CN108620121A - A kind of monoblock type molecular sieve catalyst and its preparation method and application - Google Patents
A kind of monoblock type molecular sieve catalyst and its preparation method and application Download PDFInfo
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- CN108620121A CN108620121A CN201810503167.8A CN201810503167A CN108620121A CN 108620121 A CN108620121 A CN 108620121A CN 201810503167 A CN201810503167 A CN 201810503167A CN 108620121 A CN108620121 A CN 108620121A
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- molecular sieve
- monoblock type
- sieve catalyst
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 199
- 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 199
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000006260 foam Substances 0.000 claims abstract description 80
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 238000002425 crystallisation Methods 0.000 claims abstract description 26
- 230000008025 crystallization Effects 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 22
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000006193 liquid solution Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 58
- 229910052763 palladium Inorganic materials 0.000 claims description 29
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 239000012279 sodium borohydride Substances 0.000 claims description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims 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 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000010815 organic waste Substances 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 230000007812 deficiency Effects 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000003756 stirring Methods 0.000 description 24
- 239000000523 sample Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 238000001027 hydrothermal synthesis Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000007084 catalytic combustion reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 241000264877 Hippospongia communis Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000243142 Porifera Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010336 energy treatment Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/17—Pore diameter distribution
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Abstract
The invention belongs to the technical fields of catalyst more particularly to a kind of monoblock type molecular sieve catalyst and its preparation method and application.The present invention provides a kind of preparation methods of monoblock type molecular sieve catalyst, include the following steps：Step 1：Template, soluble silicon source, soluble silicon source and solvent are mixed, molecular sieve precursor mixture is obtained；Step 2：Polyurethane foam matrix and molecular sieve precursor mixture are subjected to crystallization, crystal is obtained, after crystal is roasted, obtains the first molecular sieve carrier；Step 3：Metal front liquid solution is added dropwise in first molecular sieve carrier, the second molecular sieve foam is obtained, the second molecular sieve foam is dried, obtain third molecular sieve foam；Step 4：Reducing agent solution is added dropwise in third molecular sieve foam and is dried, monoblock type molecular sieve catalyst is obtained.The present invention can effectively solve the technological deficiency for the monoblock type molecular sieve catalyst with porous structure for being difficult to prepare self-support type at present.
Description
Technical field
The invention belongs to the technical fields of catalyst more particularly to a kind of monoblock type molecular sieve catalyst and preparation method thereof
And application.
Background technology
Volatile organic matter (Volatile organic compounds, VOCs) be atmosphere pollution important component it
One, have to environmental and human health impacts and seriously endanger, therefore effectively removes VOCs pollutions there is important Significance for Environment.Organic waste
The purified treatment of gas mainly has the technology types such as thermal incineration, biological treatment, adsorbent recycling and catalysis burning, wherein catalysis combustion
Burning method is a kind of high-efficiency cleaning combustion technology, mainly so that organic exhaust gas is fully fired under lower temperature condition using catalyst
It burns.Other opposite treatment technologies, catalysis burning have the advantages that notable：Initiation temperature is low, less energy consumption, and treatment effeciency is high, without two
Secondary pollution etc. makes current most promising VOCs processing methods.Efficient catalytic combustion catalyst is catalytic combustion technology
Key core, ordered structure catalyst is known as using the catalyst of block carrier as skeleton matrix, also referred to as monoblock type is catalyzed
Agent.Relative to traditional ordered structure carrier (such as ceramic honey comb and woven wire), self-supporting and with hierarchical porous structure
Foam carrier has big specific surface area and duct that is regular and interweaving, so adsorbance bigger, is widely used in gas
The fields such as body separation, absorption and catalysis.Since regular foam carrier has special pore passage structure, obtained monoblock type is loaded by it
Catalyst can be effectively improved the transmission of the substance in catalytic reactor bed layer, improve catalytic efficiency, reduce pressure drop, reduce operating cost
With being had been more and more widely used in the heterogeneous catalytic reactions such as petrochemical industry, fine chemistry industry.
Molecular sieve carrier has high-ratio surface, high hydrothermal stability and abundant micropore/meso-hole structure, is answered in catalytic field
With extensive.But current molecular sieve is mostly powder-product, and current is difficult to prepare the molecular sieve catalyst with porous structure, because
This, it is that those skilled in the art are urgently to be resolved hurrily to research and develop a kind of self-supporting and monoblock type molecular sieve catalyst with hierarchical porous structure
The technical issues of.
Invention content
In view of this, the present invention provides a kind of preparation of monoblock type molecular sieve catalyst, can effectively solve to be difficult at present
Prepare the technological deficiency of the monoblock type molecular sieve catalyst with porous structure of self-support type.
