CN101940934B - Catalyst for preparing dimethyl ether by synthetic gas and preparation method and application thereof - Google Patents
Catalyst for preparing dimethyl ether by synthetic gas and preparation method and application thereof Download PDFInfo
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- CN101940934B CN101940934B CN2009101578728A CN200910157872A CN101940934B CN 101940934 B CN101940934 B CN 101940934B CN 2009101578728 A CN2009101578728 A CN 2009101578728A CN 200910157872 A CN200910157872 A CN 200910157872A CN 101940934 B CN101940934 B CN 101940934B
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Abstract
The invention provides a catalyst for preparing dimethyl ether by synthetic gas and a preparation method and an application thereof. The preparation method comprises the following steps: a) carrying out parallel flow coprecipitation on mixed nitrate solution containing copper, zinc and aluminum and sodium carbonate solution, ageing the obtained precipitation solution to obtain slurry which is a precursor for methanol synthesis catalyst; b) carrying out backflow treatment on pseudo-boehmite with SO42-containing acid or salt solution, filtering and drying to obtain the modified pseudo-boehmite; and c) adding the modified pseudo-boehmite to the precursor for the methanol synthesis catalyst, stirring and mixing evenly, filtering, drying and roasting to obtain the target product. The preparation method of the invention has simple preparation process, good repeatability, mild reaction condition, high catalytic activity and good stability, and the method can help solve the problems of high reaction temperature and poor catalyst stability in the prior art.
Description
Technical field
The present invention relates to a kind of catalyst that is used for the synthesis gas preparation dimethyl ether.
The invention still further relates to above-mentioned Preparation of catalysts method.
The invention still further relates to the application of above-mentioned catalyst in preparing dimethylether from synthetic gas by reaction.
Background technology
Dimethyl ether is a kind of important chemical material; Be widely used in fields such as pharmacy, fuel, agricultural chemicals, refrigeration, daily-use chemical industry; Have nontoxic, safety, combustion thermal efficiency height, the clean no black smoke of combustion tail gas, metal had advantages such as corrosion; Can be used as propellant, domestic fuel and diesel fuel etc., is desirable liquefied fuel gas substitute; Also be the important intermediate that natural gas and coal are produced liquid fuel simultaneously; It is the green fuel of a kind of putative 21st century; Be a kind of clean energy resource carrier of potentialization, modern chemical industry has crucial status in producing, thereby at home and abroad draws attention day by day.
The Dehydration of methanol that the Traditional industrial method of producing dimethyl ether is on solid acid catalyst to be carried out.All the catalyst progress of preparing dimethyl ether by dewatering methanol is reported like Chinese patent CN 1613558A, CN 1745894A, CN 1106219C, CN1895779A, CN 1919451A, CN 1151110C and U.S. Pat 707606, US4560807 etc. from different angles; But all there is certain defective; Or reaction temperature is higher, stable unfavorable to catalyst; Or the preparation process is complicated; Or containing rare earth element or noble metal in the modified component, cost is higher.
In recent years, developed that with the synthesis gas be the new process that raw material is directly produced dimethyl ether, also more and more received researcher's attention.By the catalyst that direct synthesis of dimethyl ether from synthesis gas adopted is the bifunctional catalyst that is composited by methanol synthesis catalyst and methanol dehydration catalyst; Methanol synthesis catalyst is mainly copper, zinc-base O composite metallic oxide catalyst, like composite oxides such as Cu-Zn-Al, Cu-Zn-Zr or Cu-Zn-Cr; Methanol dehydration catalyst mainly adopts γ-Al
2O
3Or solid acid catalyst such as molecular sieve.When using this bifunctional catalyst to react; There are the synthetic and two types of reactions of methanol dehydration of methyl alcohol in the reaction system simultaneously; Have cooperative effect between each component of catalyst, the methyl alcohol of generation dewaters very soon and generates dimethyl ether, makes reaction break through the thermodynamics equilibrium limit in the simple methyl alcohol synthetic reaction; Increase the reaction motive force, can effectively reduce operating pressure and the conversion per pass that improves CO.
Patent US 5753716 discloses a kind of directly by the method for producing dimethyl ether by synthesis gas, and this method is that one or more composite oxides of employing copper, zinc, aluminium, chromium are that methanol synthesis catalyst and aluminum phosphate are methanol dehydration catalyst.This bifunctional catalyst system has good stable property, but the life-span also be merely 934h, and activity of such catalysts is lower.
