CN103447082B - A kind of method recovering the based structuring activity of molecular sieve catalysts of foam silicon carbon - Google Patents
A kind of method recovering the based structuring activity of molecular sieve catalysts of foam silicon carbon Download PDFInfo
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- CN103447082B CN103447082B CN201310401519.6A CN201310401519A CN103447082B CN 103447082 B CN103447082 B CN 103447082B CN 201310401519 A CN201310401519 A CN 201310401519A CN 103447082 B CN103447082 B CN 103447082B
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- molecular sieve
- silicon carbon
- foam silicon
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 331
- 239000006260 foam Substances 0.000 title claims abstract description 312
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 308
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 299
- 239000003054 catalyst Substances 0.000 title claims abstract description 232
- 230000000694 effects Effects 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000002779 inactivation Effects 0.000 claims abstract description 118
- 239000011248 coating agent Substances 0.000 claims abstract description 62
- 238000000576 coating method Methods 0.000 claims abstract description 62
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 239000012808 vapor phase Substances 0.000 claims abstract description 14
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 67
- 229910021536 Zeolite Inorganic materials 0.000 claims description 60
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 60
- 239000010457 zeolite Substances 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 239000011148 porous material Substances 0.000 claims description 30
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 26
- 239000011247 coating layer Substances 0.000 claims description 24
- 230000008929 regeneration Effects 0.000 claims description 22
- 238000011069 regeneration method Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000011084 recovery Methods 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 12
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 6
- 150000007529 inorganic bases Chemical class 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- 238000009992 mercerising Methods 0.000 claims description 5
- -1 4-propyl bromide Chemical compound 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 230000002427 irreversible effect Effects 0.000 abstract description 4
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 34
- 229910021641 deionized water Inorganic materials 0.000 description 34
- 230000004913 activation Effects 0.000 description 21
- 238000004140 cleaning Methods 0.000 description 20
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 20
- 238000004506 ultrasonic cleaning Methods 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 229910010271 silicon carbide Inorganic materials 0.000 description 14
- 238000013019 agitation Methods 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 7
- 229910021426 porous silicon Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000012690 zeolite precursor Substances 0.000 description 2
- YFVKHKCZBSGZPE-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(propylamino)propan-1-one Chemical compound CCCNC(C)C(=O)C1=CC=C2OCOC2=C1 YFVKHKCZBSGZPE-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000003416 augmentation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention relates to the based structuring molecular sieve catalyst field of foam silicon carbon, be specially a kind of method recovering the based structuring activity of molecular sieve catalysts of foam silicon carbon, solve in prior art due to molecular sieve be chronically exposed to high temperature, super-humid conditions under and the framework of molecular sieve aluminium silicon species that causes is converted into non-skeleton species, run off in activated centre, the problem of structure collapse etc. and irreversible inactivation.Cause the molecular sieve coating of inactivation for silicon and aluminum source with foam silicon carbon carrier surface because of loss of active component or structure collapse, by based structuring for inactivation foam silicon carbon molecular sieve catalyst hydrothermal treatment consists in the actified solution containing template or vapor phase, make deactivated molecular sieve coating at the new molecular sieve coating of the inverting synthesis of foam silicon carbon carrier surface original position.The present invention effectively can extend the service life of the based structuring molecular sieve catalyst of foam silicon carbon, improves the Technical Economy that the based structuring catalyst of foam silicon carbon is applied in chemical industry.
Description
Technical field
The present invention relates to the based structuring molecular sieve catalyst field of foam silicon carbon, be specially a kind of method recovering the based structuring activity of molecular sieve catalysts of foam silicon carbon.
Background technology
Zeolite crystal has unique stuctures and properties, is widely used in the field such as petrochemical industry, environmental protection as catalyst, catalyst carrier or adsorbent.Traditional zeolite crystal catalyst is all be applied in the form of granules in fixed bed, not only causes bed pressure drop to raise the waste causing the energy, and also produces larger concentration and thermograde in process of production, reduce the catalytic efficiency of catalyst.Meanwhile, the separation of zeolite crystal catalyst and recovery difficult greatly, cause catalyst loss and produce environmental pollution.
Structuring molecular sieve catalyst is made on molecular sieve carried carrier such as the surface such as silica, aluminium oxide to inorganic inert, is the raising molecular sieve stability that foreign latest proposes, the effective ways solving molecular sieve unsuitable separation and recovery recycling problem.The method utilizes the peptizaiton of carrier by molecular sieve stabilisation, wish, under the prerequisite keeping the advantages such as molecular sieve high reaction activity, high target selectivity, to possess following advantage: 1. can realize the combination between the chemical design of catalyst and reaction engineering design well; 2. there are stronger augmentation of heat transfer, mass transfer and reduction Pressure Drop ability, thus effectively can improve the stability of reaction efficiency and molecular sieve, and reduce discarded object discharge capacity; 3. the new reaction technology of exploitation and process integrated technology is conducive to; 4. the problem of catalyst-free wearing and tearing and catalyst and product separation, is conducive to the security improving catalyst life and operating process.These advantages have very important effect to energy-conservation, efficient, clean, the level of security that improve Chemical Manufacture.
