent: the mass ratio of reaction monomers total amount=1:100 adds 1.8ml cross-linking agent aqueous solution F(to include N in beaker, N-methylene-bisacrylamide quality 0.2g), and with 1% NaOH solution regulation system pH value to 7.
(4) after above-mentioned mixing solutions mixes, according to initiator: the mass ratio of reaction monomers total mass=0.5:100, and oxygenant equates with the quality of reductive agent, adds the potassium persulfate solution D(of 0.9ml to include Potassium Persulphate quality 0.1g in mixed solution) and 0.9ml sodium sulfite solution E(include S-WAT quality 0. 1g).Slowly stir under the condition of 50 ℃, in reaction 30 ~ 40min, the polymkeric substance that reaction is obtained is cut into fritter of uniform size to be put into pure water and soaks 48h, changes a water at interval of 12h, pulling out, is that in the vacuum drying oven of 60 ℃, oven dry can make this cyclodextrin supported hydrogel in temperature.
The mensuration of cyclodextrin supported hydrogel to heavy metal ion adsorbed amount:
At first take 4 parts of cyclodextrin supported hydrogel desciccates, every part of quality is about 0.08g(± 0.0010g), be placed in respectively the 500ml beaker, then adds respectively 250ml4 * 10
-3The Fe of mol/L
3+, Cr
3+, Cu
2+, Pb
2+Single solution, beaker is placed in constant temperature oscillator, carry out constant temperature absorption 72h under the condition of 25 ℃, then get beaker at the middle and upper levels clear liquid measure its absorbancy in maximum adsorption wavelength place separately on atomic spectrophotometer, absorbancy by solution before and after processing is calculated the hydrogel adsorptive capacity, and result is by shown in table 2
Table 2
| The heavy metal ion type | Fe 3+ | Cr 3+ | Cu 2+ | Pb 2+ |
| Hydrogel adsorptive capacity (mg/g) | 19.1209 | 2.1285 | 0.7856 | 2.7981 |
Embodiment 3
Prepare gel adsorber of the present invention according to following step:
(1) take dry MALEIC ANHYDRIDE mono-esterification-beta-cyclodextrin and be dissolved in pure water, be mixed with mass percentage concentration and be 30% MAH-β-CD water solution A; Take dry acrylamide pressed powder and be dissolved in pure water, be mixed with mass percentage concentration and be 21% AM aqueous solution B; Take dry sodium allylsulfonate dissolution of solid in pure water, be mixed with mass percentage concentration and be 10% SAS aqueous solution C; Take respectively dry Potassium Persulphate, S-WAT, be dissolved in pure water, be mixed with mass percentage concentration and be 10% potassium persulfate solution D and 10% sodium sulfite solution E; Take dry N,N methylene bis acrylamide and be dissolved in pure water, be mixed with mass percentage concentration and be 10% cross-linking agent aqueous solution F; PH adjusting agent is the NaOH solution of mass percentage concentration 1%.
(2) measure 32ml aqueous solution B(and include acrylamide quality 8.4g) in beaker, then according to the mass ratio of MAH-β-CD:AM:SAS=12.5:8.4:1.1, measure 30ml water solution A (including MAH-β-CD quality 12.5g) and 10mlSAS aqueous solution C(and include sodium allylsulfonate quality 1.1g) pour in the beaker that water solution A is housed, stir under 50 ℃ of conditions.
(3) after mentioned solution mixes, according to linking agent: the mass ratio of reaction monomers total mass=1:100 adds 2ml cross-linking agent aqueous solution F(to include N in beaker, N-methylene-bisacrylamide quality 0.22g), and with 1% NaOH solution regulator solution pH value to 7.
(4) after above-mentioned mixing solutions mixes, according to initiator: the mass ratio of reaction monomers total mass=0.5:100, and oxygenant equates with the quality of reductive agent, adds the potassium persulfate solution D(of 1ml to include Potassium Persulphate quality 0.11g in mixed solution) and 1ml sodium sulfite solution E(include S-WAT quality 0.11g).Slowly stir under the condition of 50 ℃, in reaction 30 ~ 40min, the polymkeric substance that reaction is obtained is cut into fritter of uniform size to be put into pure water and soaks 48h, changes a water at interval of 12h, pulling out, is that in the vacuum drying oven of 60 ℃, oven dry can make this cyclodextrin supported hydrogel in temperature.
