CN111167166A - Preparation method of attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material - Google Patents
Preparation method of attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material Download PDFInfo
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- CN111167166A CN111167166A CN202010106471.6A CN202010106471A CN111167166A CN 111167166 A CN111167166 A CN 111167166A CN 202010106471 A CN202010106471 A CN 202010106471A CN 111167166 A CN111167166 A CN 111167166A
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 47
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000926 separation method Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000005496 eutectics Effects 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 150000002340 glycosyl compounds Chemical class 0.000 claims abstract description 12
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims description 6
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 5
- 235000019743 Choline chloride Nutrition 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 229940010698 activated attapulgite Drugs 0.000 claims description 5
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 5
- 229960003178 choline chloride Drugs 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- 235000012209 glucono delta-lactone Nutrition 0.000 claims description 4
- 229960003681 gluconolactone Drugs 0.000 claims description 4
- 229960001031 glucose Drugs 0.000 claims description 4
- -1 glyceryl ether oxygen propyl trimethoxy silane Chemical compound 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims description 4
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 claims 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 238000009795 derivation Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 125000003147 glycosyl group Chemical group 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011664 nicotinic acid Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001719 carbohydrate derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002692 maltoses Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
Landscapes
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a preparation method of an attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material, which comprises the steps of using a silicon compound to complete the derivation of a glycosyl compound in an eutectic solvent, and then using the glycosyl derivative and a fluorine-containing silicon compound to carry out sol-gel copolymerization reaction on pretreated attapulgite in the eutectic solvent to obtain the attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material. The super-hydrophilic/super-oleophobic oil-water separation material prepared by the method disclosed by the invention has the properties of high chemical and mechanical stability, good separation effect and the like, and is expected to be widely applied to the field of oil-water separation.
Description
Technical Field
The invention relates to a preparation method of an attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material, in particular to a method for preparing a super-hydrophilic/super-oleophobic oil-water separation material from attapulgite and natural sugar derivatives, belonging to the technical field of deep processing of natural nano non-metallic ores and preparation of related new materials.
Background
In recent years, petroleum and organic chemical spills have caused extremely serious pollution and damage to the aqueous environment and even to the entire ecosystem. How to rapidly and efficiently realize the oil-water separation of the oil-polluted water source, improve the utilization rate of the water resource and relieve the water supply pressure has attracted wide attention of governments and the public.
The traditional means of oil-water separation mainly include coagulation and flocculation methods, gravity methods, adsorption methods, flotation methods, biological oxidation methods and chemical methods. However, these methods are time consuming, labor intensive, costly, and may cause secondary environmental pollution. In recent years, the rapid development of colloid, interface and bionics provides a new idea for developing a bionic oil-water separation material which is efficient, automatic and reusable. The oil-water separation material with the bionic interface characteristic has the characteristics of high separation efficiency, high selectivity and the like, and has unique advantages and good application prospects in the actual oil-water separation process. The surface of the new material has controllable wettability. According to the difference of wettability, the material can be divided into super-hydrophobic/super-oleophilic, super-hydrophilic/super-oleophobic and intelligent hydrophilic-hydrophobic adjustable materials. The most studied of the three bionic interface oil-water separation materials is the oil-water separation material with super-hydrophobic/super-oleophylic characteristics, but the material still has many defects in application, such as difficulty in separating an oil phase with density smaller than that of water, limited adsorption capacity, difficulty in recovering an oil product or poor material recycling performance and the like. To solve the above problems, super-hydrophilic/super-oleophobic materials have attracted the attention of scholars. For the super-hydrophilic/super-oleophobic material, the water phase separates the contact between the oil phase and the separating material, so that the oil phase cannot be adsorbed to a phase interface, and the pollution and scaling of the material can be avoided. The super-hydrophilic/super-oleophobic materials reported at present comprise an organic polymer coated metal mesh, an inorganic salt/metal oxide coated metal mesh, an inorganic salt deposited polymer film and a recombinant cellulose sponge. The separation performance of the materials depends on the micro-nano rough structure on the surface of the base material and/or the immobilized super-hydrophilic substance. To date, no superhydrophilic/superoleophobic material based on particulate and powder forms has been found. Because the specific surface area of the metal mesh and the polymer membrane is too small and active groups are hardly available for derivatization, in order to ensure higher loading capacity, only the hydrophilic modifier can be coated on the matrix in a crosslinking polymerization manner, but covalent bonds do not exist between the solid carrier and the matrix, so that the stability needs to be improved.
