CN102671653A - Catalyst for preparing dimethyl ether through methanol dehydration and preparation method of catalyst - Google Patents
Catalyst for preparing dimethyl ether through methanol dehydration and preparation method of catalyst Download PDFInfo
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- CN102671653A CN102671653A CN2011100601813A CN201110060181A CN102671653A CN 102671653 A CN102671653 A CN 102671653A CN 2011100601813 A CN2011100601813 A CN 2011100601813A CN 201110060181 A CN201110060181 A CN 201110060181A CN 102671653 A CN102671653 A CN 102671653A
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Abstract
The invention provides a catalyst for preparing dimethyl ether through methanol dehydration and a preparation method of the catalyst. The catalyst is prepared by using bentonite and heteropoly acid as major ingredients. The method of the catalyst is characterized in that bentonite is added into acid solution to be made into uniform pulp, the filtering, the water washing, the drying and the baking are carried out, the acid bentonite is obtained, heteropoly acid solution with a certain concentration is used for dipping the acid bentonite, and the catalyst is obtained through evaporation, baking and roasting. The catalytic performance of the catalyst provided by the invention can completely reach the level of HZSM5 industrial catalysts, but the cost is greatly reduced, and obvious environment protection benefits and economic benefits are realized.
Description
Technical field
The invention belongs to chemical field, relate in particular to a kind of Catalysts and its preparation method that is used for preparing dimethyl ether by dewatering methanol.
Background technology
Dimethyl ether is a kind of important clean energy resource and environment-friendly products, because it has higher Cetane number, and oxygen content is high, so combustion process can realize reducing black smoke, reduces the NOx discharging and reduces engine noise, can be used as the good substitute of diesel oil.Dimethyl ether is compressible under normal temperature, high pressure to be liquid, and character and oil liquefied gas are close, therefore also can be used as domestic fuel.Its also alternative freon is as aerosol, blowing agent, cold-producing medium etc., and is zero to the rupture factor of ozone layer.So the Application and Development dimethyl ether has real social benefit and economic benefit.
At present, the methanol vapor phase catalytic dehydration is to use maximum dimethylether industrial production methods both at home and abroad, and it is simple to operate, can turn round continuously, pollutes and lacks, and its catalyst mainly contains alumina series and molecular sieve system.Molecular sieve series catalysts (is representative with the HZSM5 molecular sieve) has the advantage that active temperature is low, conversion ratio is high, but cost is high, the use warm area is narrow, selectivity is relatively poor and easy carbon distribution.The alumina series catalyst selectivity is high, but low temperature active is poor, the high temperature carbon deposit is serious, is subject to the influence of the water in the methyl alcohol.Chinese patent CN101607214A, 2009; CN1106219C, 2003; The support type composite catalyst that is made up of γ-Al2O3 and heteropoly acid is successively disclosed; This type activity of such catalysts increases than the early oxidation aluminum-based catalyst with stability, and at 0.1-1MPa, 240-320 ℃ of methanol conversion ratio reaches 85%; The dimethyl ether selectivity reaches 99.99%, but cost is higher.Chinese patent CN101249448A, 2008; Disclose a kind of bentonite modified catalyst, modifier is a kind of in sulfuric acid, phosphoric acid, hydrochloric acid or the lanthanum nitrate and several kinds.At normal pressure, 250 ℃, mass space velocity 1.0h
-1Condition under, the methyl alcohol maximum conversion reaches 85%, selectivity reaches 99%.The great advantage of this catalyst is that cost is lower, but low temperature active is low, and methanol conversion only has 72% in the time of 210 ℃.
Summary of the invention
The object of the present invention is to provide a kind of Catalysts and its preparation method that is used for preparing dimethyl ether by dewatering methanol.
Technical scheme of the present invention is following:
A kind of Preparation of catalysts method that is used for preparing dimethyl ether by dewatering methanol is provided; It is characterized in that: bentonite is added in the acidic aqueous solution; Process homogeneous slurry, filtration, washing, dry, roasting get the pickling bentonite; Use finite concentration heteropoly acid solution impregnation pickling bentonite again, evaporation, oven dry, roasting get said catalyst.
