CN109833860B - Preparation method of silica gel carrier - Google Patents
Preparation method of silica gel carrier Download PDFInfo
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- CN109833860B CN109833860B CN201711211519.4A CN201711211519A CN109833860B CN 109833860 B CN109833860 B CN 109833860B CN 201711211519 A CN201711211519 A CN 201711211519A CN 109833860 B CN109833860 B CN 109833860B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000000741 silica gel Substances 0.000 title claims abstract description 51
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000007864 aqueous solution Substances 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 35
- 239000012153 distilled water Substances 0.000 claims description 30
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 22
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 20
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 20
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 19
- 239000004115 Sodium Silicate Substances 0.000 claims description 18
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 18
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 230000003213 activating effect Effects 0.000 claims description 11
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 150000002823 nitrates Chemical class 0.000 claims description 9
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 claims description 6
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 6
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 4
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229940083957 1,2-butanediol Drugs 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 235000019794 sodium silicate Nutrition 0.000 claims description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 22
- 230000000704 physical effect Effects 0.000 abstract description 5
- 239000000499 gel Substances 0.000 abstract description 4
- 229910002651 NO3 Inorganic materials 0.000 abstract description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- OHFQALRFLNKBNL-UHFFFAOYSA-N carbonic acid;ethanol Chemical compound CCO.OC(O)=O OHFQALRFLNKBNL-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 10
- 229960001545 hydrotalcite Drugs 0.000 description 10
- 229910001701 hydrotalcite Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- ZTHQBROSBNNGPU-UHFFFAOYSA-N Butyl hydrogen sulfate Chemical compound CCCCOS(O)(=O)=O ZTHQBROSBNNGPU-UHFFFAOYSA-N 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- 238000010533 azeotropic distillation Methods 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- IYAMYECUTLASCU-UHFFFAOYSA-L disodium;ethanol;carbonate Chemical compound [Na+].[Na+].CCO.[O-]C([O-])=O IYAMYECUTLASCU-UHFFFAOYSA-L 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 239000000017 hydrogel Substances 0.000 description 4
- -1 alcohol ethers Chemical class 0.000 description 3
- GTJRDLYFFWVVCZ-UHFFFAOYSA-N butane-1,3-diol;sulfuric acid Chemical compound OS(O)(=O)=O.CC(O)CCO GTJRDLYFFWVVCZ-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JJJTYYIVEITCFU-UHFFFAOYSA-N 1-[(2-methylpropan-2-yl)oxy]propan-1-ol Chemical compound CCC(O)OC(C)(C)C JJJTYYIVEITCFU-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HWQQWCJMWSKSCO-UHFFFAOYSA-L dipotassium ethanol carbonate Chemical compound C(C)O.C([O-])([O-])=O.[K+].[K+] HWQQWCJMWSKSCO-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CKSRFHWWBKRUKA-UHFFFAOYSA-N ethyl 2-ethoxyacetate Chemical compound CCOCC(=O)OCC CKSRFHWWBKRUKA-UHFFFAOYSA-N 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- FIABMSNMLZUWQH-UHFFFAOYSA-N propyl 2-methoxyacetate Chemical compound CCCOC(=O)COC FIABMSNMLZUWQH-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 1
- NTKBNCABAMQDIG-UHFFFAOYSA-N trimethylene glycol-monobutyl ether Natural products CCCCOCCCO NTKBNCABAMQDIG-UHFFFAOYSA-N 0.000 description 1
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- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a silica gel carrier, wherein two nitrate water solutions and a carbonate ethanol water solution are added in the preparation process of the silica gel carrier; during the gel reaction, the pH value of the reaction solution is adjusted by adding an organic alcohol aqueous solution of inorganic acid, and the preparation of the silica gel is completed through a high-temperature hydrothermal reaction. The process greatly improves the specific surface area of the silica gel, improves the pore volume and distribution of the silica gel, and improves the basic physical properties of the carrier silica gel.
Description
Technical Field
The invention relates to a preparation method of a silica gel carrier, in particular to a preparation method of a silica gel carrier with a high specific surface area.
