CN101301625A - Al2O3-HZSM-5 compound solid acid catalyst prepared by mechanical mixed method - Google Patents
Al2O3-HZSM-5 compound solid acid catalyst prepared by mechanical mixed method Download PDFInfo
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- CN101301625A CN101301625A CNA2008100610539A CN200810061053A CN101301625A CN 101301625 A CN101301625 A CN 101301625A CN A2008100610539 A CNA2008100610539 A CN A2008100610539A CN 200810061053 A CN200810061053 A CN 200810061053A CN 101301625 A CN101301625 A CN 101301625A
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- hzsm
- catalyst
- acid catalyst
- composite solid
- methanol
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Abstract
A process for preparing Al2O3-HZSM-5 composite solid acid catalyst by a mechanical mixing method comprises: mixing 5-95 wt. % of Al2O3, based on the total weight of the composite solid acid catalyst, with HZSM-5 molecular sieve in a ball mill, and subsequently baking, preforming the mixture to obtain the Al2O3-HZSM-5 composite solid acid catalyst. The preparation process of the invention is extremely simple, and as the catalyst of the invention is used in the methanol dehydration reaction for producing dimethyl ether, high activity and stability at low temperature are achieved.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method of preparing dimethyl ether by dewatering methanol, particularly prepare Al with mechanical mixing
2O
3-HZSM-5 composite solid-acid catalyst.
Background technology
Dimethyl ether (molecular formula: CH
3OCH
3, molecular weight: 46, boiling point 120-130 ℃, 235 ℃ of self-ignition points) aspect chemical and medicine industry, have purposes widely, can be used as pesticide, polishing agent, antirust agent, alkylating agent, solvent, also can be used as aerosol, hair jelly, air freshener, domestic fuel etc.As green chemical, dimethyl ether has more outstanding advantage aspect the alternative fuel of Diesel engine.The Cetane number height (55-60) of dimethyl ether has good burning performance, and can reduce the discharging of contaminated off-gas during burning.Simultaneously, dimethyl ether still is a kind of good environmental friendliness green refrigerant, compares with traditional fluorochlorohydrocarbon, and it does not destroy ozone layer, can not cause greenhouse effects substantially yet.Therefore, dimethyl ether is described as the clean energy resource of 21 century.
At present, dimethyl ether mainly contains two synthesis techniques, a strip adoption methanol dehydration technology.Methanol dehydration technology can be divided into liquid phase methanol dehydration method and gas phase methanol dehydration method again by the difference of reacting phase.
2CH
3OH→CH
3OCH
3+H
2O
Liquid phase methanol dehydration method adopts the concentrated sulfuric acid to make catalyst, and it is low to have reaction temperature, the conversion ratio height, the advantage that selectivity is good, but serious to equipment corrosion, raffinate and waste water environmental pollution are serious, operating condition harshness, product post processing be difficulty relatively, and be superseded substantially at present.
The gas-phase methanol evaporation adopts activated alumina, crystalline aluminosilicate etc. as catalyst, and methanol steam by solid catalyst, heterogeneous reaction is taken place, and methanol dehydration generates dimethyl ether.This method is easy and simple to handle, pollute less, can produce continuously, and Guangdong Zhong Shankang skill industrial chemicals Co., Ltd just takes this explained hereafter dimethyl ether, and range of reaction temperature is 330-400 ℃, and pressure is 15 atmospheric pressure.But the reaction temperature of this technology is harsher to the requirement of reaction unit than higher.
An other production technology is to adopt the synthesis gas direct synthesis process.For example Chinese invention patent ZL95113028.5, ZL98107687.4 and ZL00110261.3.Though the one-step method dimethyl ether synthesis carries out synthetic the lumping together with methanol dehydration of methyl alcohol, the preparation of equipment complexity, operating condition harshness, composite catalyst and activity are kept still needs further tackling key problem.
