CN113797948A - Catalyst carrier prepared by taking natural clay mineral as raw material and preparation method thereof - Google Patents
Catalyst carrier prepared by taking natural clay mineral as raw material and preparation method thereof Download PDFInfo
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- CN113797948A CN113797948A CN202111012584.0A CN202111012584A CN113797948A CN 113797948 A CN113797948 A CN 113797948A CN 202111012584 A CN202111012584 A CN 202111012584A CN 113797948 A CN113797948 A CN 113797948A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002994 raw material Substances 0.000 title abstract description 17
- 239000002734 clay mineral Substances 0.000 title abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 38
- 239000006229 carbon black Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 17
- 239000011707 mineral Substances 0.000 claims abstract description 17
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 239000010427 ball clay Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910021485 fumed silica Inorganic materials 0.000 claims description 12
- 239000012802 nanoclay Substances 0.000 claims description 12
- 239000004927 clay Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 229960000892 attapulgite Drugs 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 229910052625 palygorskite Inorganic materials 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000440 bentonite Substances 0.000 claims description 7
- 229910000278 bentonite Inorganic materials 0.000 claims description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000004113 Sepiolite Substances 0.000 claims description 5
- 239000003610 charcoal Substances 0.000 claims description 5
- 229910052624 sepiolite Inorganic materials 0.000 claims description 5
- 235000019355 sepiolite Nutrition 0.000 claims description 5
- 235000009496 Juglans regia Nutrition 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 235000020234 walnut Nutrition 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- 229920002522 Wood fibre Polymers 0.000 claims description 3
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003830 anthracite Substances 0.000 claims description 3
- 235000013312 flour Nutrition 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000002025 wood fiber Substances 0.000 claims description 3
- 238000004534 enameling Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 240000007049 Juglans regia Species 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 44
- 239000000126 substance Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 229910002027 silica gel Inorganic materials 0.000 abstract description 5
- 239000000741 silica gel Substances 0.000 abstract description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 14
- 238000005245 sintering Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 229910052570 clay Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 229940092782 bentonite Drugs 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 241000758789 Juglans Species 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000001238 wet grinding Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- -1 aromatics Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
- B01J35/613—10-100 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
- B01J35/633—Pore volume less than 0.5 ml/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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst carrier prepared by taking natural clay mineral as a raw material and a preparation method thereof, wherein the carrier comprises natural nano mineral, white carbon black and silicon carbide micro powder, the natural nano mineral contains nano particles, the natural nano mineral containing nano particles is used for replacing a part of traditional industrial raw materials, including aluminum hydroxide, activated alumina, silica gel powder, pseudo-boehmite and the like, so that the energy is saved, the emission is reduced, the manufacturing cost is reduced, meanwhile, the pore size distribution and the pore volume size are adjusted by adding a pore-forming agent, and the specific surface area of the carrier is adjusted by adding the white carbon black. The carrier with high porosity, reasonable aperture, good mechanical strength and proper specific surface area is manufactured, and the diversified requirements of chemical industry and environmental protection industry on the catalyst carrier are met.
Description
Technical Field
The invention relates to a catalyst carrier, in particular to a catalyst carrier prepared by taking natural clay minerals as raw materials and a preparation method thereof.