Patent US 4417000 discloses a kind of directly by the preparation method of the bifunctional catalyst of synthesis gas preparation dimethyl ether, and this method is to adopt the activated alumina of tungsten modification as methanol dehydration catalyst.At H
2/ CO mol ratio is 1.0, reaction pressure 6.21MPa, reaction temperature 285-300 ℃ and the about 3000h of unstripped gas air speed
-1Condition under, the CO conversion ratio is 26.7-52.5%, the DME selectivity is 98%.This shows that the reaction temperature and the reaction pressure of this catalyst are higher, the CO conversion ratio is lower, the stability problem of this patent of invention and not mentioned bifunctional catalyst.
Patent ZL 00133279.1 discloses a kind of directly by the bifunctional catalyst and the preparation technology thereof of synthesis gas preparing dimethy ether, and this catalyst comprises that mainly weight percentage is that metal oxide and the weight percentage of 30%-70% is the acidic components of 30%-70%.Wherein metal oxide is one or more mixtures in cupric oxide, zinc oxide, chromium oxide, the cerium oxide, and acidic components are one or more mixtures in molecular sieve, aluminium oxide, the aluminum phosphate.At H
2/ CO mol ratio is 3.85, reaction pressure 4.0MPa, 300 ℃ of reaction temperatures and the about 1500h of unstripped gas air speed
-1Condition under, CO conversion ratio 81.75%.The required reaction temperature of this catalyst is higher, the H in the needed raw material gas
2/ CO is than higher, and the stability problem of not mentioned catalyst in should invention.
Patent CN 101157038A discloses a kind of Catalysts and its preparation method of synthesizing dimethyl ether one-step with synthesis gas as well; Be characterized in " one pot " preparation in same environment of synthetic component of methyl alcohol and methanol dehydration component; In liquid phase environment, add Cu, Zn active component fully and form required silicon source, aluminium source and template such as Si-Al oxide, molecular sieve, preparing general formula is the slurried catalyst of CuZnMSiAl (M is an auxiliary agent).At H
2/ CO mol ratio is 1.0, under the condition of 280 ℃ of reaction pressure 4.0MPa, reaction temperature, the CO conversion ratio is 40.07%, the DME selectivity is 66.1%.The reaction temperature of this catalyst is still higher, and reactivity is very low, and is somebody's turn to do the stability problem of not mentioned catalyst in the invention.
Patent ZL 93115774.9 discloses a kind of by the process of preparation of dimethyl ether from synthesis gas reaction with catalyst and preparation dimethyl ether thereof, and this method adopts the γ-Al of the oxide modifying of boron, titanium or P elements
2O
3The bifunctional catalyst that forms for methanol dehydration component and industrial catalst for synthesis of methanol mechanical mixture.At H
2/ CO mol ratio is about 2.0, reaction pressure 3.5MPa, 260 ℃ of reaction temperatures, reaction velocity 1000h
-1Condition under, 83% before by the modification of CO conversion ratio brings up to 85%, the DME selectivity also is increased to 94% by 84% before the modification.But the reaction temperature of this catalyst still higher (being higher than 250 ℃), and the stability problem of not mentioned catalyst still in should invention.
Patent ZL 200410016391.2 discloses a kind of method by direct preparation of dimethyl ether by using synthesis gas, and this method is used through SO
4 2-γ-the Al of modification
2O
3The bifunctional catalyst that is composited with the synthetic component of Cu, Zn base methyl alcohol is as the synthetic catalyst of dimethyl ether.SO wherein
4 2-γ-the Al of modification
2O
3Be to adopt simple immersion process for preparing and get, be about to a certain amount of γ-Al
2O
3Pour into and flood 2h in the sulfate liquor, then elimination raffinate and oven dry, roasting.At H
2/ CO mol ratio is 2.0, reaction pressure 4.0MPa, 270 ℃ of reaction temperatures, reaction velocity 1500h
-1Condition under, CO conversion ratio 93.6%, DME selectivity 94.6%.Thus it is clear that, adopt SO
4 2-γ-the Al of modification
2O
3Be methanol dehydration catalyst, can make CO conversion ratio and DME selectivity that raising is significantly arranged, but still do not mention the stability problem of catalyst in this patent of invention.
This shows that there are defectives such as reaction temperature is high, the CO conversion ratio is low in the disclosed bifunctional catalyst of being made up of methanol synthesis catalyst and methanol dehydration catalyst of above-mentioned several kinds of patents of invention, and most of patent equal service life of not mentioned catalyst.Therefore the catalytic activity and the stability of this bifunctional catalyst await further raising, obtain one and synthesis gas prepared directly that the dimethyl ether reaction has high CO conversion ratio and are the target directions that catalyst preparation technology develops than the catalyst of long life.
Summary of the invention
The purpose of this invention is to provide a kind of high activity of synthesis gas preparation dimethyl ether, bifunctional catalyst of high stability of being used for.
