CN112403455A - Strip-shaped porous silicon dioxide carrier with three-dimensional order, preparation method thereof, catalyst and application - Google Patents
Strip-shaped porous silicon dioxide carrier with three-dimensional order, preparation method thereof, catalyst and application Download PDFInfo
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- CN112403455A CN112403455A CN201910785724.4A CN201910785724A CN112403455A CN 112403455 A CN112403455 A CN 112403455A CN 201910785724 A CN201910785724 A CN 201910785724A CN 112403455 A CN112403455 A CN 112403455A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 227
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 117
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910021426 porous silicon Inorganic materials 0.000 title description 9
- 239000000463 material Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 48
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 239000011148 porous material Substances 0.000 claims abstract description 28
- 229920002472 Starch Polymers 0.000 claims abstract description 24
- 235000019698 starch Nutrition 0.000 claims abstract description 24
- 239000008107 starch Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 21
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940039748 oxalate Drugs 0.000 claims abstract description 16
- 238000004898 kneading Methods 0.000 claims abstract description 14
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical group [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229940039790 sodium oxalate Drugs 0.000 claims abstract description 14
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 24
- 241000219782 Sesbania Species 0.000 claims description 17
- 239000004033 plastic Substances 0.000 claims description 17
- 238000001125 extrusion Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 238000005691 oxidative coupling reaction Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 abstract description 7
- 244000275012 Sesbania cannabina Species 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920000034 Plastomer Polymers 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910020350 Na2WO4 Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- -1 silicon ions Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to the technical field of porous materials, and discloses a strip-shaped macroporous silicon dioxide carrier with three-dimensional order, a preparation method thereof, a catalyst and application thereof. Wherein, the method comprises the following steps: (1) mixing silicon dioxide with starch and/or sesbania powder to obtain a material A; (2) mixing oxalate, silica sol and water to obtain a material B; (3) kneading and extruding the material A and the material B into strips; wherein, the oxalate is sodium oxalate and/or potassium oxalate. The method has simple process flow, and the viscosity of the system is utilized for one-step molding, so that the forming process and the molding process of the porous structure are combined into one, and the silicon dioxide porous material is rapidly synthesized in one step; the obtained carrier has a three-dimensional ordered macroporous structure, the pore structures are mutually communicated, the porosity is high, and the pore diameter is uniform and regular, so that the dispersibility of the active component is improved.
Description
Technical Field
The invention relates to the technical field of porous materials, in particular to a strip-shaped macroporous silicon dioxide carrier with three-dimensional order, a catalyst, a preparation method and application thereof.
Background
Porous materials have been widely used in high efficiency adsorbents and catalysts due to their porous form, which presents the characteristic of large surface area. The porous silicon dioxide material has the advantages of large specific surface area, good chemical stability, high temperature resistance, good insulativity and the like, so that the porous silicon dioxide material has better application prospect.
Based on the wide application prospect of the porous silicon dioxide material, the preparation method of the porous silicon dioxide material is widely researched and developed.
CN105967723A discloses a method for preparing a porous silica material, which is characterized in that tetraethoxysilane is used as a raw material, absolute ethyl alcohol and deionized water are used as solvents, a precursor solution is prepared by using a dispersing agent, and the porous silica material is obtained through processes of gelation, drying, dry pressing and heat treatment.
The porous silicon dioxide material is prepared by taking tetraethoxysilane as a raw material, taking absolute ethyl alcohol and deionized water as solvents, utilizing a dispersing agent to uniformly disperse silicon ions, utilizing proper concentration of the dispersing agent to synthesize dry gel which can be directly formed by dry pressing, and carrying out heat treatment on the block material after the dry pressing.