Because the direct dehydration dimethyl ether-preparing of methyl alcohol has characteristics such as technical maturity, device wide adaptability, post processing are simple, therefore has certain advantage; But in the document and patent of having reported for work at present, methanol dehydration need carry out under higher temperature, for example: report uses double-deck loading catalyst system among the Chinese invention patent application CN03826000.X, comprises the hydrophilic solid acid catalyst (gama-alumina or silica-alumina) of 50-95 volume % and the hydrophobic solid acid catalyst (SiO of 5-50 volume %
2/ Al
2O
3Than being the hydrophobic zeolite of 20-200), need (the liquid air speed per hour of reactant liquor feed rate/catalyst volume be 7.5h at 270-290 ℃ and underload
-1) condition under carry out.The CuO-ZnO-La that reports among the Chinese invention patent application CN1745894A
2O
3-Sm
2O
3-V
2O
5Catalyst also need (the liquid air speed per hour of reactant liquor feed rate/catalyst volume be 1-5.0h at high temperature (240-320 ℃) and lower underload
-1) condition under carry out.The catalyst of alkali metal such as the interpolation rare-earth elements La of reporting among the Chinese invention patent application CN1919451A, Ce and interpolation proper C a, Mg, Na, K and alkaline-earth metal need carry out under higher temperature (320-360 ℃).Among the Chinese invention patent application CN101108789A, control the distribution of methanol dehydration catalyst bed temperature by the methanol feeding amount of regulating the different catalysts bed, use ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, gama-alumina to be catalyst, reaction velocity is 2.0-8.0h
-1, the reaction outlet temperature is more than 300 ℃, and methanol conversion is 76-85%; Report modification gamma-alumina catalyst need carry out under 260 ℃ among the Chinese invention patent application CN1613558, and the liquid air speed of methyl alcohol is 1.5h
-1
Patent application above comprehensive is not difficult to find, at present the catalyst of the preparing dimethyl ether by dewatering methanol of reporting in the disclosed application need carry out at high temperature that (temperature of being reported is all more than 240 ℃, and optimum operating temperature is many at 280-330 ℃), low (the liquid air speed per hour of reactant liquor feed rate/catalyst volume generally is lower than 10h to Fan Ying load simultaneously
-1).
Because methanol dehydration is a strong exothermal reaction, high temperature dehydration technology mainly contains following shortcoming:
(1) Fan Ying equilibrium conversion is low, a large amount of methyl alcohol need circulation repeatedly, increased the subsequent fine cut from load;
(2) pyroreaction is to the requirement harshness of equipment, and the energy consumption of pretreatment of raw material is higher;
(3) under hot conditions, methanol dehydration easily generates hydro carbons, long chain hydrocarbon even generates carbon distribution at catalyst surface, so methanol consumption is higher, has reduced life of catalyst simultaneously.
In addition, the catalyst that adopts at present generally is independent Al
2O
3, HZSM-5, HY, SAPO etc., they all have shortcoming separately; Though high as aluminium oxide stability, reaction temperature is also high, very high to the equipment requirement of reaction, cause cost higher.Molecular sieve catalysts acidity is stronger, and initial temperature is low, but accessory substance is many, easily carbon distribution, easy inactivation.
Summary of the invention
The object of the invention provides a kind of preparation method of composite solid-acid catalyst, and Zhi Bei catalyst is used for methanol dehydration dimethyl ether-preparing reaction in this way, has characteristics such as low temperature active height, high-temperature stability are good.
Al provided by the invention
2O
3-HZSM-5 composite solid-acid catalyst is to be raw material, to adopt mechanical mixing to prepare with aluminium oxide and HZSM-5.With aluminium oxide and HZSM-5 molecular sieve raw material, in the ratio of aluminium oxide, in ball mill, to mix at the shared mass percent 5-95% of composite solid-acid catalyst, characterization step is:
(1), with powdery aluminum and powdery HZSM-5, in the ratio of aluminium oxide, put into ball mill after the mixing at the shared mass percent 5-95% of composite solid-acid catalyst; In ball mill, mixed 2-24 hour;
(2), will mix back Al
2O
3-HZSM-5 complex solid acid precursor was at 400--550 ℃ of following roasting 1-10 hour.
