CN101722028A - Catalyst for synthesizing dimethyl ether on fluidized bed - Google Patents
Catalyst for synthesizing dimethyl ether on fluidized bed Download PDFInfo
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- CN101722028A CN101722028A CN200810155299A CN200810155299A CN101722028A CN 101722028 A CN101722028 A CN 101722028A CN 200810155299 A CN200810155299 A CN 200810155299A CN 200810155299 A CN200810155299 A CN 200810155299A CN 101722028 A CN101722028 A CN 101722028A
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- catalyst
- fluidized bed
- dimethyl ether
- dme
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Abstract
The invention belongs to the technical field of catalysts. Silica sol is used as a binder, Cu-Zn-Al is used as active components for methanol synthesis, HZSM-5 is used as a bifunctional catalyst of a component for methanol dehydration, and the main active components are as follows by weight percent: 30-45% of copper, 30-45% of zinc and 10-30% of other components. The invention provides a novel high efficiency catalyst for synthesizing dimethyl ether (DME) on a fluidized bed, thereby opening a process route for producing DME with synthesis gas on the fluidized bed by a one-step method.
Description
Technical field: the invention belongs to catalyst technical field, be specifically related to a kind of catalyst that is used for synthesizing dimethyl ether on fluidized bed (DME).
Background technology: the synthetic DME of one-step method can be divided into fixed bed and starch two kinds of attitude beds by the catalytic reactor form at present.Three reactions being gone through by synthesis gas system DME: methyl alcohol is synthetic, methanol dehydration and water-gas shift reaction are strong exothermal reaction, therefore, and for fixed bed reactors, owing to move the heat difficulty, and be difficult to realize the large-scale production of DME; For paste state bed reactor, though it is easy to move thermal capacitance, can realize constant temperature method, but because inert fluid phase of extra introduction, make system have serious resistance to mass tranfer, in " coal conversion " 16 volume the 4th phase the 68th page of literary compositions, reach Guo Junwang result of study in " gas chemical industry " 25 volume the 1st phase the 4th page of literary compositions as the Du Ming celestial being: for fixed bed, methyl alcohol activation energy synthetic and dehydration is respectively 102.4 and 99.8kJ/mol, and it is respectively 14.1 and 23.5kJ/mol in slurry attitude bed, as seen, resulting activation energy data is not the activation energy under dynamics Controlling in slurry attitude bed, but the activation energy value under the DIFFUSION CONTROLLED outside, promptly starch in the synthetic DME process of attitude bed and have serious resistance to mass tranfer, the result causes the production capacity of reaction rate and reactor significantly to descend, and this has also limited the suitability for industrialized production of DME.In addition, aspect rate of heat transfer, by calculating, the overall heat-transfer coefficient of slurry attitude bed is at 200kcal/m
2.hr. ℃ about, and the overall heat-transfer coefficient of fluid bed can surpass 1000kcal/m
2.hr. ℃, be 5 times of slurry attitude bed.Therefore, fluidized-bed reactor has the ideal reactor that good heat transfer property becomes large-scale production DME because of it.
Summary of the invention: the purpose of this invention is to provide a kind of efficient catalyst that can be used for synthesizing dimethyl ether on fluidized bed (DME), thereby open up a process route of producing DME by the one-step method from syngas fluid bed.
Catalyst of the present invention is to be binding agent with the Ludox, is methyl alcohol synthesizing activity component with Cu-Zn-Al, is the bifunctional catalyst of methanol dehydration component with HZSM-5.
Technical scheme of the present invention is to be benchmark with the total catalyst weight, and the main active component weight percentage is: copper accounts for 30-45%, and zinc accounts for 30-45%, other ingredients constitute 10-30%.
The present invention at first with the nitrate solution of copper, zinc through the sodium carbonate liquor co-precipitation, in the precipitation slurries, add aluminium hydroxide, HZSM-5 type molecular sieve and adhesive silicon sol then, carry out spray-drying after fully stirring, thereby make the microspheric catalyst of certain particle size.