After the based structuring molecular sieve catalyst of foam silicon carbon runs a period of time in chemical reaction process, the inactivation due to a variety of causes.Usually, the based structuring molecular sieve catalyst inactivation of foam silicon carbon can be divided into two types: (1) to be blocked by coke due to catalyst duct or molecular sieve surface active sites is covered by coke completely, and cause reversibly inactivated; (2) due to molecular sieve be chronically exposed to high temperature, super-humid conditions under and the framework of molecular sieve aluminium silicon species that causes is converted into non-skeleton species, run off in activated centre, structure collapse etc. and irreversible inactivation.The first inactivation can by the activity recovery of making charcoal under temperate condition; And the second inactivation, because framework of molecular sieve has caved in, activity cannot have been recovered, and this certainly will cause great waste.For the based structuring catalyst of foam silicon carbon, although molecular sieve coating irreversible inactivation, because properties of SiC foam ceramics has higher mechanics, chemical stability, also do not destroyed.Thus, if discard the based structuring catalyst of whole foam silicon carbon at this point, great waste certainly will be caused.
Summary of the invention
The object of the present invention is to provide a kind of method recovering the based structuring activity of molecular sieve catalysts of foam silicon carbon, solve in prior art due to molecular sieve be chronically exposed to high temperature, super-humid conditions under and the framework of molecular sieve aluminium silicon species that causes is converted into non-skeleton species, run off in activated centre, the problem of structure collapse etc. and irreversible inactivation.
Technical scheme of the present invention is:
A kind of method recovering the based structuring activity of molecular sieve catalysts of foam silicon carbon, cause the molecular sieve coating of inactivation for silicon and aluminum source with foam silicon carbon carrier surface because of loss of active component or structure collapse, by based structuring for inactivation foam silicon carbon molecular sieve catalyst hydrothermal treatment consists in the actified solution containing silicon source, aluminium source, template; Or by the based structuring catalyst of inactivation foam silicon carbon hydrothermal treatment consists in template vapor phase of based structuring for inactivation foam silicon carbon catalyst or silicon-coating aluminium species, make the based structuring molecular sieve catalyst activity recovery of inactivation foam silicon carbon.
In the present invention, sial species refer to silicon source required for synthesis of molecular sieve, aluminium source.Specifically, can be one or more in silicon-aluminum sol, the precursor sol of paracrystalline molecular sieve or the precursor sol of paracrystalline molecular sieve and the mixture of molecular sieve powder.
In the present invention, the based structuring molecular sieve catalyst of foam silicon carbon is have the foam silicon carbon of three-dimensional communication pore passage structure for carrier, at the structural catalyst that its area load molecular sieve coating is formed as active component.The pore diameter range of foam silicon carbon carrier is 0.1mm-10mm, and pore diameter range is preferably 0.1mm-5mm; Porosity 30%-90%.Porosity is preferably 50%-85%.
In the present invention, foam silicon carbon carrier surface molecular sieve crystal is ZSM-5, β or Y-type zeolite molecular sieve.Molecular sieve carried amount is 0.5-60wt%, and molecular sieve carried amount is preferably 5-40wt%; Coating layer thickness is 2-50 micron, and coating layer thickness is preferably 5-30 micron; The specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 10-300m
2/ g, specific area is preferably 30-150m
2/ g.
In the present invention, foam silicon carbon carrier surface molecular sieve coating causes the based structuring activity of molecular sieve catalysts of foam silicon carbon to reduce because of reasons such as activated centre loss, structure collapse, can not recover completely through conventional coke-burning regeneration activity.
In the present invention, a kind of method recovering the based structuring activity of molecular sieve catalysts of foam silicon carbon, based structuring for inactivation foam silicon carbon molecular sieve catalyst is placed in containing silicon source, aluminium source, template, in the actified solution of inorganic base and water, silicon source, aluminium source, template, the molar ratio range of inorganic base and water is 0-1.0:0-0.5:0.01-0.5:0-0.5:10-500, with foam silicon carbon carrier surface deactivated molecular sieve for silicon and aluminum source carries out fabricated in situ, Hydrothermal Synthesis temperature is 120-200 DEG C, the Hydrothermal Synthesis time is 12-200 hour, the mass ratio of the based structuring catalyst of inactivation foam silicon carbon and actified solution is 1:5-50.Wherein, template used dose is selected from TPAOH, 4-propyl bromide, one or more in tetraethylammonium bromide, tetraethyl ammonium hydroxide, TMAH, 4 bromide, TBAH, TBAB, ethamine, n-propylamine, di-n-propylamine, butanediamine, ethylenediamine, MEA, diethanol amine and triethanolamine.Inorganic base used comprise in NaOH, potassium hydroxide, lithium hydroxide one or more.
In the present invention, recover a method for the based structuring activity of molecular sieve catalysts of foam silicon carbon, the steam that the based structuring catalyst of inactivation foam silicon carbon of based structuring for inactivation foam silicon carbon molecular sieve catalyst or silicon-coating aluminium species is placed in containing template is carried out hydrothermal treatment consists.In this process, first, the aqueous solution containing template is added bottom reactor; Subsequently, the based structuring catalyst of inactivation foam silicon carbon of based structuring for inactivation foam silicon carbon catalyst or silicon-coating aluminium species is placed on the support in reactor, does not contact with the aqueous solution containing template.After reactor is closed, at 150-250 DEG C of hydrothermal treatment consists 24-200 hour.Wherein, for recovery foam silicon carbon based structuring type ZSM 5 molecular sieve structured catalyst material activity, used template is one or more in TPAOH, 4-propyl bromide, ethylenediamine, triethylamine.For recovery foam silicon carbon based structuring beta molecular sieve structured catalyst material, template used is one or more in tetraethyl ammonium hydroxide, tetraethylammonium bromide, ethylenediamine, triethylamine; For recovery foam silicon carbon based structuring Y zeolite structured catalyst material activity, used template is one or more in TMAH, 4 bromide, ethylenediamine, triethylamine.