CN103086381A discloses a method for preparing silica microspheres, which comprises mixing a template structure with fully vulcanized silicone rubber emulsion, spray-drying, and burning to prepare porous silica microspheres, wherein the template structure is the fully vulcanized rubber emulsion excluding the fully vulcanized silicone rubber emulsion, the fully vulcanized rubber emulsion is prepared by irradiation, and the average particle size of rubber particles in the fully vulcanized rubber emulsion is less than 500 nm; the fully vulcanized silicone rubber emulsion is prepared by irradiating organic silicon polymer or copolymer emulsion, and the average particle size of particles in the fully vulcanized silicone rubber emulsion is less than 1000 nanometers; the solid content in the template structure accounts for 2-50% of all the solid contents in the mixed emulsion, the burning temperature is 250-1200 ℃, and the burning time is 10-600 minutes.
Although the above method can produce a porous silica material, it is difficult to realize high-efficiency mass production. In addition, most of the traditional silica porous materials are not formed into powder, so that the use is inconvenient.
Therefore, the research and development of the strip-shaped macroporous silicon dioxide carrier with three-dimensional order and the preparation method thereof have important significance.
Disclosure of Invention
The invention aims to overcome the defects of low strength and limited application of a powdery or granular silicon dioxide carrier in the prior art and the problem of complex process of a porous silicon dioxide strip agent prepared by the prior art, and provides a strip-shaped silicon dioxide carrier with three-dimensional ordered macropores, a preparation method, a catalyst and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a strip-shaped macroporous silica support having a three-dimensional order, wherein the method comprises:
(1) mixing silicon dioxide with starch and/or sesbania powder to obtain a material A;
(2) mixing oxalate, silica sol and water to obtain a material B;
(3) mixing and kneading the material A and the material B into a plastic body, extruding the plastic body into strips, and drying and roasting the strips;
wherein the oxalate is sodium oxalate and/or potassium oxalate.
In a second aspect, the invention provides a strip-shaped porous silica carrier with three-dimensional order, which is prepared by the method.
The third aspect of the present invention provides a supported catalyst, wherein the supported catalyst comprises a strip-shaped silica carrier having three-dimensionally ordered macropores prepared by the aforementioned method or the aforementioned strip-shaped silica carrier having three-dimensionally ordered macropores and active components Mn, W and Na supported on the strip-shaped silica carrier having three-dimensionally ordered macropores.
The fourth aspect of the invention provides the use of the supported catalyst in the oxidative coupling reaction of methane.
By adopting the technical scheme, the method provided by the invention has the advantages that the viscosity of the system is utilized for one-step forming, so that the forming process and the forming process of the porous structure are combined into one, and the silicon dioxide porous material is rapidly synthesized in one step; the obtained carrier has a three-dimensional ordered macroporous structure, the pore structures are mutually communicated, the porosity is high, and the pore diameter is uniform and regular, so that the dispersibility of the active component is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention without limiting the invention.
Fig. 1 is an SEM image of a silica support having a three-dimensional ordered macroporous shape in a bar shape prepared according to example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a strip-shaped macroporous silica carrier with three-dimensional order, wherein the method comprises the following steps:
(1) mixing silicon dioxide with starch and/or sesbania powder to obtain a material A;
(2) mixing oxalate, silica sol and water to obtain a material B;
(3) mixing and kneading the material A and the material B into a plastic body, extruding the plastic body into strips, and drying and roasting the strips;
wherein the oxalate is sodium oxalate and/or potassium oxalate.
In the present invention, the average particle diameter is measured by a laser particle size distribution meter, and the specific surface area and the pore volume are measured by a nitrogen adsorption method.
According to the invention, the average particle size of the silicon dioxide can be 100-150 meshes, and the average particle size of the silicon dioxide is controlled within the range, so that the material can be better molded; preferably, the average particle size of the silica is 110-140 mesh, which is more effective. In addition, in the present invention, silica can be commercially available, for example, from Qingdao oceanic chemical plants, and silica is an amorphous spherical particle.
According to the invention, the starch can be soluble starch, and the sesbania powder can be soluble sesbania powder, and in the invention, in the step (1), the total using amount of the starch and/or the sesbania powder can be 11-20 parts by weight, preferably 11-15 parts by weight based on 100 parts by weight of the silicon dioxide. In addition, in the present invention, both starch and sesbania powder are commercially available, for example, starch is available from national drug group chemical agents, ltd, and starch is white powder; sesbania powder can be purchased from yunjing biotechnology limited, lake north, and sesbania powder is a loose powder.
