CN1090222A - The preparation method of dimethyl ether catalyst - Google Patents
The preparation method of dimethyl ether catalyst Download PDFInfo
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- CN1090222A CN1090222A CN 93118884 CN93118884A CN1090222A CN 1090222 A CN1090222 A CN 1090222A CN 93118884 CN93118884 CN 93118884 CN 93118884 A CN93118884 A CN 93118884A CN 1090222 A CN1090222 A CN 1090222A
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Abstract
A kind of with CO and H
2Produce the preparation method of dimethyl ether catalyst, this method is to traditional mixed grind method, dipping mixed grind method, the preparation methods' such as coprecipitation improvement.Activated spherical gamma-the Al of the direct apparatus of the present invention
2O
3Dipping Cu, Zn soluble-salt carry out drying and roasting again and form.The Cu/Zn of maceration extract, the mol ratio is 1～8: 1 is preferably 2～4: 1.Sintering temperature is 200-500 ℃, is preferably 300-450 ℃.This preparation method has that technology is simple, cost is low.The catalyst strength height, the advantage that the life-span is long.
Description
The invention belongs to CO and H
2The preparation method of catalyst system therefor when producing dimethyl ether.
Dimethyl ether is a methyl ether, and structural formula is CH
3-O-CH
3, have advantages such as nontoxic, safety, calorific value are big, be the desirable substitute of liquefied fuel gas, also be a kind of important basic Organic Chemicals, in industry such as pharmacy, dyestuff, agricultural chemicals, refrigeration, daily-use chemical industry, many purposes are arranged.
The catalyst of early stage used for synthesizing dimethyl ether is catalyst for methanol and dehydration catalyst to be mixed make synthetic dimethyl ether catalyst and use, US4,177,167, US4,098,809 usefulness Zn-Cu and γ-Al
2O
3After the mixed grind, make together the catalyst of dimethyl ether; GB2,093,365, JP02280836, JP0308446 prepare dimethyl ether catalyst with the coprecipitation of Al, Zn-Cu, Chinese Tsing-Hua University (gas chemical industry, 92, NO, 4) is with powder γ-Al
2O
3With Cu, Zn salting liquid parallel-flow precipitation method, preparation methyl ether catalyst, the method that more than prepare dimethyl ether catalyst all need be through broken, precipitation, washing, filter, drying, granulation or beat the operation such as sheet, it is many to have operation, equipment is many, the shortcoming that production cost is high.
The objective of the invention is the improvement to preparation methods such as traditional mixed grind method, precipitation mixed grind method, coprecipitations, a kind of Cu-Zn/ γ-Al of support type is provided
2O
3The direct impregnation method of producing the methyl ether catalyst.Its preparation section is short, high efficiency, and less energy consumption, product mechanical strength height, the life-span is long.
The objective of the invention is to adopt following method to realize, with the carrier such as the spherical gamma-Al of activity
2O
3With the copper of solubility, zinc salt (as Cu(NO
3)
2, Zn(NO
3)
2, Cu(Ac)
2, Zn(Ac)
2, cuprammonia, CuCl
2, ZnCl
2Deng) soak altogether once or several in the mol ratio of certain C u, Zn.Its Cu is 1～8: 1 with the mol ratio of Zn, is preferably 2～4: 1.
Carry out drying and roasting behind the dipping, sintering temperature is 200～500 ℃, being preferably 300～450 ℃, roasting time is 2 hours.
The catalyst that makes as stated above, its active testing are that (carry out in the testing arrangement of φ 2～5mm), condition is: tube inner diameter 32mm, catalyst volume 30ml, pressure 4MPa, air speed 2400h in former granularity
-1, 270～320 ℃ of temperature, raw material are semiwater gas, wherein CO: H
2=1: 1.1, activity is represented with the conversion ratio that CO changes into dimethyl ether.
Cu-Zn/ γ-the Al that makes with this law
2O
3Dimethyl ether catalyst for spherical, mechanical strength is high, preparation section is dipping, drying and roasting, operation are short.It is good to record selection of catalysts, and CO changes into the conversion ratio height of dimethyl ether.It is low to change into conversion of methanol.
Further specify this preparation method below by example.