Another purpose of the present invention provides the method for the above-mentioned catalyst of preparation.
For realizing above-mentioned purpose, catalyst provided by the invention is to obtain through following steps:
A) preparation of methanol synthesis catalyst presoma: with the nitrate mixed solution and the sodium carbonate liquor of copper, zinc and aluminium and flow co-precipitation, the gained precipitation solution is worn out, the gained slurries are the methanol synthesis catalyst presoma; Wherein the mass ratio of institute's cupric, zinc, aluminium is 15-65: 10-40: 2-20 in the nitrate mixed solution;
B) modification boehmite preparation: the boehmite employing is contained SO
4 2-Acid or salting liquid reflow treatment, filter, after the drying the modification boehmite; SO wherein
4 2-Mass content be 1-15%;
C) the modification boehmite that step b is obtained joins in the methanol synthesis catalyst presoma of step a, mix after filter, dry, roasting gets target product.
The method of the above-mentioned catalyst of preparation provided by the invention, its key step does
A) preparation of methanol synthesis catalyst presoma: with the nitrate mixed solution of copper, zinc and aluminium and sodium carbonate liquor under 50-80 ℃, the condition of pH=6.0-10.0 and the stream co-precipitation; At 60-90 ℃ down aging 1-4 hour (h), the gained slurries are the methanol synthesis catalyst presoma with the gained precipitation solution; Wherein the mass ratio of institute's cupric, zinc, aluminium is 15-65: 10-40: 2-20 in the nitrate mixed solution.
B) modification boehmite preparation: the boehmite employing is contained SO
4 2-Acid or salting liquid handled 12-72 hour 50-90 ℃ of refluxed, filter, after the drying the modification boehmite; SO wherein
4 2-Mass content be 1-15%; Contain SO
4 2-Acid or salt be H
2SO
4, Al
2(SO
4)
3, ZnSO
4, FeSO
4, (NH
4)
2SO
4, Ti (SO
4)
2Or the mixture of its arbitrary proportion.
C) the modification boehmite that step b is obtained joins in the methanol synthesis catalyst presoma of step a, mix after filter, 80-150 ℃ of 12-72 hour drying time, again in 350-700 ℃ of roasting 2-30 hour, target product.
Among the said preparation method, the mass ratio of copper, zinc, aluminium is preferably 25-50 in the nitrate mixed solution among the step a: 15-30: 5-10.
Among the said preparation method, the co-precipitation temperature among the step a is preferably 60-70 ℃, pH value and is preferably=and 7.0-9.0, ageing time be preferably 1-3h.
Among the said preparation method, SO in the modification boehmite among the step c
4 2-The quality percentage composition be preferably 3-12%.
Among the said preparation method, contain SO among the step c
4 2-Acid or salt be preferably Al
2(SO
4)
3, ZnSO
4Or (NH
4)
2SO
4
Among the said preparation method, the SO among the step c
4 2-The reflux temperature of handling boehmite is preferably 60-80 ℃, and return time is preferably 24-72h.
Among the said preparation method, the mass ratio of the modification boehmite that adds in the steps d and institute's cupric, zinc, aluminium-mixed oxide is preferably 2: 1-4: 1.
Among the said preparation method, the baking temperature in the steps d is preferably 90-120 ℃, is preferably 12-48h drying time.
Among the said preparation method, the sintering temperature in the steps d is preferably 450-600 ℃, and roasting time is preferably 3-8h.
Catalyst of the present invention is used for preparing dimethylether from synthetic gas by reaction, and catalyst is seated in the fixed bed reactors, under normal pressure, uses N
2The H of dilution
2In 250-280 ℃, air speed 1000-3000h
-1Reduction is 6-8 hour under the condition; After being cooled to 80-100 ℃ with N
2The H of dilution
2Switch to synthesis gas, heat up and carry out synthetic reaction, reaction condition is: temperature 200-280 ℃, and pressure 1-10MPa, air speed 500-10000h
-1, reaction time 5-10 hour, chromatogram on-line analysis product and tail gas were formed.N
2The H of dilution
2Consist of by volume: N
2/ H
2=10-20/1; Synthesis gas by volume consists of: H
2/ CO/CO
2=2/1-2/0.1-2.
