CN104549409A - Preparation method of compound porous molecular sieve catalyst - Google Patents
Preparation method of compound porous molecular sieve catalyst Download PDFInfo
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- CN104549409A CN104549409A CN201310512684.9A CN201310512684A CN104549409A CN 104549409 A CN104549409 A CN 104549409A CN 201310512684 A CN201310512684 A CN 201310512684A CN 104549409 A CN104549409 A CN 104549409A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 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 45
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 title abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- -1 aliphatic alcohol ester Chemical class 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 239000013081 microcrystal Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000001089 mineralizing effect Effects 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 3
- 229940009827 aluminum acetate Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- AVPRDNCYNYWMNB-UHFFFAOYSA-N ethanamine;hydrate Chemical compound [OH-].CC[NH3+] AVPRDNCYNYWMNB-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a preparation method of a compound porous molecular sieve catalyst. According to the preparation method, the problems that the cost is high, the effluent quantity is large and the benefit of environmental protection is not achieved in the prior art are mainly solved. The preparation method comprises the following steps: (a) carrying out sealing aging on a mixture of an M source, a silicon source, a surfactant and a mineralizing agent for 5-200 hours at 20-95 DEG C, so as to obtain a precursor A; (b) carrying out solution-free crystallization on the precursor A, firstly processing the precursor A at 60-140 DEG C for 2-50 hours, and then processing the precursor A at the temperature of 140-250 DEGC and the pressure of 0.3MPa-12MPa for 2-50 hours, so as to obtain a precursor B; and (c) calcining the precursor B at 300-1000 DEG C for 3-10 hours so as to obtain the compound porous molecular sieve catalyst. According to the technical scheme, the problems are well solved. The preparation method can be applied to the industrial production for preparing the compound porous molecular sieve catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of composite holes molecular sieve catalyst.
Background technology
Zeolite molecular sieve obtains use widely in the industry as traditional solid acid catalyst, but because its aperture is less, reactant and the product diffusion difficulty in duct has had a strong impact on catalytic efficiency, and therefore molecular sieve has some limitations relating in macromolecular catalytic process.Such as in heavy oil fraction, large scale molecule occupies suitable ratio, want cracked fuel oil that large molecular energy just must be made to touch active surface, and the narrow and small pore passage structure of zeolite molecular sieve makes it be difficult to meet above requirement, the reaction such as the esterification that this " inaccessiblility " participates in for large molecule, alkylation and selective oxidation is so same, therefore to realize macromolecular Efficient Conversion, break away from diffusion mass transfer restriction and seem very necessary.Compound is foramen magnum-mesoporous-microporous molecular sieve catalyst have concurrently zeolite molecular sieve high catalytic activity, high stability and foramen magnum-mesoporous catalyst aperture large, spread the two-fold advantage such as fast, day by day become the study hotspot in porous catalytic field.
Up to the present, the method being usually used in preparing composite holes molecular sieve has crystal seed construction from part, hard template method, compound template, dealuminzation or desiliconization post treatment method etc., but above method still exists complex steps, the shortcoming such as with high costs.Utilizing cheap surfactant directly to prepare composite holes molecular sieve is the target that people pursue, but because the active force between these surfactants and sial presoma is more weak, contain the indefiniteness material of primary structure units so the composite holes molecular sieve prepared in the solution is hole wall or is assembled the aggregation formed by zeolite crystal, as: document CN101311117 is open by adjust ph, and adopts the method for fractional crystallization to prepare BETA/MCM-41 nano composite meso-microporous molecular sieve.Document CN1393403 openly in conventional manner first synthetic microporous zeolite (as Y, ZSM-5, reaction mixture gel β), carry out the crystallization in two stages under certain condition respectively, the acid-base value of adjustment reactant mixture, and add the template of synthesising mesoporous molecular sieve, obtain microporous-mesoporous composite molecular sieve composition.Document CN102464329A discloses a kind of synthetic method of micropore-mesopore compound ZSM-5/MCM-41 molecular sieve, and the method is by joining in acid or aqueous slkali by molecular sieve, the pH value of modulation solution obtains microporous-mesoporous composite molecular sieve.But the crystallization mineralising treatment step in these patents carries out mostly in the solution, and this makes to consume more template in preparation process, not only makes complicated process of preparation, cost increase, and because form the waste liquid being difficult in a large number reclaim, without environmental benefit.
