CN104591205A - Preparation method of catalyst material with composite pores - Google Patents
Preparation method of catalyst material with composite pores Download PDFInfo
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- CN104591205A CN104591205A CN201510061404.6A CN201510061404A CN104591205A CN 104591205 A CN104591205 A CN 104591205A CN 201510061404 A CN201510061404 A CN 201510061404A CN 104591205 A CN104591205 A CN 104591205A
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- catalytic material
- compound duct
- duct catalytic
- molecular sieve
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Abstract
The invention relates to a preparation method of a catalyst material with composite pores and relates to the catalyst material with composite pores. The preparation method comprises the following steps: mixing an aluminum source, a silicon source, a template, anhydrous ethanol and deionized water; carrying out aging and thermal treatment, and then cooling to room temperature; and then centrifuging, washing, drying and calcining to obtain the catalyst material with composite pores. The specific surface area of the obtained composite material is improved, and the surface acid site of the material is increased so that the catalyst material has relatively strong acidity and is suitable for hydrocracking and isomerization reaction of hydrocarbon matters; molecular sieve grains which are uniform and controllable in grain size can be obtained, and moreover, the microcosmic rodlike structure of an aluminum oxide material in the synthetic process is maintained well, and micropores and mesopores coexist in the material, so that the permeability of the material is enhanced; the molecular sieve is synthesized in situ in the aluminum oxide material, so that the preparation cost is lowered.
Description
Technical field
The present invention relates to the preparation method of compound duct catalytic material, especially relate to a kind of preparation method with compound duct catalytic material containing ZSM-5 molecular sieve and rod-like aluminum oxide.
Background technology
Molecular sieve is a kind of material with uniform cell structure, and its pore size and general small molecules size are similar to.After McBain in 1932 proposes the concept of " molecular sieve ", various natural and synthesis of molecular sieve is found successively and invents.ZSM-5 molecular sieve is in 1972 by Mobil company of U.S. reported first, and it is that a kind of high silicon 3 D with MFI type skeleton structure intersects straight channel zeolite molecular sieve, and aperture is about 0.55nm, has high specific surface area and can the acidity of modulation.3D pore passage structure and the acidity of ZSM-5 molecular sieve rule make to be used widely in its acid catalyzed reaction such as the isomerization at hydrocarbon compound and alkylation.But the single features micropore that traditional ZSM-5 molecular sieve has hinders more macromolecular entering, limit its macromolecules adsorption reaction in application.In order to solve this application limitations problem of micro porous molecular sieve, investigator considers that molecular sieve system is introduced in duct at different levels improves its permeability, thus improves the rate of diffusion of reactant and product, and improves its thermostability and anti-coking performance.Current research mainly concentrate on by the control of molecular sieve structure and pattern to reach the object improving molecular sieve pore passage characteristic.Chinese patent CN 103288100 A reports a kind of synthetic method of multi-stage porous ZSM-5 molecular sieve, there is by adding synthesis of surfactant the ZSM-5 molecular sieve of nano-lamellar structure, this molecular sieve has higher specific surface area, as can be seen from provided TEM figure, obtained sample has sheet structure, but can find that from SEM figure its sheet structure is reunited together, between without obvious gap, show that its sheet structure does not improve significantly to overall pore characteristic by the pore structure data measured by N2-physical adsorption, and its synthesis flow is complicated, preparation cycle is long.Another part Chinese patent CN10317208 A directly synthesizes MCM-48 mesopore molecular sieve, compare micro porous molecular sieve, this molecular sieve has three-dimensional spiral pore passage structure, higher specific surface area and higher permeability, but it is incomplete mostly to there is the condensation of silicon species in skeleton in the mesopore molecular sieve of directly synthesis, the shortcomings such as hydrothermal stability is relatively low, and this sample average aperture is 2.88nm, still can not meet the requirement of many catalyzed reactions.