Preparation method of the present invention is very simple, makes Al
2O
3-HZSM-5 composite solid-acid catalyst external surface area is big, the acid amount is high.Catalyst generates in the reaction of dimethyl ether at methanol dehydration, has very high activity and stable at low temperatures.
Al provided by the invention
2O
3-HZSM-5 composite solid-acid catalyst is used in the Dehydration of methanol, and the temperature of reaction is 190-270 ℃, the liquid air speed per hour 10-30h of methanol solution feed rate/catalyst volume
-1, conversion of methanol 16-88.4mol%
The present invention further describes with reference to the following example.
The specific embodiment
Embodiment 1
2 gram aluminium oxide and 8 gram HZSM-5 molecular sieves are mixed 12 hours in ball mill after, be placed on 550 ℃ of following roastings of Muffle furnace 4 hours; Compression molding then; Above-mentioned structures of samples characterizes with the ammonia absorption method with nitrogen adsorption sign, acid amount.The surface area of this catalyst is 303.6m
2/ g, external surface area are 82.8m
2/ g, total acid content are 0.353mmol/g.
Get 40-60 purpose catalyst 0.2 gram and in fixed bed reactors, carry out the methanol dehydration activity rating.Reaction condition: reaction temperature 190-270 ℃, the liquid air speed per hour 30h of reactant liquor feed rate/catalyst volume
-1, the conversion ratio under the different temperatures is as shown in table 1.
Table 1.Al
2O
3-HZSM-5 (MM-20%) conversion of methanol under the differential responses temperature
| Reaction temperature/℃ | 192 | 218 | 244 |
| Methanol conversion mol% | 22.71 | 64.40 | (89.40 reaching equilibrium conversion) |
Embodiment 2
4 gram aluminium oxide and 6 gram HZSM-5 molecular sieves are mixed 6 hours in ball mill after, be placed on 550 ℃ of following roastings of Muffle furnace 4 hours; Compression molding then; Above-mentioned structures of samples characterizes with the ammonia absorption method with nitrogen adsorption sign, acid amount.The surface area of this catalyst is 303.4m
2/ g, external surface area are 168.0m
2/ g, total acid content are 0.304mmol/g.
Get 40-60 purpose catalyst 0.2 gram and in fixed bed reactors, carry out the methanol dehydration activity rating.Reaction condition: reaction temperature 190-270 ℃, the liquid air speed per hour 30h of reactant liquor feed rate/catalyst volume
-1, the conversion ratio under the different temperatures is as shown in table 2.
Table 2.Al
2O
3-HZSM-5 (MM-40%) conversion of methanol under the differential responses temperature
| Reaction temperature/℃ | 192 | 216 | 244 | 266 |
| Methanol conversion mol% | 16.35 | 47.36 | 83.78 | (88.9 reaching equilibrium conversion) |
Embodiment 3
6 gram aluminium oxide and 4 gram HZSM-5 molecular sieves are mixed 12 hours in ball mill after, be placed on 550 ℃ of following roastings of Muffle furnace 4 hours; Compression molding then; Above-mentioned structures of samples characterizes with the ammonia absorption method with nitrogen adsorption sign, acid amount.The surface area of this catalyst is 239.1m
2/ g, external surface area are 204.3m
2/ g, total acid content are 0.210mmol/g.
Get 40-60 purpose catalyst 0.2 gram and in fixed bed reactors, carry out the methanol dehydration activity rating.Reaction condition: reaction temperature 190-270 ℃, the liquid air speed per hour 30h of reactant liquor feed rate/catalyst volume
-1, the conversion ratio under the different temperatures is as shown in table 3.