Summary of the invention
It is high that technical problem to be solved by this invention is that prior art exists cost, and waste liquid amount is large, without the problem of environmental benefit, provides a kind of preparation method of new composite holes molecular sieve catalyst.It is low that the method has cost, generates waste liquid amount little, the feature that environmental benefit is good.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is as follows: a kind of preparation method of composite holes molecular sieve catalyst, described catalyst comprises the composition of following molar relationship: M
xo
y: nSiO
2, M is selected from Al, Zr or Ti, x and y is respectively the valence state of O and M, and n is 8 ~ 1000;
Said method comprising the steps of:
A) by the mixture of M source, silicon source, surfactant and mineralizer 20 ~ 95 DEG C of condition lower seals ageing 5 ~ 200 hours, obtain precursor A;
Wherein, in mixture, the weight ratio of each material is: M source: silicon source: surfactant: mineralizer: water=(0.001 ~ 0.15): 1:(0.06 ~ 5.0): (0.02 ~ 2.0): (2.0 ~ 20);
B) precursor A is carried out without solution Crystallizing treatment, first under 60 ~ 140 DEG C of conditions, process 2 ~ 50 hours, then 140 ~ 250 DEG C, process 2 ~ 50 hours under 0.3 ~ 12MPa condition, obtain precursor B;
C) precursor B is calcined 3 ~ 10 hours at 300 ~ 1000 DEG C, obtain described composite holes molecular sieve catalyst.
In technique scheme, preferably, described catalyst has the composite pore structural of foramen magnum-mesoporous-micropore; Wherein, the pore volume of macropore of 0.5 ~ 10 micron is 0.1 ~ 3.5 centimetre
3/ gram, the mesoporous pore volume of 2 ~ 50 nanometers is 0.05 ~ 2.2 centimetre
3/ gram, the pore volume of the micropore of 0.3 ~ 2 nanometer is 0.1 ~ 0.8 centimetre
3/ gram.
In technique scheme, preferably, described M source is selected from containing at least one in the nitrate of M, chlorate, sulfate, acetate or aliphatic alcohol ester.
In technique scheme, preferably, described silicon source is selected from least one in silicic acid aliphatic alcohol ester, silicate, silica gel or waterglass.
In technique scheme, preferably, described surfactant is selected from least one in alkylsulfonate, alkylbenzenesulfonate, polyethylene glycol, glycerine, tetraethylene glycol, polyvinyl alcohol, sorbitol ester or hydramine.
In technique scheme, preferably, described mineralizer is selected from least one in NaOH, potassium hydroxide, calcium hydroxide, ammoniacal liquor, potash, sodium carbonate, sodium acid carbonate, ethylenediamine, triethylamine or fatty ammonium hydroxide.
In technique scheme, preferably, the particle diameter of described catalyst is 0.05 ~ 10 micron.
In technique scheme, preferably, the specific area of described catalyst is 300 ~ 900 meters
2/ gram.
The composite holes molecular sieve catalyst of the inventive method synthesis can be used in esterification, isomerization, selective oxidation or cracking reaction.
In the present invention, owing to employing the Crystallizing treatment process without solution, decrease the use amount of surfactant and mineralizer in preparation process, can 30% be reduced, effectively reduce production cost; Meanwhile, greatly reduce the generation of waste liquid, waste liquid amount can reduce 70%, has good environmental benefit.Composite holes molecular sieve catalyst, because create unique composite pore structural, therefore greatly accelerates the diffusion mass transfer speed of reactant and product molecule, thus effectively improves the service efficiency of catalyst.Composite holes molecular sieve catalyst of the present invention is used for the esterification of aromatic alcohol and aliphatic acid, reaction condition is 100 DEG C, 8 hours, 0.1MPa, owing to having composite holes molecular sieve structure, therefore the diffusion mass transfer of reactant and product molecule is accelerated greatly, it transforms frequency (TON) can reach 300, ether selective also up to 85%, and product and catalyst can direct isolated by filtration, achieve good technique effect.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram (XRD) of the composite holes molecular sieve catalyst of the inventive method synthesis, has XRD diffraction data as shown in table 1.