Background
Silica gel is used in a wide variety of applications. Among them, silica gel is particularly suitable for a catalyst carrier because of its high specific surface area. At present, carrier silica gel is mainly applied to traditional Ziegler-Natta catalysts and metallocene olefin polymerization catalysts, and the preparation process by adopting an inorganic method has many reports at home and abroad, such as taking silicate as mother liquor and adding silicate and inorganic acid for reaction; or silicate and inorganic acid are taken as mother liquor, and the inorganic acid is added to adjust the PH value; or adding the silicate and the inorganic acid simultaneously for reaction in a parallel flow mode. When silica gel is used as a catalyst support, the high specific surface area can greatly improve the catalyst activity when the silica gel has an appropriate pore volume, pore diameter and distribution. In order to obtain a high specific surface area, the pore volume and pore size are mostly sacrificed in the conventional method for preparing the carrier silica gel, so that a new method is required to meet the preparation process requirements of the carrier silica gel for the catalyst.
The hydrotalcite is a layered double hydroxide, and the layered plate is composed of magnesium octahedrons and aluminum octahedrons. Is prepared fromThe specific surface area of the calcined hydrotalcite is 5-20 m2The calcined hydrotalcite has a high specific surface area of 200-300 m2The specific surface area before and after calcination showed a geometric quantitative increase. The hydrotalcite has unique structural characteristics, so that the hydrotalcite can be used as a basic catalyst, a redox catalyst and a catalyst carrier.
U.S. Pat. No. 5,5372983 discloses the preparation of SiO by azeotropic distillation2. Firstly, silicate reacts with dilute sulphuric acid to prepare hydrogel, impurities are removed by washing, then C5-C6 alcohol such as pentanol, hexanol or a mixture of the pentanol and the hexanol is added, and water in pores of the hydrogel is removed by azeotropic distillation to obtain xerogel. Roasting at 450-700 ℃ to obtain SiO product2. Physical property indexes are as follows: pore volume is 2.2cm3/g～2.5cm3Per g, specific surface area 420m2/g～550m2G, bulk density 0.18g/cm3～2.5g/cm3。
Us patent 5599762, 5576262 improves the process of azeotropic distillation thereof. It is essential to find some suitable organic compounds, such as alcohol ethers, alcohol ether esters and the like, including: ethyl ethoxyacetate, tert-butoxypropanol, propyl methoxyacetate, n-butoxypropanol, and ethyl ethoxypropionate, and the like. The use of these organic compounds for boiling distillation is not only cost effective, but also improves the performance of the polyethylene catalyst. Improved azeotropic distillation technology, and the prepared carrier SiO2And the catalyst properties are: SiO22Specific surface area of 520m2/g～530m2Per g, pore volume of 2.4cm3/g～2.6cm3The product melt index is 6.5g/10 min-6.5 g/10min, and the catalyst activity is 7000 PEg/gcat.h-8000 PEg/gcat.h.
US.3959174 discloses the preparation of SiO with large specific surface area and pore volume2A method. Mainly reduces SiO in the preparation process2Solubility or solvating auxiliaries, rendering SiO2In the prepared hydrosol system, the solubility of SiO2 is reduced to precipitate hydrogel, and then the SiO2 is prepared by aging, water washing, drying and roasting. The auxiliary agent is ammonia, monohydric alcohol, dihydric alcohol, ketone and salt. They are capable of reducing the content of hydrosol systemsThereby making SiO2Precipitating to form gel. SiO22The physical property indexes of (1): specific surface area 300m2/g～450m2G, pore volume of 1.2cm3/g～2.8cm3/g。
Phillips oil company also discloses a number of patents, us.3099457, 3948806, 4081407, 4152503, 4436883, 4246139, etc., which discuss azeotropic distillation techniques in an attempt to avoid pore shrinkage and collapse when water is removed from a hydrogel. In addition, a method of removing water by replacement with an organic solvent has been attempted.
The above method has obvious advantages and disadvantages. The azeotropic distillation method has the problems of long time for removing water by distillation, expensive solvent, large energy consumption and the like; the organic solvent replacement method has the disadvantages of complicated operation steps, large solvent consumption, difficult recovery and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a silica gel carrier, and the silica gel prepared by the method has proper pore volume and pore diameter, and the specific surface area is greatly improved.
