CN112520745A - Porous silicon dioxide carrier and preparation method and application thereof - Google Patents
Porous silicon dioxide carrier and preparation method and application thereof Download PDFInfo
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- CN112520745A CN112520745A CN202011257964.6A CN202011257964A CN112520745A CN 112520745 A CN112520745 A CN 112520745A CN 202011257964 A CN202011257964 A CN 202011257964A CN 112520745 A CN112520745 A CN 112520745A
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- silicon dioxide
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 251
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 19
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 118
- 239000011148 porous material Substances 0.000 claims abstract description 55
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 32
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000003763 carbonization Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 18
- -1 saccharide compound Chemical class 0.000 claims description 18
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 16
- 229930006000 Sucrose Natural products 0.000 claims description 16
- 239000005720 sucrose Substances 0.000 claims description 16
- 235000013312 flour Nutrition 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 235000014633 carbohydrates Nutrition 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 150000001336 alkenes Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 235000012054 meals Nutrition 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- 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 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- 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 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 150000002016 disaccharides Chemical class 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 150000002772 monosaccharides Chemical class 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 60
- 238000011156 evaluation Methods 0.000 description 21
- 230000000704 physical effect Effects 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a porous silicon dioxide carrier and a preparation method and application thereof. The preparation method comprises the following steps: (1) firstly, impregnating silicon dioxide powder with an acid solution of a carbohydrate, and dehydrating and carbonizing the impregnated matter to obtain silicon dioxide with a protected pore channel, namely a carbon-containing precursor; (2) and (2) roasting the carbon-containing precursor in the step (1) to obtain the porous silicon dioxide. To obtainTo a specific surface area of not less than 200m2(iii) porous silica having a pore volume of not less than 1.0 ml/g. When the catalyst is used as an isobutylene oxyacetylation catalyst carrier, the catalyst has better catalytic performance and has the advantages of high conversion rate and stability.
Description
Technical Field
The invention belongs to the field of catalysts and catalyst carriers, and particularly relates to a porous silicon dioxide carrier and a preparation method and application thereof.
Background
Silica has a very wide application as an important catalyst and catalyst support. The preparation of silica having a large specific surface area and high porosity has been a focus of research.
Chinese patent document CN87100996.X discloses a preparation method of silica gel which can adjust the pore structure and can not crack when meeting water. However, in the process of preparing the silica carrier by using porous silica powder as a raw material and silica sol as a binder through roll forming, extrusion forming and other methods, the silica sol with fluidity enters the silica gel pore channels in the process of mixing, and silica gel particles formed after forming and roasting are attached to the silica gel pore channels to cause the blockage of the silica gel pore channels, so that the surface area and the pore volume of the carrier can be greatly reduced, and the exertion of the catalytic performance of the carrier is not facilitated.
Chinese patent document CN200910057225.X discloses that porous silicon dioxide contains 5-40 wt% of a pore channel protective agent, and the pore channel protective agent is a residue obtained by roasting an organic matter in the presence of a flame retardant and in an oxygen-containing atmosphere. However, the patent uses more complex organic substances and flame retardants, and has more complex process and higher cost.
Disclosure of Invention
The invention provides a preparation method of porous silicon dioxide, which comprises the following steps:
(1) firstly, impregnating silicon dioxide powder with an acid solution of a carbohydrate, and dehydrating and carbonizing the impregnated matter to obtain silicon dioxide with a protected pore channel, namely a carbon-containing precursor;
(2) and (2) roasting the carbon-containing precursor in the step (1) to obtain the porous silicon dioxide.
According to an embodiment of the present invention, in step (1), the saccharide compound may be selected from one, two or more of monosaccharides, disaccharides and polysaccharides, for example, from one, two or more of glucose, fructose, sucrose, soluble starch and soluble cellulose.