The mensuration of cyclodextrin supported hydrogel to heavy metal ion adsorbed amount:
At first take 4 parts of cyclodextrin supported hydrogel desciccates, every part of quality is about 0.08g(± 0.0010g), be placed in respectively the 500ml beaker, then adds respectively 250ml4 * 10
-3The Fe of mol/L
3+, Cr
3+, Cu
2+, Pb
2+Single solution, beaker is placed in constant temperature oscillator, carry out constant temperature absorption 72h under the condition of 25 ℃, then get beaker at the middle and upper levels clear liquid measure its absorbancy in maximum adsorption wavelength place separately on atomic spectrophotometer, absorbancy by solution before and after processing is calculated the hydrogel adsorptive capacity, and result is by shown in table 3
Table 3
| The heavy metal ion type | Fe 3+ | Cr 3+ | Cu 2+ | Pb 2+ |
| Hydrogel adsorptive capacity (mg/g) | 24.1376 | 1.5843 | 0.7638 | 3.8436 |
Application examples 1
Oil field waste is provided by the Liaohe Oil Field, Fe wherein
3+Content is about 103mg/L.With this oil field waste after filtering, add the cyclodextrin supported hydrogel desciccate of 1g embodiment 1 gained in the waste water solution of 1L, carry out at ambient temperature oscillation treatment, after absorption 72h, Fe in waste water
3+Adsorption rate reach more than 30%.Under identical condition, increase cyclodextrin supported hydrogel desciccate amount to 4g/L, the Fe in oil field waste
3+Adsorption rate reach more than 98%.
Application examples 2
Oil field waste is provided by PetroChina Company Limited.'s Great Wall probing, wherein Cr
3+Content be about 13mg/L.This oil field waste through after filtering, is added the cyclodextrin supported hydrogel desciccate of 2g embodiment 2 gained in the waste water solution of 1L, carry out at ambient temperature oscillation treatment, after absorption 72h, Cr in waste water
3+Adsorption rate reach and be about 32%.Under identical condition, increase cyclodextrin supported hydrogel desciccate amount to 6g/L, the Cr in oil field waste
3+Adsorption rate reach more than 98%.
Application examples 3
Oil field waste is visited by Daqing oil field and is provided, wherein Cu
2+Content be about 8mg/L.This oil field waste through after filtering, is added the cyclodextrin supported hydrogel desciccate of 2g embodiment 1 gained in the waste water solution of 1L, carry out at ambient temperature oscillation treatment, after absorption 72h, Cu in waste water
2+Adsorption rate reach and be about 50%.Under identical condition, increase cyclodextrin supported hydrogel desciccate amount to 4g/L, the Cu in oil field waste
2+Adsorption rate reach more than 99%.
Application examples 4
Oil field waste is provided by the Liaohe Oil Field, wherein Pb in oil field waste
2+Content be about 16mg/L.This oil field waste through after filtering, is added the cyclodextrin supported hydrogel desciccate of 2g embodiment 2 gained in the waste water solution of 1L, carry out at ambient temperature oscillation treatment, after absorption 72h, Pb in waste water
2+Adsorption rate reach and be about 48%.Under identical condition, increase cyclodextrin supported hydrogel desciccate amount to 5g/L, the Pb in oil field waste
2+Adsorption rate reach more than 98%.
Should be noted that, the application of cyclodextrin supported hydrogel of the present invention in oil field waste is processed is not limited to above-mentioned example, and in actual applications, the consumption of cyclodextrin supported hydrogel is made suitable adjustment according to the content of heavy metal ion in waste water solution.
Claims (2)
1. cyclodextrin supported hydrogel, it is characterized in that: this hydrogel is by MALEIC ANHYDRIDE mono-esterification-beta-cyclodextrin code name MAH-β-CD, acrylamide code name AM, sodium allylsulfonate code name SAS, initiator, linking agent, sodium hydroxide and water form, the mass ratio of each component of monomer used is that MAH-β-CD:AM:SAS is 9 ~ 13:9 ~ 13:1 ~ 3, quality in grams, MAH-β-CD9 ~ 13, be that 0.0lmol beta-cyclodextrin and 9.8g are the N that the 0.lmol MALEIC ANHYDRIDE is dissolved in the 60mL drying with 11.36g, in the dinethylformamide solvent, 10h is reacted in the water bath with thermostatic control that is placed in temperature and is 80 ℃, reaction is cooled to room temperature with reactant after finishing, be settled out product with trichloromethane, with washing with acetone 2 ~ 3 times, drain, 80 ℃ of dryings of vacuum make product MAH-β-CD, take again dry MAH-β-CD powder and be dissolved in that to be mixed with mass percentage concentration in pure water be 25 ~ 30% MAH-β-CD water solution A, AM9 ~ 13 take dry AM powder and are dissolved in that to be mixed with mass percentage concentration in pure water be 20 ~ 22% AM aqueous solution B, SAS1 ~ 3 take dry SAS powder and are dissolved in that to be mixed with mass percentage concentration in pure water be 10 ~ 15% SAS aqueous solution C, initiator is with Potassium Persulphate and S-WAT, and consumption is 0.5% of monomer total mass, takes respectively dry Potassium Persulphate, S-WAT, is dissolved in pure water, is mixed with mass percentage concentration and is 10% potassium persulfate solution D and 10% sodium sulfite solution E, linking agent is to use N,N methylene bis acrylamide, and consumption is 1% of monomer total mass, takes dry N,N methylene bis acrylamide and is dissolved in pure water, is mixed with mass percentage concentration and is 10% cross-linking agent aqueous solution F, pH adjusting agent NaOH, being mixed with mass percentage concentration with pure water is 1% NaOH solution, water is pure water, as solvent.