In the present invention, the based structuring molecular sieve catalyst of foam silicon carbon can use Chinese invention patent application (application number: porous silicon carbide carrier surface height intercrystalline pore rate ZSM-5 type zeolite coating material mentioned 201010199071.0) and preparation method thereof.The based structuring molecular sieve catalyst of foam silicon carbon can use Chinese invention patent application (application number: the porous silicon carbide carrier surface individual layer mentioned 201010199076.3), b axle orientation ZSM-5 type zeolite coating material and preparation method thereof.The based structuring molecular sieve catalyst of foam silicon carbon can use Chinese invention patent application (application number: porous zeolite molecular sieve coating material on surface of silicon carbide ceramics mentioned 200910013245.7) and preparation method thereof.The based structuring molecular sieve catalyst of foam silicon carbon can use Chinese invention patent application (application number: the superfine molecular sieves structured catalyst material based on porous silicon carbide silicon carrier mentioned 201110156980) and preparation.The based structuring molecular sieve catalyst of foam silicon carbon can use Chinese invention patent application (application number: a kind of porous silicon carbide carrier surface gradient pore molecular sieve coating mentioned 201310164573.3) and preparation method.
In the present invention, in the method for inactivation foam silicon carbon based structuring molecular sieve catalyst surface silicon-coating aluminium species, can use and can use Chinese invention patent application (application number: the superfine molecular sieves structured catalyst material based on porous silicon carbide silicon carrier mentioned 201110156980) and preparation.The based structuring molecular sieve catalyst of foam silicon carbon can use Chinese invention patent application (application number: a kind of porous silicon carbide carrier surface gradient pore molecular sieve coating mentioned 201310164573.3) and preparation method.
The present invention has following beneficial effect:
1, the method for the based structuring activity of molecular sieve catalysts of recovery foam silicon carbon provided by the invention, by based structuring for inactivation foam silicon carbon molecular sieve catalyst hydrothermal treatment consists in the actified solution containing silicon source, aluminium source, template; Or by the based structuring catalyst of inactivation foam silicon carbon hydrothermal treatment consists in template vapor phase of based structuring for inactivation foam silicon carbon catalyst or silicon-coating aluminium species, the substance release such as coke, potassium, sodium, sieve and silica-sesquioxide that can will be blocked in molecular sieve pore passage, and recrystallization forms fresh molecular sieve.Solve the problem causing the based structuring molecular sieve catalyst of foam silicon carbon discarded due to zeolite-water heat inactivation.After said process process, the activation recovering of the based structuring molecular sieve catalyst of foam silicon carbon is to fresh catalyst level.
2, the present invention effectively can extend the service life of the based structuring molecular sieve catalyst of foam silicon carbon, improves the Technical Economy that the based structuring catalyst of foam silicon carbon is applied in chemical industry.
Detailed description of the invention
Below by embodiment in detail the present invention is described in detail.Embodiment 1-4 is ZSM-5/ foam SiC structural catalyst result, and embodiment 5, embodiment 6 are HZSM-5 beaded catalyst contrast and experiment.
Embodiment 1
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load type ZSM 5 molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 0.5mm, porosity 70%.Foam silicon carbon carrier surface inactivation ZSM-5 type zeolite molecular sieve load capacity is 30wt%, and deactivated molecular sieve coating layer thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 30m
2/ g.
First preparation is containing the actified solution of template: by potassium hydroxide (KOH, analyze pure), 4-propyl bromide (TPABr, analyze pure) mix in deionized water and electromagnetic agitation 15min, add appropriate aluminum nitrate, continue to stir 15min, make Hydrothermal Synthesis solution, actified solution mol ratio is: 0.15TPABr:0.3KOH:0.01Al (NO
3)
3: 75H
2o.Hydrothermal Synthesis solution is poured into the stainless steel cauldron that polytetrafluoro liner is housed, and put into wherein by foam SiC carrier, the mass ratio of the based structuring catalyst of inactivation foam silicon carbon and actified solution is 1:40.175 DEG C of baking ovens are put into, reaction 96h after being sealed by reactor.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 600 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, foam silicon carbon carrier surface ZSM-5 type zeolite molecular sieve load capacity is 28wt%, and molecular sieve coating thickness is 19 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 130m
2/ g.
Embodiment 2
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load type ZSM 5 molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 0.2mm, porosity 50%.Foam silicon carbon carrier surface inactivation ZSM-5 type zeolite molecular sieve load capacity is 40wt%, and foam silicon carbon carrier surface deactivated molecular sieve coating layer thickness is 10 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 20m
2/ g.