Table 1
| 2θ / 0 | I/I 0×100 |
| 7.9±0.1 | 100 |
| 8.7±0.1 | 56.5 |
| 13.9±0.1 | 13.1 |
| 14.7±0.1 | 17.8 |
| 15.5±0.1 | 10.1 |
| 20.4±0.1 | 8.1 |
| 20.8±0.1 | 9.8 |
| 23.0±0.1 | 70.6 |
| 23.2±0.1 | 49.1 |
| 23.9±0.1 | 35.5 |
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
1 gram of aluminum acetate, 100 silica gel, 14 grams of polyethylene glycol, 3.4 grams of potassium hydroxide and 220 grams of water are mixed and stir; Mixed solution is stirred 20 hours at 60 DEG C, then seals ageing and obtain precursor A in 50 hours; Precursor A carried out without solution Crystallizing treatment, comprise heating and Crystallizing treatment two steps, first heat treatment temperature is 100 DEG C, and the time is 12 hours; Crystallizing treatment temperature is 170 DEG C, and the time is 15 hours, and pressure is 1.5MPa, obtains precursor B; Last precursor B in air atmosphere 600 DEG C calcining 8 hours, obtain composite holes molecular sieve catalyst of the present invention.
The XRD spectra data of product are as shown in table 1, and XRD spectra as shown in Figure 1.Product cut size is 1.2 microns, and the pore volume being recorded the macropore of product 0.5 ~ 10 micron by nitrogen physisorption adsorption desorption (BET) is 0.9 centimetre
3/ gram, the mesoporous pore volume of 2 ~ 50 nanometers is 0.5 centimetre
3/ gram, the pore volume of the micropore of 0.4 ~ 2 nanometer is 0.3 centimetre
3/ gram.Building-up process consumes surfactant and mineralizer 14 grams and 3.4 grams altogether, the raw waste liquid 25 milliliters of common property.
Catalyst performance evaluation is carried out in closed container, actual conditions is as follows: 1 mole of aromatic alcohol and 1.5 moles of fatty acids are mixed and stirred, 6 grams of catalyst to be joined in above-mentioned solution and Keep agitation, be warming up to 100 DEG C subsequently and continue insulation 8 hours, pressure remains on 0.1MPa, after reaction terminates, carry out composition analysis by chromatogram after product and catalyst separation, reaction evaluating the results are shown in table three.
[embodiment 2 ~ 10]
By [embodiment 1] described synthesis step, change M source, silicon source, surfactant, (NaOH is referred to as NaOH for mineralizer, ethyl ammonium hydroxide is referred to as TEAOH) kind and consumption, regulate preparation condition, all can synthesize and obtain composite holes molecular sieve catalyst of the present invention.Catalyst formulation, preparation condition and structure composition characteristic are in table 2 and table 3.Evaluating catalyst method is identical with [embodiment 1], and catalytic reaction evaluation result is in table 4.
[comparative example 1]
Utilize conventional method to obtain molecular sieve catalyst without composite pore structural, concrete steps are as follows: 1 gram of aluminum acetate, 100 silica gel, 14 grams of NaOH, 10 grams of TPAOHs and 220 grams of water are mixed and stirred obtain precursor A; Precursor A is stirred 20 hours at 60 DEG C, then uses conventional hydrothermal crystallizing treatment process 50 hours, obtain the precursor B of molecular sieve catalyst; Last 600 DEG C of calcinings 8 hours in air atmosphere, obtain common molecular sieve catalyst.Building-up process consumes mineralizer 14 grams altogether, the raw waste liquid 180 milliliters of common property.
Table 2
[comparative example 2]
Utilize the composite holes molecular sieve catalyst that solution crystallization legal system obtains, concrete steps are as follows: 1 gram of aluminum acetate, 100 silica gel, 25 grams of polyvinyl n-butyl ether, 10 grams of TPAOHs and 220 grams of water are mixed and stirred obtain precursor A; Precursor A is stirred 20 hours at 60 DEG C, then uses hydrothermal crystallizing treatment process 50 hours, obtain the precursor B of composite holes molecular sieve catalyst; Last 600 DEG C of calcinings 8 hours in air atmosphere, obtain common molecular sieve catalyst.Building-up process consumes surfactant and mineralizer 25 grams and 10 grams altogether, the raw waste liquid 200 milliliters of common property.