The present invention provides a kind of preparation methods of monoblock type molecular sieve catalyst, include the following steps：
Step 1：Template, soluble silicon source, soluble silicon source and solvent are mixed, molecular sieve precursor mixture is obtained；
Step 2：Polyurethane foam matrix and molecular sieve precursor mixture are subjected to crystallization, crystal is obtained, by institute
It states after crystal roasted, obtains the first molecular sieve carrier；
Step 3：Metal front liquid solution is added dropwise in first molecular sieve carrier, the second molecular sieve foam is obtained, by institute
It states the second molecular sieve foam to be dried, obtains third molecular sieve foam；
Step 4：Reducing agent solution is added dropwise in the third molecular sieve foam and is dried, monoblock type molecular sieve is obtained
Catalyst.
Preferably, the solubility silicon source includes one kind in sodium metaaluminate, aluminium isopropoxide or aluminum sulfate.
Preferably, the solubility silicon source includes one kind in ethyl orthosilicate, silica gel or sodium metasilicate.
Preferably, the template includes in tetrapropylammonium hydroxide, 4-propyl bromide or tetraethyl ammonium hydroxide
One kind.
Preferably, the crystallization temperature of the crystallization of the step 2 is 110 DEG C -210 DEG C.
Preferably, metal front liquid solution includes palladium nitrate or palladium bichloride.
Preferably, the reducing agent solution includes sodium borohydride solution or hydrazine hydrate solution.
Preferably, the step 4 specifically includes：Under the conditions of 20 DEG C -35 DEG C, the third molecular sieve foam is dripped
Add reducing agent solution and be dried, obtains monoblock type molecular sieve catalyst.
The present invention also provides a kind of monoblock type molecular sieve catalyst, be prepared according to above-mentioned preparation method.
The invention also discloses application of the monoblock type molecular sieve catalyst in cleaning organic waste gas.
Specifically, monoblock type molecular sieve catalyst provided by the invention is detached as gas, the purposes of absorption and catalysis.
Further, monoblock type molecular sieve catalyst provided by the invention is shown in toluene catalytic combustion purification reaction
Superior efficient cryogenic purification function.
For traditional molecular sieve powder carrier, the invention has the advantages that：The monoblock type of the present invention
Molecular sieve catalyst is noble-metal-supported in large specific surface area and porous molecular sieve foam (the first molecular sieve carrier)；This hair
The molecular sieve foam of bright preparation has the ordered structure of self-supporting, from the experimental data of embodiment it is found that the present invention prepare the
One molecular sieve carrier can be directly used in as regular carrier prepares monoblock type molecular sieve catalyst；And relative to traditional regular
Carrier (such as ceramic honey comb and woven wire), the first molecular sieve carrier prepared by the present invention have big specific surface area and rich again
Rich hierarchical porous structure (especially containing a large amount of mesoporous and macropore), is more advantageous to catalytic active component in regular carrier surface
Load and be uniformly distributed.Meanwhile from the result of embodiment it is found that using the obtained self-supporting of the present invention and hierarchical porous structure
First molecular sieve carrier, when preparing palladium-based monolithic molecular sieve foam catalyst for carried noble metal, in noble-metal-supported amount
Under the conditions of very low (bullion content about 0.08-0.20g in every liter of monoblock type molecular sieve catalyst), superior toluene can be shown
Low-temperature catalytic burning purification activity.So monoblock type molecular sieve catalyst prepared by the present invention has, preparation method is simple, is catalyzed
Agent is of low cost and the active high-effect advantage of catalytic purification, can be used widely in organic exhaust gas deep purifying field.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described.
Fig. 1 is that the embodiment of the present invention 1 prepares the first molecular sieve carrier obtained during monoblock type molecular sieve catalyst
XRD spectra；
Fig. 2 is that the embodiment of the present invention 1 prepares the first molecular sieve carrier obtained during monoblock type molecular sieve catalyst
Pictorial diagram；
Fig. 3 is that the embodiment of the present invention 1 prepares the first molecular sieve carrier obtained during monoblock type molecular sieve catalyst
SEM micromorphology figures；
Fig. 4 is that the embodiment of the present invention 1 prepares the first molecular sieve carrier obtained during monoblock type molecular sieve catalyst
N2Adsorption-desorption curve graph；
Fig. 5 is that the embodiment of the present invention 1 prepares the first molecular sieve carrier obtained during monoblock type molecular sieve catalyst
BJH mesoporous pore size distribution maps；
Fig. 6 is that the embodiment of the present invention 1 prepares the first molecular sieve carrier obtained during monoblock type molecular sieve catalyst
H-K micropore size distribution maps；
Fig. 7 for the monoblock type molecular sieve catalyst that the embodiment of the present invention 1 is prepared, (urge by palladium-based monolithic ZSM-5 foams
Agent) pictorial diagram.