First preparation is containing the actified solution of template: by NaOH (NaOH, analyze pure), 4-propyl bromide (TPABr analyzes pure) mixes and electromagnetic agitation 15min in deionized water, adds appropriate ethyl orthosilicate, aluminium source, continue to stir 15min, make Hydrothermal Synthesis solution.Actified solution mol ratio is: 0.3TEOS:0.01Al (NO
3)
3: 0.3TPABr:0.15NaOH:30H
2o.Hydrothermal Synthesis solution is poured into the stainless steel cauldron that polytetrafluoro liner is housed, and put into wherein by foam SiC carrier, the mass ratio of the based structuring catalyst of inactivation foam silicon carbon and actified solution is 1:20.160 DEG C of baking ovens are put into, reaction 80h after being sealed by reactor.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 500 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, foam silicon carbon carrier surface ZSM-5 type zeolite molecular sieve load capacity is 42wt%, and molecular sieve coating thickness is 10 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 156m
2/ g.
Embodiment 3
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load type ZSM 5 molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 3.0mm, porosity 90%.Foam silicon carbon carrier surface inactivation ZSM-5 type zeolite molecular sieve load capacity is 10wt%, and deactivated molecular sieve coating layer thickness is 30 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 3m
2/ g.
First preparation is containing the actified solution of template: lithium hydroxide (LiOH analyzes pure), TPAOH (TPAOH analyzes pure) are mixed in deionized water and electromagnetic agitation 15min, make Hydrothermal Synthesis solution.Actified solution mol ratio is: 0.6TPAOH:0.10LiOH:100H
2o.Hydrothermal Synthesis solution is poured into the stainless steel cauldron that polytetrafluoro liner is housed, and put into wherein by foam SiC carrier, the mass ratio of the based structuring catalyst of inactivation foam silicon carbon and actified solution is 1:10.190 DEG C of baking ovens are put into, reaction 196h after being sealed by reactor.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 570 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, foam silicon carbon carrier surface ZSM-5 type zeolite molecular sieve load capacity is 8wt%, and molecular sieve coating thickness is 25 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 50m
2/ g.
Embodiment 4
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load beta molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 5.0mm, porosity 90%.The molecular sieve carried amount of foam silicon carbon carrier surface inactivation zeolite beta is 8wt%, and deactivated molecular sieve coating layer thickness is 5 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 5m
2/ g.
First preparation is containing the actified solution of template: mixed in deionized water by tetraethyl ammonium hydroxide (TEAOH analyzes pure) and electromagnetic agitation 15min, make Hydrothermal Synthesis solution, actified solution mol ratio is: 0.2TEAOH:50H
2o.Hydrothermal Synthesis solution is poured into the stainless steel cauldron that polytetrafluoro liner is housed, and put into wherein by foam SiC carrier, the mass ratio of the based structuring catalyst of inactivation foam silicon carbon and actified solution is 1:50.150 DEG C of baking ovens are put into, reaction 24h after being sealed by reactor.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 530 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, the molecular sieve carried amount of zeolite beta is 8wt%, and molecular sieve coating thickness is 5 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 40m
2/ g.
Embodiment 5
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load beta molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 0.8mm, porosity 65%.The molecular sieve carried amount of foam silicon carbon carrier surface inactivation zeolite beta is 15wt%, and deactivated molecular sieve coating layer thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 5m
2/ g.
First preparation is containing the actified solution of template: mixed in deionized water by tetraethylammonium bromide (TEABr analyzes pure) and electromagnetic agitation 15min, add appropriate white carbon, aluminum nitrate, make Hydrothermal Synthesis solution, actified solution mol ratio is: 0.5SiO
2: Al (NO
3)
3: 0.6TEABr:30H
2o.Hydrothermal Synthesis solution is poured into the stainless steel cauldron that polytetrafluoro liner is housed, and put into wherein by foam SiC carrier, the mass ratio of the based structuring catalyst of inactivation foam silicon carbon and actified solution is 1:30.130 DEG C of baking ovens are put into, reaction 96h after being sealed by reactor.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 580 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, the molecular sieve carried amount of zeolite beta is 15wt%, and molecular sieve coating thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 75m
2/ g.
Embodiment 6
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load beta molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 0.8mm, porosity 86%.The molecular sieve carried amount of foam silicon carbon carrier surface inactivation zeolite beta is 25wt%, and deactivated molecular sieve coating layer thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 15m
2/ g.
First preparation is containing the actified solution of template: lithium hydroxide (LiOH analyzes pure), tetraethylammonium bromide (TEABr analyzes pure), aluminum nitrate are mixed in deionized water and electromagnetic agitation 15min, make Hydrothermal Synthesis solution.Actified solution mol ratio is: 0.4TEABr:0.001Al (NO
3)
3: 0.9LiOH:30H
2o.Hydrothermal Synthesis solution is poured into the stainless steel cauldron that polytetrafluoro liner is housed, and put into wherein by foam SiC carrier, the mass ratio of the based structuring catalyst of inactivation foam silicon carbon and actified solution is 1:30.130 DEG C of baking ovens are put into, reaction 96h after being sealed by reactor.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 580 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, the molecular sieve carried amount of zeolite beta is 25wt%, and molecular sieve coating thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 140m
2/ g.
