CN104549409A - Preparation method of compound porous molecular sieve catalyst - Google Patents
Preparation method of compound porous molecular sieve catalyst Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- preparation
- sieve catalyst
- precursor
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310512684.9A CN104549409B (en) | 2013-10-28 | 2013-10-28 | Preparation method of compound porous molecular sieve catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310512684.9A CN104549409B (en) | 2013-10-28 | 2013-10-28 | Preparation method of compound porous molecular sieve catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104549409A true CN104549409A (en) | 2015-04-29 |
| CN104549409B CN104549409B (en) | 2017-05-17 |
Family
ID=53067114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310512684.9A Active CN104549409B (en) | 2013-10-28 | 2013-10-28 | Preparation method of compound porous molecular sieve catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104549409B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | Method of manufacturing Y type molecular sieve having micropore and mesohole at the same time |
| CN102826565B (en) * | 2012-09-05 | 2014-08-20 | 北京化工大学 | Preparation method of multi-stage pore channel beta molecular screen |
-
2013
- 2013-10-28 CN CN201310512684.9A patent/CN104549409B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104549409B (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104030314B (en) | A kind of ZSM-5 Quito level porous molecular sieve material and preparation method thereof | |
| CN102390843B (en) | Three-dimensional interconnected hierarchical-structured zeolite molecular sieve material and preparation method thereof | |
| CN107640775B (en) | Method for preparing ZSM-5 molecular sieve by using solid waste | |
| CN101973563B (en) | Method for synthetizing ZSM-35 molecular sieve by seed crystal process | |
| CN103641131A (en) | Slice-shaped nanometer SAPO-34 molecular sieve with relatively low silicon content, preparation method and application thereof | |
| CN101643219A (en) | Preparation method of nano-ZSM-5 molecular sieve | |
| CN104556094B (en) | A kind of Y/Silicalite-1 composite molecular screen and preparation method thereof | |
| CN102372283B (en) | ZSM-5 molecular sieve and its preparation method | |
| CN102530980A (en) | Hierarchical zeolite, preparation and application thereof | |
| CN102659133A (en) | Preparation method for P type zeolite molecular sieve with core-shell structure | |
| CN103539153A (en) | Preparation method of nano hierarchical-pore ZSM-11/ZSM-5 eutectic zeolite | |
| CN102107899B (en) | Preparation method of lamellar gamma-phase nano aluminum oxide | |
| CN101934226B (en) | Inorganic composite material of catalytic degradation surface active agent waste water and preparation method thereof | |
| CN107511169B (en) | ZSM-5 molecular sieve catalyst, preparation method and application | |
| CN101664695B (en) | Method for preparing microporous-mesoporous composite molecular sieve | |
| CN104549409A (en) | Preparation method of compound porous molecular sieve catalyst | |
| CN107416859A (en) | A kind of preparation method and application of step hole Beta molecular sieves | |
| CN103058208A (en) | Preparation method of SAPO-56 molecular sieve | |
| CN102274743A (en) | High intercrystal poriness zeolite coating material on surface of porous silicon carbide carrier and preparation method thereof | |
| CN106673007A (en) | ZSM-5 (Zeolite Socony Mobil-5) molecular sieve with orderly stacked lamellae and preparation method and application of ZSM-5 molecular sieve | |
| CN103787367B (en) | Preparation method of binder-free ZSM-5 molecular sieve forming product | |
| CN105776245A (en) | Synthesis method of ZSM-5 molecular sieve and application of ZSM-5 molecular sieve in methanol synthesis to prepare propylene | |
| CN110615442B (en) | ZSM-5/MOR composite zeolite monolith for synthesizing 5-hydroxymethylfurfural and preparation method thereof | |
| CN104150506A (en) | Method for preparing mesoporous ZSM-5 zeolite | |
| CN105460949B (en) | The synthetic method of MFI zeolites containing rare earth |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |