CN101507931A - Preparation method of whisker reinforced preformed catalyst carrier or catalyst - Google Patents
Preparation method of whisker reinforced preformed catalyst carrier or catalyst Download PDFInfo
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- CN101507931A CN101507931A CNA2009100260987A CN200910026098A CN101507931A CN 101507931 A CN101507931 A CN 101507931A CN A2009100260987 A CNA2009100260987 A CN A2009100260987A CN 200910026098 A CN200910026098 A CN 200910026098A CN 101507931 A CN101507931 A CN 101507931A
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- Prior art keywords
- whisker
- preparation
- preformed catalyst
- catalyst carrier
- crystal whisker
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims description 30
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000013078 crystal Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002270 dispersing agent Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims description 26
- 238000001125 extrusion Methods 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002585 base Substances 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002472 Starch Polymers 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 235000014820 Galium aparine Nutrition 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 241000612118 Samolus valerandi Species 0.000 claims description 4
- -1 alum Chemical compound 0.000 claims description 4
- 229940037003 alum Drugs 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229960004643 cupric oxide Drugs 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical group 0.000 claims description 4
- 229910017083 AlN Inorganic materials 0.000 claims description 3
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052580 B4C Inorganic materials 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- 241000219793 Trifolium Species 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 3
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 240000005702 Galium aparine Species 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract 2
- 239000011159 matrix material Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 24
- 238000000465 moulding Methods 0.000 description 18
- 229940068984 polyvinyl alcohol Drugs 0.000 description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229920003091 Methocel™ Polymers 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- 241001101998 Galium Species 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000010099 solid forming Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
The invention discloses a method for preparing a crystal whisker enhanced forming catalyst carrier or catalyst, which comprises a method for preparing a crystal whisker enhanced forming catalyst carrier and a method for preparing a crystal whisker enhanced forming catalyst. In the method of the invention, a forming substrate is added with one or more crystal whisker enhanced materials, of which the diameter is 0.1 to 5mu m, and the length-diameter ratio is no less than 2, and a dispersing agent which is correspondingly used to improve the dispersing state of the crystal whisker in the substrate, and after evenly mixed, the mixture is subjected to forming and roasting, and the catalyst carrier is obtained. The crystal whisker enhanced forming catalyst carrier or catalyst has higher anti-crushing strength; and by the forming method, the catalyst carrier or catalyst in various shapes can be prepared the forming process is simple and convenient, and the method is suitable for mass industrialized production.
Description
Technical field
The invention belongs to catalyst field, be specifically related to the preparation method of a kind of whisker reinforced preformed catalyst carrier or whisker reinforced preformed catalyst.
Background technology
The development of chemical industry depends on the R and D of catalyst to a great extent, Gu wherein many again is that gas phase, catalyst are that the gas-heterogeneous catalysis process of solid phase is comparatively general with the reactant, as in the solid catalyst only this class of metal load type catalyst now be widely used in the middle of the various reactions such as hydrogenation, dehydrogenation and oxidation.Yet for a kind of industrial solid catalyst, it is active good not only will to possess, the selectivity height, outside the characteristics such as activity stabilized and long service life, also must possess suitable shape and high crushing strength, to resist actual carrying, filling, in the course of reaction between the particle and reactive component to its impact and abrasion, avoid catalyst breakage or efflorescence, active component comes off, catalyst carries the generation of unfavorable condition such as loss, and therefore exploitation has the preformed catalyst carrier of high crushing strength or catalyst concerning its follow-up industrialized developing with particularly necessary using.
Whisker is as a kind of mono-crystlling fibre material, because its crystal structure is more complete, internal flaw is less, mechanical strength is approximately equal to the theoretical strength of valence link power between atom, one dimension known today, bidimensional, the three-dimensional enhancing in the body, it is that intensity is the highest, the enhancing body of best performance.Yet in the process of using, if simple the interpolation do not have the effect of gaining in strength, and its normal existence is easily reunited and the situation of difficult dispersion.
Summary of the invention
The objective of the invention is micro-enhancement effect for the better utilization whisker, be difficult to problems such as crushing strength is low after moulding or the moulding at existing solid forming catalyst carrier or catalyst, the micro-enhancing of whisker is incorporated in the concrete moulding preparation process, improve the dispersity of whisker in matrix, to obtain high breaking strength preformed catalyst carrier or Preparation of catalysts method.