The attapulgite has fine granularity, rough surface, compact pore canal structure and rich silicon hydroxyl on the surface. The saccharide substance is rich in reserves in nature, is green and environment-friendly, is biodegradable, has strong polarity and strong hydrophilicity, and is rich in derivatives, cheap and easily available. It was confirmed by studies that the spherical silica gel having glucose and maltose derivatives covalently bonded to the surface thereof exhibited excellent hydrophilicity.
Disclosure of Invention
The invention aims to: the attapulgite is used as a substrate of the super-hydrophilic/super-oleophobic oil-water separation material, and natural sugar derivatives and fluorine-containing silicon compounds are immobilized on the surface of the attapulgite through covalent bonds and a mode to prepare the stable attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material.
The principle of the invention is as follows: the saccharide substance has extremely strong hydrophilicity, the saccharide derivative is formed by silane modification and then is subjected to covalent bond with Si-OH on the surface of the attapulgite, the hydrophilicity of the attapulgite is improved, and the fluorine-containing silicon compound is subjected to covalent bond with the Si-OH on the surface of the attapulgite and endows the attapulgite with oleophobicity, so that the attapulgite shows super-hydrophilicity/super-oleophobicity.
The technical solution of the invention is as follows: the derivation of glycosyl compound is completed by using silicon compound in eutectic solvent, and then the sol-gel copolymerization reaction is carried out on the pretreated attapulgite by using the sugar derivative and fluorine-containing silicon compound in the eutectic solvent to obtain the attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material.
The preparation method of the oil-water separation material comprises the following specific steps: firstly, performing surface purification and activation treatment on attapulgite; then dissolving the glycosyl compound in the eutectic solvent, adding equivalent silicon compound, heating and stirring under anhydrous and anaerobic conditions, dropwise adding an inert solvent into the system after a certain time to separate out a precipitate, and obtaining a sugar derivative; finally, dispersing a certain amount of activated attapulgite in a eutectic solvent, adding sugar derivatives according to a certain mass ratio, then respectively adding perfluoroalkylsilane, tetraethoxysilane and ammonia water, carrying out sol-gel copolymerization reaction under an airtight condition to enable the sugar derivatives to be covalently and fixedly supported on the surface of the attapulgite, centrifuging, washing a product with water and ethanol, and drying to obtain the super-hydrophilic/super-oleophobic oil-water separation material.
Wherein,the surface purifying and activating treatment method of the attapulgite comprises the following steps: h with attapulgite in the mass concentration of 3-10%2SO4Boiling, acidifying, washing with water to neutrality, and drying at 60 deg.C.
Wherein the glycosyl compound is one of gluconolactone and chitosan, and the dosage of the glycosyl compound is 2.5-3.5mmol corresponding to 1 g of attapulgite.
Wherein the eutectic solvent is prepared by mixing choline chloride serving as a hydrogen bond acceptor and one of urea, glycerol, anhydrous glucose and acetic acid serving as a hydrogen bond donor in equimolar amount and heating at 60-100 ℃ for 0.25-2 h, and the amount of the eutectic solvent is 5-8 mL corresponding to 1 g of attapulgite.
Wherein the silicon compound is one of aminopropyltrimethoxysilane, glyceryl ether oxypropyltrimethoxysilane, 3-aminoethylaminopropyltrimethoxysilane and trimethoxysilylpropyldiethylenetriamine, and the amount of the silicon compound is the same as that of the glycosyl compound.
Wherein the glycosyl compound is derived under the following conditions: heating to 80-120 deg.C, stirring for 12-16 h, and separating with inert solvent C1-4 lower alcohol.
Wherein the perfluoroalkylsilane is one of tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane and perfluorooctyltriethoxysilane, and the dosage of the perfluoroalkylsilane is 1.0-1.5 mmol relative to 1 g of attapulgite.
Wherein, the sol-gel copolymerization reaction conditions are as follows: the dosage of the sugar derivative is 25-200% of the molar weight of the attapulgite, the dosage of the perfluoroalkylsilane is 25-200% of the molar weight of the attapulgite, the dosage of the tetraethoxysilane is 50-300% of the molar weight of the attapulgite, the dosage of the ammonia water is 0.5-2% of the volume of the mixed solution, the reaction temperature is 80-120 ℃, and the reaction time is 2-10 h.