Embodiment 7
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load Y zeolite coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 0.5mm, porosity 70%.Foam silicon carbon carrier surface inactivation Y-type zeolite molecular sieve load capacity is 20wt%, and deactivated molecular sieve coating layer thickness is 10 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 13m
2/ g.
First preparation is containing the actified solution of template: by the 0.6:0.006:0.8:100 mixing in molar ratio of aluminium isopropoxide, NaOH, TMAH, deionized water.Mixing also electromagnetic agitation 15min, makes Hydrothermal Synthesis solution in deionized water.Hydrothermal Synthesis solution is poured into the stainless steel cauldron that polytetrafluoro liner is housed, and put into wherein by foam SiC carrier, the mass ratio of the based structuring catalyst of inactivation foam silicon carbon and actified solution is 1:30.130 DEG C of baking ovens are put into, reaction 96h after being sealed by reactor.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 580 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, the molecular sieve carried amount of zeolite beta is 25wt%, and molecular sieve coating thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 80m
2/ g.
Embodiment 8
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load Y zeolite coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 1.0mm, porosity 90%.Foam silicon carbon carrier surface inactivation Y-type zeolite molecular sieve load capacity is 30wt%, and deactivated molecular sieve coating layer thickness is 30 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 20m
2/ g.
First preparation is containing the actified solution of template: by the 0.1:0.8:0.01:0.05:1000 mixing in molar ratio of ethyl orthosilicate, aluminium isopropoxide, NaOH, TMAH, deionized water.Mixing also electromagnetic agitation 15min, makes Hydrothermal Synthesis solution in deionized water.Hydrothermal Synthesis solution is poured into the stainless steel cauldron that polytetrafluoro liner is housed, and put into wherein by foam SiC carrier, the mass ratio of the based structuring catalyst of inactivation foam silicon carbon and actified solution is 1:10.120 DEG C of baking ovens are put into, reaction 120h after being sealed by reactor.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 550 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, Y-type zeolite molecular sieve load capacity is 25wt%, and molecular sieve coating thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 120m
2/ g.
Embodiment 9
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load Y zeolite coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 3.0mm, porosity 80%.Foam silicon carbon carrier surface inactivation Y-type zeolite molecular sieve load capacity is 15wt%, and deactivated molecular sieve coating layer thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 5m
2/ g.
First preparation is containing the actified solution of template: by the 0.01:0.05:0.05:1000 mixing in molar ratio of Ludox, NaOH, TMAH, deionized water.Mixing also electromagnetic agitation 15min, makes Hydrothermal Synthesis solution in deionized water.Hydrothermal Synthesis solution is poured into the stainless steel cauldron that polytetrafluoro liner is housed, and put into wherein by foam SiC carrier, the mass ratio of the based structuring catalyst of inactivation foam silicon carbon and actified solution is 1:40.120 DEG C of baking ovens are put into, reaction 120h after being sealed by reactor.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 550 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, Y-type zeolite molecular sieve load capacity is 14wt%, and molecular sieve coating thickness is 14.5 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 80m
2/ g.
Embodiment 10
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load type ZSM 5 molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 0.5mm, porosity 70%.Foam silicon carbon carrier surface inactivation ZSM-5 type zeolite molecular sieve load capacity is 30wt%, and deactivated molecular sieve coating layer thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 30m
2/ g.
Above-mentioned inactivation foam silicon carbon based structuring molecular sieve catalyst polytetrafluoro bracing frame is fixed on 6.5 centimeters bottom reactor; In reactor, add the aqueous solution (concentration 10wt%) of 10 milliliters of TPAOHs, reactor volume is 500 milliliters.It is 150 DEG C that vapor phase transforms temperature used, and the time is 48 hours, and pressure is the self-generated pressure that solution boils produces.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 600 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, foam silicon carbon carrier surface ZSM-5 type zeolite molecular sieve load capacity is 30wt%, and molecular sieve coating thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 125m
2/ g.
Embodiment 11
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load type ZSM 5 molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 0.2mm, porosity 50%.Foam silicon carbon carrier surface inactivation ZSM-5 type zeolite molecular sieve load capacity is 40wt%, and foam silicon carbon carrier surface deactivated molecular sieve coating layer thickness is 10 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 20m
2/ g.
The based structuring molecular sieve catalyst of above-mentioned inactivation foam silicon carbon to be applied after the sial species of its 10% mass fraction (in the present embodiment, sial species specifically refer to the mixture of colloidal sol containing ZSM-5 molecular sieve presoma and ZSM-5 molecular sieve powder, wherein: ZSM-5 molecular sieve presoma accounts for 3wt%, ZSM-5 molecular sieve powder accounts for 7wt%), be fixed on 6.5 centimeters bottom reactor with polytetrafluoro bracing frame; In reactor, add the aqueous solution (concentration 20wt%) of 10 milliliters of tetraethylammonium bromides, reactor volume is 500 milliliters.It is 160 DEG C that vapor phase transforms temperature used, and the time is 72 hours, and pressure is the self-generated pressure that solution boils produces.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 500 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, foam silicon carbon carrier surface ZSM-5 type zeolite molecular sieve load capacity is 40wt%, and molecular sieve coating thickness is 10 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 140m
2/ g.
