CN1947833A - Catalyst used for preparing dimethyl ether by dehydration of methanol, and method for preparing the same - Google Patents
Catalyst used for preparing dimethyl ether by dehydration of methanol, and method for preparing the same Download PDFInfo
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- CN1947833A CN1947833A CN 200610022256 CN200610022256A CN1947833A CN 1947833 A CN1947833 A CN 1947833A CN 200610022256 CN200610022256 CN 200610022256 CN 200610022256 A CN200610022256 A CN 200610022256A CN 1947833 A CN1947833 A CN 1947833A
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- aluminium hydroxide
- catalyst
- dimethyl ether
- clay
- preparing dimethyl
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Abstract
A catalyst used for preparing dimether from methanol by dewatering is prepared from aluminum hydroxide through proportionally mixing it with clay or dissolving in acid, shaping, drying, and baking.
Description
Technical field
The invention belongs to chemical technology field, particularly a kind of Catalysts and its preparation method that is used for preparing dimethyl ether by dewatering methanol.
Background technology
Dimethyl ether claims methyl ether (CH again
3)
2O (abbreviation DME) is colourless non-toxic gas or compressed liquid.In fields such as pharmacy, dyestuff, agricultural chemicals and chemical industry extensive use is arranged.Because calorific value is big, combustibility is good, present substitute products mainly as oil liquefied gas.In addition, dimethyl ether also can be used as aerosol, refrigerant, solvent, alkylating agent etc., and dimethyl ether liquefaction can directly substitute motor vehicle fuel, can dimethyl ether be feedstock production high octane gasoline etc. also.
Methyl alcohol is dewatering preparing dimethy ether under solid catalyst, is the common method of preparation dimethyl ether.Mainly be by γ-Al at present both at home and abroad with methanol steam
2O
3/ SiO
2Or catalyst such as ZSM-5 solid molecular sieves, dehydration is produced under high temperature and certain pressure.
Chinese patent 88101729.9 discloses a kind of method of producing pure Dimethyl ether, and use therein catalyst is γ-Al
2O
3Catalyst (preferably contains a spot of SiO
2), SiO
2Content is preferably 0.001-0.5%, is preferably 0.001-0.2%, and can contain less or very a spot of other component, for example Na in this catalyst
2O or other alkali metal oxide, alkali metal sulfates, alkali earth metal sulfate or aluminum sulfate, cobalt oxide etc.
Chinese patent 95113028.5 discloses a kind of method by the methanol production dimethyl ether, and methanol conversion is at 75-85%, and the dimethyl ether selectivity is greater than 99%; The catalyst that this method adopted will contain γ-Al on being
2O
3With the composite solid-acid catalyst of aluminosilicate crystallization, its component (by weight) is aluminosilicate crystallization 1-20%, γ-Al
2O
3The mixed-metal oxides 0.001-1.0% of 78-98.5%, lanthanum, manganese, silicon; Its preparation method is: prepare false boehmite with acid system, add hydrothermal synthesis method then and make the aluminosilicate crystallization, make after the calcining.
Chinese patent 200510012732.3 discloses a kind of methanol dewatered two dimethyl ether catalysts and preparation method and application, and the percentage by weight of each component consists of CuO 20-40%, ZnO 5-30%, La in this catalyst
2O
31-10%, Sm
2O
31-10%, V
2O
51-10%, carrier 40-60%.Its preparation method is: adopt copper nitrate or Schweinfurt green, zinc nitrate or zinc acetate, lanthanum nitrate are dissolved in the solvent, and the dissolving back adds carrier, stirs; To be ground into the following Sm of 250 orders then
2O
3And V
2O
5Add and to continue to stir, dry 60～100 ℃ of following infrared lamps irradiations, 350～500 ℃ of roastings, are sieved at compressing tablet, make catalyst.When this catalyst was used for preparing dimethyl ether by dewatering methanol, methanol conversion was at 60-80%, and the dimethyl ether selectivity is at 90-95%.