According to an embodiment of the present invention, in the step (1), the acid solution of the saccharide is a sulfuric acid solution of the saccharide. For example, concentrated sulfuric acid may be added to an aqueous solution of the saccharide compound, preferably slowly, to prepare an acid solution of the saccharide compound. Preferably, the volume ratio of the concentrated sulfuric acid to the aqueous solution of the saccharide compound is 1 (10-150), more preferably 1 (20-120), exemplarily 1:25, 1:30, 1:50, 1:62.5, 1:100, 1:110, 1: 120. Preferably, the aqueous solution of the saccharide compound has a concentration of 5-150mg/ml, preferably 10-120mg/ml, exemplarily 20mg/ml, 30mg/ml, 40mg/ml, 50mg/ml, 80mg/ml, 100 mg/ml.
According to an embodiment of the present invention, in the step (1), the silica powder is a porous silica powder. Wherein the particle size of the silicon dioxide powder is 200-1000 meshes, such as 200-300 meshes, 300-400 meshes, 500-800 meshes, and is exemplary 1000 meshes.
According to an embodiment of the present invention, in the step (1), the impregnation of the silica powder is performed by an equal volume impregnation method. Preferably, the porous silica powder is uniformly mixed with an acid solution of the saccharide compound by an equal volume impregnation method to obtain an impregnated matter. Wherein the impregnation is a porous silica powder containing (preferably filled with) an acid solution of a saccharide compound in the pore channels.
According to the embodiment of the present invention, in the step (1), the impregnated material may be further subjected to a drying treatment before the dehydration carbonization. For example, the drying temperature is 60 to 80 ℃, preferably 65 to 75 ℃, exemplary 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃. For example, the drying time is 6 to 12 hours, preferably 8 to 10 hours, and exemplary 6 hours, 8 hours, 10 hours, 12 hours.
According to an embodiment of the present invention, in step (1), the temperature of the dehydration carbonization is 150-. For example, the time for the dehydration carbonization is 6 to 24 hours, such as 10 to 20 hours, and exemplary 6 hours, 8 hours, 10 hours, 15 hours, 20 hours, 24 hours.
According to an embodiment of the present invention, the pore channels of the pore channel-protected silica contain a carbonization product of a saccharide compound under the action of an acid.
According to an embodiment of the present invention, the step (2) further comprises a shaping step before the firing step. Preferably, the carbon-containing precursor is washed (e.g., with deionized water) and dried prior to shaping.
According to an embodiment of the present invention, in the forming step, at least one of flour, field meal, and a silica sol acid solution is further introduced into the carbon-containing precursor. In step (2), the carbon-containing precursor is mixed with at least one of flour, field meal and silica sol acid solution, and then the mixture is formed and baked to obtain the porous silica.
According to the embodiment of the invention, in the step (2), the mass ratio of the carbon-containing precursor, the flour, the refined flour and the silica sol is (100-) -150 (5-25): 0-5): 140-) -200, for example, the mass ratio is (110-) -140: (10-20): 1-4): 142- } 170, and is exemplarily 120:18:3: 143.
According to an embodiment of the present invention, in the step (2), the silica sol acid solution may be a nitric acid aqueous solution of silica sol. For example, the silica sol may be dissolved in an aqueous nitric acid solution to obtain a silica sol acid solution. Preferably, the mass fraction of the aqueous nitric acid solution is between 5 and 20%, for example between 8 and 15%.
According to an embodiment of the present invention, in the step (2), the mass fraction of the silica sol in the silica sol acid solution is 5 to 80%, for example 10 to 60%, and exemplary is 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%.
According to an embodiment of the present invention, in step (2), the silica sol acid solution is preferably used in an amount to achieve a plastic morphology of the mixture of the carbon-containing precursor and the flour and/or the field meal.
According to an embodiment of the present invention, in the step (2), the molding may be a molding manner known in the art, such as extrusion molding. For example, the mixture may be placed in a plodder to obtain a rod.
According to an embodiment of the present invention, in the step (2), the molded article may be further dried before firing. For example, the drying temperature is 60 to 150 ℃, preferably 80 to 120 ℃, exemplary 60 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃. For example, the drying time is 6 to 48 hours, preferably 10 to 40 hours, exemplary 6 hours, 10 hours, 20 hours, 30 hours, 40 hours, 48 hours.
