CN101314134A - Process for preparing bifunctional catalyst for preparing dimethyl ether directly with synthesis gas - Google Patents
Process for preparing bifunctional catalyst for preparing dimethyl ether directly with synthesis gas Download PDFInfo
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- CN101314134A CN101314134A CNA2008100405619A CN200810040561A CN101314134A CN 101314134 A CN101314134 A CN 101314134A CN A2008100405619 A CNA2008100405619 A CN A2008100405619A CN 200810040561 A CN200810040561 A CN 200810040561A CN 101314134 A CN101314134 A CN 101314134A
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Abstract
The invention discloses two methods for directly preparing a bifunctional catalyst of dimethyl ether by synthesis gas. The core principle is to add an active component for methanol synthesis to a methanol dehydration component in an oxalate precipitation mode, for example, the following steps are adopted: a. the active component which can be used as a methanol synthesis catalyst is dissolved into alcohol in a soluble salt mode to prepare a mixed solution A; b. an active component which can be used as a methanol dehydration catalyst is added into the mixed solution A to be stirred to prepare suspension B; and c. an alcoholic solution of oxalic acid is added into the suspension B during the stirring, and a generated oxalate coprecipitate is aged, filtered, dried and finally roasted at a temperature of between 250 and 550 DEG C to prepare the bifunctional catalyst. The methods have simple preparation process, and the prepared bifunctional catalyst has low reaction temperature, high transformation rate of carbon monoxide, and good selectivity of the dimethyl ether.
Description
Technical field
The present invention relates to a kind of catalyst for preparing dimethyl ether, relate to a kind of preparation method that one-step method from syngas directly prepares the bifunctional catalyst that the dimethyl ether employing is composited by methanol synthesis catalyst and methanol dehydration catalyst that is used in particular.
Background technology
Dimethyl ether is the important source material of producing multiple chemical products.The eighties, many in the world country exploitation dimethyl ether were as the safety propellant that atomizes, and forbade fluorine Lyons the beginning of the nineties, and dimethyl ether is as its desirable substitute.It also has very good combustibility discovered in recent years, can reach peace and quiet burning, be described as " clean fuel " of 21 century at home and abroad, so dimethyl ether draws attention day by day in the world.Dimethyl ether is by making after the byproduct rectifying in the high pressure methanol production the earliest.Along with the extensive use of low pressure methanol synthesis technology, side reaction significantly reduces, and the dimethylether industrial production technology develops into methanol dehydration or synthesis gas direct synthesis process very soon, promptly so-called two-step method and one-step technology.Two-step method is earlier synthesis gas to be converted into methyl alcohol, then methanol dehydration is converted into dimethyl ether.The methanol dehydration method comprises two kinds of liquid phase method and vapor phase methods.The former is reflected in the liquid phase and carries out, and methyl alcohol makes through concentrated sulfuric acid dehydration.This technology has reaction condition gentleness (130～160 ℃), methyl alcohol conversion per pass height (about 90%), but can be intermittently also quantity-produced advantage.But, progressively be eliminated because of there are problems such as equipment corrosion, environmental pollution, operating condition be abominable in this method.Because the dimethyl ether demand growth is very fast, various countries develop reduced investment again in succession, operating condition is good, free of contamination methanol gas phase dehydration method new technology.Research and develop out the methanol vapor phase method dewatering preparing dimethy ether method of utilizing crystalline aluminosilicate to make catalyst as nineteen sixty-five Mobil company.Early 1980s Mobil company improves catalysis again, and dimethyl ether selectivity and methanol conversion all improve a lot.Mitsui east pressed chemical company also to develop new catalyst in 1991.Domestic southwestern chemical research institute and Shanghai petrochemical industry research institute etc. have also all developed the solid acid catalyst of methanol gas phase dewatering preparing dimethy ether, and are applied on the commercial plant of different scales.