Background
Catalysis is an important technology that affects our daily lives in many ways. Catalysis, such as hydrogenation, oxidation, and dehydrogenation, cracking, reforming, etc., plays a crucial role in the current chemical industry for the production of important chemicals and intermediates. Over 90% of chemical manufacturing is based on or dependent on catalytic processes. It is estimated that catalytic reactions account for approximately 35% of the total production value (GDP) in the world, the demand for catalysts has reached $ 195 million in 2016, and the value of catalysts will be higher in 2021. In many catalytic reactions, hydrogenation and oxidation play a key role in the current chemical industry. Catalytic hydrogenation, particularly the hydrogenation products of alkenes, alkynes, aromatics, aldehydes, ketones, esters, carboxylic acids, nitro groups, nitriles and imines, has attracted considerable interest as a key to the synthesis and production of petrochemicals and fine chemicals. Oxidation is the second largest process after polymerization and represents about 30% of the total chemical industry yield. A large number of key chemicals and intermediates can be produced by selective oxidation, such as alcohols, aldehydes, ketones, acids and epoxides. The increasingly developed high-activity catalyst of Nano Particles (NPs) brings a new revolution to the field of catalysis. However, nanoparticles, while providing high activity centers, are very small in size and are thermodynamically unstable. Therefore, the nanoparticles are easily aggregated during the catalytic process and poisoned during the reaction, resulting in deactivation and reduced reusability. The method of highly dispersing and uniformly mixing the nanoparticles with other raw materials and pore-forming agents and then loading the mixture on a suitable carrier is one of the most effective methods for solving the problems. Therefore, the supported catalyst is widely used in industrial hydrogenation and oxidation reactions, has good catalytic performance, and is easy to separate and recover. Factors affecting the catalytic performance of the supported catalyst are: the particle size, composition, surface morphology and structure of the catalyst, the nature of the support, and the interaction between the nanoparticles and the support. By adjusting and controlling these parameters, the supported catalyst can enhance the catalytic performance. However, the design and preparation of catalysts that can simultaneously meet the requirements of high catalytic activity, selectivity and stability remains a long standing problem for heterogeneous catalysts.
The catalyst carrier is also called a supporter (support), is one of the components of the supported catalyst, is a framework of the active components of the catalyst, supports the active components, enables the active components to be dispersed, and can also increase the strength of the catalyst.
The natural raw materials are adopted to replace part of the traditional industrial raw materials so as to save energy, reduce emission and reduce manufacturing cost, but the natural raw materials are directly used for replacement, and the prepared carrier has low porosity, insufficient specific surface area and general mechanical strength and can not meet the diversified requirements.
Disclosure of Invention
The invention aims to provide a catalyst carrier prepared by taking natural clay minerals as raw materials and a preparation method thereof, the catalyst carrier uses natural raw materials to replace part of traditional industrial raw materials, and the obtained carrier has high porosity, reasonable pore diameter, good mechanical strength and proper specific surface area, and meets the diversified requirements of chemical and environmental industries on the catalyst carrier.
In order to achieve the purpose, the invention provides the following technical scheme:
the catalyst carrier is prepared by taking natural clay mineral as a raw material, and comprises natural nano clay mineral, white carbon black and silicon carbide micro powder, wherein the natural nano clay mineral contains nano particles.
Preferably, the natural nanoclay mineral is one or more of ball clay, bentonite, attapulgite clay, sepiolite clay.
Preferably, the white carbon black comprises one or two of fumed silica and precipitated white carbon black, and the fumed silica preferably has a specific surface area of 200-300 m2The preferable specific surface area of the precipitated white carbon black is 150-200 m2Type/g
A method for preparing a catalyst carrier prepared from a natural clay mineral as a raw material, comprising: the preparation method comprises the steps of mixing natural nano clay mineral, white carbon black and silicon carbide micro powder to obtain a primary mixture, adding ammonium polyacrylate with the mass of 0.2-0.4% of that of the primary mixture, adding water into a ball mill, crushing and mixing for 3-4 hours, adding a combustible pore-forming agent, mixing for 60 minutes, grinding, removing water to prepare powder or paste, respectively molding by a rolling method enameling process, a hydraulic dry process or a wet plastic extrusion process to prepare a spherical or Raschig ring, drying, and calcining for 2-5 hours at 850-900 ℃ in a kiln.
Preferably, the premix comprises 44-71% of natural nano clay mineral, 24-42% of white carbon black and 4-15% of silicon carbide micro powder; and adding a combustible pore-forming agent, wherein the mass of the combustible pore-forming agent is 5-55% of that of the premix.