Purpose of the present invention can reach by following measure:
A kind of whisker reinforced preformed catalyst carrier or Preparation of catalysts method are divided into the preparation method of whisker reinforced preformed catalyst carrier or the preparation method of whisker reinforced preformed catalyst, wherein,
The preparation method of whisker reinforced preformed catalyst carrier may further comprise the steps:
(1), in becoming mold base, add crystal whisker materials, mix, wherein to account for the mass percent of batch mixing (mold base and crystal whisker materials composite material) be 0.1～50wt% to crystal whisker materials, and preferable range is 0.5～25%;
(2), in the batch mixing that above-mentioned steps obtains, add dispersant, after fully mediating, extrusion molding on extruder obtains formed body;
(3), formed body is dry and in 200～1000 ℃ of following calcination process, obtain whisker reinforced preformed catalyst carrier;
The preparation method of whisker reinforced preformed catalyst may further comprise the steps:
(1), in becoming mold base, add crystal whisker materials, mix, wherein to account for the mass percent of batch mixing (mold base and crystal whisker materials composite material) be 0.1～50wt% to crystal whisker materials, and preferable range is 0.5～25%;
(2), in the batch mixing that above-mentioned steps obtains, add dispersant, after fully mediating, extrusion molding on banded extruder obtains formed body;
(3), obtain preformed catalyst carrier with the formed body drying and in 200～1000 ℃ of following calcination process;
(4), with containing the above-mentioned preformed catalyst carrier of solution impregnation of active metal component, drying and in 200～1000 ℃ of following roastings obtains whisker reinforced preformed catalyst;
Perhaps, the preparation method of whisker reinforced preformed catalyst is made of following steps:
(1), in becoming mold base, add crystal whisker materials, mix, wherein to account for the mass percent of batch mixing (mold base and crystal whisker materials composite material) be 0.1～50wt% to crystal whisker materials, and preferable range is 0.5～25%;
(2), in the batch mixing that above-mentioned steps obtains, add dispersant and contain the solution of active metal component, after abundant kneading, extrusion molding on banded extruder obtains formed body;
(3), formed body is dry and in 200～1000 ℃ of following calcination process, obtain whisker reinforced preformed catalyst.
Which kind of material the present invention selects for use there is no particular requirement to becoming mold base, so long as the one-tenth mold base of catalyst carrier or catalyst gets final product.In order more to adapt to method of the present invention, become mold base to be selected from least a in the following material: the oxide of silicon, aluminium, titanium, zirconium, cerium, alum, iron, copper, zinc or its corresponding acid or corresponding alkali, molecular sieve, diatomite, bentonite.Molecular sieve can be at least a among A type, X type, Y type, SBA-15 or the MCM-41.
The present invention mainly utilizes the physical property of crystal whisker materials, and therefore the scope of the crystal whisker materials that can utilize is extremely wide, can be selected from metal whisker or the nonmetal whisker one or more.Wherein the metal in the metal whisker is gold, silver, iron, nickel, copper, iron, tin, aluminium, platinum or beryllium; Nonmetal whisker is aluminium oxide, titanium oxide, zirconia, cupric oxide, manganese oxide, beryllium oxide, magnesia or its corresponding hydroxide whisker, perhaps is carborundum, titanium carbide, silicon nitride, titanium nitride, aluminium nitride, charcoal or boron carbide whisker.The diameter of the crystal whisker materials among the present invention is preferably 0.1～5 μ m, and length diameter ratio is not less than 2 (upper limit of draw ratio and no requirement (NR) can reach hundreds of or thousands of, even bigger).
Dispersant among the present invention is preferably selected from one or more in carboxymethyl cellulose, methylcellulose, soluble starch, polyvinyl alcohol or the polyethylene glycol.Dispersant dosage is into 0.1～20% of mold base and crystal whisker materials gross mass, and preferable range is 0.5～10%.Dispersant adds in the mode of the aqueous solution, and its concentration is not strict with, as long as can reach the effect of disperseing mixing.Interaction between crystal whisker materials and the dispersant in becoming mold base can strengthen the crushing strength of catalyst carrier or catalyst greatly.