According to the present invention, when starch and sesbania powder are used, wherein the ratio of starch and sesbania powder is not particularly limited as long as the total amount of starch and sesbania powder used is 11 to 20 parts by weight with respect to 100 parts by weight of silica.
According to the invention, the silicon dioxide and the starch and/or the sesbania powder are mixed to obtain the material A, wherein the mixing process comprises one or more of grinding mixing, sieving mixing, stirring mixing and the like, and the mixing is preferably carried out under stirring conditions, wherein the stirring conditions are not particularly limited, and can be carried out under stirring conditions of 50-150r/min, for example.
According to the invention, the oxalate may be sodium oxalate and/or potassium oxalate, preferably sodium oxalate; in the step (2), the oxalate may be used in an amount of 5 to 12 parts by weight based on 100 parts by weight of silica, and the silica sol may be used in an amount of 10 to 20 parts by weight based on silica; according to the invention, the use amounts of the starch and/or the sesbania powder, the oxalate, the silica sol and the water are controlled within the above ranges, so that the extruded cylindrical strip-shaped plastic body is suitable for drying and roasting treatment, and a strip-shaped silicon dioxide carrier with better specific surface area, pore structure and strength is formed; in the present invention, preferably, the oxalate is used in an amount of 5 to 10 parts by weight based on 100 parts by weight of silica, and the silica sol is used in an amount of 10 to 15 parts by weight based on silica, so that the extruded cylindrical strip-shaped plastic body is more suitable for drying and baking treatment, and the strip-shaped silica carrier having a better specific surface area, pore structure and strength can be more favorably formed.
Further, in the process of mixing the oxalate, the silica sol and water to obtain the material B, the amount of water used is not particularly limited as long as the obtained material B can be mixed with the material A and kneaded into a plastomer, and for example, the amount of water used may be 40 to 60 parts by weight, preferably 50 to 60 parts by weight, based on 100 parts by weight of the silica; the water is not particularly limited, and is preferably deionized water.
According to the invention, the silica sol may have a silica content of 25 to 30 wt% in mass. In the present invention, the silica sol is used as a forming aid, and in addition, the silica sol can be commercially available, for example, from Qingdao ocean factories, and the average particle diameter of the silica sol is 10 to 20 nm.
According to the invention, in step (3), the material a and the material B are mixed and kneaded into a plastic body; the plastomer in the viscosity range is more beneficial to extrusion into strips, so that the extruded cylindrical strip-shaped plastomer is more suitable for drying and roasting treatment, and the strip-shaped silicon dioxide carrier with better specific surface area, pore structure and strength is more favorably formed. Preferably, the mixing is performed under stirring conditions, wherein the stirring conditions are not particularly limited, and may be performed under stirring conditions of 50 to 150r/min, for example.
According to the invention, the extrusion into strands is carried out in a strand extruder, for example, the plastic body can be extruded into strands by means of a stainless steel kneading strand extruder, wherein the strand extruder can be a type-F-26 twin-screw strand extruder from the manufacturing company of the general technical industries of the university of south China. The extrusion rate of the strip extruder can be 150-450r/min, and the temperature can be 10-100 ℃, so that the strip extruder is more favorable for extruding strips. In addition, the prepared wet molded plastomer as described above can be kneaded in a bar extruder for 10 minutes to obtain a wet elongated molded catalyst of a desired shape. In addition, depending on the differences in the size of the extrusion orifice in the rod extruder, shaped silicas having a diameter of 1.5 to 6mm, preferably 2 to 5mm, can be produced. The extrusion length is preferably 50-300mm, which facilitates drying and firing.
According to the invention, then, the extruded cylindrical strip-shaped plastic body is subjected to drying treatment and roasting treatment, wherein the drying temperature is 80-150 ℃, and the drying time is 4-10 h; preferably, the wet shaped silica obtained is dried beforehand at room temperature for 5 to 12 hours, preferably 6 to 10 hours; then, the dried material is dried again for 4-10 hours at the temperature of 80-150 ℃, so that the effect is better; the drying atmosphere is an inert gas or air atmosphere, preferably air atmosphere.