The concrete preparation process of new catalyst provided by the invention is: the mixed nitrate solution and the sodium carbonate liquor that (a) dispose certain density copper, zinc; (b) above-mentioned solution constantly stirs in the precipitation process 60-80 ℃ of following co-precipitation, PH=7-8 when precipitation stops; (C) with above-mentioned precipitation slurries deionized water cyclic washing, until no Na
+The back adds auxiliary agent, HZSM-5 type molecular sieve and binding agent making beating; (d) with the press spray drier by the requirement granularity carry out spray shaping, catalyst granules diameter average out to 50-300 μ m is preferably 80-200 μ m, particle is ball-type; (e) 120 ℃ of dryings, 300-500 ℃ of following roasting 3-6hr.
The catalyst of the present invention's preparation has following characteristics:
1. introduce binding agent in the Preparation of Catalyst, make it have certain wearability.
2. catalyst adopts spray drying forming, thereby obtains to be suitable for the microspheric catalyst particle that fluid bed uses.
3. catalyst copper, zinc mol ratio are 1: 1, at H
2Show catalytic performance preferably under the condition of/CO=1.
The specific embodiment:
Comparative Examples
Cu and Zn are made into certain density mixed liquor with the form of nitrate solution, carry out co-precipitation at 65 ℃ of following sodium carbonate liquors with 15%, need abundant stirring in the precipitation process, final mother liquor PH is 7-8, precipitation is aging after 1 hour, spends deionised water until detecting less than Na
+Till the ion, add auxiliary agent aluminium hydroxide and HZSM-5 making beating, moulding on the press spray drier, raw meal particle size is 80-200 μ m, 120 ℃ of dryings, it is stand-by that 320 ℃ of roastings promptly get product.
Embodiment 1
Be that with the Comparative Examples difference catalyst does not contain the auxiliary agent aluminium oxide.
Embodiment 2
Be before spray-drying that with Comparative Examples 1 difference adding quality percentage composition is 8% Ludox in slurries.
Embodiment 3
Be before spray-drying that with Comparative Examples 1 difference adding quality percentage composition is 10% Ludox in slurries.
Embodiment 4
Be before spray-drying that with Comparative Examples 1 difference adding quality percentage composition is 12% Ludox in slurries.
The catalyst activity evaluation experimental carries out in the stainless steel fixed bed reactors of φ 10 * 300mm, the pure H of catalyst before the reaction
2At 300 ℃ of reduction 3hr, heating rate is 1 ℃/min, and reaction condition and reaction result are as follows:
H
2/CO＝1，T＝260℃，P＝3MPa，SV＝3000ml/g.h，
Can find out that by experimental data in the table adding of auxiliary agent aluminium hydroxide can improve catalyst activity greatly.Influence is not very big to the Ludox of introducing in catalyst for the wear-resisting property of raising catalyst to catalyst activity, and when the quality percentage composition of Ludox is 10%, catalyst activity the best.
Claims (2)
1. catalyst that is used for synthesizing dimethyl ether on fluidized bed, it is characterized in that this catalyst is is binding agent with the Ludox, with Cu-Zn-Al is methyl alcohol synthesizing activity component, with HZSM-5 is the bifunctional catalyst of methanol dehydration component, the main active component weight percentage is: copper accounts for 30-45%, zinc accounts for 30-45%, other ingredients constitute 10-30%.
2. a catalyst according to claim 1 is characterized in that copper in the catalyst component, zinc mol ratio are 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810155299A CN101722028A (en) | 2008-10-30 | 2008-10-30 | Catalyst for synthesizing dimethyl ether on fluidized bed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810155299A CN101722028A (en) | 2008-10-30 | 2008-10-30 | Catalyst for synthesizing dimethyl ether on fluidized bed |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101722028A true CN101722028A (en) | 2010-06-09 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810155299A Pending CN101722028A (en) | 2008-10-30 | 2008-10-30 | Catalyst for synthesizing dimethyl ether on fluidized bed |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855209A (en) * | 2018-07-13 | 2018-11-23 | 武汉理工大学 | A kind of ormolu support type grade hole titanium molecular sieve catalysis material and preparation method thereof |
-
2008
- 2008-10-30 CN CN200810155299A patent/CN101722028A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855209A (en) * | 2018-07-13 | 2018-11-23 | 武汉理工大学 | A kind of ormolu support type grade hole titanium molecular sieve catalysis material and preparation method thereof |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100609 |