Directly producing dimethyl ether by synthesis gas is that one-step technology is a kind of new technology of developing in recent years, allow synthetic being reflected in the same reactor of methyl alcohol not have pilot process exactly with two of methanol dehydrations, because there is the synthetic and methanol dehydration two classes reaction of methyl alcohol simultaneously in reaction system, therefore broken the thermodynamics equilibrium limit that exists in the simple methyl alcohol building-up process, produce bigger forward reaction motive force, thereby can reduce the conversion per pass of operating pressure and raising CO effectively.Because on the whole, one-step method is better than two step method, so the research of synthesizing about dimethyl ether both at home and abroad at present mainly concentrates on the research to one-step method.The bifunctional catalyst of the catalyst that synthesis of dimethyl ether with synthesis gas one-step adopted for being composited by methanol synthesis catalyst and methanol dehydration catalyst.Methanol synthesis catalyst is mainly the copper base oxide catalyst, as composite oxides such as Cu-Zn-Al or Cu-Zn-Cr.Methanol dehydration catalyst is mainly aluminium oxide or molecular sieve solid acid catalysts such as (as HZSM-5, HY and modenites).The reactivity worth of the bifunctional catalyst that synthesis of dimethyl ether with synthesis gas one-step adopted is not only relevant with the catalytic performance of synthetic component of methyl alcohol and methanol dehydration component itself, but also to be combined into the preparation method of bifunctional catalyst closely related with component with two kinds of difference in functionalitys.At present, the complex method that is adopted is main two kinds, i.e. mechanical mixing and infusion process.
Mechanical mixing is that earlier to make the synthetic component of methyl alcohol by coprecipitation be copper, zinc and/or aluminium/or the composite oxides of chromium etc., then itself and methanol dehydration component such as aluminium oxide or molecular sieve is directly carried out mechanical mixture and forms.The Chinese patent CN 1085824A (1994) that is called " a kind of by preparation of dimethyl ether from synthesis gas reaction with catalyst and preparation dimethyl ether technology thereof " as name has disclosed by methanol dehydration component (for the aluminium oxide through B, P and Ti modification) and the synthetic component of methyl alcohol and (has been the catalyst C of the suitability for industrialized production methyl alcohol of southwestern chemical research institute production
302) through the bifunctional catalyst of mechanical mixing preparation, the powder that is about to two kinds of catalyst mixes through mechanical agitation, compression molding obtains bifunctional catalyst then.This catalyst is at H
2/ CO mol ratio is 2,260 ℃ of reaction temperatures, reaction pressure 3.5MPa and unstripped gas air speed 1000h
-1Reaction condition under, the conversion ratio of carbon monoxide is 83～85%, the dimethyl ether selectivity is 84～94%.Name is called the United States Patent (USP) 4 of " catalyst of preparation dimethyl ether ", 177,167 (1979) with the activated alumina of silicon modification as methanol dehydration catalyst, adopt mechanical mixing to be prepared into bifunctional catalyst with the synthetic component Cu-Zn-Al composite oxides of methyl alcohol, the powder that is about to two kinds of catalyst mixes through mechanical agitation, then compression molding.This catalyst is at H
2/ CO mol ratio is 3,300 ℃ of reaction temperatures, reaction pressure 5MPa and unstripped gas air speed 3500h
-1Reaction condition under, the conversion ratio of carbon monoxide is 62%, behind the successive reaction 475h, the conversion ratio of carbon monoxide is reduced to 57%, the selectivity of dimethyl ether substantially becomes.As seen the carbon monoxide conversion ratio of this bifunctional catalyst and dimethyl ether selectivity are all lower.As seen by above-mentioned, the shortcoming of the bifunctional catalyst that mechanical mixing is prepared is can not contact closely owing between two kinds of difference in functionality components, thereby causes the reactivity worth of catalyst to reduce.
The immersion process for preparing bifunctional catalyst is to introduce in the methanol dehydration component by infusion process to have the active component of methyl alcohol complex functionality.Be called the U.S. Pat 4,375 of the catalyst of dimethyl ether " preparation " as name, 424 (1983) have disclosed and adopt infusion process that the synthetic component copper-zinc of methyl alcohol is loaded on the bifunctional catalyst that forms on acidic components γ-Al2O3.Concrete method for making among the embodiment adds 30 gram aluminium oxide then for 7.2 gram copper nitrates and 7.8 gram zinc nitrates are dissolved in 30 ml waters, and dry behind the dipping 0.5h, roasting promptly makes bifunctional catalyst.This catalyst is 1: 1, about 300 ℃ of reaction temperature, reaction pressure 12MPa and unstripped gas air speed 3000h in the H2/CO mol ratio
-1Reaction condition under, the conversion ratio of carbon monoxide is 60～70%.This shows that reaction pressure that above-mentioned catalyst is required and reaction temperature are all higher, and reactivity lower (conversion ratio of carbon monoxide is the highest to be no more than 70%).The Chinese patent CN 1090222A (1994) that name is called " preparation method of dimethyl ether catalyst " has disclosed with aluminium oxide or has been the methanol dehydration component through the aluminium oxide of modifications such as silicon, tungsten, introduces synthetic component copper of methyl alcohol and the prepared bifunctional catalyst of zinc by infusion process.This activity of such catalysts reaction temperature higher (＞290 ℃), and at reaction pressure 4MPa and raw material (semiwater gas) air speed 2400h
-1Reaction condition under, the conversion ratio of carbon monoxide is the highest to be no more than 61%.In addition, reach certain content, need repeatedly repeated impregnations, drying and roasting process in order to make active component.By as seen above-mentioned, though the immersion process for preparing bifunctional catalyst has the simple advantage of preparation technology, but also there is significant disadvantages, promptly need repeatedly process such as repeated impregnations, roasting, man-hour is longer, and prepared catalyst is because the particle of active component Cu is bigger, so the conversion ratio of CO is on the low side and/or reaction temperature is higher.
In order to eliminate the existing shortcoming of above-mentioned preparation method, the new preparation method that recently patent report arranged.It is that the synthetic component of methyl alcohol is the bifunctional catalyst that methanol dehydration component employing precipitation of joint sedimentation is prepared from aluminium oxide that the Chinese patent CN 1356163A (2002) that is called the bifunctional catalyst and the preparation technology thereof of synthesis gas preparing dimethy ether " directly by " as name has disclosed with composite oxides such as copper, zinc.Concrete method for making is that a certain amount of copper nitrate and zinc nitrate are dissolved in the water, and adds acidic components and sodium carbonate liquor then and carries out co-precipitation, and active component is deposited on the surface of acidic components, gained precipitation deposit compression molding after washing, drying and roasting.This catalyst is at H
2/ CO mol ratio is 3.85,300 ℃ of reaction temperatures, reaction pressure 4MPa and unstripped gas air speed 1490h
-1Reaction condition under, the conversion ratio of carbon monoxide is 81.75%, the dimethyl ether selectivity is 93.56%.The patent USP 6147125 (2000) of Japan NKK company and EP 1174408 (2002) have also disclosed and have adopted precipitation of joint sedimentation to prepare two kinds of methods that are used for by the directed preparing dimethyl ether by synthetic gas bifunctional catalyst.(1) in the mixed solution of active component such as copper, zinc and aluminium, adds acidic components such as γ-Al
2O
3Make suspension, add then the precipitating reagent sodium carbonate liquor with the active component co-precipitation at γ-Al
2O
3The surface, the gained sediment after filtration with the washing to remove nitrate ion.In order to eliminate alkaline sodium carbonate, above-mentioned sediment is immersed in certain density acid such as the salpeter solution filtration behind the immersion certain hour, washing, drying and roasting to the adverse effect that acidic components produced.(2) with the sodium carbonate in the aqueous ammonia to replace (1) as precipitating reagent with the active component co-precipitation at γ-Al
2O
3The surface because ammoniacal liquor removes in roasting process subsequently easily, so resulting precipitation deposit need not to use the acid solution immersion treatment.Though the above-mentioned precipitation of joint sedimentation that is used for the direct preparation of dimethyl ether by using synthesis gas bifunctional catalyst has improved the exposure level between two kinds of difference in functionality components, but have following shortcoming: (1) if with sodium carbonate as precipitating reagent with the surface of active component co-precipitation at acidic components, in order to eliminate alkaline sodium carbonate to the adverse effect that acidic components produced, resulting precipitation deposit need be used the acid solution immersion treatment.So preparation process is comparatively loaded down with trivial details, and the washing process of repeated multiple times also can produce adverse influence to the performance of catalyst.(2) with ammoniacal liquor as precipitating reagent with the surface of active component co-precipitation at acidic components, though resulting precipitation deposit need not to use the acid solution immersion treatment, relatively poor as the prepared catalyst performance of precipitating reagent with ammoniacal liquor.