Therefore, the invention provides a preparation method of a silica gel carrier, which takes silicate and inorganic acid as raw materials and comprises the following preparation processes:
1) taking an inorganic acid aqueous solution as a base solution, adding an alkaline medium solution, wherein the volume ratio of the alkaline medium solution to the inorganic acid aqueous solution is 1: 5-1: 30;
2) adding an aqueous solution of a metal nitrate;
3) adding a silicate aqueous solution with the concentration of 1.0-3.0 mol/L, adjusting the pH value of the solution to 6-7, adding distilled water to disperse the sol, and reacting at constant temperature for 0.5-2.0 h;
4) adding an ethanol water solution of alkali metal carbonate, wherein the volume ratio of ethanol to water is 1: 1-1: 10;
5) adding a silicate aqueous solution with the concentration of 1.0-3.0 mol/L, and adjusting the pH value of the reaction solution to 10-12;
6) adding an organic alcohol aqueous solution of inorganic acid, wherein the volume ratio of the organic alcohol to the water is 1: 5-1: 30, and adjusting the pH value of the reaction solution to 6-8;
7) carrying out hydrothermal reaction at 70-100 ℃;
8) and acidifying, washing, drying and activating to obtain the silica gel carrier.
Specifically, the preparation method of the silica gel carrier comprises the following steps:
1) adding 30-60 ml of 1.0-3.0 mol/L inorganic acid aqueous solution into a reaction kettle, adding an alkaline medium solution at 20-50 ℃, and reacting at constant temperature for 10-30 min; the volume ratio of the alkaline medium solution to the inorganic acid aqueous solution is preferably 1: 10-1: 20;
2) heating to 40-60 ℃ under the condition of stirring, and adding 10-25 ml of 2-8% by mass of aqueous solution of metal nitrate;
3) adding a silicate aqueous solution with the concentration of 1.0-3.0 mol/L, controlling the flow rate at 3-6 ml/min, adjusting the pH value of the reaction solution to 6-7, adding distilled water to completely disperse sol in the reaction kettle, and reacting at constant temperature for 0.5-1.5 h;
4) adding 15-25 ml of ethanol aqueous solution of alkali metal carbonate with the mass fraction of 3-10% into a reaction kettle, wherein the volume ratio of ethanol to water is preferably 1: 5-1: 9, the flow rate is controlled at 2-5 ml/min, and the constant temperature reaction is carried out for 0.5-1.0 h;
5) adding a silicate aqueous solution with the concentration of 1.0-3.0 mol/L, controlling the flow rate at 3-6 ml/min, adjusting the pH value of the reaction solution to 10-12, and reacting at constant temperature for 0.5-1.5 h;
6) adding 1.0-3.0 mol/L of an organic alcohol aqueous solution of inorganic acid, wherein the volume ratio of the organic alcohol to the water is preferably 1: 10-1: 20, the flow rate is controlled to be 4-9 ml/min, the pH value of the solution is adjusted to be 6-8, and the constant temperature reaction is carried out for 1.0-2.5 hours;
7) carrying out hydrothermal reaction for 3.0-6.0 h at 70-100 ℃;
8) adding 1.0-3.0 mol/L of inorganic acid aqueous solution, adjusting the pH value of the solution to 3-5, cooling the reaction system to normal temperature, washing with distilled water and/or a mixed solution of distilled water and ethanol, drying at 300-335 ℃, and activating for 3.0-6.0 h at 400-600 ℃ under the condition of inert gas to obtain the silica gel carrier.
The inorganic acid is selected from one or more of sulfuric acid, hydrochloric acid and nitric acid, and the concentration of the inorganic acid aqueous solution is 1.0-1.3 mol/L.
The alkaline medium solution is selected from ammonia water, an ammonium bicarbonate solution, an ammonium carbonate solution, an ammonium sulfide solution or an ammonium acetate solution, preferably the ammonia water and the ammonium carbonate solution, and the concentration of the alkaline medium solution is 1.0-5.0 mol/L.
The metal nitrate is selected from at least two of magnesium nitrate, aluminum nitrate, nickel nitrate, manganese nitrate, cobalt nitrate, chromium nitrate, terbium nitrate and cerium nitrate, preferably the mixture of magnesium nitrate and aluminum nitrate and the mixture of zinc nitrate and aluminum nitrate, and the molar ratio of the two metal nitrates is 1: 1.
The silicate is selected from one or more of sodium silicate, potassium silicate and water glass, and the concentration of the aqueous solution of the silicate is 1.0-1.5 mol/L.
The carbonate in the alkali metal carbonate is selected from one or more of potassium carbonate and sodium carbonate.
The organic alcohol is at least one selected from n-butanol, isobutanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol, 2-dimethyl-1-propanol, preferably at least one selected from n-butanol and 1, 3-butanediol.