Preferably, the premix comprises 54-70% of natural nano clay mineral, 24-42% of white carbon black, 4-15% of silicon carbide micro powder and a combustible pore-forming agent, wherein the mass of the combustible pore-forming agent is 21-55% of that of the premix.
Preferably, the combustible pore-forming agent comprises one or more of coke powder, anthracite powder, charcoal powder, flour, rice bran powder, walnut shell powder, starch, wood fiber, polyvinyl alcohol and methyl cellulose.
In the carrier manufacturing industry, the carrier is manufactured by industrial products such as aluminum hydroxide, pseudo-boehmite, gamma alumina, silica gel, molecular sieve, activated carbon, titanium dioxide and the like, and has the defects of high price and high cost. The patent creatively and directly adopts natural clay minerals (including ball clay, bentonite, attapulgite clay and sepiolite clay) containing nano particles as forming binders, sintering aids and main raw materials, can solve the problems to a certain extent, is beneficial to comprehensive utilization and sustainable development of resources, and is also beneficial to reducing cost and improving benefits of carrier manufacturing enterprises.
Alumina, silica and molecular sieve carriers, which are commonly used as sintering aids, are made of nano materials. Like the active alumina carrier, pseudo-boehmite is adopted to become sol after being dissolved by nitric acid, namely a liquid nano alumina material, and the high sintering activity of the nano material is utilized to be used as a sintering aid (the alumina sol can also play a role of a forming binder) so as to ensure and improve the mechanical strength of the alumina carrier; for another example, the silica gel carrier system uses silica sol with a certain concentration, namely liquid nano-silica, as a sintering aid to improve the compressive strength of the silica gel carrier (the silica sol can also play a role of a forming binder); the molecular sieve carrier mainly uses kaolin powder as a forming binder and a sintering aid in the past, 5-10% of kaolin is generally added into the molecular sieve powder, and the prepared molecular sieve carrier has low strength due to the high fire resistance of the kaolinHigh; in practice, the ball clay has high sintering strength at 700-800 ℃, and is widely applied to shaped and amorphous refractory materials, and the bentonite has high strength after being calcined at 600 ℃. Heating ball clay and bentonite to 925 deg.C to obtain amorphous metakaolin (Al)2O3·2SiO2) And amorphous SiO2All have catalytic activity. However, when the temperature of the bentonite and the ball clay is higher than 925 ℃, aluminum-silicon spinel crystals are generated, and mullite crystals and quartz crystals are generated at 1050 ℃, so that the activity and the specific surface area of the material are obviously reduced. In addition, it has been found that when kaolin, ball clay and bentonite are heated to 950 ℃, gamma-Al is formed2O3And amorphous SiO2Both of them are active and are the main materials for preparing the carrier, but mullite crystal is generated at 1100 ℃ (the reference document: published by Chinese architecture industry Press 1981, edited by south China college of Industrial science, Nanjing chemical industry college, Wuhan building materials college, ceramic technology, page 168), and the activity begins to decline. The present patent discloses that the above-mentioned natural clay mineral containing nanoparticles is used as a main raw material and fired at a temperature of 900 ℃ or lower, thereby achieving the effects of improving the strength of the carrier and ensuring the catalytic activity. Because the system is solid-phase sintering and no fluxing agent is used, a melt (glass phase) is not generated during sintering, so that pores are not blocked, the compatibility of the pores (porosity) and the strength of the carrier are ensured, and the problem that the porosity and the mechanical strength of the porous material are difficult to synchronously improve is solved to a certain extent.
The pore volume, specific surface area, etc. of the catalyst support are important indicators of catalyst performance. The specific surface area is measured as the surface area inside or outside of 1g by weight of the catalyst or catalyst support. The porous solid particles have extremely large internal surface areas, and the internal surfaces are hidden in the pores of the particles, and if the porous solid particles are fine pores, the surface areas are large, but when the porous solid particles are used as a catalyst carrier, reactant molecules are prevented from diffusing into the pores, the reaction is influenced, so that not all the surfaces play a catalytic role, and the specific surface area is not as large as possible, but indexes such as pore volume and the like are combined, and the porous solid particles can be manually adjusted and set according to needs.