Embodiment 12
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load type ZSM 5 molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 3.0mm, porosity 90%.Foam silicon carbon carrier surface inactivation ZSM-5 type zeolite molecular sieve load capacity is 10wt%, and deactivated molecular sieve coating layer thickness is 30 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 3m
2/ g.
Above-mentioned inactivation foam silicon carbon based structuring molecular sieve catalyst polytetrafluoro bracing frame is fixed on 6.5 centimeters bottom reactor; In reactor, add the aqueous solution (ethylenediamine concentration 10wt%, triethylamine concentration 5wt%) of 10 milliliters of ethylenediamines, triethylamine, reactor volume is 500 milliliters.It is 180 DEG C that vapor phase transforms temperature used, and the time is 24 hours, and pressure is the self-generated pressure that solution boils produces.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 570 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, foam silicon carbon carrier surface ZSM-5 type zeolite molecular sieve load capacity is 9wt%, and molecular sieve coating thickness is 28 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 55m
2/ g.
Embodiment 13
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load beta molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 5.0mm, porosity 90%.The molecular sieve carried amount of foam silicon carbon carrier surface inactivation zeolite beta is 8wt%, and deactivated molecular sieve coating layer thickness is 5 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 5m
2/ g.
Above-mentioned inactivation foam silicon carbon based structuring molecular sieve catalyst polytetrafluoro bracing frame is fixed on 6.5 centimeters bottom reactor; In reactor, add the aqueous solution (concentration 5wt%) of 10 milliliters of tetraethyl ammonium hydroxides, reactor volume is 500 milliliters.It is 180 DEG C that vapor phase transforms temperature used, and the time is 72 hours, and pressure is the self-generated pressure that solution boils produces.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 530 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, the molecular sieve carried amount of zeolite beta is 8wt%, and molecular sieve coating thickness is 5 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 45m
2/ g.
Embodiment 14
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load beta molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 0.8mm, porosity 65%.The molecular sieve carried amount of foam silicon carbon carrier surface inactivation zeolite beta is 15wt%, and deactivated molecular sieve coating layer thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 5m
2/ g.
The based structuring molecular sieve catalyst of above-mentioned inactivation foam silicon carbon is applied the sial species of its 20% mass fraction (in the present embodiment, sial species specifically refer to beta-molecular sieve precursor sol) after, be fixed on 6.5 centimeters bottom reactor with polytetrafluoro bracing frame; In reactor, add the aqueous solution (concentration 5wt%) of 10 milliliters of tetraethylammonium bromides, reactor volume is 500 milliliters.It is 160 DEG C that vapor phase transforms temperature used, and the time is 96 hours, and pressure is the self-generated pressure that solution boils produces.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 580 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, the molecular sieve carried amount of zeolite beta is 15wt%, and molecular sieve coating thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 75m
2/ g.
Embodiment 15
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load beta molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 0.8mm, porosity 86%.The molecular sieve carried amount of foam silicon carbon carrier surface inactivation zeolite beta is 25wt%, and deactivated molecular sieve coating layer thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 15m
2/ g.
Above-mentioned inactivation foam silicon carbon based structuring molecular sieve catalyst polytetrafluoro bracing frame is fixed on 3.5 centimeters bottom reactor; In reactor, add the aqueous solution (tetraethylammonium bromide concentration 5wt%, methylamine concentration 5wt%) of 10 milliliters of tetraethylammonium bromides, methylamine, reactor volume is 500 milliliters.It is 150 DEG C that vapor phase transforms temperature used, and the time is 72 hours, and pressure is the self-generated pressure that solution boils produces.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 580 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, the molecular sieve carried amount of zeolite beta is 25wt%, and molecular sieve coating thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 140m
2/ g.
Embodiment 16
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load Y zeolite coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 0.5mm, porosity 70%.Foam silicon carbon carrier surface inactivation Y-type zeolite molecular sieve load capacity is 20wt%, and deactivated molecular sieve coating layer thickness is 10 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 13m
2/ g.
The based structuring molecular sieve catalyst of above-mentioned inactivation foam silicon carbon to be applied after the sial species of its 5% mass fraction (in the present embodiment, sial species specifically refer to the mixture of Y zeolite precursor sol and Y zeolite powder, wherein: Y zeolite presoma accounts for 1wt%, Y zeolite powder accounts for 4wt%), be fixed on 3.5 centimeters bottom reactor with polytetrafluoro bracing frame; In reactor, add the aqueous solution (concentration 15wt%) of 10 milliliters of 4 bromides, reactor volume is 500 milliliters.It is 150 DEG C that vapor phase transforms temperature used, and the time is 72 hours, and pressure is the self-generated pressure that solution boils produces.Mixing also electromagnetic agitation 15min, makes Hydrothermal Synthesis solution in deionized water.Hydrothermal Synthesis solution is poured into the stainless steel cauldron that polytetrafluoro liner is housed, and put into wherein by foam SiC carrier, the mass ratio of the based structuring catalyst of inactivation foam silicon carbon and actified solution is 1:30.130 DEG C of baking ovens are put into, reaction 96h after being sealed by reactor.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 580 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, Y-type zeolite molecular sieve load capacity is 20wt%, and molecular sieve coating thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 85m
2/ g.