Specific implementation mode
The present invention provides a kind of monoblock type molecular sieve catalysts and its preparation method and application, can effectively solve current difficulty
To prepare the technological deficiency of the monoblock type molecular sieve catalyst with porous structure of self-support type.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
The every other embodiment that technical staff is obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention specifically provides a kind of preparation method of monoblock type molecular sieve catalyst, includes the following steps：
Step 1：Template, soluble silicon source, soluble silicon source and solvent are mixed, molecular sieve precursor mixture is obtained；
Step 2：Polyurethane foam matrix and molecular sieve precursor mixture are subjected to crystallization, crystal is obtained, will tie
After brilliant object is roasted, the first molecular sieve carrier is obtained；
Step 3：Metal front liquid solution is added dropwise in first molecular sieve carrier, the second molecular sieve foam is obtained, by second point
Son sieve foam is dried, and obtains third molecular sieve foam；
Step 4：Reducing agent solution is added dropwise in third molecular sieve foam and is dried, monoblock type molecular sieve catalytic is obtained
Agent.
Further, soluble silicon source includes one kind in sodium metaaluminate, aluminium isopropoxide or aluminum sulfate.
Preferably, soluble silicon source is sodium metaaluminate.
Preferably, a concentration of 0.5-2mol/L of soluble silicon source；
Further, soluble silicon source includes one kind in ethyl orthosilicate, silica gel or sodium metasilicate.
Preferably, soluble silicon source is ethyl orthosilicate.
Preferably, in soluble silicon source the content of element silicon with SiO2When conversion, the quality of element silicon in soluble silicon source
Percentage composition is 20-30%.
Wherein, the solvent in step 1 is water, preferably distilled water.
Further, template includes a kind of in tetrapropylammonium hydroxide, 4-propyl bromide and tetraethyl ammonium hydroxide
Or it is a variety of.
Preferably, template is tetrapropylammonium hydroxide.
Preferably, template is a concentration of 0.5-2mol/L of template solution.
Preferably, step 1 specifically includes：Tetrapropylammonium hydroxide, water and ethyl orthosilicate are sequentially added, and in 20-35
After DEG C stirring 2-5h, under 20-35 DEG C and stirring condition, after sodium metaaluminate is added dropwise into mixture, continue to stir 2-5h,
Obtain molecular sieve precursor mixture, wherein a concentration of 0.5-2mol/L of sodium aluminate solution, tetrapropylammonium hydroxide solution
A concentration of 0.5-2mol/L, relative to 1g sodium metaaluminates, tetrapropylammonium hydroxide dosage is 5-30mL, and ethyl orthosilicate dosage is
15-50mL, water consumption 50-200mL.
Further, the crystallization temperature of the crystallization of step 2 is 110-210 DEG C.
Preferably, crystallization temperature is 140-180 DEG C；Crystallization time is 1-4 days.
Preferably, crystallization time is 2-3 days.
Preferably, further include that crystal is cleaned and dried before crystal is roasted in step 2.
Preferably, crystal is cleaned for several times using deionized water and acetone.
Preferably, to the crystal of cleaning in 120 DEG C of dry 3h.
Preferably, the condition roasted to crystal is：5-7h is roasted at 500-650 DEG C.
Preferably, step 2 specifically includes：Polyurethane foam matrix is immersed in molecular sieve precursor mixture, and constantly
It squeezes polyurethane foam matrix and excludes air；Then the polyurethane foam matrix impregnated and molecular sieve precursor mixture are transferred to
Crystallization is carried out in hydrothermal reaction kettle, obtains sample after hydro-thermal reaction, after being cleaned for several times with deionized water and acetone, 120
DEG C dry 3h, then 5-7h is roasted at 500-650 DEG C, obtain the first molecular sieve carrier.
Further, metal front liquid solution includes palladium nitrate or palladium bichloride.
Wherein, the solvent of metal front liquid solution is water.
Preferably, metal front liquid solution is palladium bichloride.
Preferably, a concentration of 0.5-1.5g/L of metal front liquid solution, relative to the first molecular sieve carriers of 1g, noble metal
Precursor solution dosage 2-8mL.
Preferably, step 3, which specifically includes, will drop evenly metal front liquid solution (chlorination on the first molecular sieve carrier
Palladium), then in 80-120 DEG C of dry 3-5h, obtain third molecular sieve foam.
Further, reducing agent solution includes sodium borohydride solution or hydrazine hydrate solution.
Wherein, the solvent of reducing agent solution is water.
Preferably, reducing agent is sodium borohydride.
Preferably, a concentration of 1-4.5g/L of reducing agent solution, relative to the first molecular sieve carriers of 1g, the reducing agent
Solution usage 2-8mL.
Further, step 4 specifically includes：Under the conditions of 20 DEG C -30 DEG C, reducing agent is added dropwise in third molecular sieve foam
Solution is simultaneously dried, and obtains monoblock type molecular sieve catalyst.
Preferably, step 4 specifically includes：Reducing agent solution is added dropwise in room temperature aeration-drying 1- in third molecular sieve foam
3h, then in 90-130 DEG C of dry 3-5h, obtain monoblock type molecular sieve catalyst.
Wherein, it is self-control or commercially available that following embodiment is raw materials used, and polyurethane foam matrix is commercial carwash sponge, tool
Body is polyetherurethane foam.
Embodiment 1
The present embodiment specifically provides the first monoblock type molecular sieve catalyst, and preparation process is as follows：
(1) tetrapropylammonium hydroxide, 50mL water and the 18mL ethyl orthosilicates of the 1.0mol/L of 10mL are sequentially added, and
25 DEG C of stirring 4h；
(2) under 25 DEG C and stirring condition, the 1.0mol/L of 3.2mL is added dropwise in the mixture obtained to step (1)
After sodium metaaluminate, continues to stir 4h, obtain molecular sieve precursor mixture；
(3) polyurethane foam matrix is immersed in the molecular sieve precursor mixture that step (2) obtains, and constantly squeezes bubble
Foam excludes air；Then the polyurethane foam matrix impregnated and molecular sieve precursor mixture are transferred in hydrothermal reaction kettle,
Crystallization is carried out under the conditions of 120 DEG C of hydrothermal temperature 3 days；
(4) step (3) is obtained into sample after hydro-thermal reaction, after being cleaned for several times with deionized water and acetone, in 120 DEG C of dryings
3h, then 6h is roasted at 550 DEG C, obtain the first molecular sieve carrier (the ZSM-5 foams of self-supporting and hierarchical porous structure)；
(5) the 1g/L palladium bichlorides that 0.63mL is dropped evenly on the first molecular sieve carrier of the 0.08g obtained to step (4) are molten
Liquid obtains third molecular sieve foam then in 80 DEG C of dry 4h；
(6) the 2g/L sodium borohydride solutions for dropping evenly 0.58mL at 25 DEG C to step (5) third molecular sieve foam；
(7) sample for obtaining step (6) obtains monoblock type molecule in room temperature aeration-drying 2h, then in 100 DEG C of dry 5h
Sieve catalyst (palladium-based monolithic ZSM-5 foam catalysts).
Embodiment 2
The present embodiment specifically provides second of monoblock type molecular sieve catalyst, and preparation process is as follows：
(1) 1.0mol/L tetrapropylammonium hydroxide, 85mL water and the 40mL ethyl orthosilicates of 20mL are sequentially added, and 20
DEG C stirring 5h；
(2) under 25 DEG C and stirring condition, the 1.0mol/L of 3.2mL is added dropwise in the mixture obtained to step (1)
After sodium metaaluminate, continues to stir 4h, obtain molecular sieve precursor mixture；
(3) polyurethane foam matrix is immersed in the molecular sieve precursor mixture that step (2) obtains, and constantly squeezes bubble
Foam excludes air；Then the polyurethane foam matrix and mixture solution that impregnated are transferred in hydrothermal reaction kettle, in hydro-thermal temperature
Crystallization is carried out under the conditions of 140 DEG C of degree 2 days；
(4) step (3) is obtained into sample after hydro-thermal reaction, after being cleaned for several times with deionized water and acetone, in 120 DEG C of dryings
3h, then 6h is roasted at 600 DEG C, obtain the first molecular sieve carrier (the ZSM-5 foams of self-supporting and hierarchical porous structure)；
(5) the 1g/L palladium bichlorides that 0.72mL is dropped evenly on the first molecular sieve carrier of the 0.11g obtained to step (4) are molten
Liquid obtains third molecular sieve foam then in 80 DEG C of dry 4h；
(6) the 3g/L sodium borohydride solutions of 0.68mL are dropped evenly in 20 DEG C to step (5) third molecular sieve foam；
(7) sample for obtaining step (6) obtains monoblock type molecule in room temperature aeration-drying 2h, then in 120 DEG C of dry 5h
Sieve catalyst (palladium-based monolithic ZSM-5 foam catalysts).