According to an embodiment of the present invention, in the step (2), the firing includes firing the formed object in an inert atmosphere and an oxygen-containing atmosphere, preferably firing until the formed object is pure white and the tail gas does not contain CO2. For example, the firing temperature is 300 ℃ 800 ℃, preferably 550 ℃ 650 ℃, exemplary 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 800 ℃. For example, the time for calcination is 2 to 24 hours, preferably 5 to 20 hours, and exemplified by 2 hours, 5 hours, 10 hours, 15 hours, 20 hours, 24 hours. For example, the firing temperature rise rate is 1-5 deg.C/min, illustratively 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, 5 deg.C/min.
Preferably, the firing may comprise two stages: inert atmosphere roasting and oxygen-containing atmosphere roasting. For example, the shaped article may be calcined in an inert atmosphere, then oxygen-containing gas may be introduced into the calcined article to form an oxygen-containing atmosphere, and the calcined article may be heated until the tail gas does not contain CO2。
According to an exemplary embodiment of the present invention, the method for preparing the porous silica includes the steps of:
(1) uniformly mixing a saccharide compound aqueous solution and concentrated sulfuric acid, and uniformly mixing porous silicon dioxide powder and the prepared saccharide compound acid solution by using an isometric impregnation method; then drying, dehydrating and carbonizing the porous silicon dioxide powder impregnated with the carbohydrate acid solution to obtain porous silicon dioxide powder with pore channels protected by carbonized products of the carbohydrate under the action of acid, namely a carbon-containing precursor;
(2) mixing the carbon-containing precursor with flour, refined field powder and silica sol acid solution, extruding into strips, drying the strips, and roasting until the tail gas contains no CO2And obtaining the porous silicon dioxide.
The invention also provides the porous silicon dioxide prepared by the method.
According to an embodiment of the present invention, the porous silica has a specific surface area of not less than 200m2G, e.g. not less than 205m2G, preferably at 210-2Between/g, exemplary 210m2/g、214m2/g、215m2/g。
According to an embodiment of the invention, the porous silica has a pore volume not lower than 1.0ml/g, for example not lower than 1.02ml/g, preferably from 1.05 to 1.25ml/g, exemplarily 1.02ml/g, 1.08ml/g, 1.10ml/g, 1.14 ml/g.
According to an embodiment of the invention, the porous silica is free of carbon.
The invention also provides the application of the porous silica as a catalyst or a catalyst carrier.
The invention also provides a catalyst carrier containing the porous silica.
The invention also provides the use of the above porous silica or catalyst support in the preparation of a catalyst. Preferably, the catalyst is an olefin oxyacetylation catalyst, such as an isobutylene oxyacetylation catalyst.
The invention also provides a catalyst containing the porous silica.
According to an embodiment of the invention, the catalyst is an olefin oxoacetylation catalyst, such as a catalyst for the oxoacetylation of isobutylene.
The invention has the beneficial effects that:
the invention provides a preparation method of porous silicon dioxide, which adopts cheap, easily-obtained and environment-friendly carbohydrate as an auxiliary agent, the carbohydrate is dehydrated and carbonized under the action of concentrated sulfuric acid to obtain a carbon-containing precursor, and a carbonized product occupies a silicon dioxide pore channel, so that the silicon sol can be prevented from entering the pore channel, a certain supporting effect is achieved, and the collapse of the pore channel caused by compression during extrusion forming is reduced; burning the carbonized product after roasting with CO2The form is discharged from the pore channels to obtain silica with high specific surface area, large pore volume and porosity (shown as b in figure 1), which is suitable for catalysisA carrier, in particular an olefin oxyacetylation catalyst.
The invention solves the problems that in the prior art (a in figure 1), porous silica powder is used as a raw material, liquid containing silica sol is used as a binder, and in the process of preparing a silica carrier by extrusion forming and other methods, the silica sol with fluidity enters a silica gel pore channel in the process of mixing materials, and silica gel particles formed after extrusion forming and roasting are attached to the silica gel pore channel, so that the surface area and the pore volume of the carrier can be greatly reduced, the pore channel structure of the silica gel powder collapses under higher pressure in the extrusion strip process, and the conversion rate and the stability of an isobutylene oxyacetylation catalyst prepared from the silica carrier are lower.