Embodiment 1,17.5 gram copper nitrate and 3.0 gram zinc nitrates are dissolved in the 60ml water, with spherical gamma-Al of 40 gram φ, 3～5mm
2O
3Dipping wherein 30 minutes immerses in this solution after the taking-up drying again, and dry rear in 350 ℃ of roastings 2 hours, the repeated impregnations roasting once.
Embodiment 2,24.8 gram copper nitrates and 10.8 gram zinc acetates are dissolved in the 100ml water, 120 gram φ, 3～5mm γ-Al
2O
3Dipping wherein after the drying, in 300 ℃ of lower roastings 20 minutes, repeats secondary again and immerses in this solution after the cooling, after the drying, bake 2 hours in 400 ℃.
Embodiment 3,13.9 gram copper nitrates and 14.2 gram zinc nitrates and 7.6 gram chromic nitrates are dissolved in the 50ml water, with 30 gram φ, 3～5mm γ-Al
2O
3Dipping wherein takes out dryly after 30 minutes, 400 ℃ of lower roastings 30 minutes were immersed in this solution 30 minutes again, dry after in 460 ℃ of roastings 2 hours.
The spherical φ 3～5mm γ-Al of embodiment 4,100 grams
2O
3Immerse SiO
2Content is in 2% the solution, immerse again after the drying to restrain zinc nitrates with 35 gram copper nitrates and 18.5 and be made in the 100ml aqueous solution, drying, again repeated impregnations once, 400 ℃ of roastings 2 hours.
Embodiment 5,3.8 gram metatungstic acid ammonia are made into 80ml solution, immerse 100 gram φ, 3～5ml spherical gamma-Al
2O
3, dry after in 650 ℃ of roastings 1 hour, immerse again in the mixed solution of 37 gram copper nitrates and 19 gram zinc nitrates, repeatedly flood three times, in 350 ℃ of roastings 2 hours.
Embodiment 6,18.3 gram copper nitrates and 13.5 gram zinc acetates are dissolved in the 120ml water, with 30 gram φ, 3～5mm spherical gamma-Al
2O
3Immerse wherein after 30 minutes dry, repeatedly dipping, dry three an ancient unit of weight equal to 20 or 24 *taels of silvers, last roasting 2 hours under the Oxygen Flow of 350 ℃ of temperature.
Embodiment 7,14.8 gram chromium acetates are made into the 100ml aqueous solution, dipping φ 3～5mm γ-Al
2O
3, after the drying, with its γ-Al
2O
3Immersed again in 28.4 gram copper carbonates and the 13.5 ammino-complex solution that are made into of gram zinc acetates 20 minutes, then 350 ℃ lower dry 2 hours, impregnation drying secondary repeatedly.
Embodiment 8,44 gram copper carbonates and 8.6 gram zinc acetates are made into the 150ml ammino-complex, with 100 gram φ, 3～5mm γ-Al
2O
3Immerse wherein, then in 350 ℃ of drying and roastings 2 hours, impregnation drying secondary repeatedly.
Embodiment 9,16.8 gram copper carbonates and 8.6 gram zinc carbonates are made into ammino-complex solution 120ml, with 60 gram φ, 3～5mm γ-Al
2O
3Immersed wherein 30 minutes, then in 450 ℃ of roastings 2 hours.
Embodiment 10,25 gram copper nitrates and 12.5 gram zinc nitrates are made into the 100ml mixed aqueous solution.Get 30 gram γ-Al
2O
3Immersed in the mixed solution 20 minutes, 350 ℃ of lower drying and roastings 2 hours, impregnation-calcination is 2 times repeatedly.
Embodiment 11,18.8 gram copper chlorides and 9.0 gram zinc chloride are made into 120ml solution, with 40 gram φ, 3～5mm γ-Al
2O
3Immersed wherein 20 minutes, then dry, impregnation drying is three times repeatedly, at last in 500 ℃ of roastings 2 hours.
Embodiment 12,14.4 gram copper chlorides and 18.0 gram zinc acetates are made into the 100ml aqueous solution, with 30 gram γ-Al
2O
3Immersed wherein 20 minutes, then dry, impregnation drying is three times repeatedly, at last in 450 ℃ of roastings 2 hours.
Embodiment 13, and it contains the Cu13.0 gram cuprammonia 120ml, add zinc acetate 120 grams and are made into ammino-complex solution, with 30 gram φ, 3～5mm γ-Al
2O
3Immersed wherein 20 minutes, in 300 ℃ of roastings 2 hours, repeatedly dipping, dry secondary.