Embodiment 3
The present embodiment specifically provides the third monoblock type molecular sieve catalyst, and preparation process is as follows：
(1) 1.0mol/L tetrapropylammonium hydroxide, 150mL water and the 25mL ethyl orthosilicates of 15mL are sequentially added, and
35 DEG C of stirring 2h；
(2) under 35 DEG C and stirring condition, the 0.5mol/L of 7.8mL is added dropwise in the mixture obtained to step (1)
After sodium metaaluminate, continues to stir 4h, obtain molecular sieve precursor mixture；
(3) polyurethane foam matrix is immersed in the molecular sieve precursor mixture that step (2) obtains, and constantly squeezes bubble
Foam excludes air；Then the polyurethane foam matrix impregnated and molecular sieve precursor mixture are transferred in hydrothermal reaction kettle,
Crystallization is carried out under the conditions of 160 DEG C of hydrothermal temperature 2 days；
(4) step (3) is obtained into sample after hydro-thermal reaction, after being cleaned for several times with deionized water and acetone, in 120 DEG C of dryings
3h, then 5h is roasted at 650 DEG C, obtain the first molecular sieve carrier (the ZSM-5 foams of self-supporting and hierarchical porous structure)；
(5) the 0.5g/L palladium bichlorides of 1.6mL are dropped evenly on the first molecular sieve carrier of the 0.20g obtained to step (4)
Solution obtains third molecular sieve foam then in 100 DEG C of dry 3h；
(6) the 1g/L sodium borohydride solutions for dropping evenly 0.72mL at 28 DEG C to step (5) third molecular sieve foam；
(7) sample for obtaining step (6) obtains monoblock type molecule in room temperature aeration-drying 3h, then in 120 DEG C of dry 3h
Sieve catalyst (palladium-based monolithic ZSM-5 foam catalysts).
Embodiment 4
The present embodiment specifically provides the 4th kind of monoblock type molecular sieve catalyst, and preparation process is as follows：
(1) 1.0mol/L tetrapropylammonium hydroxide, 200mL water and the 50mL ethyl orthosilicates of 30mL are sequentially added, and
25 DEG C of stirring 4h；
(2) under 25 DEG C and stirring condition, the 2mol/L that 2.0mL is added dropwise in the mixture obtained to step (1) is inclined
After sodium aluminate, continues to stir 4h, obtain molecular sieve precursor mixture；
(3) polyurethane foam matrix is immersed in the molecular sieve precursor mixture that step (2) obtains, and constantly squeezes bubble
Foam excludes air；Then the polyurethane foam matrix impregnated and molecular sieve precursor mixture are transferred in hydrothermal reaction kettle,
Crystallization is carried out under the conditions of 180 DEG C of hydrothermal temperature 1 day；
(4) step (3) is obtained into sample after hydro-thermal reaction, after being cleaned for several times with deionized water and acetone, in 120 DEG C of dryings
3h, then 4h is roasted at 600 DEG C, obtain the first molecular sieve carrier (the ZSM-5 foams of self-supporting and hierarchical porous structure)；
(5) the first molecular sieve carrier of the 0.26g obtained to step (4) is in the upper 1.5g/L chlorinations for dropping evenly 0.78mL
Palladium solution obtains third molecular sieve foam then in 100 DEG C of dry 3h；
(6) the 4.5g/L sodium borohydride solutions for dropping evenly 0.58mL at 30 DEG C to step (5) third molecular sieve foam；
(7) sample for obtaining step (6) obtains monoblock type molecule in room temperature aeration-drying 2h, then in 120 DEG C of dry 3h
Sieve catalyst (palladium-based monolithic ZSM-5 foam catalysts).
Embodiment 5
The present embodiment specifically provides the 5th kind of monoblock type molecular sieve catalyst, and preparation process is as follows：
(1) 1.0mol/L tetrapropylammonium hydroxide, 90mL water and the 30mL ethyl orthosilicates of 13mL are sequentially added, and 25
DEG C stirring 4h；
(2) under 25 DEG C and stirring condition, the 1mol/L that 3.5mL is added dropwise in the mixture obtained to step (1) is inclined
After sodium aluminate, continues to stir 4h, obtain molecular sieve precursor mixture；
(3) polyurethane foam matrix is immersed in the molecular sieve precursor mixture that step (2) obtains, and constantly squeezes bubble
Foam excludes air；Then the polyurethane foam matrix impregnated and molecular sieve precursor mixture are transferred in hydrothermal reaction kettle,
Crystallization is carried out under the conditions of 200 DEG C of hydrothermal temperature 1 day；
(4) step (3) is obtained into sample after hydro-thermal reaction, after being cleaned for several times with deionized water and acetone, in 120 DEG C of dryings
3h, then 4h is roasted at 550 DEG C, obtain the first molecular sieve carrier (the ZSM-5 foams of self-supporting and hierarchical porous structure)；
(5) the 1.0g/L palladium bichlorides of 0.88mL are dropped evenly on the first molecular sieve carrier of the 0.19g obtained to step (4)
Solution obtains third molecular sieve foam then in 100 DEG C of dry 3h；
(6) the 0.1g/L sodium borohydride solutions for dropping evenly 0.98mL at 25 DEG C to step (5) third molecular sieve foam；
(7) sample for obtaining step (6) obtains monoblock type molecule in room temperature aeration-drying 3h, then in 120 DEG C of dry 3h
Sieve catalyst (palladium-based monolithic ZSM-5 foam catalysts).