According to the present invention, the calcination temperature may be 700-900 deg.C, the calcination time may be 6-18 hours, preferably, the calcination time may be 6-15 hours at 750-850 deg.C, the temperature increase rate from room temperature to the set calcination temperature is 4-6 deg.C/min, and the calcination atmosphere may be an inert gas or air atmosphere, preferably, an air atmosphere.
According to the present invention, the inventors of the present invention have unexpectedly found that: mixing silicon dioxide with starch and/or sesbania powder to obtain a material A; mixing oxalate, silica sol and water to obtain a material B; and mixing and kneading the material A and the material B into a plastic body, extruding the plastic body into strips, drying and roasting to obtain the strip-shaped porous silicon dioxide carrier with three-dimensional order. The method utilizes the viscosity of the system to form at one time, so that the forming process and the forming process of the porous structure are combined into one, and the silicon dioxide porous material is quickly synthesized in one step; the obtained carrier has a three-dimensional ordered macroporous structure, the pore channel structures are mutually communicated, the porosity is high, the pore diameter is uniform and regular, and the dispersibility of the active components is improved
In a second aspect, the invention provides a strip-shaped porous silica carrier with three-dimensional order, which is prepared by the method.
According to the invention, the length of the carrier is between 5 and 40 cm, preferably between 5 and 30cm, the specific surface area is 335-350 square meters/g, preferably 339-350 square meters/g, the pore volume can be 0.25-0.30 ml/g, the pore diameter is uniform and regular, and the average pore diameter is 700-900 nm.
According to the invention, the strip-shaped porous silica support with three-dimensional order contains silica and oxides of sodium and/or potassium, and the silica content is 90 to 98.5 wt.%, preferably 94.2 to 98 wt.%, and the sodium and/or potassium component content, calculated as oxides, is 1.5 to 6 wt.%, preferably 2 to 5.8 wt.%, based on the total weight of the strip-shaped porous silica support with three-dimensional order.
According to the invention, the sum of the content of silica and the content of the sodium and/or potassium components, calculated as oxides, in the support is one hundred percent.
The third aspect of the present invention provides a supported catalyst, wherein the supported catalyst comprises a strip-shaped silica carrier having three-dimensionally ordered macropores prepared by the aforementioned method or the aforementioned strip-shaped silica carrier having three-dimensionally ordered macropores and active components Mn, W and Na supported on the strip-shaped silica carrier having three-dimensionally ordered macropores.
According to the present invention, the method for preparing the supported catalyst comprises supporting the active components Mn, W and Na on the silica support having a three-dimensionally ordered macroporous shape in a strip form prepared by the aforementioned method or the silica support having a three-dimensionally ordered macroporous shape in a strip form, wherein, in the present invention, only the active components Mn, W and Na may be supported on the support according to various methods conventionally used in the art, and for example, any one of an impregnation method, an extrusion-into-strip method, a ball-milling method, a precipitation method and a microwave method, preferably an impregnation method, may be employed. In the present invention, the carrier prepared by the present invention is mixed with Na-containing solution2WO4And Mn (NO)3)2The corresponding supported catalyst is prepared by impregnation.
The fourth aspect of the invention provides an application of the supported catalyst in the oxidative coupling reaction of methane.
According to the invention, the conditions of the reaction include: the reaction temperature is 830-: (1.5-2), the reaction gas hourly space velocity in terms of methane and oxygen is 9000ml/gh, and the reaction is carried out for 1-1.5 hours.
The present invention will be described in detail below by way of examples.
Scanning electron microscopy analysis was performed on a scanning electron microscope, model XL-30, available from FEI, USA; the pore structure parameter analysis was performed on a nitrogen desorption apparatus model Autosorb-1 available from corna, usa, wherein the sample was degassed at 200 ℃ for 4 hours before the test was performed.
Example 1
This example illustrates a silica support in the form of a strip having three-dimensionally ordered macropores prepared by the method of the present invention.