This shows, above-mentioned several preparation method who the synthetic component of methyl alcohol and methanol dehydration component is combined into bifunctional catalyst, all there is significant disadvantages, for example loaded down with trivial details, the consuming time long and/or prepared bifunctional catalyst of preparation process is used for direct preparation of dimethyl ether by using synthesis gas, and its performance comprises that the conversion ratio of carbon monoxide, the selectivity of dimethyl ether etc. can't make us very satisfied.
Summary of the invention
Technical problem to be solved by this invention is loaded down with trivial details, consuming time longer in order to overcome in the prior art dimethyl ether bifunctional catalyst preparation process, and catalyst is used for one-step method from syngas and prepares dimethyl ether when reaction temperature height, not high, the not high shortcoming of dimethyl ether selectivity of carbon monoxide conversion ratio, provide a kind of preparation process simple method for preparing catalyst, and the catalyst of this method preparation have that reaction temperature is low, carbon monoxide conversion ratio height and the good advantage of dimethyl ether selectivity.
Central principle of the present invention is that the active component that methyl alcohol is synthetic is added on the methanol dehydration component in the mode of oxalate precipitation, specifically comprises two kinds of modes:
Preparation method one by the bifunctional catalyst of direct preparation of dimethyl ether by using synthesis gas comprises the following steps:
The active component that a. will can be used as methanol synthesis catalyst is dissolved in the mode of soluble-salt and is mixed with mixed solution A in the alcohol, and the wherein said active component that can be used as methanol synthesis catalyst is selected from the mixture of Cu, Zn, Al, Cr one of them or they;
The active component that b. will can be used as methanol dehydration catalyst joins to stir in the above-mentioned mixed solution A and obtains suspension B, and the wherein said active component that can be used as methanol dehydration catalyst is selected from γ-Al
2O
3, HZSM-5, HY one of them;
C. under agitation add the alcoholic solution of oxalic acid in suspension B, the oxalate coprecipitation thing that reaction generates 250～550 ℃ of following roastings, makes described bifunctional catalyst at last through aging, filtration, drying.
Described alcohol be selected from anhydrous ethanol, normal propyl alcohol, isopropyl alcohol one of them.
The oxalate coprecipitation thing that reaction generates among the step c 300～450 ℃ of following roastings, makes described bifunctional catalyst at last through aging, filtration, drying.
Preparation method two by the bifunctional catalyst of direct preparation of dimethyl ether by using synthesis gas comprises the following steps:
The active component that a. will can be used as methanol synthesis catalyst is dissolved in the mode of soluble-salt and is mixed with mixed solution A in the alcohol, and the wherein said active component that can be used as methanol synthesis catalyst is selected from the mixture of Cu, Zn, Al, Cr one of them or they;
B. oxalic acid is dissolved in the alcoholic solution B that obtains oxalic acid in the alcohol;
The active component that c. will can be used as methanol dehydration catalyst joins and obtains suspension C in the alcohol, and the wherein said active component that can be used as methanol dehydration catalyst is selected from γ-Al
2O
3, HZSM-5, HY one of them;
D. under agitation, two kinds of solution of above-mentioned A, B are added drop-wise among the suspension C simultaneously, the oxalate coprecipitation thing that reaction generates is after wearing out, and directly filtration, drying 250～550 ℃ of following roastings, make described bifunctional catalyst at last.
Described alcohol be selected from anhydrous ethanol, normal propyl alcohol, isopropyl alcohol one of them.
The oxalate coprecipitation thing that reaction generates in the steps d 300～450 ℃ of following roastings, makes described bifunctional catalyst at last through aging, filtration, drying.
The beneficial effect of the invention: its central principle of dimethyl ether bifunctional catalyst of the inventive method preparation is that the active component that methyl alcohol is synthetic is added on the methanol dehydration component in the mode of oxalate precipitation, therefore preparation process is simple, in preparation process, saved cyclic washing, drying and other steps, overcome that prior art for preparing dimethyl ether bifunctional catalyst process is loaded down with trivial details, the shortcoming of length consuming time.And the inventive method has improved the degree that methyl alcohol synthesizing activity component, two kinds of difference in functionality components of methanol dehydration component contact greatly, reduced preparation process to the adverse effect that catalyst produced, prepared bifunctional catalyst has also that reaction temperature is low, carbon monoxide conversion ratio height and dimethyl ether good selective.