The invention has the advantages that: the prepared attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material is powdery, can be used as a filtering oil-water separation material and an adsorption oil-water separation material, and has high stability and good oil-water separation effect.
Detailed Description
The technical solution of the present invention will be described in further detail below with reference to specific examples, but the technical solution of the present invention is not limited to the specific examples.
Example 1: choline chloride and ethylene glycol in equal molar equivalent are mixed and placed in a round-bottom flask, and the mixture is heated at 100 ℃ under mechanical stirring until a solid phase completely disappears, so that a homogeneous transparent liquid, namely a eutectic solvent-1, is obtained; dissolving 50 mmol of 3-aminopropyltrimethoxysilane and 55 mmol of gluconolactone in 50 mL of eutectic solvent-1, stirring and heating for 12 h under anhydrous and anaerobic conditions to obtain a glucosamide derivative; taking 20 g of warp H2SO4Dispersing the activated attapulgite in the eutectic solvent of the glucose amide derivative, adding 30 mmol of perfluorooctyl triethoxysilane, 80 mmol of tetraethoxysilane and 0.8 mL of ammonia water, and performing sol-gel copolymerization reaction under airtight condition for 2 h; and then carrying out centrifugal separation, washing a solid product with water and ethanol, and drying to obtain the super-hydrophilic/super-oleophobic oil-water separation material, wherein the contact angle of the material to dichloroethane is =151 °.
Example 2: choline chloride and urea with equal molar equivalent are mixed in a round-bottom flask, and the mixture is heated at 80 ℃ under mechanical stirring until a solid phase completely disappears, so that a homogeneous transparent liquid, namely the eutectic solvent-2, is obtained; dissolving 45 mmol of 3-aminopropyltrimethoxysilane and 50 mmol of gluconolactone in 50 mL of eutectic solvent-2, stirring and heating for 14 h under anhydrous and anaerobic conditions to obtain gluconolactone derivatives; taking 20 g of warp H2SO4Dispersing the activated attapulgite in the eutectic solvent containing the glucolactone derivative, adding 40 mmol of perfluorooctyltriethoxysilane, 90 mmol of tetraethoxysilane and 1.0 mL of ammonia water, and performing sol-gel copolymerization for 4 h under airtight condition; and then carrying out centrifugal separation, washing a solid product with anhydrous methanol, and drying to obtain the super-hydrophilic/super-oleophobic oil-water separation material, wherein the contact angle of the material to dichloroethane is =152.5 °.
Example 3: mixing choline chloride and glycerol at equal molar equivalent, placing in round bottom flask, heating at 90 deg.C under mechanical stirring until solid phase completely disappears to obtain homogeneous transparent liquidEutectic solvent-3; dissolving 100 mmol of glyceryl ether oxypropyltrimethoxysilane and 50 mmol of chitosan in 50 mL of eutectic solvent-1, stirring and heating for 16 h under anhydrous and anaerobic conditions to obtain a chitosan derivative; taking 20 g of warp H2SO4Dispersing the activated attapulgite in the eutectic solvent of the chitosan derivative, adding 40 mmol of tridecafluorooctyltrimethoxysilane, 60 mmol of tetraethoxysilane and 1 mL of ammonia water, and carrying out sol-gel copolymerization reaction under airtight condition for 8 hours; and then carrying out centrifugal separation, washing a solid product with water and ethanol, and drying to obtain the super-hydrophilic/super-oleophobic oil-water separation material, wherein the contact angle of the material to dichloroethane is =150.5 °.
Claims (8)
1. A preparation method of an attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material is characterized by comprising the following steps: firstly, performing surface purification and activation treatment on attapulgite; then dissolving the glycosyl compound in the eutectic solvent, adding equivalent silicon compound, heating and stirring under anhydrous and anaerobic conditions, dropwise adding an inert solvent into the system after a certain time to separate out a precipitate, and obtaining a sugar derivative; finally, dispersing a certain amount of activated attapulgite in a eutectic solvent, adding sugar derivatives according to a certain mass ratio, then respectively adding perfluoroalkylsilane, tetraethoxysilane and ammonia water, carrying out sol-gel copolymerization reaction under an airtight condition to enable the sugar derivatives to be covalently and fixedly supported on the surface of the attapulgite, centrifuging, washing a product with water and ethanol, and drying to obtain the super-hydrophilic/super-oleophobic oil-water separation material.