The solution that contains active metal component among the present invention is for loading on active material the solution on the catalyst carrier, and the concentration of solution has difference according to the characteristic of different active materials, there is no specific requirement in the present invention.And do not relate among the present invention and specifically select for use which kind of active material and catalyst specifically to be applied to which reaction of catalysis.Yet according to the character of such catalyst, the active metal component in the active material is generally selected transition metal (metallic element on the 3rd～12 subgroup) for use.The solution that contains active metal component is meant the solution of the material that contains transition metal, as contains the solution of transition metal oxide or its corresponding acid or materials such as corresponding alkali or its corresponding metal organic compound.Wherein active component (material that contains transition metal) accounts for 0.1～90wt% of matrix and whisker gross mass.
Dipping method during with the solution impregnation preformed catalyst carrier that contains active metal component can be in excessive dipping, incipient impregnation, vacuum impregnation, vapor phase dipping or the multiple maceration at least a.
Whisker reinforced preformed catalyst carrier that the present invention obtains or catalyst can be granular, cylindric, sheet, sphere, spoke-like, hollow columnar, clover shape or bunge bedstraw herb shape, and its volume equivalent diameter is not less than 0.1mm.
The present invention has the following advantages:
1, can obtain whisker good dispersion and preformed catalyst carrier or catalyst in matrix with high breaking strength;
2, forming process is simple, need not introduce the former of new complexity;
3, the inventive method has versatility, is fit to the preformed catalyst carrier or the Preparation of catalysts of various components and shape;
4, the inventive method prepares simple and conveniently, and cost is lower, and preparation process is not polluted, suitable industry's enlarging production.
The specific embodiment
Below by specific embodiment explanation the present invention, but the present invention not merely is defined in these embodiment.
Embodiment one
(press the conversion of silica amount with silica sol 50wt%, below information slip of the same race reach mode implication unanimity) for matrix, alumina whisker is that (diameter is 0.1 μ m to 50wt%, the draw ratio scope is 2～50), after mixing, continue to add the dispersant cmc soln, wherein to account for the percentage of matrix and whisker (batch mixing) gross mass be 1wt% to carboxymethyl cellulose, after fully mediating evenly, 550 ℃ of roastings of Muffle furnace are put in extrusion molding after the drying.The moulding material that obtains is a column, and the volume equivalent diameter is 2.5mm, and crushing strength is 8MPa.
Embodiment two
With cerium oxide 99.5wt% is matrix, (diameter is 1 μ m to zirconia whisker 0.5wt%, draw ratio is more than 50), after mixing, continue to add dispersant methocel solution and active component liquor argenti nitratis ophthalmicus, wherein to account for the percentage of batch mixing quality respectively be 0.1wt% and 10wt% for methylcellulose and silver nitrate, fully mediate evenly after, 200 ℃ of roastings of Muffle furnace are put in extrusion molding after the drying.The moulding material that obtains is for spherical, and the volume equivalent diameter is 2mm, and crushing strength is 4MPa.
Embodiment three
With titanium oxide 30wt%, cerium oxide 20wt% is a matrix, (diameter is 2 μ m to zirconia whisker 50wt%, the draw ratio scope is 50～100), after mixing, continue to add dispersant soluble starch solution, wherein to account for the percentage of matrix and whisker gross mass be 5wt% to starch, after fully mediating evenly, 800 ℃ of roastings of Muffle furnace are put in extrusion molding after the drying.The moulding material that obtains is a spoke-like, and the volume equivalent diameter is 5.5mm, and crushing strength is 11MPa.
Embodiment four
With 4A molecular sieve 40wt%, boehmite 30wt% is a matrix, (diameter is 5 μ m to al whisker 15wt%, the draw ratio scope is 1～80), (diameter is 2 μ m to alumina whisker 15wt%, the draw ratio scope is 50～200), after mixing, continue to add dispersant soluble starch solution and active component cobalt nitrate and nickel nitrate aqueous solution, wherein to account for the percentage of matrix and whisker gross mass respectively be 10wt%, 5wt% and 10wt% for starch, cobalt nitrate, nickel nitrate, after fully mediating evenly, 1000 ℃ of roastings of Muffle furnace are put in extrusion molding after the drying.The moulding material that obtains is a column, and the volume equivalent diameter is 5mm, and crushing strength is 14MPa.