The specific embodiment
Below by preparation embodiment and comparing embodiment the present invention is described in further detail, preparation method one by the bifunctional catalyst of direct preparation of dimethyl ether by using synthesis gas, comprising the following steps: that active component that a. will can be used as methanol synthesis catalyst is dissolved in the mode of soluble-salt is mixed with mixed solution A in the alcohol, the wherein said active component that can be used as methanol synthesis catalyst is selected from the mixture of Cu, Zn, Al, Cr one of them or they; The active component that b. will can be used as methanol dehydration catalyst joins to stir in the above-mentioned mixed solution A and obtains suspension B, and the wherein said active component that can be used as methanol dehydration catalyst is selected from γ-Al
2O
3, HZSM-5, HY one of them; C. under agitation add the alcoholic solution of oxalic acid in suspension B, the oxalate coprecipitation thing that reaction generates 250～550 ℃ of following roastings, makes described bifunctional catalyst at last through aging, filtration, drying.Described alcohol be selected from anhydrous ethanol, normal propyl alcohol, isopropyl alcohol one of them.The oxalate coprecipitation thing that reaction generates among the step c 300～450 ℃ of following roastings, makes described bifunctional catalyst at last through aging, filtration, drying.
Preparation method two by the bifunctional catalyst of direct preparation of dimethyl ether by using synthesis gas, comprising the following steps: that active component that a. will can be used as methanol synthesis catalyst is dissolved in the mode of soluble-salt is mixed with mixed solution A in the alcohol, the wherein said active component that can be used as methanol synthesis catalyst is selected from the mixture of Cu, Zn, Al, Cr one of them or they; B. oxalic acid is dissolved in the alcoholic solution B that obtains oxalic acid in the alcohol; The active component that c. will can be used as methanol dehydration catalyst joins and obtains suspension C in the alcohol, and the wherein said active component that can be used as methanol dehydration catalyst is selected from γ-Al
2O
3, HZSM-5, HY one of them; D. under agitation, two kinds of solution of above-mentioned A, B are added drop-wise among the suspension C simultaneously, the oxalate coprecipitation thing that reaction generates is after wearing out, and directly filtration, drying 250～550 ℃ of following roastings, make described bifunctional catalyst at last.Described alcohol be selected from anhydrous ethanol, normal propyl alcohol, isopropyl alcohol one of them.The oxalate coprecipitation thing that reaction generates in the steps d 300～450 ℃ of following roastings, makes described bifunctional catalyst at last through aging, filtration, drying.
The bifunctional catalyst of the present invention's preparation can be used for fixed bed reactors or fluidized-bed reactor, and also can be used for gas-liquid-solid three-phase bed reactor is paste state bed reactor.Before reaction, need reduce processing earlier with the prepared bifunctional catalyst of the present invention.The mixture that consists of hydrogen and inert gas of reducing gases, inert gas are one or more the mixture in nitrogen, helium and the argon gas etc.The content of hydrogen is 0.5～20% in the reducing gases, is preferably 1～10%; Reduction temperature is 180～300 ℃, is preferably 220～280 ℃; The air speed of reducing gases is 500～5000h
-1, be preferably 1000～3000h
-1The bifunctional catalyst of the inventive method preparation is used for by direct preparation of dimethyl ether by using synthesis gas, and its reaction condition that is suitable for is: the mol ratio of raw material of synthetic gas hydrogen and carbon monoxide is 0.8: 1～5: 1, is preferably 1: 1～3: 1; And preferably contain a certain amount of carbon dioxide in the gaseous mixture, its content is 0.5～10%, is preferably 1～5%.The volume space velocity of reaction gas is 100～10000h
-1, be preferably 500～3000h
-1Reaction temperature is 200～400 ℃, is preferably 220～300 ℃.Reaction pressure is 2.0～8.0MPa, is preferably 3.5～6.0MPa.
An example of the inventive method of using fixed bed reactors is hereinafter described.