Table 3.Al
2O
3-HZSM-5 (MM-60%) conversion of methanol under the differential responses temperature
| Reaction temperature/℃ | 191 | 216 | 240 | 263 |
| Methanol conversion mol% | 13.04 | 43.92 | 74.96 | (88.4 reaching equilibrium conversion) |
Embodiment 4
8 gram aluminium oxide and 2 gram HZSM-5 molecular sieves are mixed 24 hours in ball mill after, be placed on 550 ℃ of following roastings of Muffle furnace 4 hours; Compression molding then; Above-mentioned structures of samples characterizes with the ammonia absorption method with nitrogen adsorption sign, acid amount.The surface area of this catalyst is 230.3m
2/ g, external surface area are 203.5m
2/ g, total acid content are 0.148mmol/g.
Get 40-60 purpose catalyst 0.2 gram and in fixed bed reactors, carry out the methanol dehydration activity rating.Reaction condition: reaction temperature 190-270 ℃, the liquid air speed per hour 30h of reactant liquor feed rate/catalyst volume
-1, the conversion ratio under the different temperatures is as shown in table 4.
Table 4.Al
2O
3-HZSM-5 (MM-80%) conversion of methanol under the differential responses temperature
| Reaction temperature/℃ | 190 | 212 | 236 | 260 | 280 |
| Methanol conversion mol% | 5.87 | 22.94 | 56.68 | 80.45 | (88.4 reaching equilibrium conversion) |
Claims (2)
1, a kind of Al
2O
3The preparation method of-HZSM-5 composite solid-acid catalyst, it is characterized in that: with the mechanical mixing preparation, with aluminium oxide and HZSM-5 molecular sieve raw material, in the ratio of aluminium oxide in the shared mass percent 5～95% of composite solid-acid catalyst, mix in ball mill, step is:
(1) with powdery aluminum and powdery HZSM-5 molecular sieve, in the ratio of aluminium oxide, put into ball mill after the mixing in the shared mass percent 5～95% of composite solid-acid catalyst, in ball mill, mixed 2～24 hours;
(2) will mix back Al
2O
3-HZSM-5 complex solid acid precursor makes Al 400～550 ℃ of following roastings 1～10 hour
2O
3-HZSM-5 composite solid-acid catalyst.
2, prepare Al according to claim 1 with mechanical mixing
2O
3-HZSM-5 composite solid-acid catalyst is characterized in that: catalyst is used for the reaction that methanol dehydration generates dimethyl ether, 190～270 ℃ of reaction temperatures, the liquid air speed per hour 10～30h of reactant liquor feed rate/catalyst volume
-1, methanol conversion is 16～88.4mol%.
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|---|---|---|---|
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|---|---|---|---|
| CN2008100610539A CN101301625B (en) | 2008-04-25 | 2008-04-25 | Al2O3-HZSM-5 compound solid acid catalyst prepared by mechanical mixed method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786009A (en) * | 2010-03-04 | 2010-07-28 | 西北化工研究院 | Preparation method of catalyst in preparation of dimethyl ether by methyl alcohol |
| CN102627287A (en) * | 2012-04-20 | 2012-08-08 | 浙江大学 | Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials |
| CN105107544A (en) * | 2015-08-24 | 2015-12-02 | 北京理工大学 | Solid acid catalyst for producing dimethyl ether and preparation method thereof |
-
2008
- 2008-04-25 CN CN2008100610539A patent/CN101301625B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786009A (en) * | 2010-03-04 | 2010-07-28 | 西北化工研究院 | Preparation method of catalyst in preparation of dimethyl ether by methyl alcohol |
| CN101786009B (en) * | 2010-03-04 | 2011-08-31 | 西北化工研究院 | Preparation method of catalyst in preparation of dimethyl ether by methyl alcohol |
| CN102627287A (en) * | 2012-04-20 | 2012-08-08 | 浙江大学 | Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials |
| CN105107544A (en) * | 2015-08-24 | 2015-12-02 | 北京理工大学 | Solid acid catalyst for producing dimethyl ether and preparation method thereof |
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| CN101301625B (en) | 2010-06-16 |
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