Embodiment 14,44.6 gram copper nitrates and 4.1 gram zinc chloride are dissolved in the 120ml water, with 40 gram φ, 3～5mm γ-Al
2O
3Immersed wherein 20 minutes, in 400 ℃ of drying and roastings 2 hours, 2 times repeatedly.
Embodiment 15,36.2 copper acetates and 13.2 gram zinc chloride are made into 150ml ammino-complex solution, get 40 gram φ, 3～5mm γ-Al
2O
3Immersed wherein 20 minutes, and took out drying, repeated impregnations, dry secondary is for the last time in 400 ℃ of roastings 2 hours.
With the dimethyl ether catalyst that each example makes, measure the performance condition semiwater gas by the aforementioned method of measuring activity, under 4MPa, 2400h
-1Air speed, its result's row are as table 1.
Table 1
Above-mentioned example gained catalyst has been carried out the active lifetime test, CO conversion ratio in the highest CO conversion ratio of survey initial stage and the 500h, its result's row are such as table 2.
Table 2
Notes condition: semiwater gas, pressure 4MPa, air speed 2400h
-1
Claims (3)
1, a kind of preparation method for the manufacture of dimethyl ether catalyst is characterized in that active γ-Al
2O
3Directly with being selected from a kind of soluble copper salt or cuprammonia in copper nitrate, copper acetate, copper carbonate, the copper chloride and being selected from a kind of soluble zinc salt in zinc nitrate, zinc acetate, zinc carbonate, the zinc chloride or the zinc ammoniacal liquor is that 1～8: 1 mixed solution that is made into soaks one or many altogether by the mol ratio of Cu/Zn, carry out drying behind the dipping, in 200-500 ℃ of lower roasting.
2, the method for claim 1 is characterized in that active γ-Al
2O
3Be that the mixed solution of 2～4: 1 bronze medal zinc salt soaks altogether with the mol ratio of Cu/Zn, dry behind the dipping, in 200-500 ℃ of lower roasting.
3, such as claim 1,2 described methods, it is characterized in that active γ-Al
2O
3After soluble copper, zinc salt mixed liquor dipping, drying, in 300-450 ℃ of lower roasting 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93118884 CN1043409C (en) | 1993-10-22 | 1993-10-22 | Preparation of dimethyl ether catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93118884 CN1043409C (en) | 1993-10-22 | 1993-10-22 | Preparation of dimethyl ether catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1090222A true CN1090222A (en) | 1994-08-03 |
| CN1043409C CN1043409C (en) | 1999-05-19 |
Family
ID=4992697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93118884 Expired - Lifetime CN1043409C (en) | 1993-10-22 | 1993-10-22 | Preparation of dimethyl ether catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1043409C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1048917C (en) * | 1994-10-20 | 2000-02-02 | 中国科学院山西煤炭化学研究所 | Method for preparing high-activity methylated copper-zinc/alumina catalyst with metal surfactant by phase transfer |
| CN1876237B (en) * | 2005-06-10 | 2011-01-26 | 上海天丰环保科技有限公司 | Composite catalyst for catalytic and oxidized treatment of three-phase waste water |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100556538C (en) | 2006-12-14 | 2009-11-04 | 太原理工大学 | A kind of slurried catalyst and preparation method thereof |
-
1993
- 1993-10-22 CN CN 93118884 patent/CN1043409C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048917C (en) * | 1994-10-20 | 2000-02-02 | 中国科学院山西煤炭化学研究所 | Method for preparing high-activity methylated copper-zinc/alumina catalyst with metal surfactant by phase transfer |
| 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 |
| CN1876237B (en) * | 2005-06-10 | 2011-01-26 | 上海天丰环保科技有限公司 | Composite catalyst for catalytic and oxidized treatment of three-phase waste water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1043409C (en) | 1999-05-19 |
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Denomination of invention: Method for preparing catalyst for synthesizing dimethyl ether on fluidized bed Effective date of registration: 20100907 Granted publication date: 19990519 Pledgee: Bank of Hankou, Limited by Share Ltd, Optics Valley branch Pledgor: Huashuo Technology Co., Ltd. Registration number: 2010990000869 |
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