It is 6mm that a certain amount of catalyst granules (20～40 order) is loaded in internal diameter, and length is in the stainless steel reactor of 300mm.Adopt electrical heating, temperature is controlled automatically.Reactor bottom filling 20～40 purpose inert materials are as supporter, a certain amount of catalyst of filling in the reactor, and filling 20～40 purpose inert materials in catalyst top are made for the usefulness of raw material preheating.Co hydrogenation and Dehydration of methanol take place from top to bottom by beds in material synthesis gas, generate purpose product dimethyl ether and accessory substances such as methyl alcohol and a spot of alkane.Catalyst filling back reducing gases (5%H
2/ 95%N
2) after (240 ℃) reduction that heats up, switch unstripped gas and react.The composition of unstripped gas (volume fraction) is CO:31.1%, CO
2: 5.7%, all the other are H
2Reaction pressure 4.0MPa; Reaction temperature is 230 ℃～290 ℃; The volume space velocity of unstripped gas is 1500h
-1Adopt HP 4890D type gas chromatograph to carry out on-line analysis, use thermal conductivity detector (TCD), carbon molecular sieve chromatogram column analysis carbon monoxide and carbon dioxide; Use hydrogen flame ionization detector, Porapak-N chromatogram column analysis methyl alcohol, dimethyl ether and hydro carbons accessory substance.
According to each components contents in the reaction end gas,, adopt following formula to calculate the conversion ratio of carbon monoxide and the selectivity of the hydro carbons in the product, methyl alcohol and dimethyl ether in the molal quantity of carbon atom:
Carbon monoxide conversion ratio (%)=(amount of the amount+dimethyl ether of the amount+methyl alcohol of the amount+hydro carbons of carbon dioxide * 2)/(amount of the amount+dimethyl ether of the amount+methyl alcohol of the amount+hydro carbons of the amount+carbon dioxide of carbon monoxide * 2) * 100%
The amount of the selectivity=dimethyl ether of dimethyl ether * 2/ (amount of the amount+dimethyl ether of the amount+methyl alcohol of hydro carbons * 2) * 100%
The amount of the selectivity=methyl alcohol of methyl alcohol/(amount of the amount+dimethyl ether of the amount+methyl alcohol of hydro carbons * 2) * 100%
The amount of the selectivity=hydro carbons of hydro carbons/(amount of the amount+dimethyl ether of the amount+methyl alcohol of hydro carbons * 2) * 100%
[embodiment 1]
43.5 gram copper nitrates, 26.8 gram zinc nitrates and 11.2 gram aluminum nitrates are dissolved in and make mixed solution in the absolute ethyl alcohol, HZSM-5 (Si/Al=60) molecular sieve of 11 grams as the methanol dehydration component joined in the above-mentioned mixed solution, fully stir then and obtain suspension.Under agitation add the ethanolic solutions that contain 45 gram oxalic acid in the above-mentioned suspension and obtain precipitation, the gained deposit is through aged at room temperature half an hour, filters then, drying, obtains catalyst fines in 6 hours 350 ℃ of following roastings again.After compressing tablet, pulverizing and sieve are got 20-40 purpose particle and obtained bifunctional catalyst A, wherein the weight percentage of each component is CuO 40%, and ZnO 20%, Al
2O
37%, H-ZSM-5 33%.
[embodiment 2]
43.5 gram copper nitrates, 26.8 gram zinc nitrates and 11.2 gram aluminum nitrates are dissolved in and make mixed solution a in the absolute ethyl alcohol, 45 gram oxalic acid are dissolved in and make solution b in the absolute ethyl alcohol, 11 grams are joined as HZSM-5 (Si/Al=60) molecular sieve of methanol dehydration component make suspension c in the absolute ethyl alcohol.Under agitation add solution a and b in the above-mentioned suspension c simultaneously and obtain precipitation, the gained deposit is through aged at room temperature half an hour, filters then, drying, obtains catalyst fines in 6 hours 350 ℃ of following roastings again.After compressing tablet, pulverizing and sieve are got 20-40 purpose particle and obtained bifunctional catalyst B, wherein the weight percentage of each component is identical with embodiment 1.
[comparative example 1]
Adopt coprecipitation to prepare methanol synthesis catalyst earlier, soon 43.5 gram copper nitrates, 26.8 gram zinc nitrates and 11.2 gram aluminum nitrates are dissolved in and make mixed solution in the distilled water, under strong agitation, above-mentioned mixed solution and sodium carbonate liquor be added drop-wise to simultaneously with certain flow velocity and obtain precipitation in the beaker in 70 ℃, the gained deposit was through aging one hour, filter, use the distilled water cyclic washing then, after 110 ℃ of dryings, obtained the catalst for synthesis of methanol powder in 6 hours 360 ℃ of following roastings again.11 grams are synthesized component as HZSM-5 (Si/Al=60) molecular sieve of methanol dehydration component and resulting methyl alcohol fully mills and mixes, get 20-40 purpose particle through compressing tablet, pulverizing and sieve then and obtain bifunctional catalyst C, wherein the weight percentage of each component is identical with embodiment 1.