The solid-phase sintering exists in the roasting process of the nano mineral material, so that the specific surface area of the carrier is reduced, and the adaptability is not wide. The fumed silica and the precipitated silica both have extremely high specific surface areas, for example, the specific surface area of the fumed silica can reach 200-400 m2The particles are more than dozens of nanometers in size, and the specific surface area of the precipitated white carbon black is 100-200 m2The specific surface area of the carrier can be adjusted because the specific surface area of the carrier is adjusted because the particles are aggregated into micron-sized particles with the original particle size of tens of nanometers and can be dispersed by a mechanical method such as ball milling. Meanwhile, combustible materials (including coke powder, anthracite powder, charcoal powder, flour, rice bran powder, walnut shell powder, starch, wood fiber and polyvinyl alcohol) with corresponding particle size and quantity are taken as pore-forming agents, so that the pore volume, apparent porosity (water absorption) and pore diameter of the carrier can be controlled, and even a through-hole carrier can be manufactured; the silicon carbide is properly added to improve the heat conductivity and heat resistance of the carrier, so that the adjustable aluminum silicate catalyst carrier with specific surface area, pore volume and the like is prepared to meet the diversified objective requirements in the fields of chemical industry and environmental protection.
Advantageous effects
According to the invention, a part of traditional industrial raw materials including aluminum hydroxide, activated alumina, silica gel powder and the like are replaced by the natural nano mineral containing nano particles, so that the energy conservation and emission reduction and the reduction of the manufacturing cost are realized, meanwhile, the pore size distribution and the pore volume size are adjusted by adding the pore-forming agent, and the specific surface area of the carrier is regulated and controlled by adding the white carbon black. The carrier with high porosity, reasonable aperture, good mechanical strength and proper specific surface area is manufactured by the method, and the diversified requirements of chemical industry and environmental protection industry on the catalyst carrier are met
Detailed Description
To highlight the implementation objects, technical solutions and structural advantages of the present invention, the following detailed description is made in conjunction with technical solutions in examples of the present invention, which are a part of examples of the present invention, but not all examples. All other examples, which can be obtained by a person skilled in the art without any inventive step based on the examples of the present invention, are within the scope of the present invention.
Example 1 mixing Jilin ball clay 44 wt%, Guangxi ball clay 4.5 wt%, Liuyang sepiolite 7.5 wt%, fumed silica 11 wt%, precipitated silica 24 wt%, and silicon carbide micropowder 9 wt%, adding 0.2% ammonium polyacrylate, adding 120 mesh Henan walnut shell powder 31% in a ball mill, mixing for 30 minutes, grinding, removing water to obtain powder, molding by rolling method to obtain spherical particles with diameter of 4-5 mm, drying, calcining at 900 deg.C in a kiln for 5 hours to obtain a carrier, detecting specific surface area and pore diameter of the carrier by a Beschild specific surface and pore diameter analyzer 3H-2000PS2, and detecting specific surface area 44m2(iv)/g, total pore volume 0.356mL/g, average pore diameter (4V/A by BET, same below) 30.73 nm; the compressive strength of the carrier is more than 2.4 kg/granule.
Example 2 blending 54 wt% of Jilin ball clay, 5 wt% of Guangxi ball clay, 4 wt% of fumed silica, 25 wt% of precipitated silica and 12% of 600 mesh silicon carbide, adding 0.2% of ammonium polyacrylate, adding water in a ball mill for wet grinding and mixing for 3-4 hours, then adding 55% of 80 mesh coke powder, mixing for 60 minutes, grinding, dehydrating to prepare powder, carrying out rolling method for slush molding to prepare spherical particles with the diameter of 4-5 mm, drying, calcining at 900 ℃ in a kiln for 5 hours to obtain a carrier, detecting the specific surface area and the pore diameter of the carrier by a Behcet specific surface and pore diameter analyzer 3H-2000PS2 to obtain the specific surface area of 19m2(iv)/g, total pore volume 0.361mL/g, average pore diameter 38.87 nm; the compressive strength of the carrier is more than 2.2 kg/particle.