Embodiment 17
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load Y zeolite coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 1.0mm, porosity 90%.Foam silicon carbon carrier surface inactivation Y-type zeolite molecular sieve load capacity is 30wt%, and deactivated molecular sieve coating layer thickness is 30 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 20m
2/ g.
Above-mentioned inactivation foam silicon carbon based structuring molecular sieve catalyst polytetrafluoro bracing frame is fixed on 5.5 centimeters bottom reactor; In reactor, add the aqueous solution (concentration 10wt%) of 10 milliliters of TMAHs, reactor volume is 500 milliliters.It is 160 DEG C that vapor phase transforms temperature used, and the time is 96 hours, and pressure is the self-generated pressure that solution boils produces.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 550 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, Y-type zeolite molecular sieve load capacity is 25wt%, and molecular sieve coating thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 120m
2/ g.
Embodiment 18
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load Y zeolite coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 3.0mm, porosity 80%.Foam silicon carbon carrier surface inactivation Y-type zeolite molecular sieve load capacity is 15wt%, and deactivated molecular sieve coating layer thickness is 20 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 5m
2/ g.
The based structuring molecular sieve catalyst of above-mentioned inactivation foam silicon carbon is applied the sial species of its 3% mass fraction (in the present embodiment, sial species specifically refer to Y zeolite precursor sol) after, be fixed on 5.5 centimeters bottom reactor with polytetrafluoro bracing frame; In reactor, add the aqueous solution (4 bromide concentration 10wt%, ethylenediamine concentration 5wt%, triethylamine concentration 5wt%) of 10 milliliters of 4 bromides, ethylenediamine, triethylamine, reactor volume is 500 milliliters.It is 200 DEG C that vapor phase transforms temperature used, and the time is 120 hours, and pressure is the self-generated pressure that solution boils produces.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 550 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, Y-type zeolite molecular sieve load capacity is 14wt%, and molecular sieve coating thickness is 19 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 100m
2/ g.
Embodiment 19
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load type ZSM 5 molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 0.5mm, porosity 70%.Foam silicon carbon carrier surface inactivation mercerising type zeolite molecular sieve load capacity is 20wt%, and deactivated molecular sieve coating layer thickness is 15 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 10m
2/ g.
First preparation is containing the actified solution of template: by potassium hydroxide (KOH, analyze pure), tetraethylammonium bromide (TPABr, analyze pure) mix in deionized water and electromagnetic agitation 15min, add appropriate ethyl orthosilicate, aluminum nitrate, continue to stir 15min, make Hydrothermal Synthesis solution, actified solution mol ratio is: 0.3TEOS:0.15TPABr:0.3NaOH:0.01Al (NO
3)
3: 75H
2o.Hydrothermal Synthesis solution is poured into the stainless steel cauldron that polytetrafluoro liner is housed, and put into wherein by foam SiC carrier, the mass ratio of the based structuring catalyst of inactivation foam silicon carbon and actified solution is 1:40.175 DEG C of baking ovens are put into, reaction 96h after being sealed by reactor.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 600 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, foam silicon carbon carrier surface ZSM-5 type zeolite molecular sieve load capacity is 18wt%, and molecular sieve coating thickness is 14 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 100m
2/ g.
Embodiment 20
In the present embodiment, the based structuring molecular sieve catalyst of inactivation foam silicon carbon, the based structuring molecular sieve catalyst of foam silicon carbon formed for foam silicon carbon carrier surface load type ZSM 5 molecular sieve coating.The based structuring molecular sieve catalyst of foam silicon carbon used, foam silicon carbon carrier used, pore diameter range is 0.5mm, porosity 70%.Foam silicon carbon carrier surface inactivation mercerising type zeolite molecular sieve load capacity is 20wt%, and deactivated molecular sieve coating layer thickness is 15 microns, and the specific area of the based structuring molecular sieve catalyst of inactivation foam silicon carbon is 10m
2/ g.
Above-mentioned inactivation foam silicon carbon based structuring molecular sieve catalyst polytetrafluoro bracing frame is fixed on 6.5 centimeters bottom reactor; In reactor, add the aqueous solution (20wt%) of 10 milliliters of tetraethyl ammonium hydroxides, reactor volume is 500 milliliters.It is 150 DEG C that vapor phase transforms temperature used, and the time is 48 hours, and pressure is the self-generated pressure that solution boils produces.After having reacted, sample is fully cleaned in the deionized water of 100 DEG C, then be the Ultrasonic Cleaning 40min of 40Hz by frequency.By cleaning after sample 100 DEG C dry 12h, then in 600 DEG C of Muffle furnaces roasting 6h, obtain the based structuring molecular sieve catalyst of foam silicon carbon of activation recovering.Wherein, after regeneration, foam silicon carbon carrier surface ZSM-5 type zeolite molecular sieve load capacity is 20wt%, and molecular sieve coating thickness is 15 microns, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 105m
2/ g.