Embodiment 6
The present embodiment specifically provides the 6th kind of monoblock type molecular sieve catalyst, and preparation process is as follows：
(1) 1.0mol/L tetrapropylammonium hydroxide, 50mL water and the 18mL ethyl orthosilicates of 10mL are sequentially added, and 25
DEG C stirring 4h；
(2) under 25 DEG C and stirring condition, the 1.0mol/L of 3.2mL is added dropwise in the mixture obtained to step (1)
After sodium metaaluminate, continues to stir 4h, obtain molecular sieve precursor mixture；
(3) polyurethane foam matrix is immersed in the molecular sieve precursor mixture that step (2) obtains, and constantly squeezes bubble
Foam excludes air；Then the polyurethane foam matrix impregnated and molecular sieve precursor mixture are transferred in hydrothermal reaction kettle,
Crystallization is carried out under the conditions of 110 DEG C of hydrothermal temperature 4 days；
(4) step (3) is obtained into sample after hydro-thermal reaction, after being cleaned for several times with deionized water and acetone, in 120 DEG C of dryings
3h, then 6h is roasted at 600 DEG C, obtain the first molecular sieve carrier (the ZSM-5 foams of self-supporting and hierarchical porous structure)；
(5) the 1g/L palladium bichlorides that 0.73mL is dropped evenly on the first molecular sieve carrier of the 0.12g obtained to step (4) are molten
Liquid obtains third molecular sieve foam then in 80 DEG C of dry 4h；
(6) the 2g/L sodium borohydride solutions for dropping evenly 0.65mL at 26 DEG C to step (5) third molecular sieve foam；
(7) sample for obtaining step (6) obtains monoblock type molecule in room temperature aeration-drying 2h, then in 100 DEG C of dry 5h
Sieve catalyst (palladium-based monolithic ZSM-5 foam catalysts).
Embodiment 7
The present embodiment specifically provides the 7th kind of monoblock type molecular sieve catalyst, and preparation process is as follows：
(1) 1.0mol/L tetrapropylammonium hydroxide, 50mL water and the 18mL ethyl orthosilicates of 10mL are sequentially added, and 25
DEG C stirring 4h；
(2) under 25 DEG C and stirring condition, the 1.0mol/L of 3.2mL is added dropwise in the mixture obtained to step (1)
After sodium metaaluminate, continues to stir 4h, obtain molecular sieve precursor mixture；
(3) polyurethane foam matrix is immersed in the molecular sieve precursor mixture that step (2) obtains, and constantly squeezes bubble
Foam excludes air；Then the polyurethane foam matrix impregnated and molecular sieve precursor mixture are transferred in hydrothermal reaction kettle,
Crystallization is carried out under the conditions of 210 DEG C of hydrothermal temperature 2 days；
(4) step (3) is obtained into sample after hydro-thermal reaction, after being cleaned for several times with deionized water and acetone, in 120 DEG C of dryings
3h, then 6h is roasted at 600 DEG C, obtain the first molecular sieve carrier (the ZSM-5 foams of self-supporting and hierarchical porous structure)；
(5) the 1g/L palladium bichlorides that 0.73mL is dropped evenly on the first molecular sieve carrier of the 0.11g obtained to step (4) are molten
Liquid obtains third molecular sieve foam then in 80 DEG C of dry 4h；
(6) the 2g/L sodium borohydride solutions for dropping evenly 0.65mL at 22 DEG C to step (5) third molecular sieve foam；
(7) sample for obtaining step (6) obtains monoblock type molecule in room temperature aeration-drying 2h, then in 100 DEG C of dry 5h
Sieve catalyst (palladium-based monolithic ZSM-5 foam catalysts).
Prepared by the first molecular sieve carrier obtained during monoblock type molecular sieve catalyst (self-supporting and more to embodiment 1
The ZSM-5 foams of grade pore structure) carry out XRD standard spectrograms (Fig. 1 of XRD spectra and ZSM-5 object phases that lattice structure is tested
JCPDS：It 42-0023) is compared, the result is shown in Figure 1.As seen from Figure 1, use the ZSM-5 foams that prepare of the present invention 2 θ for
8.01, have an apparent characteristic diffraction peak for 8.92,23.17 and 24.08 ° etc., and with the standard spectrum graph card of ZSM-5 crystalline phases
JCPDS42-0023 fits like a glove, and illustrates that the first molecular sieve carrier (ZSM-5 foams) sample purity that the present invention obtains is very high, removes
Exist without other impurity outside ZSM-5 crystalline phases.