Example 3 mixing Jilin ball clay 25 wt%, Anhui attapulgite clay 24 wt%, Guangxi ball clay 8 wt%, sepiolite of 200 mesh 5 wt%, precipitated white carbon black 20 wt%, fumed white carbon black 13 wt%, silicon carbide of 600 mesh 5%, adding 0.2% ammonium polyacrylate, pulverizing and mixing in a ball mill by water-wet method for 3-4 hours, adding bran powder of 60 mesh 27%, mixing for 60 minutes, grinding, removing water to obtain powder, molding by rolling method to obtain spherical particles with diameter of 4-5 mm, drying, calcining at 890 deg.C in a kiln for 4 hours to obtain carrier, and separating by Behcet's specific surface and pore sizeThe analyzer 3H-2000PS2 detects the specific surface area and pore diameter of the carrier, the specific surface area is 36m2(iv)/g, total pore volume 0.31mL/g, average pore diameter 28.77 nm; the compressive strength of the carrier is more than 2.7 kg/particle.
Example 4 mixing 9 wt% of Jilin ball clay, 34 wt% of Anhui attapulgite clay, 6 wt% of Guangxi ball clay, 5 wt% of Zhejiang natural sodium bentonite, 4 wt% of fumed silica, 27 wt% of precipitated silica and 15% of 600 mesh silicon carbide, crushing and mixing in a ball mill for 3-4 hours, adding 3% of 30-60 mesh polyvinyl alcohol, 1% of methyl cellulose and 21% of coal powder, mixing for 30 minutes without smoke, grinding, press-filtering to remove water to obtain a paste, extruding into Raschig rings with an outer diameter of 10mm and an inner diameter of 4mm by a vacuum pug mill, cutting into a height of 10mm, drying, calcining at 900 ℃ in a kiln for 5 hours to obtain a carrier, detecting the specific surface area and pore diameter of the carrier by a Beschild specific surface and pore diameter analyzer 3H-2000PS2, and detecting the specific surface area of 26m2(ii)/g, total pore volume 0.29mL/g, average pore diameter 45.13 nm; the compressive strength of the carrier is more than 2.1 kg/cm.
Example 5 blending 39 wt% of Jilin ball clay, 15 wt% of Jiangsu attapulgite clay, 12 wt% of precipitated white carbon black, 30 wt% of fumed white carbon black and 4% of silicon carbide, adding 0.2% of ammonium polyacrylate, adding water in a ball mill for wet grinding and mixing for 3-4 hours, then adding 21% of 80-mesh sawdust powder, mixing for 60 minutes, grinding, dehydrating to prepare powder, carrying out slush molding by a rolling method to prepare spherical particles with the diameter of 4-5 mm, drying, calcining at 890 ℃ in a kiln for 5 hours to obtain a carrier, detecting the specific surface area and the pore diameter of the carrier by a Behcet specific surface and pore diameter analyzer 3H-2000PS2, and detecting the specific surface area and the pore diameter of 51m2(iv)/g, total pore volume 0.41mL/g, average pore diameter 27.13 nm; the compressive strength of the carrier is more than 2.0 kg/particle.