Catalyst of the present invention is in preparing dimethylether from synthetic gas by reaction, and preferred reaction temperature is 230-260 ℃, and reaction pressure is 3-5MPa, air speed 1000-3000h
-1
Among the preparation method of the present invention, SO
4 2-The modification boehmite is compound with the catalst for synthesis of methanol precursor after dry and roasting heat are handled compares with the catalyst of present document and patent report; At first be chemical composition and physical arrangement homogeneous, obviously be different from the mechanical mixture of Traditional industrial catalyst for methanol and dehydration catalyst.Adopt SO
4 2-The modification boehmite is easy on the one hand and the methanol synthesis catalyst precursor is compound; After calcination process, form the proper acidic position on the other hand; Particularly under the reaction in-situ condition, induce activation; Metal active center and dehydration activity center show the obvious synergistic effect, have overcome two kinds of activated centres from microcosmic mechanism and have poisoned the deactivation phenomenom that causes each other.The overall performance of composite catalyst is embodied in has very high reactivity, particularly low temperature active, thereby has effectively suppressed coking and the sintering of active component in the direct synthesis of dimethyl ether from synthesis gas process.In fixed bed reactors, the reaction test of the direct dimethyl ether synthesis of synthesis gas is explained that bifunctional catalyst of the present invention has shown good stable property, line duration has surpassed 1000h.Therefore, bifunctional catalyst of the present invention has the advantage that reaction temperature is low, catalytic activity is high, catalytic performance is stable.
Catalyst of the present invention is suitable for the synthesizing dimethyl ether by synthetic gas in various sources such as coal, natural gas and living beings, is suitable for various types of reactors such as fixed bed, slurry attitude bed, bubble tower, fluid bed simultaneously.
Description of drawings
Fig. 1 is the estimation of stability experimental result that embodiment 1 prepared catalyst original position is induced activation and 1000h.
The specific embodiment:
The present invention solves that the reaction temperature that exists in the prior art is high, catalyst activity is not high and the problem of poor stability; Provide a kind of and have lower reaction temperature, higher CO conversion ratio and dimethyl ether, a kind of bifunctional catalyst and preparation and method for using of high stability especially is provided optionally by the bifunctional catalyst and the preparation technology thereof of direct preparation of dimethyl ether by using synthesis gas.
The technical scheme that the present invention adopts is following:
(1) Preparation of catalysts
The preparation method of the bifunctional catalyst of the high activity by direct preparation of dimethyl ether by using synthesis gas provided by the invention, high stability may further comprise the steps successively:
1. the preparation of methanol synthesis catalyst presoma: is under 50-80 ℃, the condition of pH=6.0-10.0 and the stream co-precipitation with the nitrate mixed solution of copper, zinc, aluminium and sodium carbonate liquor in temperature; With gained precipitation solution aging 1-4h under 60-90 ℃; The gained slurries are the methanol synthesis catalyst presoma, and wherein the mass ratio of institute's cupric, zinc, aluminium is 15-65: 10-40: 2-20 in the nitrate mixed solution;
2. modification boehmite preparation: adopt commercial boehmite and contain SO4
2-Acid or salting liquid handle 12-72h 50-90 ℃ condition refluxed, cross then and filter solid sample, with obtaining the modification boehmite after the solid sample washing of gained, the drying, SO wherein
4 2-Mass content be 1-15%;
3. the modification boehmite that step is obtained in 2. joins in the methanol synthesis catalyst presoma that step obtains in 1., mixes after filtration, washing, 80-150 ℃ dry 12-72h, a 350-700 ℃ roasting 2-30h make dimethyl ether synthetic catalyst.
(2) use of catalyst
Be crushed to the 40-60 order behind the catalyst compression molding, be seated in the pressurization static bed reactor of stainless steel of 5mm internal diameter, under normal pressure, use N
2The H of dilution
2In 250-280 ℃, air speed 1000-3000h
-1Reduce 6-8h under the condition, be cooled to 80-100 ℃ after with N
2The H of dilution
2Switch to the high pressure synthesis gas, synthetic reaction is carried out in temperature programming then, and reaction condition is: temperature 200-280 ℃, and pressure 1-10MPa, air speed 500-10000h
-1Reach the optimum response state after under reaction condition, inducing 5-10h, chromatogram on-line analysis product and tail gas are formed.
Below in conjunction with embodiment the present invention is further described.
Embodiment 1
With 48.3g Cu (NO
3)
2.3H
2O, 24.3g Zn (NO
3)
2.6H
2O and 17.4g Al (NO
3)
3.9H
2O is dissolved in the 600ml distilled water, be made into the mixed solution of stable homogeneous after, under the condition of 70 ℃ of temperature of control and pH=7.5, (take by weighing the 50g anhydrous Na with sodium carbonate liquor
2CO
3Be dissolved in the 800mL deionized water) and flow co-precipitation, make deposition evenly mixed, after deposition was complete, precipitation solution continued at 70 ℃ of aging 1h, and the gained slurries are the precursor of methanol synthesis catalyst.Wherein the mass ratio of copper, zinc, aluminium is 43: 18: 4.24.