The invention adopts sol-gel reaction to prepare a silica gel carrier, and two nitrate water solutions and carbonate ethanol water solution are added in the sol preparation process; during the gel reaction, the pH value of the reaction solution is adjusted by adding an organic alcohol aqueous solution of inorganic acid, and the preparation of the silica gel is completed through a high-temperature hydrothermal reaction. On one hand, the nitrate reacts with the carbonate of the alkali metal to generate hydrotalcite, and the hydroxyl of the hydrotalcite laminate and the hydroxyl of the silica gel can form perfect bonding, so that the layering condition can not occur; on the other hand, the double-layered hydrotalcite can greatly increase the specific surface area of the carrier silica gel, because CO is continuously removed between layers when the hydrotalcite is heated2And water, the ordered layered structure is destroyed, the surface area is increased, and the pore volume is increased. The ethanol is added in the process to better precipitate hydrotalcite, and the alkaline medium and the organic alcohol are added to improve the pore volume and distribution of the silica gel. TheThe process can greatly improve the specific surface area of the silica gel under the condition of not influencing the pore volume of the silica gel, thereby improving the basic physical properties of the carrier silica gel; the process preparation is simple to operate, good in repeatability and low in energy consumption, and provides technical support for industrial device production.
Detailed Description
The present invention is described in further detail below by way of examples, which should not be construed as limiting the invention thereto.
In an embodiment, the relevant indexes are tested according to the following method:
specific surface area: gas adsorption BET method test, GB/T19587-2004.
Pore volume: BJH (Barrett-Joyner-Halenda) method, ISO 15901-2.
The average pore diameter d is 4V/A, A is the specific surface area, V is the pore volume, and d is the pore diameter.
Example 1
Placing 60ml of dilute sulfuric acid solution with the concentration of 1.1mol/L in a closed reactor, adding 3.0ml of 5.0mol/L ammonia water solution at 30 ℃ and reacting for 20 min; the temperature is raised to 50 ℃ under the condition of stirring, 16mL of magnesium nitrate and aluminum nitrate aqueous solution with the mass fraction of 4 percent is added at the flow rate of 8mL/min (the molar ratio of the two nitrates is 1: 1). Adding 1.2mol/L sodium silicate aqueous solution at the flow rate of 3ml/min, adjusting the pH value of the reaction solution to 7, adding distilled water to thoroughly disperse the sol, and reacting at constant temperature for 0.5 h. 20ml of sodium carbonate ethanol water solution with the mass fraction of 6 percent (the volume ratio of ethanol to water is 1:6) is added at the flow rate of 4ml/min, and the mixture reacts for 0.5h at constant temperature. Adding 1.2mol/L sodium silicate aqueous solution at the flow rate of 4ml/min, adjusting the pH value of the reaction solution to 11, and reacting for 1.0h at constant temperature. Adding 1.0mol/L aqueous solution of n-butyl sulfate at the flow rate of 6mL/min (the volume ratio of n-butyl alcohol to water is 1:15), stopping adding the aqueous solution of n-butyl sulfate when the pH value of the solution is 7, and reacting at constant temperature for 2.0 h. The reaction system is heated to 85 ℃ and reacts for 5.0h at constant temperature. Adding 1.0mol/L sulfuric acid water solution, and stopping adding when the pH value of the solution is 3. Cooling to room temperature, washing for three times by respectively using distilled water, a mixed solution of distilled water and ethanol, drying at 335 ℃, and activating for 4 hours at 600 ℃ under the protection of inert gas to obtain a carrier silica gel product. The test results are shown in table 1.
Example 2
The preparation process is the same as example 1, except that 6.0ml of 5.0mol/L ammonia water solution is added at 30 ℃ for reaction for 20 min; the temperature is raised to 50 ℃, 16mL of magnesium nitrate and aluminum nitrate aqueous solution with the mass fraction of 4 percent are added at the flow rate of 8mL/min (the molar ratio of the two nitrates is 1: 1). Adding 1.2mol/L potassium silicate aqueous solution at the flow rate of 3ml/min, adjusting the pH value of the reaction solution to 6, adding distilled water to thoroughly disperse the sol, and reacting at constant temperature for 0.5 h. Other conditions were the same as in example 1. The test results are shown in table 1.
Example 3
The preparation process is the same as example 1, except that 20ml of potassium carbonate ethanol water solution with the mass fraction of 8 percent (the volume ratio of ethanol to water is 1:9) is added at the flow rate of 4ml/min, and the reaction is carried out for 0.5h at constant temperature. Adding sodium silicate with the concentration of 1.2mol/L at the flow rate of 4ml/min for water dissolution, adjusting the pH value of the reaction solution to 12, and reacting for 1.0h at constant temperature. Other conditions were the same as in example 1. The test results are shown in table 1.