Example 6 mixing Jilin ball clay 42 wt%, Guangxi ball clay 10 wt%, Jiangsu attapulgite clay 14 wt%, precipitated silica 24 wt%, fumed silica 4 wt%, and silicon carbide 6%, adding 0.2% ammonium polyacrylate, wet-pulverizing and mixing in a ball mill for 3-4 hours, grinding, spray drying to remove water, and making into the final productPulverizing into powder, mixing with 23% of charcoal powder of 120 mesh and 0.5% of calcium stearate, pressing and molding with hydraulic press to obtain Raschig ring with outer diameter of 8mm, inner diameter of 4mm and height of 8mm, oven drying, calcining at 880 deg.C for 5 hr to obtain carrier, detecting specific surface area and aperture with Behcet specific surface and aperture analyzer 3H-2000PS2, and detecting specific surface area of 21m2(iv)/g, total pore volume 0.21mL/g, average pore diameter 35.66 nm; the compressive strength of the carrier is more than 3.6 kg/cm.
Example 7 the ingredients of 39 wt% of Jilin ball clay, 10 wt% of Guangxi ball clay, 21 wt% of Jiangsu attapulgite clay, 4 wt% of precipitated white carbon black, 20 wt% of fumed silica and 6% of silicon carbide are mixed, 0.2% of ammonium polyacrylate is added, adding water into a ball mill for wet grinding and mixing for 3-4 hours, adding 14 wt% of rice hull carbon powder of 120 meshes and 19 wt% of charcoal powder of 120 meshes, supplementing water, carrying out mixed grinding for 1 hour, then taking out the mixture from the mill, carrying out filter pressing to remove water and preparing pug, adopting a vacuum pug mill for molding to prepare a Raschig ring with the outer diameter of 10mm, the inner diameter of 5mm and the height of 10mm, drying, calcining for 4 hours at 870 ℃ in a kiln to obtain a carrier, detecting the specific surface area and the pore diameter of the carrier by a Behcet specific surface and pore diameter analyzer 3H-2000PS2, wherein the specific surface area is 31m2/g, the total pore volume is 0.24mL/g, and the average pore diameter is 45.66 nm; the radial compressive strength of the carrier is more than 3.2 kg/cm. The carrier properties in examples 1-7 show that the catalyst carrier obtained by the method has high porosity, reasonable pore diameter, good mechanical strength and appropriate specific surface area, and meets the diversified requirements of chemical and environmental industries on the catalyst carrier.
What is last stated is: the above detailed description is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. It should be noted that, within the scope of the concept of the present invention, a person skilled in the art may make several changes and modifications, or may make relevant substitutions for some technical features, all of which fall within the scope of the present invention. The scope of protection of the above patent shall be indicated finally by the appended claims: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The catalyst carrier is characterized by comprising natural nano clay minerals, white carbon black and silicon carbide micro powder, wherein the natural nano clay minerals contain a part of nano particles.
2. The catalyst support of claim 1, wherein the natural nanoclay mineral is one or more of ball clay, bentonite, attapulgite clay, sepiolite clay.
3. The catalyst carrier according to claim 1, wherein the fumed silica comprises one or two of fumed silica and precipitated silica, and the fumed silica preferably has a specific surface area of 200-300 m2The preferable specific surface area of the precipitated white carbon black is 150-200 m2Form/g.
4. A method of preparing the catalyst carrier of any one of claims 1-3, comprising: the preparation method comprises the steps of mixing natural nano clay mineral, white carbon black and silicon carbide micro powder to obtain a primary mixture, adding ammonium polyacrylate with the mass of 0.2-0.4% of that of the primary mixture, adding water into a ball mill, crushing and mixing for 3-4 hours, adding a combustible pore-forming agent, mixing for 60 minutes, grinding, removing water to prepare powder or paste, respectively molding by a rolling method enameling process, a hydraulic dry process or a wet plastic extrusion process to prepare a spherical or Raschig ring, drying, and calcining for 2-5 hours at 850-900 ℃ in a kiln.
5. The method according to claim 4, characterized in that the premix comprises 44-71% of natural nano clay mineral, 24-42% of white carbon black and 4-15% of silicon carbide micro powder; and adding a combustible pore-forming agent, wherein the mass of the combustible pore-forming agent is 5-55% of that of the premix.