With 50.8g (NH
4)
2SO
4Be dissolved in the 320ml distilled water, be made into SO
4 2-Mass content is 7.5% (NH
4)
2SO
4Solution toward wherein pouring the commercial boehmite powder of 20g into, is handled 24h 65 ℃ condition refluxed then, cross then and filter solid sample, with the solid sample washing back of gained in 110 ℃ of dry 12h.With the SO that makes
4 2-The boehmite of modification joins in the precursor slurries of methanol synthesis catalyst of preparation, mixes after filtration washing in 110 ℃ of dry 12h, is transferred in the Muffle furnace in 500 ℃ of following roasting 4h then, promptly gets dimethyl ether synthetic catalyst.
With being crushed to the 40-60 order behind the dimethyl ether synthetic catalyst compression molding, be seated in the pressurization static bed reactor of stainless steel of 5mm internal diameter, under normal pressure, use N
2The H of dilution
2(H
2Molar content: 5%, air speed 1500h
-1) 270 ℃ of reduction 6 hours.Cool to 100 ℃ and switch to synthesis gas (H
2/ CO/CO
2=1: 1: 0.16) synthetic reaction is carried out in pressurization, temperature programming again, and reaction condition is following: 250 ℃ of temperature, pressure 4.0MPa, air speed 1500h
-1, reaction time 1000h.Reach the optimum response state after under reaction condition, inducing 5-10h, chromatogram on-line analysis product and tail gas are formed.Reaction result is seen Fig. 1.
Embodiment 2
With 48.3g Cu (NO
3)
2.3H
2O, 24.3g Zn (NO
3)
2.6H
2O and 17.4g Al (NO
3)
3.9H
2O is dissolved in the 600ml distilled water, be made into the mixed solution of stable homogeneous after, under the condition of 60 ℃ of temperature of control and pH=9, (take by weighing the 50g anhydrous Na with sodium carbonate liquor
2CO
3Be dissolved in the 800mL deionized water) and flow co-precipitation, make deposition evenly mixed, after deposition was complete, precipitation solution continued at 70 ℃ of aging 3h, and the gained slurries are the precursor of methanol synthesis catalyst.Wherein the mass ratio of copper, zinc, aluminium is 43: 18: 4.24.
With 11.85g Al
2(SO
4)
3Be dissolved in the 320ml distilled water, be made into SO
4 2-Mass content is 3% Al
2(SO
4)
3Solution toward wherein pouring the commercial boehmite powder of 20g into, is handled 24h 75 ℃ condition refluxed then, cross then and filter solid sample, with the solid sample washing back of gained in 110 ℃ of dry 12h.With the SO that makes
4 2-The boehmite of modification joins in the precursor slurries of methanol synthesis catalyst of preparation, mixes after filtration washing in 110 ℃ of dry 12h, is transferred in the Muffle furnace in 500 ℃ of following roasting 4h then, promptly gets dimethyl ether synthetic catalyst.
With being crushed to the 40-60 order behind the dimethyl ether synthetic catalyst compression molding, be seated in the pressurization static bed reactor of stainless steel of 5mm internal diameter, under normal pressure, use N
2The H of dilution
2(H
2Molar content: 10%, air speed 1500h
-1) 270 ℃ of reduction 6 hours.Cool to 100 ℃ and switch to synthesis gas (H
2/ CO/CO
2=1: 1: 0.16) synthetic reaction is carried out in pressurization, temperature programming again, and reaction condition is following: 260 ℃ of temperature, pressure 4.0MPa, air speed 1000h
-1, reaction time 40h.Reach the optimum response state after under reaction condition, inducing 5-10h, chromatogram on-line analysis product and tail gas are formed.Reaction result is seen table 1.
Embodiment 3
With 48.3g Cu (NO
3)
2.3H
2O, 24.3g Zn (NO
3)
2.6H
2O and 17.4g Al (NO
3)
3.9H
2O is dissolved in the 600ml distilled water, be made into the mixed solution of stable homogeneous after, under the condition of 60 ℃ of temperature of control and pH=8, (take by weighing the 50g anhydrous Na with sodium carbonate liquor
2CO
3Be dissolved in the 800mL deionized water) and flow co-precipitation, make deposition evenly mixed, after deposition was complete, precipitation solution continued at 70 ℃ of aging 2h, and the gained slurries are the precursor of methanol synthesis catalyst.Wherein the mass ratio of copper, zinc, aluminium is 43: 18: 4.24.