Example 4
The preparation process is the same as example 1, except that 1.0mol/L sulfuric acid 1, 3-butanediol aqueous solution (1, 3-butanediol/water volume ratio is 1:20) is added at the flow rate of 6mL/min, the addition of the sulfuric acid 1, 3-butanediol aqueous solution is stopped when the pH value of the solution is 6, and the reaction is carried out for 2.0 hours at constant temperature. Other conditions were the same as in example 1. The test results are shown in table 1.
Example 5
The preparation process is the same as example 1, except that the temperature of the reaction system is slowly increased to 90 ℃, and the reaction is carried out for 4.0h at constant temperature. Adding 1.0mol/L sulfuric acid water solution, and stopping adding when the pH value of the solution is 5. Other conditions were the same as in example 1. The test results are shown in table 1.
Example 6
The preparation process is the same as example 1, except that 20ml of sodium carbonate ethanol water solution with the mass fraction of 6 percent (the volume ratio of ethanol to water is 1:5) is added at the flow rate of 4ml/min, and the reaction is carried out for 0.5h at constant temperature. Adding sodium silicate with the concentration of 1.2mol/L at the flow rate of 4ml/min for water dissolution, adjusting the pH value of the reaction solution to 11, and reacting for 1.0h at constant temperature. Adding 1.0mol/L aqueous solution of n-butyl sulfate at the flow rate of 6mL/min (the volume ratio of n-butyl alcohol to water is 1:10), stopping adding the aqueous solution of n-butyl sulfate when the pH value of the solution is 7, and reacting at constant temperature for 2.0 h. Other conditions were the same as in example 1. The test results are shown in table 1.
Comparative example 1
Placing 60ml of dilute sulfuric acid solution with the concentration of 1.1mol/L in a closed reactor, heating to 50 ℃, adding sodium silicate aqueous solution with the concentration of 1.2mol/L at the flow rate of 3ml/min, adjusting the pH value of the reaction solution to 7, adding distilled water to thoroughly disperse the sol, and reacting at constant temperature for 0.5 h. Adding sodium silicate with the concentration of 1.2mol/L at the flow rate of 4ml/min for water dissolution, adjusting the pH value of the reaction solution to 11, and reacting for 1.0h at constant temperature. Adding 1.0mol/L sulfuric acid aqueous solution at the flow rate of 6mL/min, stopping adding the sulfuric acid aqueous solution when the pH value of the solution is 7, and reacting for 2.0h at constant temperature. The reaction system is heated to 85 ℃ and reacts for 5.0h at constant temperature. Adding 1.0mol/L sulfuric acid water solution, and stopping adding when the pH value of the solution is 3. Cooling to room temperature, washing for three times by respectively using distilled water, a mixed solution of distilled water and ethanol, drying at 335 ℃, and activating for 4 hours at 600 ℃ under the protection of inert gas to obtain a carrier silica gel product. The test results are shown in table 1.
Comparative example 2
60mL of dilute sulfuric acid solution with the concentration of 1.1mol/L is placed in a closed reactor, the temperature is raised to 50 ℃, 16mL of magnesium nitrate and aluminum nitrate aqueous solution with the mass fraction of 4 percent are added at the flow rate of 8mL/min (the molar ratio of the two nitrates is 1: 1). Adding 1.2mol/L sodium silicate aqueous solution at the flow rate of 3ml/min, adjusting the pH value of the reaction solution to 7, adding distilled water to thoroughly disperse the sol, and reacting at constant temperature for 0.5 h. 20ml of sodium carbonate ethanol water solution with the mass fraction of 6 percent (the volume ratio of ethanol to water is 1:6) is added at the flow rate of 4ml/min, and the mixture reacts for 0.5h at constant temperature. Adding sodium silicate with the concentration of 1.2mol/L at the flow rate of 4ml/min for water dissolution, adjusting the pH value of the reaction solution to 11, and reacting for 1.0h at constant temperature. Adding 1.0mol/L aqueous solution of n-butyl sulfate at the flow rate of 6mL/min (the volume ratio of n-butyl alcohol to water is 1:15), stopping adding the aqueous solution of n-butyl sulfate when the pH value of the solution is 7, and reacting at constant temperature for 2.0 h. The reaction system is heated to 85 ℃ and reacts for 5.0h at constant temperature. Adding 1.0mol/L sulfuric acid water solution, and stopping adding when the pH value of the solution is 3. Cooling to room temperature, washing for three times by respectively using distilled water, a mixed solution of distilled water and ethanol, drying at 335 ℃, and activating for 4 hours at 600 ℃ under the protection of inert gas to obtain a carrier silica gel product. The test results are shown in table 1.