(1) Fully mixing 100g of powdery silicon dioxide (100 meshes) and 13g of starch to obtain a material A;
(2) fully mixing 20g of silica sol (calculated by silica) with the silica content of 30%, 5g of sodium oxalate and 40g of water to obtain a material B;
(3) fully mixing the materials A and B under the condition of continuous stirring with the stirring speed of 150r/min and kneading the materials A and B into a wet plastic body; extruding the long-strip solid cylinder through a pore plate with the diameter of 1.5mm in a stainless steel kneading and extruding machine under the condition that the extrusion rate is 250 r/min;
(4) drying at room temperature for 10 hours, drying at 150 ℃ for 4 hours, then roasting at 750 ℃ for 16 hours, wherein the heating rate from room temperature to the set roasting temperature is 4 ℃/minute, the roasting atmosphere is air atmosphere, and the molding aid starch is roasted and removed.
As a result, a high-strength porous silica support in the form of a strip was obtained, the performance parameters of which are shown in Table 1.
In addition, fig. 1 is an SEM image of a silica support having a three-dimensional ordered macroporous shape in a stripe shape prepared according to example 1 of the present invention. As can be seen from FIG. 1, a high-strength porous silica carrier in the form of a strip can be obtained by the extrusion-striping method, and the length of the carrier is 5 to 30cm, and the surface of the carrier is smooth, uniform in thickness, and regular in shape.
Example 2
This example illustrates a silica support in the form of a strip having three-dimensionally ordered macropores prepared by the method of the present invention.
(1) Fully mixing 100g of powdery silicon dioxide (110 meshes) and 11g of starch to obtain a material A;
(2) fully mixing 10g of silica sol (calculated by silica) with the silica content of 25%, 12g of sodium oxalate and 59g of water to obtain a material B;
(3) fully mixing the materials A and B under the condition of continuous stirring with the stirring speed of 50r/min and kneading the materials A and B into a wet plastic body; extruding the mixture through a pore plate with the diameter of phi 5mm in a stainless steel kneading and extruding machine at the extrusion rate of 450r/min to form a long-strip solid cylinder;
(4) drying at room temperature for 10 hours, drying at 80 ℃ for 10 hours, then roasting at 850 ℃ for 10 hours, wherein the heating rate from room temperature to the set roasting temperature is 5 ℃/minute, the roasting atmosphere is air atmosphere, and the molding aid starch in the molding aid is roasted and removed.
The result is a strip-shaped porous silica carrier with three-dimensional order, which has smooth surface, uniform thickness and regular shape, and the performance parameters are shown in Table 1.
Example 3
This example illustrates a silica support in the form of a strip having three-dimensionally ordered macropores prepared by the method of the present invention.
(1) Fully mixing 100g of powdery silicon dioxide (120 meshes) and 20g of starch to obtain a material A;
(2) fully mixing 15g of silica sol (calculated by silica) with the silica content of 30%, 6g of sodium oxalate and 52g of water to obtain a material B;
(3) fully mixing the materials A and B under the condition of continuous stirring with the stirring speed of 70r/min and kneading the materials A and B into a wet plastic body; extruding the long-strip solid cylinder through a pore plate with the diameter of 4mm in a stainless steel kneading and extruding machine under the condition that the extrusion rate is 150 r/min;
(4) drying at room temperature for 6 hours, drying at 120 ℃ for 6 hours, then roasting at 800 ℃ for 10 hours, wherein the heating rate from room temperature to the set roasting temperature is 6 ℃/minute, the roasting atmosphere is air atmosphere, and the forming aid starch in the molding aid is roasted and removed.
The result is a strip-shaped porous silica carrier with three-dimensional order, which has smooth surface, uniform thickness and regular shape, and the performance parameters are shown in Table 1.
Example 4
This example illustrates a silica support in the form of a strip having three-dimensionally ordered macropores prepared by the method of the present invention.