Table 3
Continued 3
Table 4
Claims (8)
1. a preparation method for composite holes molecular sieve catalyst, described catalyst comprises the composition of following molar relationship: M
xo
y: nSiO
2, M is selected from Al, Zr or Ti, x and y is respectively the valence state of O and M, and n is 8 ~ 1000;
Said method comprising the steps of:
A) by the mixture of M source, silicon source, surfactant and mineralizer 20 ~ 95 DEG C of condition lower seals ageing 5 ~ 200 hours, obtain precursor A;
Wherein, in mixture, the weight ratio of each material is: M source: silicon source: surfactant: mineralizer: water=(0.001 ~ 0.15): 1:(0.06 ~ 5.0): (0.02 ~ 2.0): (2.0 ~ 20);
B) precursor A is carried out without solution Crystallizing treatment, first under 60 ~ 140 DEG C of conditions, process 2 ~ 50 hours, then 140 ~ 250 DEG C, process 2 ~ 50 hours under 0.3 ~ 12MPa condition, obtain precursor B;
C) precursor B is calcined 3 ~ 10 hours at 300 ~ 1000 DEG C, obtain described composite holes molecular sieve catalyst.
2. the preparation method of composite holes molecular sieve catalyst according to claim 1, the composite pore structural of the foramen magnum-mesoporous-micropore that it is characterized in that described catalyst has; Wherein, the pore volume of macropore of 0.5 ~ 10 micron is 0.1 ~ 3.5 centimetre
3/ gram, the mesoporous pore volume of 2 ~ 50 nanometers is 0.05 ~ 2.2 centimetre
3/ gram, the pore volume of the micropore of 0.3 ~ 2 nanometer is 0.1 ~ 0.8 centimetre
3/ gram.
3. the preparation method of composite holes molecular sieve catalyst according to claim 1, is characterized in that described M source is selected from containing at least one in the nitrate of M, chlorate, sulfate, acetate or aliphatic alcohol ester.
4. the preparation method of composite holes molecular sieve catalyst according to claim 1, is characterized in that described silicon source is selected from least one in silicic acid aliphatic alcohol ester, silicate, silica gel or waterglass.
5. the preparation method of composite holes molecular sieve catalyst according to claim 1, is characterized in that described surfactant is selected from least one in alkylsulfonate, alkylbenzenesulfonate, polyethylene glycol, glycerine, tetraethylene glycol, polyvinyl alcohol, sorbitol ester or hydramine.
6. the preparation method of composite holes molecular sieve catalyst according to claim 1, is characterized in that described mineralizer is selected from least one in NaOH, potassium hydroxide, calcium hydroxide, ammoniacal liquor, potash, sodium carbonate, sodium acid carbonate, ethylenediamine, triethylamine or fatty ammonium hydroxide.
7. the preparation method of composite holes molecular sieve catalyst according to claim 1, is characterized in that the size of microcrystal of described catalyst is 0.05 ~ 10 micron.
8. the preparation method of composite holes molecular sieve catalyst according to claim 1, is characterized in that the specific area of described catalyst is 300 ~ 900 meters
2/ gram.
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| CN110642697A (en) * | 2019-10-31 | 2020-01-03 | 江苏润普食品科技股份有限公司 | Production method for preparing sorbic acid by acidolysis of sorbic acid polyester with macroporous solid acid catalyst |
| CN111099602A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Iron-containing composite porous molecular sieve |
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| CN1325375C (en) * | 2004-10-29 | 2007-07-11 | 中国石油化工股份有限公司 | Beta zeolite granule possessing multiple grade pore passage and its preparation method |
| CN101108736B (en) * | 2006-07-21 | 2010-09-29 | 中国石油天然气集团公司 | Preparation method of a class of Y-type molecular sieves having both micropores and mesoporous pores |
| CN102826565B (en) * | 2012-09-05 | 2014-08-20 | 北京化工大学 | Preparation method of multi-stage pore channel beta molecular screen |
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2013
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111099602A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Iron-containing composite porous molecular sieve |
| CN110642697A (en) * | 2019-10-31 | 2020-01-03 | 江苏润普食品科技股份有限公司 | Production method for preparing sorbic acid by acidolysis of sorbic acid polyester with macroporous solid acid catalyst |
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