Comparative example 3
60mL of dilute sulfuric acid solution with the concentration of 1.1mol/L is placed in a closed reactor, the temperature is raised to 50 ℃, 16mL of magnesium nitrate and aluminum nitrate aqueous solution with the mass fraction of 4 percent are added at the flow rate of 8mL/min (the molar ratio of the two nitrates is 1: 1). Adding 1.2mol/L sodium silicate aqueous solution at the flow rate of 3ml/min, adjusting the pH value of the reaction solution to 7, adding distilled water to thoroughly disperse the sol, and reacting at constant temperature for 0.5 h. 20ml of sodium carbonate solution with the mass fraction of 6 percent is added at the flow rate of 4ml/min, and the reaction is carried out for 0.5h at constant temperature. Adding sodium silicate with the concentration of 1.2mol/L at the flow rate of 4ml/min for water dissolution, adjusting the pH value of the reaction solution to 11, and reacting for 1.0h at constant temperature. Adding 1.0mol/L sulfuric acid aqueous solution at the flow rate of 6mL/min, stopping adding the sulfuric acid aqueous solution when the pH value of the solution is 7, and reacting for 2.0h at constant temperature. The reaction system is heated to 85 ℃ and reacts for 5.0h at constant temperature. Adding 1.0mol/L sulfuric acid water solution, and stopping adding when the pH value of the solution is 3. Cooling to room temperature, washing for three times by respectively using distilled water, a mixed solution of distilled water and ethanol, drying at 335 ℃, and activating for 4 hours at 600 ℃ under the protection of inert gas to obtain a carrier silica gel product. The test results are shown in table 1.
Comparative example 4
60mL of dilute sulfuric acid solution with the concentration of 1.1mol/L is placed in a closed reactor, the temperature is raised to 50 ℃, 16mL of magnesium nitrate and aluminum nitrate aqueous solution with the mass fraction of 4 percent are added at the flow rate of 8mL/min (the molar ratio of the two nitrates is 1: 1). Adding 1.2mol/L sodium silicate aqueous solution at the flow rate of 3ml/min, adjusting the pH value of the reaction solution to 7, adding distilled water to thoroughly disperse the sol, and reacting at constant temperature for 0.5 h. 20ml of sodium carbonate ethanol water solution with the mass fraction of 6 percent (the volume ratio of ethanol to water is 1:6) is added at the flow rate of 4ml/min, and the mixture reacts for 0.5h at constant temperature. Adding sodium silicate with the concentration of 1.2mol/L at the flow rate of 4ml/min for water dissolution, adjusting the pH value of the reaction solution to 11, and reacting for 1.0h at constant temperature. Adding 1.0mol/L sulfuric acid aqueous solution at the flow rate of 6mL/min, stopping adding the sulfuric acid aqueous solution when the pH value of the solution is 7, and reacting for 2.0h at constant temperature. The reaction system is heated to 85 ℃ and reacts for 5.0h at constant temperature. Adding 1.0mol/L sulfuric acid water solution, and stopping adding when the pH value of the solution is 3. Cooling to room temperature, washing for three times by respectively using distilled water, a mixed solution of distilled water and ethanol, drying at 335 ℃, and activating for 4 hours at 600 ℃ under the protection of inert gas to obtain a carrier silica gel product. The test results are shown in table 1.
Comparative example 5
60mL of dilute sulfuric acid solution with the concentration of 1.1mol/L is placed in a closed reactor, the temperature is raised to 50 ℃, 16mL of magnesium nitrate and aluminum nitrate aqueous solution with the mass fraction of 4 percent are added at the flow rate of 8mL/min (the molar ratio of the two nitrates is 1: 1). Adding 1.2mol/L sodium silicate aqueous solution at the flow rate of 3ml/min, adjusting the pH value of the reaction solution to 7, adding distilled water to thoroughly disperse the sol, and reacting at constant temperature for 0.5 h. 20ml of sodium carbonate solution with the mass fraction of 6 percent is added at the flow rate of 4ml/min, and the reaction is carried out for 0.5h at constant temperature. Adding sodium silicate with the concentration of 1.2mol/L at the flow rate of 4ml/min for water dissolution, adjusting the pH value of the reaction solution to 11, and reacting for 1.0h at constant temperature. Adding 1.0mol/L aqueous solution of n-butyl sulfate at the flow rate of 6mL/min (the volume ratio of n-butyl alcohol to water is 1:15), stopping adding the aqueous solution of n-butyl sulfate when the pH value of the solution is 7, and reacting at constant temperature for 2.0 h. The reaction system is heated to 85 ℃ and reacts for 5.0h at constant temperature. Adding 1.0mol/L sulfuric acid water solution, and stopping adding when the pH value of the solution is 3. Cooling to room temperature, washing for three times by respectively using distilled water, a mixed solution of distilled water and ethanol, drying at 335 ℃, and activating for 4 hours at 600 ℃ under the protection of inert gas to obtain a carrier silica gel product. The test results are shown in table 1.