Aforesaid a kind of Preparation of catalysts method that is used for preparing dimethyl ether by dewatering methanol is characterized in that: said acidic aqueous solution is one or more the aqueous solution in hydrochloric acid, nitric acid, sulfuric acid, the phosphoric acid, and the total concentration of acid is 0.01-1mol/l.
The aforesaid Preparation of catalysts method that is used for preparing dimethyl ether by dewatering methanol is characterized in that: said sintering temperature is 250-350 ℃, roasting time 2-8h.
Aforesaid a kind of catalyst that is used for preparing dimethyl ether by dewatering methanol, it is characterized in that: the content of heteropoly acid is in the said catalyst: 1-20wt%.
Aforesaid a kind of catalyst that is used for preparing dimethyl ether by dewatering methanol is characterized in that: said heteropoly acid is one or more in silicomolybdic acid, phosphomolybdic acid, silico-tungstic acid, the phosphotungstic acid.
Distinguishing feature of the present invention is: this catalyst is a body material with bentonite cheap, that be easy to get; Warp is compound and process with heteropoly acid, and with low cost, the preparation process is simple: have quite high methanol conversion and dimethyl ether selectivity under the catalyst low temperature of preparation; The catalytic performance of catalyst of the present invention reaches the level of industrial catalyst HZSM5 fully; Therefore but cost significantly reduces, and pollutes for a short time, has significant environmental protection benefit and economic benefit.
The specific embodiment
Raw material: bentonite, heteropoly acid, acidic aqueous solution
Heteropoly acid is one or more in silicomolybdic acid, phosphomolybdic acid, silico-tungstic acid, the phosphotungstic acid.
Acid in the acidic aqueous solution is one or more in hydrochloric acid, nitric acid, sulfuric acid, the phosphoric acid.Hydrogen ion concentration in the acidic aqueous solution is 0.01-1mol/l.
Bentonite is added in the acidic aqueous solution, process homogeneous slurry, filtration, washing, dry, roasting get the pickling bentonite, use finite concentration heteropoly acid solution impregnation pickling bentonite again, and evaporation, oven dry, roasting get said catalyst.
Said front and back double roasting temperature range is 200-350 ℃, roasting time 2-8h.
Reaction equation is as follows:
2CH3OH＝CH3OCH3+H2O ΔH
298＝-22.52kJ/mol
Catalytic reaction is carried out in fixed bed reactors, at normal pressure, 220 ℃, mass space velocity 1.0h
-1Under the condition, methanol conversion reaches 86-88%, and the dimethyl ether selectivity reaches 99.99%.
Adopt the gas chromatograph analysis reactor to import and export constituent content, calculate preparing dimethyl ether by dewatering methanol conversion ratio and dimethyl ether selectivity.
Embodiment:
Compare below in conjunction with embodiment, but be not limited to the said scope of embodiment:
Embodiment 1
Getting 10 gram bentonites, to add the 100ml concentration be in the salpeter solution of 1mol/L, and stirring at room 1 hour is filtered, washing, and filter cake is in 120 ℃ of oven dry, 290 ℃ of roastings 5 hours.Spend the night with the heteropoly acid solution impregnation, 120 ℃ of oven dry, 290 ℃ of roastings 5 hours, catalyst, wherein heteropoly acid content 14wt%.
Get the such catalyst of 60-80 order 0.4 gram, join in the fixed bed reactors, the speed with 100ml/min feeds nitrogen then, and the conditioned reaction actuator temperature is 220 ℃ simultaneously, is 1h with the mass space velocity with methyl alcohol
-1Speed through beds, during reactor remain on normal pressure and 220 ℃. the result sees shown in the table 1:
Embodiment 2
Catalyst system therefor is identical with embodiment 1, and different is that heteropoly acid content is 10wt%.Carry out the preparing dimethyl ether by dewatering methanol measuring like embodiment 1.The result sees shown in the table 1:
Embodiment 3
Catalyst system therefor is identical with embodiment 1, and different is that heteropoly acid content is 4wt%.Carry out the preparing dimethyl ether by dewatering methanol measuring like embodiment 1.The result sees shown in the table 1.