2. preparation method of cyclodextrin supported hydrogel as claimed in claim 1, it is characterized in that: first get 30 ~ 36mL AM aqueous solution B and put into beaker, add 25 ~ 30mlLMAH-β-CD water solution A and 8 ~ 15mLSAS aqueous solution C, the mass ratio of its MAH-β-CD:AM:SAS is 9 ~ 13:9 ~ 13:1 ~ 3 again; Be to stir under 45 ~ 50 ℃ in temperature, adding the linking agent mass percentage concentration is N,N methylene bis acrylamide aqueous solution F1.6 ~ 2.2mL of 10%, and is 1% NaOH solution regulation system pH value to 7 with mass percentage concentration; Adding at last the initiator mass percentage concentration in the above-mentioned system is 10% K
2S
2O
8Solution D 0.09 ~ 1.2mL and mass percentage concentration are 10% Na
2SO
3Solution E 0.09 ~ 1.2mL, be slowly to stir under 45 ~ 50 ℃ of conditions in temperature, reaction 30 ~ 40min, the polymkeric substance that reaction is made is cut into fritter of uniform size to be put into pure water and soaks 48h, change a water at interval of 12h, to remove the reaction monomers that there is no polymerization in product, pulling polymkeric substance out is that in the vacuum drying oven of 60 ℃, oven dry can make the cyclodextrin supported hydrogel product in temperature.
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| CN103433003B (en) * | 2013-09-11 | 2015-10-14 | 江南大学 | A kind of cyclodextrin/montmorillonite composite material and preparation method thereof |
| CN103627383A (en) * | 2013-11-12 | 2014-03-12 | 吉林化工学院 | Supermolecular composite retardance acidifying agent for carbonate reservoir and preparation method thereof |
| CN103611507A (en) * | 2013-12-16 | 2014-03-05 | 武汉纺织大学 | Polysaccharide-based gel adsorbent for dye wastewater treatment and preparation method thereof |
| CN103896421A (en) * | 2014-04-23 | 2014-07-02 | 安徽理工大学 | Floating-type automatic river wastewater purification device |
| CN104327198B (en) * | 2014-05-15 | 2016-11-02 | 中国农业科学院原子能利用研究所 | Maleic acid beta-schardinger dextrin-ester and preparation method thereof |
| CN105859969B (en) * | 2016-05-06 | 2018-01-19 | 西南石油大学 | A kind of polymer oil-displacing agent based on host-guest interaction and preparation method thereof |
| CN106179243B (en) * | 2016-07-28 | 2019-02-05 | 东北林业大学 | A kind of preparation method of dye sorbent |
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| CN111499887A (en) * | 2017-11-27 | 2020-08-07 | 湖南辰砾新材料有限公司 | Antibacterial heavy metal-removing photocatalyst composite hydrogel |
| CN111718722A (en) * | 2019-03-18 | 2020-09-29 | 安徽中医药大学 | Modified polypropylene glycol soil remediation agent and preparation method thereof |
| CN112441675A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | Treatment method of oily sewage and application thereof |
| CN113121758B (en) * | 2019-12-31 | 2022-03-15 | 华南农业大学 | Nano-iron oxyhydroxide gel composite material and preparation method and application thereof |
| CN111992181B (en) * | 2020-08-17 | 2022-07-08 | 北京林业大学 | Cationic cyclodextrin-based hydrogel adsorption material and synthesis method thereof |
| CN114957550B (en) * | 2022-06-14 | 2023-08-18 | 中国石油大学(华东) | Deep profile control and re-adhesion supermolecule gel particles and preparation method thereof |
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