Comparative example 6
Placing 60ml of dilute sulfuric acid solution with the concentration of 1.1mol/L in a closed reactor, adding 3.0ml of 5.0mol/L ammonia water solution at 30 ℃ and reacting for 20 min; the temperature is raised to 50 ℃, 16mL of magnesium nitrate and aluminum nitrate aqueous solution with the mass fraction of 4 percent are added at the flow rate of 8mL/min (the molar ratio of the two nitrates is 1: 1). Adding 1.2mol/L sodium silicate aqueous solution at the flow rate of 3ml/min, adjusting the pH value of the reaction solution to 7, adding distilled water to thoroughly disperse the sol, and reacting at constant temperature for 0.5 h. 20ml of sodium carbonate aqueous solution with the mass fraction of 6 percent is added at the flow rate of 4ml/min, and the reaction is carried out for 0.5h at constant temperature. Adding sodium silicate with the concentration of 1.2mol/L at the flow rate of 4ml/min for water dissolution, adjusting the pH value of the reaction solution to 11, and reacting for 1.0h at constant temperature. Adding 1.0mol/L sulfuric acid aqueous solution at the flow rate of 6mL/min, stopping adding the sulfuric acid aqueous solution when the pH value of the solution is 7, and reacting for 2.0h at constant temperature. The reaction system is heated to 85 ℃ and reacts for 5.0h at constant temperature. Adding 1.0mol/L sulfuric acid water solution, and stopping adding when the pH value of the solution is 3. Cooling to room temperature, washing for three times by respectively using distilled water, a mixed solution of distilled water and ethanol, drying at 335 ℃, and activating for 4 hours at 600 ℃ under the protection of inert gas to obtain a carrier silica gel product. The test results are shown in table 1.
TABLE 1 test results of physical Properties of Carrier silica gel
| Item | Specific surface area/(m)2/g) | Pore volume/(cm)3/g) | Pore size/nm |
| Example 1 | 532.6 | 2.36 | 17.72 |
| Example 2 | 526.3 | 2.27 | 17.25 |
| Example 3 | 521.4 | 2.18 | 16.72 |
| Example 4 | 525.2 | 2.31 | 17.59 |
| Example 5 | 521.5 | 2.24 | 17.18 |
| Example 6 | 520.3 | 2.23 | 17.14 |
| Comparative example 1 | 268.3 | 1.34 | 19.98 |
| Comparative example 2 | 412.5 | 2.05 | 19.88 |
| Comparative example 3 | 376.8 | 1.78 | 18.90 |
| Comparative example 4 | 386.7 | 1.92 | 19.86 |
| Comparative example 5 | 388.2 | 1.97 | 20.30 |
| Comparative example 6 | 368.7 | 1.92 | 20.83 |
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (10)
1. The preparation method of the silica gel carrier is characterized in that silicate and inorganic acid are used as raw materials, and the preparation process is as follows:
1) taking an inorganic acid aqueous solution as a base solution, adding an alkaline medium solution, wherein the volume ratio of the alkaline medium solution to the inorganic acid aqueous solution is 1: 5-1: 30;
2) adding a metal nitrate aqueous solution selected from a mixed aqueous solution of magnesium nitrate and aluminum nitrate or a mixed aqueous solution of zinc nitrate and aluminum nitrate;
3) adding a silicate aqueous solution with the concentration of 1.0-3.0 mol/L, adjusting the pH value of the solution to 6-7, adding distilled water to disperse the sol, and reacting at constant temperature for 0.5-2.0 h;
4) adding an ethanol water solution of alkali metal carbonate, wherein the volume ratio of ethanol to water is 1: 1-1: 10;
5) adding a silicate aqueous solution with the concentration of 1.0-3.0 mol/L, and adjusting the pH value of the reaction solution to 10-12;
6) adding an organic alcohol aqueous solution of inorganic acid, wherein the volume ratio of the organic alcohol to the water is 1: 5-1: 30, and adjusting the pH value of the reaction solution to 6-8;
7) carrying out hydrothermal reaction at 70-100 ℃;
8) and acidifying, washing, drying and activating to obtain the silica gel carrier.