6. The method according to claim 4, characterized in that the premix comprises 54-70% of natural nano clay mineral, 24-42% of white carbon black, 4-15% of silicon carbide micro powder and a combustible pore-forming agent, wherein the mass of the combustible pore-forming agent is 21-55% of that of the premix.
7. The method of claim 4, wherein the combustible pore-forming agent comprises one or more of coke powder, anthracite powder, charcoal powder, flour, rice bran powder, walnut shell powder, starch, wood fiber, polyvinyl alcohol, and methyl cellulose.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115611606A (en) * | 2022-10-13 | 2023-01-17 | 江西环宇工陶技术研究有限公司 | One-time sintered TiO 2 Photocatalytic ceramic and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4253990A (en) * | 1979-09-11 | 1981-03-03 | Johns-Manville Corporation | Preparation method for catalyst supports and materials produced thereby |
| CN1442392A (en) * | 2003-04-11 | 2003-09-17 | 中国科学院上海硅酸盐研究所 | Preparation method of silicon carbide porous ceramic using yeast powder as pore forming agent |
| CN1915520A (en) * | 2005-08-17 | 2007-02-21 | 陈庆华 | Carrier of ceramics catalyst, and microparticles collection device of constituting the carrier and their preparation method |
| CN101966471A (en) * | 2010-04-23 | 2011-02-09 | 周江林 | High-efficiency environmental-friendly catalyst carrier |
| CN102039199A (en) * | 2009-10-16 | 2011-05-04 | 中国科学院化学研究所 | Clay catalyst carrier and preparation method and application thereof |
| CN104529506A (en) * | 2015-01-16 | 2015-04-22 | 临江北峰硅藻土有限公司 | Preparation method of compound natural porous mineral ceramic microbeads |
| CN110327989A (en) * | 2019-07-23 | 2019-10-15 | 西北化工研究院有限公司 | A kind of preparation method and applications of catalyst carrier |
| CN113042109A (en) * | 2021-03-25 | 2021-06-29 | 煤炭科学技术研究院有限公司 | Ozone catalyst carrier and preparation method thereof |
-
2021
- 2021-08-31 CN CN202111012584.0A patent/CN113797948A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4253990A (en) * | 1979-09-11 | 1981-03-03 | Johns-Manville Corporation | Preparation method for catalyst supports and materials produced thereby |
| CN1442392A (en) * | 2003-04-11 | 2003-09-17 | 中国科学院上海硅酸盐研究所 | Preparation method of silicon carbide porous ceramic using yeast powder as pore forming agent |
| CN1915520A (en) * | 2005-08-17 | 2007-02-21 | 陈庆华 | Carrier of ceramics catalyst, and microparticles collection device of constituting the carrier and their preparation method |
| CN102039199A (en) * | 2009-10-16 | 2011-05-04 | 中国科学院化学研究所 | Clay catalyst carrier and preparation method and application thereof |
| CN101966471A (en) * | 2010-04-23 | 2011-02-09 | 周江林 | High-efficiency environmental-friendly catalyst carrier |
| CN104529506A (en) * | 2015-01-16 | 2015-04-22 | 临江北峰硅藻土有限公司 | Preparation method of compound natural porous mineral ceramic microbeads |
| CN110327989A (en) * | 2019-07-23 | 2019-10-15 | 西北化工研究院有限公司 | A kind of preparation method and applications of catalyst carrier |
| CN113042109A (en) * | 2021-03-25 | 2021-06-29 | 煤炭科学技术研究院有限公司 | Ozone catalyst carrier and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115611606A (en) * | 2022-10-13 | 2023-01-17 | 江西环宇工陶技术研究有限公司 | One-time sintered TiO 2 Photocatalytic ceramic and preparation method thereof |
| CN115611606B (en) * | 2022-10-13 | 2023-09-01 | 江西环宇工陶技术研究有限公司 | One-time fired TiO 2 Photocatalytic ceramic and preparation method thereof |
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