The porous silica with larger surface area and pore volume provided by the invention is used as a catalyst carrier, for example, the porous silica has better catalytic performance when used as an isobutylene oxyacetylation catalyst carrier, and has the advantages of high conversion rate and stability.
Drawings
FIG. 1 shows a route (a) for preparing porous silica according to the prior art and a route (b) for preparing porous silica according to the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
1.1 preparation of pore protected silica
10g of sucrose was dissolved in 500ml of water, and 5ml of concentrated sulfuric acid was added. Then, 1000 mesh silicon dioxide powder is immersed into the acid solution of sucrose in equal volume and stirred uniformly. The silica powder used had a specific surface area of 339m2Pore volume was 1.18 ml/g. Impregnating the impregnated productAnd placing the silicon oxide powder in an oven at 80 ℃ for 6h for drying, and then heating to 160 ℃ for heat preservation for 6h for dehydration and carbonization. The carbonized silicon dioxide powder is washed by deionized water until the silicon dioxide powder is neutral and then is dried in an oven at 120 ℃ for 24 hours.
1.2 preparation of the silica support
After the silicon dioxide powder, flour and field fine powder after carbonization are mixed evenly, 30 wt% of silica sol is dissolved in 10 wt% of nitric acid aqueous solution, and the nitric acid aqueous solution of the silica sol is sprayed evenly in the silicon dioxide powder after carbonization to be mixed into a plastic shape. The mass ratio of the silicon dioxide powder to the flour to the field fine powder to the silica sol is 120:18:3: 143. Then, the silica powder was extruded into a bar-like body having a cross-sectional diameter of 2.0mm by a bar-extruding machine at 50 rpm, and dried in an oven at 120 ℃ to obtain a molded article. Placing 20g of formed product in a tube furnace, introducing nitrogen into the tube furnace at the flow rate of 200ml/min, heating to 350 ℃ at the speed of 2 ℃/min, introducing oxygen into the tube furnace at the speed of 2ml/min under the condition of keeping the flow rate of nitrogen, keeping the temperature for 300min, heating to 600 ℃ at the heating rate of 2 ℃/min, and roasting until no CO is detected in tail gas2And after the roasting is finished, obtaining the porous silicon dioxide.
The physical properties of the porous silica samples were as follows: specific surface area: 210m2Per g, pore volume: 1.02 ml/g.
1.3 preparation of the catalyst
A catalyst was prepared by using the porous silica successfully prepared in example 1.2 as a carrier and Na2SiO3·9H2Dissolving O in deionized water, soaking in the silica carrier in the same volume, standing for 1h, and drying at 120 deg.C for 24 h; then 0.92g of Na is added2PdCl4、0.15g CuCl2·2H2Dissolving O and 0.5g of glycol in deionized water, uniformly soaking the mixture on the silicon dioxide carrier, standing for 24 hours, and drying at 110 ℃ for 12 hours to obtain a catalyst precursor; putting the catalyst precursor into a muffle furnace, raising the temperature to 550 ℃ by a program, and roasting for 5 hours; reducing the roasted precursor by hydrazine hydrate, washing and drying for 24h at 110 ℃; will CH3Dissolving COOK in deionized water, soaking on the reduced catalyst precursor, standing for 1 hr at 110 deg.CDrying for 12h, and vacuum drying at 130 ℃ for 6h to obtain the catalyst.
1.4 evaluation of catalyst Performance
The catalyst prepared in step 1.3 is used for the isobutylene oxyacetylation reaction. A fixed bed reactor was used as the evaluation apparatus. Filling 15g of the catalyst obtained in the step 1.3 into a reaction tube, slowly introducing nitrogen into the system until the pressure in the tube reaches 1.6MPa, setting the flow rate of the nitrogen at 380ml/min, setting the temperatures of a gasification chamber and a heat preservation box at 150 ℃, and carrying out temperature programmed heating on a heating furnace at the heating rate of 5 ℃/min, when the temperature of the reaction tube reaches 150 ℃, introducing reaction raw materials of isobutene, acetic acid and oxygen, wherein the flow rates of reactants are respectively 0.61ml/min, 0.12ml/min and 22 ml/min. The product was analyzed by gas chromatography and the conversion of acetic acid and selectivity of monoester were calculated.