With 76.2g (NH
4)
2SO
4Be dissolved in the 320ml distilled water, be made into SO
4 2-Mass content is 10% (NH
4)
2SO
4Solution toward wherein pouring the commercial boehmite powder of 20g into, is handled 24h 75 ℃ condition refluxed then, cross then and filter solid sample, with the solid sample washing back of gained in 110 ℃ of dry 12h.With the SO that makes
4 2-The boehmite of modification joins in the precursor slurries of methanol synthesis catalyst of preparation, mixes after filtration washing in 110 ℃ of dry 12h, is transferred in the Muffle furnace in 500 ℃ of following roasting 4h then, promptly gets dimethyl ether synthetic catalyst.
With being crushed to the 40-60 order behind the dimethyl ether synthetic catalyst compression molding, be seated in the pressurization static bed reactor of stainless steel of 5mm internal diameter, under normal pressure, use N
2The H of dilution
2(H
2Molar content: 5%, air speed 1000h
-1) 260 ℃ of reduction 6 hours.Cool to 100 ℃ and switch to synthesis gas (H
2/ CO/CO
2=1: 1: 0.16) synthetic reaction is carried out in pressurization, temperature programming again, and reaction condition is following: 250 ℃ of temperature, pressure 4.0MPa, air speed 1500h
-1, reaction time 40h.Reach the optimum response state after under reaction condition, inducing 5-10h, chromatogram on-line analysis product and tail gas are formed.Reaction result is seen table 1.
Embodiment 4
With 48.3g Cu (NO
3)
2.3H
2O, 24.3g Zn (NO
3)
2.6H
2O and 17.4g Al (NO
3)
3.9H
2O is dissolved in the 600ml distilled water, be made into the mixed solution of stable homogeneous after, under the condition of 60 ℃ of temperature of control and pH=7.5, (take by weighing the 50g anhydrous Na with sodium carbonate liquor
2CO
3Be dissolved in the 800mL deionized water) and flow co-precipitation, make deposition evenly mixed, after deposition was complete, precipitation solution continued at 70 ℃ of aging 1h, and the gained slurries are the precursor of methanol synthesis catalyst.Wherein the mass ratio of copper, zinc, aluminium is 43: 18: 4.24.
With 107.6g ZnSO
4Be dissolved in the 320ml distilled water, be made into SO
4 2-Mass content is 15% ZnSO
4Solution toward wherein pouring the commercial boehmite powder of 20g into, is handled 24h 75 ℃ condition refluxed then, cross then and filter solid sample, with the solid sample washing back of gained in 110 ℃ of dry 12h.With the SO that makes
4 2-The boehmite of modification joins in the precursor slurries of methanol synthesis catalyst of preparation, mixes after filtration washing in 110 ℃ of dry 12h, is transferred in the Muffle furnace in 500 ℃ of following roasting 4h then, promptly gets dimethyl ether synthetic catalyst.
With being crushed to the 40-60 order behind the dimethyl ether synthetic catalyst compression molding, be seated in the pressurization static bed reactor of stainless steel of 5mm internal diameter, under normal pressure, use N
2The H of dilution
2(H
2Molar content: 5%, air speed 3000h
-1) 280 ℃ of reduction 6 hours.Cool to 100 ℃ and switch to synthesis gas (H
2/ CO/CO
2=1: 1: 0.16) synthetic reaction is carried out in pressurization, temperature programming again, and reaction condition is following: 250 ℃ of temperature, pressure 6.0MPa, air speed 1500h
-1, reaction time 40h.Reach the optimum response state after under reaction condition, inducing 5-10h, chromatogram on-line analysis product and tail gas are formed.Reaction result is seen table 1.
Embodiment 5
Preparation of catalysts method and appreciation condition be with embodiment 1, and the mass ratio of copper, zinc, aluminium is 25.8: 12: 4.24 in the precursor slurries of different is methanol synthesis catalyst.Reaction time 40h, reaction result is seen table 1.
Embodiment 6
Preparation of catalysts method and appreciation condition are with embodiment 1, and different is to pour (NH into
4)
2SO
4The quality of the boehmite in the solution is 30g.Reaction time 40h, reaction result is seen table 1.
Embodiment 7
Preparation of catalysts method and appreciation condition are with embodiment 1, and that different is (NH
4)
2SO
4The time of solution reflow treatment boehmite is 48h.Reaction time 60h, reaction result is seen table 1.
Embodiment 8
Preparation of catalysts method and appreciation condition are with embodiment 1, and that different is the SO that makes
4 2-The precursor slurry mixture of the methanol synthesis catalyst among the boehmite of modification and the embodiment 1 is transferred to after filtration, washing, drying in the Muffle furnace in 400 ℃ of following roasting 4h.Reaction temperature is 230 ℃, air speed 1000h
-1, pressure 5.0Mpa, reaction time 40h, reaction result is seen table 1.