2. The preparation method of the attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material according to claim 1, which is characterized by comprising the following steps: the surface purifying and activating treatment method of the attapulgite comprises the following steps: h with attapulgite in the mass concentration of 3-10%2SO4Boiling, acidifying, washing with water to neutrality, and drying at 60 deg.C.
3. The preparation method of the attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material according to claim 1, which is characterized by comprising the following steps: the glycosyl compound is one of gluconolactone and chitosan, and the dosage of the glycosyl compound is 2.5-3.5mmol corresponding to 1 g of attapulgite.
4. The preparation method of the attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material according to claim 1, which is characterized by comprising the following steps: the eutectic solvent is prepared by mixing choline chloride serving as a hydrogen bond acceptor and one of urea, glycerol, anhydrous glucose and acetic acid serving as a hydrogen bond donor in equimolar amount and heating at 60-100 ℃ for 0.25-2 h, wherein the amount of the eutectic solvent is 5-8 mL corresponding to 1 g of attapulgite.
5. The preparation method of the attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material according to claim 1, which is characterized by comprising the following steps: the silicon compound is one of aminopropyl trimethoxy silane, 3-aminoethylaminopropyl trimethoxy silane, glyceryl ether oxygen propyl trimethoxy silane and trimethoxy silicon propyl diethylene triamine, and the amount of the silicon compound is the same as that of the glycosyl compound.
6. The preparation method of the attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material according to claim 1, which is characterized by comprising the following steps: the glycosyl compound is derived under the following conditions: heating to 80-120 deg.C, stirring for 12-16 h, and separating with inert solvent C1-4 lower alcohol.
7. The preparation method of the attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material according to claim 1, which is characterized by comprising the following steps: the perfluoroalkyl silane is one of tridecafluorooctyl trimethoxy silane, heptadecafluorodecyl trimethoxy silane and perfluorooctyl triethoxy silane, and the dosage of the perfluoroalkyl silane is 1.0-1.5 mmol, which corresponds to 1 g of attapulgite.
8. The preparation method of the attapulgite-based super-hydrophilic/super-oleophobic oil-water separation material according to claim 1, which is characterized by comprising the following steps: the sol-gel copolymerization reaction conditions are as follows: the dosage of the sugar derivative is 25-200% of the molar weight of the attapulgite, the dosage of the perfluoroalkylsilane is 25-200% of the molar weight of the attapulgite, the dosage of the tetraethoxysilane is 50-300% of the molar weight of the attapulgite, the dosage of the ammonia water is 0.5-2% of the volume of the mixed solution, the reaction temperature is 80-120 ℃, and the reaction time is 2-10 h.
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| CN112207012A (en) * | 2020-09-04 | 2021-01-12 | 厦门大学 | Preparation method of underwater oleophobic cellulose hydrogel coating grid |
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| CN103626171A (en) * | 2013-11-28 | 2014-03-12 | 中国科学技术大学 | Preparation method of oil-water separation material |
| CN106732422A (en) * | 2016-12-27 | 2017-05-31 | 中国石油大学(华东) | A kind of preparation method of the Graphene composite foam for water-oil separating |
| CN109665942A (en) * | 2018-11-29 | 2019-04-23 | 山东东岳高分子材料有限公司 | The preparation method of fluorine-containing ether compound |
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| CN103626171A (en) * | 2013-11-28 | 2014-03-12 | 中国科学技术大学 | Preparation method of oil-water separation material |
| CN106732422A (en) * | 2016-12-27 | 2017-05-31 | 中国石油大学(华东) | A kind of preparation method of the Graphene composite foam for water-oil separating |
| CN109665942A (en) * | 2018-11-29 | 2019-04-23 | 山东东岳高分子材料有限公司 | The preparation method of fluorine-containing ether compound |
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| CN112207012A (en) * | 2020-09-04 | 2021-01-12 | 厦门大学 | Preparation method of underwater oleophobic cellulose hydrogel coating grid |
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