Claims (8)
1. one kind is recovered the method for the based structuring activity of molecular sieve catalysts of foam silicon carbon, it is characterized in that, cause the molecular sieve coating of inactivation for silicon and aluminum source with foam silicon carbon carrier surface because of loss of active component or structure collapse, by based structuring for inactivation foam silicon carbon molecular sieve catalyst hydrothermal treatment consists in the actified solution containing silicon source, aluminium source, template; Or by the based structuring catalyst of inactivation foam silicon carbon hydrothermal treatment consists in template vapor phase of based structuring for inactivation foam silicon carbon catalyst or silicon-coating aluminium species, make the based structuring molecular sieve catalyst activity recovery of inactivation foam silicon carbon;
Based structuring for inactivation foam silicon carbon molecular sieve catalyst is placed in the actified solution containing silicon source, aluminium source, template, inorganic base and water, the molar ratio range of silicon source, aluminium source, template, inorganic base and water is 0-1.0:0-0.5:0.01-0.5:0-0.5:10-500, with foam silicon carbon carrier surface deactivated molecular sieve for silicon and aluminum source carries out fabricated in situ, Hydrothermal Synthesis temperature is 120-200 DEG C, the Hydrothermal Synthesis time is 12-200 hour, and the mass ratio of the based structuring catalyst of inactivation foam silicon carbon and actified solution is 1:5-50;
Wherein, template used dose is selected from one or more in TPAOH, 4-propyl bromide, tetraethylammonium bromide, tetraethyl ammonium hydroxide, TMAH, 4 bromide, TBAH, TBAB, ethamine, n-propylamine, di-n-propylamine, butanediamine, ethylenediamine, MEA, diethanol amine and triethanolamine; Inorganic base used be selected from NaOH, potassium hydroxide, lithium hydroxide one or more;
The steam that based structuring for inactivation foam silicon carbon molecular sieve catalyst is placed in containing template is carried out hydrothermal treatment consists; In this process, first, add bottom reactor by the aqueous solution containing template, the concentration of template is 1-40 wt%; Subsequently, based structuring for inactivation foam silicon carbon catalyst is placed on the support in reactor, does not contact with the aqueous solution containing template; After reactor is closed, at 150-250 DEG C of hydrothermal treatment consists 24-200 hour;
The steam that the based structuring molecular sieve catalyst of inactivation foam silicon carbon of silicon-coating aluminium species is placed in containing template is carried out hydrothermal treatment consists; In this process, first, add bottom reactor by the aqueous solution containing template, the concentration of template is 1-40 wt%; Subsequently, based structuring for inactivation foam silicon carbon catalyst is placed on the support in reactor, does not contact with the aqueous solution containing template; After reactor is closed, at 150-250 DEG C of hydrothermal treatment consists 24-200 hour.
2. according to the method for the based structuring activity of molecular sieve catalysts of recovery foam silicon carbon according to claim 1, it is characterized in that, the based structuring molecular sieve catalyst of described foam silicon carbon has the foam silicon carbon of three-dimensional communication pore passage structure for carrier, at the structural catalyst that its area load molecular sieve coating is formed as active component.
3. according to the method for the based structuring activity of molecular sieve catalysts of recovery foam silicon carbon according to claim 2, it is characterized in that, described foam silicon carbon carrier has three-dimensional networks structure, and pore diameter range is 0.1 mm-10 mm, porosity 30%-90%.
4. according to the method for the based structuring activity of molecular sieve catalysts of recovery foam silicon carbon according to claim 2, it is characterized in that, described foam silicon carbon carrier has three-dimensional networks structure, and pore diameter range is 0.1 mm-5 mm, and porosity is 50%-85%.
5. according to the method for the based structuring activity of molecular sieve catalysts of recovery foam silicon carbon according to claim 2, it is characterized in that, described molecular sieve crystal is ZSM-5, β, mercerising or Y-type zeolite molecular sieve; Molecular sieve carried amount is 0.5-60 wt%, and coating layer thickness is 2-50 micron, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 10-300 m
2/ g.
6. according to the method for the based structuring activity of molecular sieve catalysts of recovery foam silicon carbon according to claim 2, it is characterized in that, described molecular sieve crystal is ZSM-5, β, mercerising or Y-type zeolite molecular sieve; Molecular sieve carried amount is 5-40 wt%, and coating layer thickness is 5-30 micron, and the specific area of the based structuring molecular sieve catalyst of foam silicon carbon is 30-150 m
2/ g.
7. according to the method for the based structuring activity of molecular sieve catalysts of recovery foam silicon carbon described in claims 1, it is characterized in that, described foam silicon carbon carrier surface molecular sieve coating because of activated centre run off, structure collapse reason and cause the based structuring activity of molecular sieve catalysts of foam silicon carbon to reduce, can not recover completely through conventional coke-burning regeneration activity.
8. according to the method for the based structuring activity of molecular sieve catalysts of recovery foam silicon carbon described in claims 1 or 5 or 6, be characterised in that, for recovery foam silicon carbon based structuring type ZSM 5 molecular sieve structured catalyst material activity, used template is one or more in TPAOH, 4-propyl bromide, ethylenediamine, triethylamine; For recovery foam silicon carbon based structuring beta molecular sieve structured catalyst material, template used is one or more in tetraethyl ammonium hydroxide, tetraethylammonium bromide, ethylenediamine, triethylamine; For recovery foam silicon carbon based structuring mercerising type molecular sieve structure catalysis material is active, used template is one or more in tetraethyl ammonium hydroxide, tetraethylammonium bromide, ethylenediamine, triethylamine; For recovery foam silicon carbon based structuring Y zeolite structured catalyst material activity, used template is one or more in TMAH, 4 bromide, ethylenediamine, triethylamine.
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