The catalyst has 60% conversion rate of acetic acid and 83% selectivity of monoester, which is evaluated by a fixed bed reactor.
Comparative example 1
The pre-impregnated silica powder used in step 1.1 of example 1 was used in place of the carbonized silica powder as a raw material for molding, and the other steps of the support preparation, the step of the isobutylene oxyacetylation catalyst preparation and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 1.
The physical properties of the prepared silica samples were as follows: specific surface area: 166m2Per g, pore volume: 0.96 ml/g.
The catalyst using the catalyst as a catalyst carrier has a conversion rate of acetic acid of 53% and a monoester selectivity of 81% as evaluated by a fixed bed reactor.
Example 2
15g of sucrose was dissolved in 500ml of water, and 8ml of concentrated sulfuric acid was added. Then, 1000 mesh silicon dioxide powder is immersed into the acid solution of sucrose in equal volume and stirred uniformly. The specific surface area of the silica powder was 339m2Pore volume was 1.18 ml/g. And (3) placing the impregnated silicon dioxide powder in an oven at 80 ℃ for 6h for drying, and then heating to 160 ℃ and placing for 12h for dehydration and carbonization. The carbonized silicon dioxide powder needs to be deionizedWashing with water until it is neutral, and drying in an oven at 120 deg.C for 24 hr.
The procedure of carrier formation and calcination was the same as in example 1 to obtain porous silica.
The procedure for the preparation of the isobutylene oxyacetylation catalyst and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 1.
The physical properties of the porous silica samples were as follows: specific surface area: 214m2Per g, pore volume: 1.08 ml/g.
The catalyst had an acetic acid conversion of 61% and monoester selectivity of 82% as evaluated in a fixed bed reactor.
Comparative example 2
The silicon dioxide powder after carbonization was replaced with the silicon dioxide powder before impregnation used in example 2 as a raw material for molding, and the other steps of the support preparation, the step of preparing the isobutylene oxyacetylation catalyst, and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 2.
The physical properties of the prepared silica samples were as follows: specific surface area: 165m2Per g, pore volume: 0.97 ml/g.
The catalyst using the catalyst as a catalyst carrier has a conversion rate of acetic acid of 51% and a monoester selectivity of 81% as evaluated by a fixed bed reactor.
Example 3
25g of sucrose was dissolved in 500ml of water, and 10ml of concentrated sulfuric acid was added. Then, 1000 mesh silicon dioxide powder is immersed into the acid solution of sucrose in equal volume and stirred uniformly. The specific surface area of the silica powder was 339m2Pore volume was 1.18 ml/g. And (3) placing the impregnated silicon dioxide powder in an oven at 80 ℃ for 6h for drying, and then heating to 160 ℃ and placing for 24h for dehydration and carbonization. The carbonized silicon dioxide powder is washed by deionized water until the silicon dioxide powder is neutral and then is dried in an oven at 120 ℃ for 24 hours.
And the procedure of carrier molding and calcination was the same as in example 1, to obtain porous silica.
The procedure for the preparation of the isobutylene oxyacetylation catalyst and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 1.
The physical properties of the porous silica samples were as follows: specific surface area: 215m2Per g, pore volume: 1.10 ml/g.
The catalyst has an acetic acid conversion of 62% and monoester selectivity of 82% as evaluated by a fixed bed reactor.
Comparative example 3
The silicon dioxide powder after carbonization was replaced with the silicon dioxide powder before impregnation used in example 3 as a raw material for molding, and the other steps of the support preparation, the step of preparing the isobutylene oxyacetylation catalyst, and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 3.
The physical properties of the prepared silica samples were as follows: specific surface area: 166m2Per g, pore volume: 0.96 ml/g.
The catalyst using the catalyst as a catalyst carrier has a conversion rate of acetic acid of 54% and a monoester selectivity of 80% as evaluated by a fixed bed reactor.
Example 4
50g of sucrose was dissolved in 500ml of water, and 15ml of concentrated sulfuric acid was added. Then, 1000 mesh silicon dioxide powder is immersed into the acid solution of sucrose in equal volume and stirred uniformly. The specific surface area of the silica powder was 339m2Pore volume was 1.18 ml/g. And (3) placing the impregnated silicon dioxide powder in an oven at 80 ℃ for 6h for drying, and then heating to 160 ℃ and placing for 24h for dehydration and carbonization.