γ-Al
2o
3(a kind of activated alumina), as one of the of paramount importance catalytic material of current industrial widespread use, have aboundresources, the advantage such as cheap, the present invention utilizes the bar-shaped γ-Al synthesized voluntarily
2o
3material is aluminium source, adopt single stage method directly to synthesize to there is compound duct namely there is aluminum oxide-molecular sieve compound catalyze material that is mesoporous and microvoid structure, reach simultaneously and improve material specific surface area, regulate material surface acid and introduce the object of multistage pore canal, have no the report of this respect at present.
Summary of the invention
The object of this invention is to provide a kind of preparation method with compound duct catalytic material.
Concrete steps of the present invention are as follows:
By aluminium source, silicon source, template, dehydrated alcohol and deionized water mixing, after aging, thermal treatment, be down to room temperature, then through centrifugal, washing, dry, roasting, compound duct catalytic material must be had.
Described aluminium source can adopt bar-shaped γ-Al
2o
3presoma, described bar-shaped γ-Al
2o
3presoma is at 550 DEG C of roasting 2h or carry out pre-treatment with silylating reagent; Described silylating reagent can adopt trimethylchlorosilane or TERT-BUTYL DIMETHYL CHLORO SILANE etc.; The consumption of described silylating reagent can be silylating reagent in molar ratio: Al
2o
3=(0.1 ~ 0.2): 1.
Described silicon source can be selected from the one in water glass, silicon sol, solid silicone, tetraethoxy etc.
Described template can be selected from 4-propyl bromide and alkali, or TPAOH; Described alkali selected from sodium hydroxide or sodium metaaluminate etc., the mol ratio of described 4-propyl bromide and alkali can be 1: 1.
The mol ratio of described aluminium source, silicon source, template, dehydrated alcohol and deionized water can be: the Al in aluminium source
2o
3: the SiO in silicon source
2: template: dehydrated alcohol: deionized water=1: (0.1 ~ 50): (0.3 ~ 0.6): 3: 56.
The described aging time can be 1 ~ 24h.
Described thermal treatment can adopt atmospheric pressure reflux or hydrothermal treatment consists; The temperature of described atmospheric pressure reflux can be 80 ~ 120 DEG C, and the time of atmospheric pressure reflux can be 12 ~ 48h; The temperature of described hydrothermal treatment consists can be 140 ~ 200 DEG C, and the time of hydrothermal treatment consists can be 12 ~ 36h.
The temperature of described drying can be 70 ~ 120 DEG C, and the dry time can be 6 ~ 24h.
The temperature of described roasting can be 400 ~ 650 DEG C, and the time of roasting can be 2 ~ 6h.
The present invention take Nano bars of alumina as aluminium source, and organic amine is template, and water is solvent, fully carries out aging after mixing, then through hydrothermal treatment consists, must have the catalytic material in compound duct after centrifugal, washing, drying.The material that the present invention obtains is made up of Nano bars of alumina and zeolite crystal, the zeolite crystal of synthesis distributes comparatively equably at alumina surface, and remain the original club shaped structure of aluminum oxide, make the duct of molecular sieve and aluminum oxide mutually through, drastically increase the permeability of material compared with simple molecular sieve.With simple alumina phase ratio, the catalytic material obtained by the present invention has stronger acidity.Therefore, the catalyzer prepared by catalytic material of the present invention is applicable to organism hydrocracking and isomerization reaction.
The catalytic material preparation method tool in compound duct provided by the present invention has the following advantages:
1, molecular sieve is introduced alumina material, improve the specific surface area of prepared matrix material, add the surface acidity position of material, make catalytic material have stronger acidity, be applicable to hydrocarbons hydrocracking and isomerization reaction.
2, uniform particle diameter can be obtained and controlled zeolite crystal, and the microcosmic club shaped structure of alumina material is maintained well in building-up process, to ensure that in material micropore and mesoporous while exist, improve the permeability of material compared with simple molecular sieve.
3, at alumina material situ synthesis of molecular sieve, decrease the steps such as washing, separation and ion-exchange, save water consumption and generated time, reduce further material preparation cost.