Embodiment 1 prepares the first molecular sieve carrier (self-supporting and the multistage obtained during monoblock type molecular sieve catalyst
The ZSM-5 foams of pore structure) pictorial diagram and SEM microscopic appearance figures see Fig. 2 and Fig. 3.By sample object figure Fig. 2 as it can be seen that using
The first molecular sieve carrier that the present invention obtains has complete self-supporting skeleton structure；Further by SEM microscopic appearance figures as it can be seen that
The self-supporting skeleton structure of first molecular sieve carrier is the hole (macropore) and 2-5 μ m thicks by a large amount of 100-400 μm of scales
Hole wall forms；And hole wall is piled up by the mutual close-packed arrays of ZSM-5 nanocrystals of strip.
Prepared by the first molecular sieve carrier obtained during monoblock type molecular sieve catalyst (self-supporting and more to embodiment 1
The ZSM-5 foams of grade pore structure) specific surface area and pore-size distribution test are carried out, as a result see Fig. 3 to Fig. 6.By N2Adsorption-desorption is bent
Line is as it can be seen that the first molecular sieve carrier obtained using the present invention has apparent hysteresis loop, it was demonstrated that there are meso-hole structures for sample；By
BJH mesoporous pore sizes distribution map further proves sample, and there are the mesoporous of 2-5nm scales；Sample is illustrated by H-K micropore size distribution maps
There is also the micropores of 0.4-0.6nm scales for product.Prove that the first molecular sieve carrier also has 100-400 μm of scale in conjunction with SEM in Fig. 2
Macropore, it is possible thereby to prove the multi-stage porous that there is micropore-mesopore-macropore using the monoblock type molecular sieve catalyst that the present invention obtains
Structure.The first molecular sieve carrier for preparing of the present invention can also be seen that also by Fig. 4 simultaneously have higher BET specific surface area (for
301m2/ g) and a large amount of meso-hole structure (mesoporous pore volume be 0.234cm3/g).Therefore, what the present invention obtained is first molecular sieve supported
Body is due to high specific surface area and abundant mesoporous and macroporous structure, as regular carrier loaded catalytic active component
When (precious metal palladium) prepares monoblock type molecular sieve catalyst, it can be more advantageous to active component being uniformly distributed in carrier surface, from
And improve catalytic activity.
The pictorial diagram for the monoblock type molecular sieve catalyst that embodiment 1 obtains is shown in 7.As seen from Figure 7, with the first molecular sieve carrier
For matrix palladium-based monolithic ZSM-5 catalyst mistakes are prepared by step 3 and step 4 supporting catalytic active component (precious metal palladium)
Cheng Zhong, the shape and volume of molecular sieve foam base plate are held essentially constant, and illustrate the first molecular sieve carrier tool prepared by the present invention
There is good skeleton mechanical strength, can smoothly realize that follow-up supporting catalytic active component prepares wanting for monoblock type molecular sieve catalyst
It asks.
It is prepared by embodiment 2-7 the first molecular sieve carrier obtained during monoblock type molecular sieve catalyst carry out XRD,
SEM, specific surface area and pore-size distribution test, can obtain phenetic analysis result similar to Example 1.
The monoblock type molecular sieve catalyst (palladium-based monolithic ZSM-5 foam catalysts) obtained using each embodiment 1-7 as
Catalyst sample is burnt using the catalysis of toluene as probe reaction, in toluene inlet concentration 1.0g/m3With air speed 10000h-1Item
Catalysis burning purifying property evaluation, reaction temperature T when reaching 10% and 90% with toluene conversion are carried out under part10And T90Make
For toluene catalytically purifying property evaluation criterion, 1 the results are shown in Table.It is by table 1 as it can be seen that very low in precious metal palladium (palladium bichloride) load capacity
When (palladium metal quality 0.08-0.20g in every liter of catalyst), using the monoblock type molecular sieve catalyst (palladium base of the invention prepared
Monoblock type ZSM-5 foam catalysts), after about 190 DEG C of ignitions, 207-238 DEG C can reach and be fully cleaned up toluene, show very well
Low temperature toluene purification activity.