[comparative example 2]
43.5 gram copper nitrates, 26.8 gram zinc nitrates and 11.2 gram aluminum nitrates are dissolved in and make mixed solution in the distilled water, under agitation 11 grams were joined in the prepared mixed solution dipping 2 hours as HZSM-5 (Si/Al=60) molecular sieve of methanol dehydration component, evaporate to dryness in water-bath obtained catalyst fines in 6 hours through 110 ℃ of dryings and 360 ℃ of following roastings more then.After compressing tablet, pulverizing and sieve are got 20-40 purpose particle and obtained bifunctional catalyst D, wherein the weight percentage of each component is identical with embodiment 1.
[comparative example 3]
43.5 gram copper nitrates, 26.8 gram zinc nitrates and 11.2 gram aluminum nitrates are dissolved in and make mixed solution in the distilled water, HZSM-5 (Si/A1=60) molecular sieve of 11 grams as the methanol dehydration component joined in the above-mentioned mixed solution, fully stir then and obtain suspension.Under vigorous stirring, in above-mentioned suspension, add certain amount of ammonia water solution in 70 ℃, after dropwising being deposited in of gained continued in the mother liquor to stir to wear out in 1 hour, filter then, wash and drying, obtained catalyst fines in 6 hours 350 ℃ of following roastings again.After compressing tablet, pulverizing and sieve are got 20-40 purpose particle and obtained bifunctional catalyst E, wherein the weight percentage of each component is identical with embodiment 1.
[embodiment 5]
Carry out gas-phase reaction with embodiment 1,2 and the prepared catalyst A of comparative example 1-3, B, C, D and E in continuous-flow fixed bed compressive reaction evaluating apparatus, the loadings of catalyst is 1g.After catalyst has loaded, at logical reducing gases (5%H
2/ 95%N
2, flow velocity is 25ml/min) condition under be warming up to 240 ℃, through after the 6h reduction, under the condition that continues logical reducing gases, reaction bed temperature is reduced to 200 ℃, switch unstripped gas then and be warming up to required reaction temperature gradually and react.The composition of unstripped gas (volume fraction) is CO:31.1%, CO
2: 5.7%, all the other are H
2Reaction condition is pressure: 4MPa, air speed: 1500ml/g
Cath
-1System reaches balance behind reaction 3h, then sample analysis.Adopt HP 4890D type gas chromatograph onlinely carry out, with thermal conductivity detector (TCD), carbon molecular sieve chromatogram column analysis carbon monoxide and carbon dioxide, with hydrogen flame ionization detector, Porapak-N chromatogram column analysis methyl alcohol, dimethyl ether and hydro carbons accessory substance, the evaluation result of catalyst sees Table 1.
The reactivity worth of table 1 catalyst
By table 1 data as seen, the bifunctional catalyst that adopts the inventive method to make, for being reacted by directed preparing dimethyl ether by synthetic gas, the conversion ratio of carbon monoxide and/or the selectivity of dimethyl ether are compared by the prepared bifunctional catalyst of existing method and are greatly improved.
Foregoing only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (6)
1. by the preparation method one of the bifunctional catalyst of direct preparation of dimethyl ether by using synthesis gas, comprise the following steps:
The active component that a. will can be used as methanol synthesis catalyst is dissolved in the mode of soluble-salt and is mixed with mixed solution A in the alcohol, and the wherein said active component that can be used as methanol synthesis catalyst is selected from the mixture of Cu, Zn, Al, Cr one of them or they;
The active component that b. will can be used as methanol dehydration catalyst joins to stir in the above-mentioned mixed solution A and obtains suspension B, and the wherein said active component that can be used as methanol dehydration catalyst is selected from γ-Al
2O
3, HZSM-5, HY one of them;
C. under agitation add the alcoholic solution of oxalic acid in suspension B, the oxalate coprecipitation thing that reaction generates 250～550 ℃ of following roastings, makes described bifunctional catalyst at last through aging, filtration, drying.
2. according to the preparation method of the described a kind of bifunctional catalyst by direct preparation of dimethyl ether by using synthesis gas of claim 1, it is characterized in that described alcohol be selected from anhydrous ethanol, normal propyl alcohol, isopropyl alcohol one of them.