And the procedure of carrier molding and calcination was the same as in example 1, to obtain porous silica.
The procedure for the preparation of the isobutylene oxyacetylation catalyst and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 1.
The physical properties of the porous silica samples were as follows: specific surface area: 214m2Per g, pore volume: 1.14 ml/g.
The catalyst has an acetic acid conversion of 62% and monoester selectivity of 82% as evaluated by a fixed bed reactor.
Comparative example 4
The porous silica before impregnation used in example 4 was used in place of the carbonized silica powder as a raw material for molding, and the other steps of the support preparation, the step of preparing the isobutylene oxyacetylation catalyst, and the evaluation of the isobutylene oxyacetylation catalyst were the same as those of example 4.
The physical properties of the prepared silica samples were as follows: specific surface area: 165m2Per g, pore volume: 0.97 ml/g.
The catalyst using the catalyst as a catalyst carrier has a conversion rate of acetic acid of 53% and a monoester selectivity of 80% as evaluated by a fixed bed reactor.
Example 5
80g of sucrose was dissolved in 500ml of water, and 20ml of concentrated sulfuric acid was added. Then, 1000 mesh silicon dioxide powder is immersed into the acid solution of sucrose in equal volume and stirred uniformly. The specific surface area of the silica powder was 339m2Pore volume was 1.18 ml/g. And (3) placing the impregnated silicon dioxide powder in an oven at 80 ℃ for 6h for drying, then heating to 160 ℃ and placing for 36h for dehydration and carbonization.
And the procedure of carrier molding and calcination was the same as in example 1, to obtain porous silica.
The procedure for the preparation of the isobutylene oxyacetylation catalyst and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 1.
The physical properties of the porous silica samples were as follows: specific surface area: 145m2Per g, pore volume: 0.89 ml/g.
The catalyst has a conversion rate of 51% for acetic acid and a selectivity of 78% for monoester, as evaluated by a fixed bed reactor.
Indicating that too much sucrose is detrimental to a further increase in the specific surface area and pore volume of the silica support. And is also not beneficial to the exertion of the catalytic performance of the catalyst.
Comparative example 5
The porous silica before impregnation used in example 5 was used in place of the carbonized silica powder as a raw material for molding, and the other steps of the support preparation, the step of preparing the isobutylene oxyacetylation catalyst, and the evaluation of the isobutylene oxyacetylation catalyst were the same as those of example 5.
The physical properties of the prepared silica samples were as follows: specific surface area: 165m2Per g, pore volume: 0.97 ml/g.
The catalyst using the catalyst as a catalyst carrier has a conversion rate of acetic acid of 53% and a monoester selectivity of 80% as evaluated by a fixed bed reactor.
Example 6
3g of sucrose was dissolved in 500ml of water, and 3ml of concentrated sulfuric acid was added. Then, 1000 mesh silicon dioxide powder is immersed into the acid solution of sucrose in equal volume and stirred uniformly. The specific surface area of the silicon dioxide is 339m2Pore volume was 1.18 ml/g. And (3) placing the impregnated silicon dioxide powder in an oven at 80 ℃ for 6h for drying, and then heating to 160 ℃ and placing for 3h for dehydration and carbonization.
And the procedure of carrier molding and firing was the same as in example 1.
The procedure for the preparation of the isobutylene oxyacetylation catalyst and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 1.
The physical properties of the carrier samples were as follows: specific surface area: 169m2Per g, pore volume: 0.97 ml/g.
The catalyst has a conversion rate of 56% for acetic acid and a selectivity of 80% for monoester, as evaluated by a fixed bed reactor.
It is shown that too little sucrose, while not yielding the parameters and catalyst performance of the porous silicas of examples 1-4, is still slightly advantageous compared to comparative example 6.
Comparative example 6
The porous silica before impregnation used in example 6 was used in place of the carbonized silica powder as a raw material for molding, and the other steps of the support preparation, the step of preparing the isobutylene oxyacetylation catalyst, and the evaluation of the isobutylene oxyacetylation catalyst were the same as those of example 6.