Embodiment five
With diatomite 20wt%, iron oxide 20wt%, alumina sol 25wt% are matrix, (diameter is 1 μ m to silicon carbide whisker 30wt%, the draw ratio scope is 500～2000), silver-colored whisker 5wt% (diameter is 0.5 μ m, and the draw ratio scope is 2～25), after mixing, continue to add the polyethylene of dispersing agent alcoholic solution, wherein to account for the percentage of matrix and whisker gross mass be 7wt% to polyvinyl alcohol, fully mediate evenly after, 600 ℃ of roastings of Muffle furnace are put in extrusion molding after the drying.The moulding material that obtains is a hollow columnar, and the volume equivalent diameter is 7mm, and crushing strength is 9MPa.
Embodiment six
With SBA-15 40wt%, oxidation alum 30wt% is a matrix, aluminium nitride whisker 25wt% (diameter is 3 μ m, and the draw ratio scope is 1000～2000), (diameter is 0.3 μ m to Jin Jing's palpus 5wt%, the draw ratio scope is 10～100), after mixing, continue to add the polyethylene of dispersing agent alcoholic solution, wherein to account for the percentage of matrix and whisker gross mass be 2wt% to polyvinyl alcohol, after fully mediating evenly, 300 ℃ of roastings of Muffle furnace are put in extrusion molding after the drying.The moulding material that obtains is for spherical, and the volume equivalent diameter is 3.5mm, and crushing strength is 7MPa.
Embodiment seven
With MCM-41 10wt%, boehmite 30wt%, two silicic acid 20wt%, metasilicic acid 25wt% is a matrix, (diameter is 3 μ m to potassium tetratitanate whisker 15wt%, the draw ratio scope is 500～2000), after mixing, continue to add dispersant cmc soln and poly-vinyl alcohol solution, wherein to account for the percentage of matrix and whisker gross mass respectively be 10wt% and 5wt% for carboxymethyl cellulose and polyvinyl alcohol, after fully mediating evenly, 700 ℃ of roastings of Muffle furnace are put in extrusion molding after the drying.The percentage that accounts for matrix and whisker gross mass in chloroplatinic acid is the ratio of 0.1wt%, adopt the method for excessive dipping that the moulding material that obtains is supported, dry back is 500 ℃ of following calcination process, and the catalyst that finally obtains is for spherical, the volume equivalent diameter is 2.5mm, and crushing strength is 10MPa.
Embodiment eight
With zirconia 50wt% is matrix, (diameter is 2 μ m with the alumina whisker of 50wt%, the draw ratio scope is 1500～2500) mix after, continue to add the dispersant polyglycol solution, wherein to account for the percentage of matrix and whisker gross mass be 12wt% to polyethylene glycol, after fully mediating evenly, 500 ℃ of roastings of Muffle furnace are put in extrusion molding after the drying.The percentage that accounts for matrix and whisker gross mass in gold chloride, cobalt nitrate, manganese nitrate is respectively the ratio of 5wt%, 70wt%, 15wt%, adopt the method for incipient impregnation that the moulding material that obtains is supported, dry back is 500 ℃ of following calcination process, the catalyst shape that finally obtains is a sheet, the volume equivalent diameter is 6mm, and crushing strength is 8MPa.
Embodiment nine
With titanium oxide sol 20wt%, boehmite 45wt% is a matrix, (diameter is 1 μ m to cupric oxide whisker 10wt%, the draw ratio scope is 50～250), (diameter is 1 μ m to manganese oxide whisker 10wt%, the draw ratio scope is 10～50), (diameter is 2 μ m to two metatitanic acid whisker 15wt%, the draw ratio scope is 10～150), after mixing, continue to add the dispersant polyglycol solution, wherein to account for the percentage of matrix and whisker gross mass be 1wt% to polyethylene glycol, after fully mediating evenly, 650 ℃ of roastings of Muffle furnace are put in extrusion molding after the drying.The moulding material that obtains is a bunge bedstraw herb, and the volume equivalent diameter is 4.5mm, and crushing strength is 10MPa.
Embodiment ten
With cupric oxide 10wt%, zinc oxide 15wt%, aluminium oxide 30wt%, oxidation alum 15wt% is a matrix, (diameter is 5 μ m to titanium carbide crystal whisker 20wt%, the draw ratio scope is 100～500), (diameter is 3 μ m to titanium nitride whisker 10wt%, the draw ratio scope is 200～800), after mixing, continue to add dispersant methocel solution and polyglycol solution, wherein to account for the percentage of matrix and whisker gross mass respectively be 2wt% and 7wt% for methylcellulose and polyethylene glycol, after fully mediating evenly, 750 ℃ of roastings of Muffle furnace are put in extrusion molding after the drying.The moulding material that obtains is a column, and the volume equivalent diameter is 3.5mm, and crushing strength is 10MPa.