Methanol dehydration catalyst is often selected solid acidic materials for use, comprises γ-Al
2O
3, SiO
2-Al
2O
3, crystal aluminosilicate, crystalline zeolite, clay, phosphate, sulfate, acidic resins, load phosphoric acid and heteropoly acid etc.Since the production of traditional catalyst adopt precipitation (or glue), aging, filter, washing, dry, molding procedure, complex manufacturing, energy consumption height, contaminated environment, production cost height.
Summary of the invention
The purpose of this invention is to provide a kind of new catalyst that is used for preparing dimethyl ether by dewatering methanol.Adopt this catalyst component simple, activity is high, intensity is big, the life-span is long.
Another object of the present invention provides the above-mentioned Preparation of catalysts method that is used for preparing dimethyl ether by dewatering methanol, and this method technology is simple, and energy consumption is low, and is pollution-free, and production cost is low.
The technical solution adopted for the present invention to solve the technical problems is: a kind of catalyst that is used for preparing dimethyl ether by dewatering methanol, with aluminium hydroxide is that primary raw material is made, is that 3～10: 1 ratio is mixed by aluminium hydroxide and clay with weight ratio, perhaps with aluminium hydroxide through volumetric concentration be 1～6% sour molten, then through moulding, drying, roasting and make.
Above-mentioned aluminium hydroxide can be selected from boehmite, false boehmite, β-gibbsite, the low crystalline aluminum oxide hydrate etc. any one or multiple.
Clay can be selected from bentonite, Xuyong china clay, the kaolin etc. any one or multiple.
The acid that is used for the dissolved hydrogen aluminium oxide can be selected from any one or multiple mixed acid of phosphoric acid, sulfuric acid, nitric acid etc.
Can also add a certain amount of expanding agent in the above-mentioned catalyst, as ammonium oxalate etc.; Its consumption is 1/15～1/5 of an aluminium hydroxide weight.
The above-mentioned Preparation of catalysts method that is used for preparing dimethyl ether by dewatering methanol is as follows:
The aluminium hydroxide of described deal and clay are mixed, and perhaps with aluminium hydroxide sour molten through described concentration, moulding then, drying in 300～700 ℃ of roastings 2～10 hours, promptly make the described catalyst that is used for preparing dimethyl ether by dewatering methanol.
As required, in above-mentioned preparation method's process, can in the aluminium hydroxide of described deal, add an amount of expanding agent, mix, mix with the clay of described deal then, carry out operations such as moulding, drying, roasting again.
Perhaps: add the expanding agent of described deal in the mixture of the aluminium hydroxide of described deal or aluminium hydroxide and clay aforementioned proportion, mix, sour molten through described concentration carries out operations such as moulding, drying, roasting more then.
Compared with prior art, the invention has the beneficial effects as follows: catalyst component of the present invention is simple, and cost is low, and activity is high, intensity is big, the life-span is long.In addition, Preparation of catalysts method of the present invention is simple, and energy consumption is low, and is pollution-free, and production cost is low.
The specific embodiment
The present invention is described in further detail below in conjunction with the specific embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
The present embodiment catalyst is for to make by following method:
Get the 60g boehmite, about 3 hours of 600 ℃ of roastings, add 15g kaolin, be extruded into Φ 3 * 5-7mm bar shaped, oven dry is in 400 ℃ of following roastings 4 hours, promptly.
Embodiment 2
The present embodiment catalyst is for to make by following method:
Get the 60g boehmite, about 2 hours of 700 ℃ of roastings, add 15g kaolin, be extruded into Φ 3 * 5-7mm bar shaped, oven dry is in 400 ℃ of following roastings 4 hours, promptly.
Embodiment 3
The present embodiment catalyst is for to make by following method:
Get the false boehmite of 50g, about 10 hours of 300 ℃ of roastings, add 10g kaolin, be extruded into Φ 3 * 5-7mm bar shaped, oven dry is in 500 ℃ of following roastings 2 hours, promptly.
Embodiment 4
The present embodiment catalyst is for to make by following method:
Get the 60g boehmite, add the 20g bentonite, mixing is extruded into Φ 3 * 5-7mm bar shaped, and oven dry in 600 ℃ of following roastings 2 hours, is cooled to 400 ℃ of following roastings 3 hours, promptly.