The physical properties of the prepared silica samples were as follows: specific surface area: 166m2Per g, pore volume: 0.96 ml/g.
The catalyst using the catalyst as a catalyst carrier has a conversion rate of acetic acid of 53% and a monoester selectivity of 80% as evaluated by a fixed bed reactor.
Example 7
10g of glucose are dissolved in 500ml of water, and 5ml of concentrated sulfuric acid are added. The silica raw material, the carrier preparation process, the preparation procedure of the isobutylene oxyacetylation catalyst and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 1.
The physical properties of the porous silica samples prepared were as follows: specific surface area: 209m2Per g, pore volume: 1.08 ml/g.
The catalyst using the catalyst as a catalyst carrier has a conversion rate of acetic acid of 61% and a monoester selectivity of 80% as evaluated by a fixed bed reactor.
Comparative example 7
The pre-impregnated silica powder used in example 7 was used in place of the carbonized silica powder as a raw material for molding, and the other steps of the support preparation, the step of preparing the isobutylene oxyacetylation catalyst and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 7.
The physical properties of the prepared silica samples were as follows: specific surface area: 165m2Per g, pore volume: 0.95 ml/g.
The catalyst using the catalyst as a catalyst carrier has a conversion rate of acetic acid of 53% and a monoester selectivity of 79% as evaluated by a fixed bed reactor.
Example 8
10g of fructose are dissolved in 500ml of water, and 5ml of concentrated sulfuric acid are added. The silica raw material, the carrier preparation process, the preparation procedure of the isobutylene oxyacetylation catalyst and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 1.
The physical properties of the porous silica samples prepared were as follows: specific surface area: 209m2Per g, pore volume: 1.06 ml/g.
The catalyst using the catalyst as a catalyst carrier has the conversion rate of acetic acid of 62 percent and the selectivity of monoester of 81 percent through evaluation of a fixed bed reactor.
Comparative example 8
The pre-impregnated silica powder used in example 8 was used in place of the carbonized silica powder as a raw material for molding, and the other steps of the support preparation, the step of preparing the isobutylene oxyacetylation catalyst and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 8.
The physical properties of the prepared silica samples were as follows: specific surface area: 164m2Per g, pore volume: 0.96 ml/g.
The catalyst using the catalyst as a catalyst carrier has the conversion rate of acetic acid of 52 percent and the selectivity of monoester of 80 percent through evaluation of a fixed bed reactor.
Example 9
The carbonization process of the silica powder was the same as in step 1.1 of example 1.
The carbonized silicon dioxide powder is uniformly mixed with flour, 30 wt% of silica sol is dissolved in 10 wt% of nitric acid aqueous solution, and the nitric acid aqueous solution of the silica sol is uniformly sprayed in the carbonized silicon dioxide powder to be mixed into a plastic shape. The mass ratio of the carbonized silica powder, flour and silica sol, and the molding process and the process of carrier calcination were the same as in example 1, to obtain porous silica.
The physical properties of the porous silica samples were as follows: specific surface area: 209m2Per g, pore volume: 1.03 ml/g.
The procedure for the preparation of the isobutylene oxyacetylation catalyst and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 1.
The catalyst had an acetic acid conversion of 61% and monoester selectivity of 82% as evaluated in a fixed bed reactor.
Comparative example 9
The silicon dioxide powder after carbonization was replaced with the silicon dioxide powder before impregnation used in example 9 as a raw material for molding, and the other steps of the support preparation, the step of preparing the isobutylene oxyacetylation catalyst, and the evaluation of the isobutylene oxyacetylation catalyst were the same as in example 9.
Preparation ofThe physical properties of the obtained silica samples were as follows: specific surface area: 167m2Per g, pore volume: 0.96 ml/g.
The catalyst using the catalyst as a catalyst carrier has a conversion rate of acetic acid of 53% and a monoester selectivity of 80% as evaluated by a fixed bed reactor.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing porous silica, characterized in that the method comprises the following steps:
(1) firstly, impregnating silicon dioxide powder with an acid solution of a carbohydrate, and dehydrating and carbonizing the impregnated matter to obtain silicon dioxide with a protected pore channel, namely a carbon-containing precursor;
(2) and (2) roasting the carbon-containing precursor in the step (1) to obtain the porous silicon dioxide.