(1) Fully mixing 100g of powdery silicon dioxide (150 meshes) and 15g of sesbania powder to obtain a material A;
(2) fully mixing 15g of silica sol (calculated by silica) with the silica content of 30%, 8g of sodium oxalate and 45g of water to obtain a material B;
(3) fully mixing the materials A and B under the condition of continuous stirring with the stirring speed of 120r/min and kneading the materials A and B into a wet plastic body; extruding the mixture through a pore plate with the diameter of phi 3mm in a stainless steel kneading and extruding machine at the extrusion rate of 320r/min to form a long-strip solid cylinder;
(4) drying at room temperature for 8 hours, drying at 140 ℃ for 4 hours, then roasting at 900 ℃ for 8 hours, wherein the heating rate from room temperature to the set roasting temperature is 4 ℃/minute, the roasting atmosphere is air atmosphere, and the forming aid starch in the molding aid is roasted and removed.
The result is a strip-shaped porous silica carrier with three-dimensional order, which has smooth surface, uniform thickness and regular shape, and the performance parameters are shown in Table 1.
Example 5
This example illustrates a silica support in the form of a strip having three-dimensionally ordered macropores prepared by the method of the present invention.
A silica support was prepared in the same manner as in example 1, except that: sodium oxalate was replaced with potassium oxalate.
The result is a strip-shaped porous silica carrier with three-dimensional order, which has smooth surface, uniform thickness and regular shape, and the performance parameters are shown in Table 1.
Example 6
This example illustrates a silica support in the form of a strip having three-dimensionally ordered macropores prepared by the method of the present invention.
A silica support was prepared in the same manner as in example 2, except that: sodium oxalate was replaced with potassium oxalate.
The result is a strip-shaped porous silica carrier with three-dimensional order, which has smooth surface, uniform thickness and regular shape, and the performance parameters are shown in Table 1.
Comparative example 1
A silica support was prepared in the same manner as in example 1, except that: instead of sodium oxalate, NaOH was used.
As a result, a silica carrier having a three-dimensionally ordered macroporous shape was not obtained, and the performance parameters thereof are shown in Table 1.
Comparative example 2
A silica support having a three-dimensionally ordered macroporous structure in the form of a strand was prepared in the same manner as in example 1 and the catalyst was used in the reaction for producing ethylene by oxidative coupling of methane in the same manner as in example 1, except that: the amount of sodium oxalate used was 30g, and as a result, the three-dimensional ordered macroporous structure of the strip-shaped silica carrier was poor.
TABLE 1
The results in table 1 show that the strip-shaped silica carriers obtained by the carrier preparation method provided by the invention all have regular three-dimensional ordered macroporous structures, the specific surface area of the formed strip-shaped silica with three-dimensional ordered macroporous structures is greatly increased, and in addition, the high-strength three-dimensional ordered macroporous silica carriers have interconnected pore channel structures, so that the porosity is high, the pore diameter is uniform and regular, and the void size and distribution controllability are good; comparative example 1 and comparative example 2 since the extrusion into a bar was not performed under the conditions defined in the present invention, comparative example 1 did not obtain a silica support having a three-dimensionally ordered macroporous structure, and comparative example 2 obtained a three-dimensionally ordered macroporous structure that was inferior.
Examples 7 to 12
Examples 7-12 illustrate the use of the supported catalysts provided by the present invention.
The strip-shaped silica supports having three-dimensionally ordered macropores prepared in examples 1 to 6 were mixed with a solution containing Na2WO4And Mn (NO)3)2The solution is co-impregnated to prepare corresponding supported catalysts FC7-FC12, FC7-FC12 are applied to methane oxidative coupling reaction, and catalysts FC7-FC12 are applied to the reaction of preparing ethylene by methane oxidative coupling, wherein the reaction temperature is 830 ℃, the alkane-oxygen ratio is 3, and the alkane-water ratio is 1: 1.5, the reaction gas hourly space velocity in terms of methane and oxygen was 9000ml/gh, and the evaluation results after 1 hour of reaction are shown in Table 2.