Embodiment 9
Preparation of catalysts method and appreciation condition are with embodiment 1, and that different is the SO that makes
4 2-The precursor slurry mixture of the methanol synthesis catalyst among the boehmite of modification and the embodiment 1 is transferred to after filtration, washing, drying in the Muffle furnace in 700 ℃ of following roasting 4h.Reaction time 40h, reaction result is seen table 1.
Embodiment 10
Preparation of catalysts method and service condition be with embodiment 3, and the reaction condition of different is catalyst is: 250 ℃ of temperature, pressure 6.0MPa, air speed 3000h
-1Reaction time 40h, reaction result is seen table 1.
Embodiment 11
Preparation of catalysts method and service condition be with embodiment 3, and the reaction condition of different is catalyst is: 250 ℃ of temperature, pressure 3.0MPa, air speed 1000h
-1Reaction time 40h, reaction result is seen table 1.
Embodiment 12
Preparation of catalysts method and service condition be with embodiment 3, and the reaction condition of different is catalyst is: synthesis gas consists of H
2/ CO/CO
2=1: 1: 1,250 ℃ of temperature, pressure 4.0MPa, air speed 1000h
-1Reaction time 40h, reaction result is seen table 1.
Embodiment 13
Preparation of catalysts method and service condition are with embodiment 3, and that different is the reaction pressure 5.0MPa of catalyst.Reaction time 40h, reaction result is seen table 1.
Embodiment 14
Preparation of catalysts method and service condition are with embodiment 3, and different is that synthesis gas consists of H
2/ CO/CO
2=2: 1: 0.16.Reaction time 40h, reaction result is seen table 1.
Subordinate list 1: embodiment catalyst reaction result
| The instance sequence number | CO conversion ratio mol% | The DME selectivity * (％) | The instance sequence number | CO conversion ratio mol% | The DME selectivity * (％) |
| 2 | 80.41 | 95.67 | 9 | 70.88 | 95.82 |
| 3 | 74.82 | 91.99 | 10 | 75.48 | 96.17 |
| 4 | 81.01 | 91.20 | 11 | 76.87 | 92.61 |
| 5 | 70.35 | 97.22 | 12 | 72.13 | 88.69 |
| 6 | 70.44 | 96.37 | 13 | 82.36 | 90.27 |
| 7 | 72.86 | 93.61 | 14 | 82.16 | 93.25 |
| 8 | 72.28 | 86.23 |
*CO
2Do not count, other minor by-products is methyl alcohol, carbon two and carbon three hydro carbons.
Claims (10)
1. catalyst that is used for the synthesis gas preparing dimethy ether obtains through following steps:
A) preparation of methanol synthesis catalyst presoma: with the nitrate mixed solution of copper, zinc and aluminium and sodium carbonate liquor under 50-80 ℃, the condition of pH=6.0-10.0 and the stream co-precipitation; The gained precipitation solution was worn out 1-4 hour down at 60-90 ℃, and the gained slurries are the methanol synthesis catalyst presoma; Wherein the mass ratio of institute's cupric, zinc, aluminium is 15-65: 10-40: 2-20 in the nitrate mixed solution;
B) modification boehmite preparation: the boehmite employing is contained SO
4 2-Acid or salting liquid handled 12-72 hour 50-90 ℃ of refluxed, filter, after the drying the modification boehmite; SO wherein
4 2-Mass content be 1-15%;
C) the modification boehmite that step b is obtained joins in the methanol synthesis catalyst presoma of step a, and the mass ratio of modification boehmite and institute's cupric, zinc, aluminium-mixed oxide is 1-5: 1; Mix after filter, 80-150 ℃ dry 12-72 hour, again in 350-700 ℃ of roasting 3-30 hour, target product.
2. one kind prepares the said Preparation of catalysts method of claim 1, and its key step does
A) preparation of methanol synthesis catalyst presoma: with the nitrate mixed solution of copper, zinc and aluminium and sodium carbonate liquor under 50-80 ℃, the condition of pH=6.0-10.0 and the stream co-precipitation; The gained precipitation solution was worn out 1-4 hour down at 60-90 ℃, and the gained slurries are the methanol synthesis catalyst presoma; Wherein the mass ratio of institute's cupric, zinc, aluminium is 15-65: 10-40: 2-20 in the nitrate mixed solution;
B) modification boehmite preparation: the boehmite employing is contained SO
4 2-Acid or salting liquid handled 12-72 hour 50-90 ℃ of refluxed, filter, after the drying the modification boehmite; SO wherein
4 2-Mass content be 1-15%;
C) the modification boehmite that step b is obtained joins in the methanol synthesis catalyst presoma of step a, and the mass ratio of modification boehmite and institute's cupric, zinc, aluminium-mixed oxide is 1-5: 1; Mix after filter, 80-150 ℃ dry 12-72 hour, again in 350-700 ℃ of roasting 3-30 hour, target product.