Embodiment 11
With hydrous titanium oxide 30wt%, aluminium oxide 20wt%, four metatitanic acid 15wt% are matrix, (diameter is 1 μ m to boron carbide whisker 20wt%, the draw ratio scope is 20～150), (diameter is 0.8 μ m to charcoal whisker 15wt%, the draw ratio scope is 2～100), after mixing, continue to add dispersant methocel solution, soluble starch solution and poly-vinyl alcohol solution, the percentage that they account for matrix and whisker gross mass respectively is 8wt%, 8wt% and 6wt%, fully after the kneading evenly, 380 ℃ of roastings of Muffle furnace are put in extrusion molding after the drying.The moulding material that obtains is shaped as clover, and the volume equivalent diameter is 4mm, and crushing strength is 8MPa.
Embodiment 12
With sodium metasilicate 30wt%, the molten 35wt% of silica is a matrix, (diameter is 1 μ m to iron whiskers 15wt%, the draw ratio scope is 10～500), (diameter is 2 μ m to iron oxide whisker 10wt%, the draw ratio scope is 1000～2000), (diameter is 0.2 μ m to platinum whisker 10wt%, the draw ratio scope is 10～50), after mixing, continue to add the dispersant methocel solution, cmc soln and polyglycol solution, the percentage that they account for matrix and whisker gross mass respectively is 1wt%, after 3wt% and 5wt% fully mediate evenly, 850 ℃ of roastings of Muffle furnace are put in extrusion molding after the drying.The moulding material that obtains is shaped as bunge bedstraw herb, and the volume equivalent diameter is 6.5mm, and crushing strength is 12MPa.
Comparative example 1
Do not add alumina whisker, and directly be raw material with the silica sol, add the cmc soln of same ratio according to the method for embodiment 1, the compression strength of the catalyst carrier that obtains behind the shaping and roasting has only 3MPa, is 1/3～1/2 of embodiment 1.
Comparative example 2
This comparison example is the moulding material that is prepared by the method that CN100421783C describes
With meso-porous titanium oxide whisker, titanium oxide sol is raw material, wherein the meso-porous titanium oxide whisker is 80wt% (diameter is 0.1～10 μ m), and titanium oxide is 20wt%, after the adding suitable quantity of water is fully mixed, through the banded extruder extruded moulding, put into 400 ℃ of roastings of Muffle furnace after the drying.The moulding material that obtains is a strip, and equivalent diameter is 2mrm, and degree of crystallinity is 45%, specific area is 132m2/g, and crushing strength is 0.54MPa, and porosity is 77%, pore volume is 0.67cm3/g, and the pore-size distribution peak can very be put and lay respectively at 5.5nm, 55nm and 7.6 μ m.
By embodiment and comparative example as can be seen, the present invention is owing to introduced high-intensity whisker reinforcing material and corresponding dispersant in forming process, and therefore preformed catalyst carrier or the catalyst of preparing has higher crushing strength.Because the present invention has certain versatility, be fit to the preformed catalyst carrier or the Preparation of catalysts of various components and shape, simple owing to forming process in addition, cost is lower, and preparation process is not polluted, and production is amplified in suitable industrial scale.
Claims (10)
1, a kind of whisker reinforced preformed catalyst carrier or Preparation of catalysts method are divided into the preparation method of whisker reinforced preformed catalyst carrier or the preparation method of whisker reinforced preformed catalyst, wherein,
The preparation method of whisker reinforced preformed catalyst carrier may further comprise the steps:
(1), in becoming mold base, add crystal whisker materials, mix, wherein to account for the mass percent of batch mixing be 0.1～50wt% to crystal whisker materials;
(2), in the batch mixing that above-mentioned steps obtains, add dispersant, after fully mediating, extrusion molding;
(3), formed body is dry and in 200～1000 ℃ of following calcination process, obtain whisker reinforced preformed catalyst carrier;
The preparation method of whisker reinforced preformed catalyst may further comprise the steps:
(1), in becoming mold base, add crystal whisker materials, mix, wherein to account for the mass percent of batch mixing be 0.1～50w% to crystal whisker materials;
(2), in the batch mixing that above-mentioned steps obtains, add dispersant, after fully mediating, extrusion molding on banded extruder;
(3), obtain preformed catalyst carrier with the formed body drying and in 200～1000 ℃ of following calcination process;
(4), with containing the above-mentioned preformed catalyst carrier of solution impregnation of active metal component, drying and in 200～1000 ℃ of following roastings obtains whisker reinforced preformed catalyst;
Perhaps, the preparation method of whisker reinforced preformed catalyst is made of following steps:
(1), in becoming mold base, add crystal whisker materials, mix, wherein to account for the mass percent of batch mixing be 0.1～50wt% to crystal whisker materials;
(2), in the batch mixing that above-mentioned steps obtains, add dispersant and contain the solution of active metal component, after abundant kneading, extrusion molding;
(3), formed body is dry and in 200～1000 ℃ of following calcination process, obtain whisker reinforced preformed catalyst.