3. according to the preparation method of the described a kind of bifunctional catalyst by direct preparation of dimethyl ether by using synthesis gas of claim 1, the oxalate coprecipitation thing that it is characterized in that reaction generation among the step c is through aging, filtration, drying, 300～450 ℃ of following roastings, make described bifunctional catalyst at last.
4. by the preparation method two of the bifunctional catalyst of direct preparation of dimethyl ether by using synthesis gas, comprise the following steps:
The active component that a. will can be used as methanol synthesis catalyst is dissolved in the mode of soluble-salt and is mixed with mixed solution A in the alcohol, and the wherein said active component that can be used as methanol synthesis catalyst is selected from the mixture of Cu, Zn, Al, Cr one of them or they;
B. oxalic acid is dissolved in the alcoholic solution B that obtains oxalic acid in the alcohol;
The active component that c. will can be used as methanol dehydration catalyst joins and obtains suspension C in the alcohol, and the wherein said active component that can be used as methanol dehydration catalyst is selected from γ-Al
2O
3, HZSM-5, HY one of them;
D. under agitation, two kinds of solution of above-mentioned A, B are added drop-wise among the suspension C simultaneously, the oxalate coprecipitation thing that reaction generates is after wearing out, and directly filtration, drying 250～550 ℃ of following roastings, make described bifunctional catalyst at last.
5. according to the preparation method of the described a kind of bifunctional catalyst by direct preparation of dimethyl ether by using synthesis gas of claim 4, it is characterized in that described alcohol be selected from anhydrous ethanol, normal propyl alcohol, isopropyl alcohol one of them.
6. according to the preparation method of the described a kind of bifunctional catalyst by direct preparation of dimethyl ether by using synthesis gas of claim 4, the oxalate coprecipitation thing that it is characterized in that reaction generation in the steps d is through aging, filtration, drying, 300～450 ℃ of following roastings, make described bifunctional catalyst at last.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110105306A1 (en) * | 2009-10-30 | 2011-05-05 | Atomic Energy Council-Institute Of Nuclear Energy Research | Method of Fabricating Cu-Zn-Al Catalyst for Producing Methanol and Dimethyl Ether |
| CN101940934B (en) * | 2009-07-09 | 2012-04-18 | 青岛生物能源与过程研究所 | Catalyst for preparing dimethyl ether by synthetic gas and preparation method and application thereof |
| CN103949258A (en) * | 2014-04-08 | 2014-07-30 | 太原理工大学 | Method and application of catalyst for slurry-state bed synthesis gas preparation of dimethyl ether |
| CN104245126A (en) * | 2012-04-24 | 2014-12-24 | 巴斯夫欧洲公司 | Catalytically active body for the synthesis of dimethyl ether from synthesis gas |
| CN104646049A (en) * | 2013-11-20 | 2015-05-27 | 正大能源材料(大连)有限公司 | Preparation method of catalyst for directly synthesizing dimethyl ether from synthesis gas |
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2008
- 2008-07-15 CN CNA2008100405619A patent/CN101314134A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940934B (en) * | 2009-07-09 | 2012-04-18 | 青岛生物能源与过程研究所 | Catalyst for preparing dimethyl ether by synthetic gas and preparation method and application thereof |
| US20110105306A1 (en) * | 2009-10-30 | 2011-05-05 | Atomic Energy Council-Institute Of Nuclear Energy Research | Method of Fabricating Cu-Zn-Al Catalyst for Producing Methanol and Dimethyl Ether |
| TWI462777B (en) * | 2009-10-30 | 2014-12-01 | Atomic Energy Council | Method of fabricating cu-zn-al catalyst through synthesizing methanol and dimethyl ether |
| CN104245126A (en) * | 2012-04-24 | 2014-12-24 | 巴斯夫欧洲公司 | Catalytically active body for the synthesis of dimethyl ether from synthesis gas |
| CN104646049A (en) * | 2013-11-20 | 2015-05-27 | 正大能源材料(大连)有限公司 | Preparation method of catalyst for directly synthesizing dimethyl ether from synthesis gas |
| CN103949258A (en) * | 2014-04-08 | 2014-07-30 | 太原理工大学 | Method and application of catalyst for slurry-state bed synthesis gas preparation of dimethyl ether |
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