Accompanying drawing explanation
The XRD spectra of the catalytic material of Fig. 1 obtained by embodiment 1 ~ 4 and comparative example 1 ~ 2.
Embodiment
Further describe compound duct of the present invention catalytic material and preparation method thereof with comparative example by the following examples, to help reader, methods of this invention will be better understood, but do not form can any restriction of practical range to the present invention.
Embodiment 1
After bar-shaped activated alumina presoma 550 DEG C of roasting 2h, take 2g and add 1.5g silicon sol, 1.25g TPAOH, 2.84g dehydrated alcohol and 20.35g deionized water, at room temperature vigorous stirring evenly rear aging 24h, be transferred to and have in teflon-lined water heating kettle in 180 DEG C of hydro-thermal 12h, 70 DEG C of dry 24h after washing, 550 DEG C of roasting 3h, obtain ZSM-5/ alumina composite material S-1.
Embodiment 2
After bar-shaped activated alumina presoma 550 DEG C of roasting 2h, take that 2g adds 2.2g water glass, 2.5g TPAOH, 2.84g dehydrated alcohol join 20.35g deionized water, at room temperature vigorous stirring evenly rear aging 12h, be transferred to and have in teflon-lined water heating kettle in 160 DEG C of hydro-thermal 24h, 120 DEG C of dry 6h after washing, 650 DEG C of roasting 2h, obtain ZSM-5/ alumina composite material S-2.
Embodiment 3
After 2g rod-like aluminum oxide presoma is added the pre-treatment of 0.43g trimethylchlorosilane, add 5.54g tetraethoxy, 3.2g 4-propyl bromide, 0.48g sodium hydroxide, 2.84g dehydrated alcohol and 20.35g deionized water, at room temperature vigorous stirring evenly rear aging 24h, be transferred to and have in teflon-lined water heating kettle in 180 DEG C of hydro-thermal 12h, 90 DEG C of dry 24h after washing, again through 500 DEG C of roasting 3h, obtain ZSM-5/ alumina composite material S-3.
Embodiment 4
2g rod-like aluminum oxide presoma and 9.23g tetraethoxy, 2.5g TPAOH, 2.84g dehydrated alcohol are joined in 20.35g deionized water, at room temperature vigorous stirring is even, be transferred to after aging 1h in flask in 80 DEG C of atmospheric pressure reflux 24h, 100 DEG C of dry 16h after washing, again through 400 DEG C of roasting 4h, obtain ZSM-5/ alumina composite material S-4.
Comparative example 1
Repeat the building-up process of embodiment 1, but do not add silicon source and template, product obtains contrast material DA-1 after washing drying and roasting.
Comparative example 2
Repeat the building-up process of embodiment 3, but do not add silylating reagent, product obtains contrast material DA-2 after washing drying and roasting.
The pore characteristic of each routine resulting materials lists in table 1 above.
The pore characteristic of table 1 matrix material
From table 1, specific surface area and the pore volume of the molecular sieve obtained by the present invention-alumina composite material celled portion are obtained for significant raising, mesoporous part is retained simultaneously, effectively can solve the blockage problem of recurrent molecular sieve pore passage in the processes such as hydrocracking heavy oil.
The result of comprehensive above embodiment and comparative example is known: method for composite material provided by the present invention, and it is simple for process, preparation cycle is short, cost is low, is easy to suitability for industrialized production; And preparation process saves bath water, decreases sewage discharge, meets the requirement of environmental protection; Under the prerequisite guaranteeing duct permeability, drastically increase specific surface area and the surface acidity of solid support material, there is good prospects for commercial application.
Claims (10)
1. there is a preparation method for compound duct catalytic material, it is characterized in that its concrete steps are as follows:
By aluminium source, silicon source, template, dehydrated alcohol and deionized water mixing, after aging, thermal treatment, be down to room temperature, then through centrifugal, washing, dry, roasting, compound duct catalytic material must be had.