2. The method for preparing a silica gel carrier according to claim 1, wherein the preparation process is as follows:
1) adding 30-60 ml of 1.0-3.0 mol/L inorganic acid aqueous solution into a reaction kettle, adding an alkaline medium solution at 20-50 ℃, and reacting at constant temperature for 10-30 min; the volume ratio of the alkaline medium solution to the inorganic acid aqueous solution is 1: 10-1: 20;
2) heating to 40-60 ℃ under the condition of stirring, and adding 10-25 ml of 2-8% by mass of aqueous solution of metal nitrate;
3) adding a silicate aqueous solution with the concentration of 1.0-3.0 mol/L, controlling the flow rate at 3-6 ml/min, adjusting the pH value of the reaction solution to 6-7, adding distilled water to completely disperse sol in the reaction kettle, and reacting at constant temperature for 0.5-1.5 h;
4) adding 15-25 ml of ethanol aqueous solution of alkali metal carbonate with the mass fraction of 3-10% into a reaction kettle, wherein the volume ratio of ethanol to water is 1: 5-1: 9, the flow rate is controlled at 2-5 ml/min, and the reaction is carried out for 0.5-1.0 h at constant temperature;
5) adding a silicate aqueous solution with the concentration of 1.0-3.0 mol/L, controlling the flow rate at 3-6 ml/min, adjusting the pH value of the reaction solution to 10-12, and reacting at constant temperature for 0.5-1.5 h;
6) adding 1.0-3.0 mol/L of an organic alcohol aqueous solution of inorganic acid, wherein the volume ratio of organic alcohol to water is 1: 10-1: 20, the flow rate is controlled to be 4-9 ml/min, the pH value of the solution is adjusted to be 6-8, and reacting for 1.0-2.5 h at constant temperature;
7) carrying out hydrothermal reaction for 3.0-6.0 h at 70-100 ℃;
8) adding 1.0-3.0 mol/L of inorganic acid aqueous solution, adjusting the pH value of the solution to 3-5, cooling the reaction system to normal temperature, washing with distilled water and/or a mixed solution of distilled water and ethanol, drying at 300-335 ℃, and activating for 3.0-6.0 h at 400-600 ℃ under the condition of inert gas to obtain the silica gel carrier.
3. The method for preparing a silica gel support according to claim 1 or 2, wherein the inorganic acid is one or more selected from sulfuric acid, hydrochloric acid, and nitric acid, and the concentration of the aqueous solution of the inorganic acid is 1.0 to 1.3 mol/L.
4. The method for preparing a silica gel support according to claim 1 or 2, wherein the alkaline medium solution is selected from the group consisting of ammonia water, an ammonium bicarbonate solution, an ammonium carbonate solution, an ammonium sulfide solution, and an ammonium acetate solution, and the concentration of the alkaline medium solution is 1.0 to 5.0 mol/L.
5. The method for preparing a silica gel support according to claim 4, wherein the alkaline medium solution is selected from the group consisting of aqueous ammonia and ammonium carbonate solution.
6. The method for preparing a silica gel support according to claim 1 or 2, wherein the metal nitrate salt is a mixture of magnesium nitrate and aluminum nitrate or a mixture of zinc nitrate and aluminum nitrate, and the molar ratio of the two metal nitrate salts is 1: 1.
7. The method for preparing a silica gel carrier according to claim 1 or 2, wherein the silicate is selected from one or more of sodium silicate, potassium silicate and water glass, and the concentration of the aqueous silicate solution is 1.0 to 1.5 mol/L.
8. The method for preparing a silica gel carrier according to claim 1 or 2, wherein the carbonate in the alkali metal carbonate is one or more selected from potassium carbonate and sodium carbonate.
9. The method for preparing a silica gel support according to claim 1 or 2, wherein the organic alcohol is at least one selected from the group consisting of n-butanol, isobutanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol, and 2, 2-dimethyl-1-propanol.
10. The method for preparing a silica gel support according to claim 1 or 2, wherein the organic alcohol is at least one selected from n-butanol and 1, 3-butanediol.
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