3. preparation method as claimed in claim 2, wherein, the mass ratio of institute's cupric, zinc, aluminium is 25-50: 15-30: 5-10 in the nitrate mixed solution.
4. preparation method as claimed in claim 2 wherein, contains SO among the step b
4 2-Acid or salt be H
2SO
4, Al
2(SO
4)
3, ZnSO
4, FeSO
4, (NH
4)
2SO
4, Ti (SO
4)
2Or the mixture of its arbitrary proportion.
5. preparation method as claimed in claim 2, wherein, co-precipitation temperature is 60-70 ℃ among the step a, pH value=7.0-9.0, ageing time is 1-3 hour.
6. preparation method as claimed in claim 2, wherein, SO among the step b
4 2-The reflux temperature of handling boehmite is 60-80 ℃, and return time is 24-72 hour.
7. preparation method as claimed in claim 2, wherein, the mass ratio of the modification boehmite that adds among the step c and institute's cupric, zinc, aluminium-mixed oxide is 2-4: 1.
8. the application of the said catalyst of claim 1 in preparing dimethylether from synthetic gas by reaction is seated in catalyst in the fixed bed reactors, under normal pressure, uses N
2The H of dilution
2In 250-280 ℃, air speed 1000-3000h
-1Under the condition reduction 6-8 hour, be cooled to 80-100 ℃ after with N
2The H of dilution
2Switch to synthesis gas, the intensification synthetic reaction, synthetic reaction condition is: temperature 200-280 ℃, pressure 1-10MPa, air speed 500-10000h
-1, reaction time 5-10 hour.
9. application as claimed in claim 8, wherein, N
2The H of dilution
2Consist of by volume: N
2/ H
2=10-20/1; Synthesis gas by volume consists of: H
2/ CO/CO
2=2/1-2/0.1-2.
10. application as claimed in claim 8, wherein, synthetic reaction condition is: temperature 230-260 ℃, pressure 3-5MPa, air speed 1000-6000h
-1
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| CN102698762B (en) * | 2012-05-22 | 2013-12-11 | 太原理工大学 | Method for preparing dimethyl ether (DME) catalyst from synthesis gas |
| CN103627417A (en) * | 2013-04-15 | 2014-03-12 | 夏津县阳光新能源开发有限公司 | Method for preparing biomass charcoal and jointly producing dimethyl ether from straw briquette |
| CN104275184A (en) * | 2013-07-12 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method of low-impurity-content copper-based methanol synthesis catalyst |
| 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 |
| CN105642306B (en) * | 2014-12-06 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of method for preparing catalyst of synthesis gas full methanation preparing natural gas |
| CN105233832B (en) * | 2015-11-09 | 2018-08-14 | 华东理工大学 | Composite catalyst and preparation method thereof for one-step method from syngas preparation of dimethyl ether |
| CN106693854B (en) * | 2017-01-22 | 2019-01-25 | 浙江大学 | The method of low-temperature plasma modified catalyst device and catalysis oxidation methyl sulfide |
| CN107216907B (en) * | 2017-06-12 | 2023-04-07 | 中国科学院青岛生物能源与过程研究所 | Method and system for producing gasoline from biomass synthesis gas through dimethyl ether |
| CN114920627B (en) * | 2022-04-11 | 2024-02-20 | 南方海洋科学与工程广东省实验室(广州) | Method for preparing dimethyl ether by catalyzing natural gas hydrate through one-step method |
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| CN101121143A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Catalyst used for synthesized gas directly preparing dimethy ether |
| CN101264448A (en) * | 2008-04-25 | 2008-09-17 | 太原理工大学 | Aluminium base slurried catalyst and preparation thereof |
| CN101314134A (en) * | 2008-07-15 | 2008-12-03 | 上海应用技术学院 | Process for preparing bifunctional catalyst for preparing dimethyl ether directly with synthesis gas |
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| CN101264448A (en) * | 2008-04-25 | 2008-09-17 | 太原理工大学 | Aluminium base slurried catalyst and preparation thereof |
| CN101314134A (en) * | 2008-07-15 | 2008-12-03 | 上海应用技术学院 | Process for preparing bifunctional catalyst for preparing dimethyl ether directly with synthesis gas |
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