2. a kind of preparation method with compound duct catalytic material as claimed in claim 1, is characterized in that described aluminium source adopts bar-shaped γ-Al
2o
3presoma, described bar-shaped γ-Al
2o
3presoma is at 550 DEG C of roasting 2h or carry out pre-treatment with silylating reagent.
3. a kind of preparation method with compound duct catalytic material as claimed in claim 2, is characterized in that described silylating reagent adopts trimethylchlorosilane or TERT-BUTYL DIMETHYL CHLORO SILANE; The consumption of described silylating reagent can be silylating reagent in molar ratio: Al
2o
3=(0.1 ~ 0.2): 1.
4. a kind of preparation method with compound duct catalytic material as claimed in claim 1, is characterized in that described silicon source is selected from the one in water glass, silicon sol, solid silicone, tetraethoxy.
5. a kind of preparation method with compound duct catalytic material as claimed in claim 1, is characterized in that described template is selected from 4-propyl bromide and alkali, or TPAOH; Described alkali selected from sodium hydroxide or sodium metaaluminate, the mol ratio of described 4-propyl bromide and alkali can be 1: 1.
6. a kind of preparation method with compound duct catalytic material as claimed in claim 1, it is characterized in that described aluminium source, silicon source, template, dehydrated alcohol and deionized water mol ratio be: the Al in aluminium source
2o
3: the SiO in silicon source
2: template: dehydrated alcohol: deionized water=1: (0.1 ~ 50): (0.3 ~ 0.6): 3: 56.
7. a kind of preparation method with compound duct catalytic material as claimed in claim 1, is characterized in that the described aging time is 1 ~ 24h.
8. a kind of preparation method with compound duct catalytic material as claimed in claim 1, is characterized in that described thermal treatment adopts atmospheric pressure reflux or hydrothermal treatment consists; The temperature of described atmospheric pressure reflux can be 80 ~ 120 DEG C, and the time of atmospheric pressure reflux can be 12 ~ 48h; The temperature of described hydrothermal treatment consists can be 140 ~ 200 DEG C, and the time of hydrothermal treatment consists can be 12 ~ 36h.
9. a kind of preparation method with compound duct catalytic material as claimed in claim 1, is characterized in that the temperature of described drying is 70 ~ 120 DEG C, and the dry time is 6 ~ 24h.
10. a kind of preparation method with compound duct catalytic material as claimed in claim 1, it is characterized in that the temperature of described roasting is 400 ~ 650 DEG C, the time of roasting is 2 ~ 6h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1751994A (en) * | 2004-09-24 | 2006-03-29 | 中国石油化工股份有限公司 | Porous material and its synthesis method |
| CN103172081A (en) * | 2013-04-02 | 2013-06-26 | 常州大学 | High-molecular organic polymer template synthesized compound pore structure molecular sieve and preparation method thereof |
| CN103288100A (en) * | 2013-05-21 | 2013-09-11 | 宁夏大学 | Hierarchical pore ZSM-5 molecular sieve and synthetic method thereof |
| CN103466654A (en) * | 2013-08-29 | 2013-12-25 | 华南理工大学 | Preparation method of ZSM-5 mesoporous and microporous composite molecular sieve |
-
2015
- 2015-02-06 CN CN201510061404.6A patent/CN104591205B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1751994A (en) * | 2004-09-24 | 2006-03-29 | 中国石油化工股份有限公司 | Porous material and its synthesis method |
| CN103172081A (en) * | 2013-04-02 | 2013-06-26 | 常州大学 | High-molecular organic polymer template synthesized compound pore structure molecular sieve and preparation method thereof |
| CN103288100A (en) * | 2013-05-21 | 2013-09-11 | 宁夏大学 | Hierarchical pore ZSM-5 molecular sieve and synthetic method thereof |
| CN103466654A (en) * | 2013-08-29 | 2013-12-25 | 华南理工大学 | Preparation method of ZSM-5 mesoporous and microporous composite molecular sieve |
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