The toluene catalytic combustion purifying property of 1 monoblock type molecular sieve catalyst of table
Relative to existing molecular sieve precursor liquid, molecular sieve precursor mixture of the invention does not contain highly basic, due to being not added with
Enter highly basic so that molecular sieve precursor mixture avoids acceleration generation and the crystallization of ZSM-5 nucleus in follow-up hydrothermal crystallization process
The high defect of growth rate, the present invention are not in the excessive phenomenon of ZSM-5 crystal grain, therefore, molecular sieve foam bone of the invention
Fine and close hole wall structure is all to be piled up by the nanocrystalline close-packed arrays of ZSM-5, and then improve the frame machine of ZSM-5 foams in frame
Tool intensity is conducive to the load of subsequent catalyst active component.In addition, the pH value of molecular sieve precursor mixture will not be excessively high, it will not
The decomposition rate for influencing polyurethane matrix (PUF), to influence the skeleton mechanical strength of ZSM-5 foams or lead to PUF impurity
Residual；Meanwhile the hydrothermal temperature of the crystallization of this patent is than existing temperature higher, is 110-210 DEG C, and crystallization is anti-
The hydrothermal temperature answered can influence the decomposition rate of the crystallization growth rate and PUF matrixes of ZSM-5 nucleus, to influence ZSM-
The skeleton mechanical strength and sample degree of purity of 5 foams.This patent finds the hydrothermal temperature (110- of higher crystallization
210 DEG C) it is more advantageous to the skeleton mechanical strength for improving ZSM-5 foams, and also the degree of purity of the first molecular sieve carrier is high, does not appoint
What impurity residual.The BET specific surface area higher of molecular sieve foam prepared by this patent is (for 301m2/ g), mesoporous pore volume is also more
It is more (for 0.234cm3/g).Specific surface area due to the molecular sieve foam of this patent preparation and mesoporous pore volume higher, more favorably
In the uniform load of subsequent catalyst active component (noble metal).In addition, this patent is using molecular sieve foam as carrier-supported precious metal
It is expensive in order to avoid the heated reunion of noble metal nano particles that reduction generates becomes larger during preparing monoblock type molecular sieve catalyst
Metal active constituent presoma does not suffer from heat treatment during reduction activation.Therefore the technical program is uniform using 20-30 DEG C
The method that reducing agent is added dropwise, on the one hand can make the active component presoma (metal precursor being immersed in early period on molecular sieve foam
Solution) in-situ reducing be noble metal；Another aspect low-temperature operation is it is possible to prevente effectively from the noble metal nano particles group that reduction generates
It is poly-.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of monoblock type molecular sieve catalyst, which is characterized in that include the following steps：
Step 1：Template, soluble silicon source, soluble silicon source and solvent are mixed, molecular sieve precursor mixture is obtained；
Step 2：Polyurethane foam matrix and molecular sieve precursor mixture are subjected to crystallization, crystal is obtained, by the knot
After brilliant object is roasted, the first molecular sieve carrier is obtained；
Step 3：Metal front liquid solution is added dropwise in first molecular sieve carrier, obtains the second molecular sieve foam, by described the
Two molecular sieve foams are dried, and obtain third molecular sieve foam；
Step 4：Reducing agent solution is added dropwise in the third molecular sieve foam and is dried, monoblock type molecular sieve catalytic is obtained
Agent.
2. the preparation method of monoblock type molecular sieve catalyst according to claim 1, which is characterized in that the soluble aluminum
Source includes one kind in sodium metaaluminate, aluminium isopropoxide or aluminum sulfate.
3. the preparation method of monoblock type molecular sieve catalyst according to claim 1, which is characterized in that the soluble silicon
Source includes one kind in ethyl orthosilicate, silica gel or sodium metasilicate.
4. the preparation method of monoblock type molecular sieve catalyst according to claim 1, which is characterized in that the template packet
Include one kind in tetrapropylammonium hydroxide, 4-propyl bromide or tetraethyl ammonium hydroxide.
5. the preparation method of monoblock type molecular sieve catalyst according to claim 1, which is characterized in that the step 2
The crystallization temperature of crystallization is 110 DEG C -210 DEG C.
6. the preparation method of monoblock type molecular sieve catalyst according to claim 1, which is characterized in that metal precursor is molten
Liquid includes palladium nitrate or palladium bichloride.
7. the preparation method of monoblock type molecular sieve catalyst according to claim 1, which is characterized in that the reducing agent is molten
Liquid includes sodium borohydride solution or hydrazine hydrate solution.
8. the preparation method of monoblock type molecular sieve catalyst according to claim 1, which is characterized in that the step 4 tool
Body includes：Under the conditions of 20 DEG C -30 DEG C, reducing agent solution is added dropwise in the third molecular sieve foam and is dried, is obtained whole
Body formula molecular sieve catalyst.
9. a kind of monoblock type molecular sieve catalyst, is prepared according to the preparation method described in claim 1 to 8 any one.
10. the monoblock type that the preparation method of the monoblock type molecular sieve catalyst according to any one of claim 1-8 obtains
Application of the monoblock type molecular sieve catalyst in cleaning organic waste gas described in molecular sieve catalyst or claim 9.
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| CN111420699A (en) * | 2020-05-27 | 2020-07-17 | 浙江大学 | Preparation method of molecular sieve surface organic base etching and Pt-loaded catalyst |
| CN113548672A (en) * | 2021-07-22 | 2021-10-26 | 南通斐腾新材料科技有限公司 | Method for preparing foam structure zeolite molecular sieve by organic foam chemical growth method |
| CN116174016A (en) * | 2023-03-01 | 2023-05-30 | 浙江天地环保科技股份有限公司 | Propane catalytic combustion platinum-based catalyst and preparation method thereof |
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