Embodiment 5
The present embodiment catalyst is for to make by following method:
Get the 60g boehmite, put into 80 ℃ of water-baths, slowly the sulfuric acid solution of adding 1.0% is 4～5 to PH, and adding ammonium oxalate 10g leaving standstill aging oven dry as expanding agent, be extruded into Φ 3 * 5-7mm bar shaped, oven dry in 600 ℃ of following roastings 1 hour, is cooled to 400 ℃ of following roastings 2 hours, be warming up to 600 ℃ of following roastings 3 hours again, promptly.
Embodiment 6
The present embodiment catalyst is for to make by following method:
Get the 60g boehmite, put into 80 ℃ of water-baths, slowly add 6.0% phosphoric acid solution to PH be 3～4, add 10g Xuyong china clay, be extruded into Φ 3 * 5-7mm bar shaped, oven dry in 700 ℃ of following roastings 1 hour, is cooled to 600 ℃ of following roastings 3 hours, promptly.
Embodiment 7
The present embodiment catalyst is for to make by following method:
Get 100g β-three boehmite, put into 80 ℃ of water-baths, slowly the salpeter solution of adding 4.0% is 4～5 to PH, and adding 10g ammonium oxalate leaving standstill aging oven dry as expanding agent, add 15g kaolin, be extruded into Φ 3 * 5-7mm bar shaped, oven dry was in 700 ℃ of following roastings 4 hours, be cooled to 400 ℃ of following roastings 4 hours, promptly.
Embodiment 8
The present embodiment catalyst is for to make by following method:
Get 100g β-three boehmite, put into 80 ℃ of water-baths, slowly the salpeter solution of adding 6.0% is 4～5 to PH, and adding 20g ammonium oxalate leaving standstill aging oven dry as expanding agent, add the 10g bentonite, be extruded into Φ 3 * 5-7mm bar shaped, oven dry was in 700 ℃ of following roastings 4 hours, be cooled to 400 ℃ of following roastings 4 hours, promptly.
Embodiment 9
The present embodiment catalyst is for to make by following method:
Get the low crystalline aluminum oxide hydrate of 90g, put into 80 ℃ of water-baths, slowly add 2.0% salpeter solution to PH be 2～3, add the 10g ammonium oxalate as expanding agent, leave standstill aging oven dry, add the 10g clay,, add 10g kaolin in 700 ℃ of following roastings 4 hours, be extruded into Φ 3 * 5-7mm bar shaped, oven dry is in 400 ℃ of following roastings 4 hours, promptly.
Embodiment 10
The present embodiment catalyst is for to make by following method:
Get the low crystalline aluminum oxide hydrate of 100g, put into 80 ℃ of water-baths, slowly add 3% phosphoric acid solution to PH be 4～5, add the 10g bentonite, be extruded into Φ 3 * 5-7mm bar shaped, oven dry, in 600 ℃ of following roastings 4 hours, be cooled to 400 ℃ of following roastings 4 hours, promptly.
Embodiment 11
The present embodiment catalyst is for to make by following method:
Get the 70g boehmite, put into 80 ℃ of water-baths, slowly the sulfuric acid solution of adding 1.5% is 1～2 to PH, and adding 10g ammonium oxalate leaving standstill aging oven dry as expanding agent, in 550 ℃ of following roastings 4 hours, add 10g Xuyong china clay, be extruded into Φ 3 * 5-7mm bar shaped, oven dry, in 400 ℃ of following roastings 4 hours, promptly.
Claims (9)
1. catalyst that is used for preparing dimethyl ether by dewatering methanol, with aluminium hydroxide is that primary raw material is made, is that 3～10: 1 ratio is mixed by aluminium hydroxide and clay with weight ratio, perhaps: with the mixture of aluminium hydroxide or aluminium hydroxide and clay aforementioned proportion through volumetric concentration be 1～6% sour molten, then through moulding, drying, roasting and make.