2, preparation method according to claim 1, it is characterized in that, described one-tenth mold base is selected from least a in the following material: the oxide of silicon, aluminium, titanium, zirconium, cerium, alum, iron, copper, zinc or its corresponding acid or corresponding alkali, molecular sieve, diatomite, bentonite.
3, preparation method according to claim 1 is characterized in that, described crystal whisker materials is selected from one or more in metal whisker or the nonmetal whisker.
4, preparation method according to claim 3 is characterized in that, the metal in the described metal whisker is gold, silver, iron, nickel, copper, iron, tin, aluminium, platinum or beryllium; Described nonmetal whisker is aluminium oxide, titanium oxide, zirconia, cupric oxide, manganese oxide, beryllium oxide, magnesia or its corresponding hydroxide whisker, perhaps is carborundum, titanium carbide, silicon nitride, titanium nitride, aluminium nitride, charcoal or boron carbide whisker.
According to claim 1,3 or 4 described preparation methods, it is characterized in that 5, the diameter of described crystal whisker materials is 0.1～5 μ m, length diameter ratio is not less than 2.
6, preparation method according to claim 1 is characterized in that, described dispersant is selected from one or more in carboxymethyl cellulose, methylcellulose, soluble starch, polyvinyl alcohol or the polyethylene glycol.
7, preparation method according to claim 1 is characterized in that, described dispersant dosage is into 0.1～20% of mold base and crystal whisker materials gross mass.
8, preparation method according to claim 1 is characterized in that, described active metal component is a transition metal.
9, preparation method according to claim 1 is characterized in that, described whisker reinforced preformed catalyst carrier or catalyst are granular, cylindric, sheet, sphere, spoke-like, hollow columnar, clover shape or bunge bedstraw herb shape.
10, preparation method according to claim 1 is characterized in that, the volume equivalent diameter of described whisker reinforced preformed catalyst carrier or catalyst is not less than 0.1mm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103706405A (en) * | 2012-09-28 | 2014-04-09 | 中国石油天然气股份有限公司 | Preparation method of TiO2/gamma-Al2O3 composite carrier material |
| CN104226240A (en) * | 2014-07-08 | 2014-12-24 | 杭州最清环保科技有限公司 | Preparation method for catalysis/adsorption material by taking kieselguhr as carrier |
| CN114260007A (en) * | 2021-12-13 | 2022-04-01 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by high mechanical strength propane dehydrogenation and preparation method thereof |
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| CN1258009C (en) * | 2002-05-13 | 2006-05-31 | 武汉科技大学 | ZnO nano crystal whisker material and its preparing method |
| CN1552959A (en) * | 2003-05-26 | 2004-12-08 | 青海海兴科技开发有限公司 | Preparing process for calcium carbonate crystal whisker |
| WO2006137163A1 (en) * | 2005-06-24 | 2006-12-28 | Ibiden Co., Ltd. | Honeycomb structure body |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706405A (en) * | 2012-09-28 | 2014-04-09 | 中国石油天然气股份有限公司 | Preparation method of TiO2/gamma-Al2O3 composite carrier material |
| CN103706405B (en) * | 2012-09-28 | 2016-03-09 | 中国石油天然气股份有限公司 | A kind of TiO 2/ γ-Al 2o 3the preparation method of composite carrier |
| CN104226240A (en) * | 2014-07-08 | 2014-12-24 | 杭州最清环保科技有限公司 | Preparation method for catalysis/adsorption material by taking kieselguhr as carrier |
| CN114260007A (en) * | 2021-12-13 | 2022-04-01 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by high mechanical strength propane dehydrogenation and preparation method thereof |
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