2. The method according to claim 1, wherein the saccharide compound is selected from one, two or more of monosaccharides, disaccharides and polysaccharides, preferably from one, two or more of glucose, fructose, sucrose, soluble starch and soluble cellulose.
3. The production method according to claim 1 or 2, wherein in the step (1), the acid solution of the saccharide compound is a sulfuric acid solution of the saccharide compound.
Preferably, concentrated sulfuric acid is added to the aqueous solution of the saccharide compound to obtain a sulfuric acid solution of the saccharide compound.
Preferably, the volume ratio of the concentrated sulfuric acid to the aqueous solution of the saccharide compound is 1 (10-150), more preferably 1 (20-120).
Preferably, the aqueous solution of the saccharide compound has a concentration of 5-150mg/ml, preferably 10-120 mg/ml.
Preferably, in the step (1), the silica powder is a porous silica powder.
Preferably, in the step (1), the impregnation of the silica powder is carried out by an equal volume impregnation method.
Preferably, in the step (1), the impregnated material is further subjected to a drying treatment before the dehydration carbonization.
Preferably, in the step (1), the temperature of the dehydration carbonization is 150-200 ℃; preferably, the time for dehydrating and carbonizing is 6-24 h.
Preferably, the pore channels of the pore channel-protected silica contain a carbonization product of the carbohydrate compound under the action of an acid.
4. The production method according to any one of claims 1 to 3, wherein in the step (2), a molding step is further included before the firing step.
Preferably, the carbon-containing precursor is washed and dried before shaping.
Preferably, in the step (2), at least one of flour, field meal and silica sol acid solution is further introduced into the carbon-containing precursor in the forming step.
Preferably, in the step (2), the carbon-containing precursor is mixed with at least one of flour, field powder and a silica sol acid solution, and then the mixture is formed and roasted to obtain the porous silica.
5. The method according to claim 4, wherein in step (2), the mass ratio of the carbon-containing precursor, the flour, the refined flour and the silica sol is (100-.
Preferably, in the step (2), the silica sol acid solution is a nitric acid aqueous solution of silica sol.
Preferably, in the step (2), the mass fraction of the silica sol in the silica sol acid solution is 5-80%.
Preferably, in the step (2), the molding is extrusion molding.
Preferably, in the step (2), the molded product is further dried before being fired.
Preferably, in the step (2), the roasting comprises roasting the formed product in an inert atmosphere and an oxygen-containing atmosphere, preferably until the tail gas does not contain CO2. For example, the temperature of the calcination is 300-800 ℃. For example, the calcination time is 2 to 24 hours. For example, the temperature increase rate of the calcination is 1 to 5 ℃/min.
Preferably, the firing comprises two stages: inert atmosphere roasting and oxygen-containing atmosphere roasting. For example, the shaped article is first calcined in an inert atmosphere, then oxygen-containing gas is introduced into the calcined article to form an oxygen-containing atmosphere, and the calcined article is heated until the tail gas does not contain CO2。
6. Porous silica prepared by the process of any one of claims 1 to 5.
Preferably, the porous silica has a specific surface area of not less than 200m2G, e.g. not less than 205m2G, preferably at 210-2Between/g.
Preferably, the porous silica has a pore volume of not less than 1.0ml/g, for example not less than 1.02ml/g, preferably 1.05 to 1.25 ml/g.
Preferably, the porous silica does not contain carbon therein.
7. Use of the porous silica of claim 6 as a catalyst or catalyst support.
8. A catalyst carrier comprising the porous silica according to claim 6.
9. Use of the porous silica of claim 6 or the catalyst support of claim 8 in the preparation of a catalyst.
Preferably, the catalyst is an olefin oxyacetylation catalyst, such as an isobutylene oxyacetylation catalyst.
10. A catalyst comprising the porous silica according to claim 6 or the catalyst carrier according to claim 8.
Preferably, the catalyst is an olefin oxyacetylation catalyst, such as a catalyst for the oxyacetylation of isobutylene.
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