2. the catalyst that is used for preparing dimethyl ether by dewatering methanol according to claim 1 is characterized in that: described aluminium hydroxide be selected from boehmite, false boehmite, β-gibbsite, the low crystalline aluminum oxide hydrate any one or multiple.
3. the catalyst that is used for preparing dimethyl ether by dewatering methanol according to claim 1 is characterized in that: described clay be selected from bentonite, Xuyong china clay, the kaolin any one or multiple.
4. the catalyst that is used for preparing dimethyl ether by dewatering methanol according to claim 1 is characterized in that: the described acid that is used for the dissolved hydrogen aluminium oxide is selected from any one or multiple mixed acid of phosphoric acid, sulfuric acid, nitric acid.
5. the catalyst that is used for preparing dimethyl ether by dewatering methanol according to claim 1 is characterized in that: described raw material also comprises expanding agent, and its consumption is 1/15～1/5 of an aluminium hydroxide weight.
6. the catalyst that is used for preparing dimethyl ether by dewatering methanol according to claim 5 is characterized in that: described expanding agent is an ammonium oxalate.
7. described Preparation of catalysts method that is used for preparing dimethyl ether by dewatering methanol of claim 1, it is characterized in that: the aluminium hydroxide and the clay of described deal are mixed, perhaps: with sour molten through described concentration of the mixture of aluminium hydroxide or aluminium hydroxide and clay aforementioned proportion, moulding then, drying, in 300～700 ℃ of roastings 2～10 hours, promptly make described catalyst.
8. Preparation of catalysts method according to claim 7 is characterized in that: add the expanding agent of described deal in the aluminium hydroxide of described deal, mix, mix with the clay of described deal then, carry out moulding, drying, calcining process again.
9. Preparation of catalysts method according to claim 7, it is characterized in that: the expanding agent that in the mixture of the aluminium hydroxide of described deal or aluminium hydroxide and clay aforementioned proportion, adds described deal, mix, sour molten through described concentration carries out moulding, drying, calcining process more then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100222568A CN100453168C (en) | 2006-11-13 | 2006-11-13 | Catalyst used for preparing dimethyl ether by dehydration of methanol, and method for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100222568A CN100453168C (en) | 2006-11-13 | 2006-11-13 | Catalyst used for preparing dimethyl ether by dehydration of methanol, and method for preparing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1947833A true CN1947833A (en) | 2007-04-18 |
| CN100453168C CN100453168C (en) | 2009-01-21 |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671653A (en) * | 2011-03-06 | 2012-09-19 | 天门市天宝化工科技有限公司 | Catalyst for preparing dimethyl ether through methanol dehydration and preparation method of catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB915186A (en) * | 1958-01-29 | 1963-01-09 | Pechiney Prod Chimiques Sa | Improvements in or relating to the production of activated alumina |
| CN1043343C (en) * | 1995-10-13 | 1999-05-12 | 化学工业部西南化工研究院 | Method for producing dimethyl ether from methyl alcohol |
| US5753716A (en) * | 1997-02-21 | 1998-05-19 | Air Products And Chemicals, Inc. | Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process |
| CN1175086C (en) * | 2001-12-25 | 2004-11-10 | 中国石油化工股份有限公司 | Cracking catalyst containing laminar clay and its preparation method |
-
2006
- 2006-11-13 CN CNB2006100222568A patent/CN100453168C/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671653A (en) * | 2011-03-06 | 2012-09-19 | 天门市天宝化工科技有限公司 | Catalyst for preparing dimethyl ether through methanol dehydration and preparation method of catalyst |
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| CN100453168C (en) | 2009-01-21 |
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Owner name: SOUTHWEST RESEARCH + DESIGN INSTITUTE OF CHEMICAL Free format text: FORMER NAME: SOUTHWEST RESEARCH + DESIGN INSTITUTE OF CHEMICAL INDUSTRY |
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Address after: 445 box 610255, South Airport Road, Sichuan, Chengdu Patentee after: Southwest Chemical Research & Design Institute Co., Ltd. Address before: 445 box 610255, South Airport Road, Sichuan, Chengdu Patentee before: Xinan Chemical Research & Design Inst. |