Embodiment 4
Catalyst system therefor is identical with embodiment 1, and different is that sintering temperature is 250 ℃.Carry out the preparing dimethyl ether by dewatering methanol measuring like embodiment 1.The result sees shown in the table 1:
Embodiment 5
Catalyst system therefor is identical with embodiment 1, and different is that salpeter solution changes into the concentration sulfuric acid solution.Carry out the preparing dimethyl ether by dewatering methanol measuring like embodiment 1.The result sees shown in the table 1.
Table 1 embodiment result
Though preceding text have shown detailed embodiment of the present invention, those skilled in the art revises and changes can carry out part under prerequisite of the present invention; The content of mentioning in the description of preceding text is not a limitation of the present invention only as illustrative case, has a kind of Catalysts and its preparation method that is used for preparing dimethyl ether by dewatering methanol of technical characterictic according to the invention, all falls into scope of patent protection shown in the present.
Claims (5)
1. Preparation of catalysts method that is used for preparing dimethyl ether by dewatering methanol; It is characterized in that: bentonite is added in the acidic aqueous solution; Process homogeneous slurry, filtration, washing, dry, roasting get the pickling bentonite; Use finite concentration heteropoly acid solution impregnation pickling bentonite again, evaporation, oven dry, roasting get said catalyst.
2. a kind of Preparation of catalysts method that is used for preparing dimethyl ether by dewatering methanol as claimed in claim 1; It is characterized in that: said acidic aqueous solution is one or more the aqueous solution in hydrochloric acid, nitric acid, sulfuric acid, the phosphoric acid, and the total concentration of acid is 0.01-1mol/l.
3. a kind of Preparation of catalysts method that is used for preparing dimethyl ether by dewatering methanol as claimed in claim 1, it is characterized in that: said sintering temperature is 250-350 ℃, roasting time 2-8h.
4. catalyst that is used for preparing dimethyl ether by dewatering methanol, it is characterized in that: the content of heteropoly acid is in the said catalyst: 1-20wt%.
5. a kind of catalyst that is used for preparing dimethyl ether by dewatering methanol as claimed in claim 4 is characterized in that: said heteropoly acid is one or more in silicomolybdic acid, phosphomolybdic acid, silico-tungstic acid, the phosphotungstic acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100601813A CN102671653A (en) | 2011-03-06 | 2011-03-06 | Catalyst for preparing dimethyl ether through methanol dehydration and preparation method of catalyst |
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| CN2011100601813A CN102671653A (en) | 2011-03-06 | 2011-03-06 | Catalyst for preparing dimethyl ether through methanol dehydration and preparation method of catalyst |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1947833A (en) * | 2006-11-13 | 2007-04-18 | 西南化工研究设计院 | Catalyst used for preparing dimethyl ether by dehydration of methanol, and method for preparing the same |
| CN101249448A (en) * | 2008-03-25 | 2008-08-27 | 福州大学 | Catalyst for methanol dewatered dimethyl ether and preparation method thereof |
| CN102463128A (en) * | 2010-11-05 | 2012-05-23 | 天门市天宝化工科技有限公司 | Catalyst used for preparing dimethyl ether through methanol dehydration and preparation method thereof |
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- 2011-03-06 CN CN2011100601813A patent/CN102671653A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1947833A (en) * | 2006-11-13 | 2007-04-18 | 西南化工研究设计院 | Catalyst used for preparing dimethyl ether by dehydration of methanol, and method for preparing the same |
| CN101249448A (en) * | 2008-03-25 | 2008-08-27 | 福州大学 | Catalyst for methanol dewatered dimethyl ether and preparation method thereof |
| CN102463128A (en) * | 2010-11-05 | 2012-05-23 | 天门市天宝化工科技有限公司 | Catalyst used for preparing dimethyl ether through methanol dehydration and preparation method thereof |
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Application publication date: 20120919 |