Comparative examples 3 to 4
The silica carrier prepared in comparative examples 1-2 was mixed with Na2WO4And Mn (NO)3)2The supported catalysts DFC3 and DFC4 are prepared by co-dipping the solution, and DFC3 and DFC4 are applied to the methane oxidative coupling reaction, wherein the reaction temperature is 830 ℃, the alkane-oxygen ratio is 3, and the alkane-water ratio is 1: 1.5, the reaction gas hourly space velocity in terms of methane and oxygen was 9000ml/gh, and the evaluation results after 1 hour of reaction are shown in Table 2.
TABLE 2
| Serial number | CH4Conversion rate% | C2Selectivity% |
| Example 7 | 39.45 | 46.96 |
| Example 8 | 39.86 | 46.04 |
| Example 9 | 38.31 | 47.18 |
| Example 10 | 40.08 | 45.92 |
| Example 11 | 38.94 | 47.55 |
| Example 12 | 39.17 | 45.83 |
| Comparative example 3 | 10.59 | 41.58 |
| Comparative example 4 | 35.16 | 20.17 |
From the above results, it can be seen that the formed supported catalyst provided by the present invention has high methane (CH) when used in the oxidative coupling reaction of methane4) Conversion and C2Selectivity and stability at high temperature.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A preparation method of a strip-shaped macroporous silica carrier with three-dimensional order is characterized by comprising the following steps:
(1) mixing silicon dioxide with starch and/or sesbania powder to obtain a material A;
(2) mixing oxalate, silica sol and water to obtain a material B;
(3) mixing and kneading the material A and the material B into a plastic body, extruding the plastic body into strips, and drying and roasting the strips;
wherein the oxalate is sodium oxalate and/or potassium oxalate.
2. The method as claimed in claim 1, wherein the silica has an average particle size of 100-150 mesh, preferably 110-140 mesh.
3. A process according to claim 1 or 2, wherein in step (1), the total amount of said starch and/or said sesbania powder used is from 11 to 20 parts by weight, based on 100 parts by weight of silica.
4. The method according to claim 1 or 2, wherein, in the step (2), the oxalate is used in an amount of 5 to 12 parts by weight based on 100 parts by weight of silica, and the silica sol is used in an amount of 10 to 20 parts by weight based on silica;
preferably, the oxalate is used in an amount of 5 to 10 parts by weight based on 100 parts by weight of silica, and the silica sol is used in an amount of 10 to 15 parts by weight based on silica;
preferably, the mass percent content of the silicon dioxide in the silica sol is 25-30 wt%.
5. The method as claimed in claim 1, wherein, in step (3), the extrusion into strands is carried out in a strand extruder, wherein the average diameter of the extrusion orifice plate in the strand extruder is 1.5-6mm, and the extrusion rate is 150-450 r/min;
preferably, the drying conditions include: the drying temperature is 80-150 ℃, and the drying time is 4-10 h;
preferably, the conditions of the calcination include: the roasting temperature is 700-900 ℃, the roasting time is 6-18 hours, and the heating rate of the roasting temperature is 4-6 ℃/min.
6. A silica support having a three-dimensionally ordered macroporous shape in the form of a strip produced by the method of any one of claims 1 to 5.
7. The carrier as claimed in claim 6, wherein the silica carrier in the form of a strip having three-dimensionally ordered macropores has a length of 5 to 40 cm, a specific surface area of 335 and 350 m/g and a pore volume of 0.25 to 0.30 ml/g.
8. The carrier according to claim 6 or 7, wherein the strip-shaped three-dimensionally ordered macroporous silica carrier contains silica and oxides of sodium and/or potassium, and the content of silica is 90 to 98.5% by weight and the content of sodium and/or potassium components in terms of oxides is 1.5 to 6% by weight, based on the total weight of the strip-shaped three-dimensionally ordered macroporous silica carrier.
9. A supported catalyst comprising a silica support having three-dimensionally ordered macropores in the form of stripes produced by the method according to any one of claims 1 to 5 or a silica support having three-dimensionally ordered macropores in the form of stripes according to any one of claims 6 to 8 and active components Mn, W and Na supported on the silica support having three-dimensionally ordered macropores in the form of stripes.
10. Use of the supported catalyst of claim 9 in oxidative coupling of methane reactions.
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