CN103949258A - Method and application of catalyst for slurry-state bed synthesis gas preparation of dimethyl ether - Google Patents
Method and application of catalyst for slurry-state bed synthesis gas preparation of dimethyl ether Download PDFInfo
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Abstract
The invention discloses a method and an application of a catalyst for slurry-state bed synthesis gas preparation of dimethyl ether. The method comprises the steps: carrying out parallel flow and co-precipitation of a mixed solution of nitrates of copper, zinc and aluminum with sodium carbonate, after carrying out aging, suction filtration and washing on the obtained precipitation solution, dispersing into ethanol with a surfactant, and carrying out ultrasonic stirring; and then adding silica sol, a hexamethylenediamine ethanol solution and an aluminum nitrate solution into the ultrasonic suspension, aging, carrying out suction filtration on the aged catalyst to obtain a filter cake, adding the filter cake into liquid paraffin, and carrying out heat treatment to obtain a slurried catalyst. The method is simple, and the raw materials are easy to get; compared with same-kind catalysts, the catalyst has the advantages of high catalytic activity and stability, relatively high selectivity of dimethyl ether in the product, small CO2 selectivity and the like, and importantly, solves the catalyst stability and the influence caused by a side-reaction water gas transformation reaction in preparation of dimethyl ether by the slurry-state bed one-step method.
Description
Technical field
The present invention relates to a kind of catalyst of preparing dimethyl ether, concrete can be described as is a kind of for starching the bifunctional catalyst of the direct preparing dimethy ether of state bed one-step method from syngas.
Background technology
Along with the fast development of national economy, China's energy shortage and problem of environmental pollution are increasingly outstanding, are petroleum reserves and underproduce on the one hand, and externally interdependency improves year by year, directly threatens national energy security; Be that coal utilizaton rate is on the low side on the other hand, in combustion process, produce a large amount of SO
2, NO
xand the material such as flue dust, major polluting atmosphere environment.Be based on the coal resources of China's abundant, exploitation turns to basic Poly-generation technology with coal gas, utilizes coal based synthetic gas (CO+H
2) produce dimethyl ether environmental friendliness fuel, the deficiency that can supplement petroleum resources, can realize again efficient, the clean utilization of coal, is that the key that solves energy source in China and environmental problem is selected.
Direct preparation of dimethyl ether by using synthesis gas adopts bifunctional catalyst more, and essence is that methanol synthesis catalyst and dehydration catalyst are combined.And the reaction mechanism that generally believes one-step method dimethyl ether synthesis is that methyl alcohol is synthetic, the combination of methanol dehydration and water gas shift reaction mechanism.
Early stage bifunctional catalyst is to have industrial methanol synthetic catalyst and the industrial methanol dehydration catalyst composite catalyst that mechanical mixture forms according to a certain percentage.Yet double-function catalyzing agent solution prepared by the method causes two kinds of active components can not close contact or mutually cover and affect the performance of catalyst performance.
In order to overcome the deficiency of mechanical mixture bifunctional catalyst, CN1153080, CN01136842.x and CN101934233A openly adopt respectively precipitation of joint sedimentation, colloidal deposition method and chemical uniform deposition legal system for the method for directed preparing dimethyl ether by synthetic gas catalyst, between catalyst components prepared by these methods, contact closely, has strengthened the synergy between two kinds of active components.But still exist methyl alcohol synthesizing activity center and methanol dehydration center mutually to cover formation new species, or the problem such as catalyst activity component bad dispersibility, and cause catalyst activity and poor selectivity.
At present a lot of patents and document have been announced the process of one-step method from syngas preparing dimethy ether.For example CN101940934A adopts the boehmite of modification to join in methanol synthesis catalyst presoma, after evenly mixing, after filtration, dry, roasting obtains bifunctional catalyst.For another example CN101862685A proposes to prepare the bifunctional catalyst of nucleocapsid structure.Methanol dehydration part presoma forms colloidal sol, utilizes hydrothermal synthesis method on methanol synthesis catalyst particle, to form methanol dehydration catalyst thin layer, and finally separated from synthesis mother liquid and roasting obtains dimethyl ether synthetic catalyst.Also just like CN103212418A, a kind of technical scheme with the bifunctional catalyst machine preparation method by direct preparation of dimethyl ether by using synthesis gas of nucleocapsid structure has also been proposed.The method be take methanol synthesis catalyst as kernel, methanol dehydration catalyst Si0
2-Al
20
3for shell.Wherein use ethyl orthosilicate, Ludox or waterglass and aluminum nitrate for raw material.Although it is selective that above catalyst has improved activity and the dimethyl ether of catalyst to a certain extent, because heat treatment mode is all roasting, and evaluating catalyst all carries out at fixed bed reactors, so all there is the short problem of catalyst life in various degree.
The Zhang Qiang of this seminar reports the > > < < sial proportioning of publishing an article to mention during the catalyst performance of slurry state bed one-step method preparing dimethy ether is affected to > > and be analogous to preparation method of the present invention in < < Institutes Of Technology Of Taiyuan, and the present invention selects in the synthetic precipitation method of methyl alcohol, silicon source and charging sequence has all been made very large change.
Summary of the invention
The object of this invention is to provide a kind of for starching state bed synthesis gas catalyst for producing dimethyl ether and its preparation method and application, the method is simple to operate, raw materials used be easy to get and cost low, on the basis of CuZnAl catalyst, introduce Ludox, can improve performance and the stability of catalyst, can increase substantially again the selective of dimethyl ether, and reduce CO
2output.After evaluating 360h, still can keep higher catalyst activity and dimethyl ether selective.
Of the present inventionly a kind ofly for starching the preparation of state bed synthesis gas catalyst for producing dimethyl ether and the aim of application, be, apply the complete liquid phase method (patent No.: CN1314491) of this seminar, on original Cu-Zn-Al catalyst basis, introduce the Ludox of different model different content, and then significantly reduce cost of material, improve the activity of catalyst, the selective and stability of dimethyl ether.Its concrete technical scheme is as follows:
For starching a preparation method for state bed synthesis gas catalyst for producing dimethyl ether, described in it, catalyst is by following steps gained:
A) by the nitrate mixed solution of copper, zinc and aluminium and sodium carbonate liquor co-precipitation, gained precipitation solution to be carried out aging, gained precipitation is methanol synthesis catalyst presoma; It is characterized in that: in nitrate mixed solution used, the molal weight ratio of institute's cupric, zinc, aluminium is 1 ~ 6:1 ~ 5:0.5 ~ 3, bath temperature is 50 ~ 80 ℃, and Flow Velocity is 1.0mL/min ~ 13ml/min, pH=7 ~ 10 during titration end-point, obtain methanol synthesis catalyst presoma;
B) after gained precipitation filtering and washing, be distributed to ultrasonic agitation in ethanol and obtain suspension together with surfactant; Described different surfaces activating agent is PVP or PEG;
C) by Ludox with by the solution of the formulated hexamethylene diamine of hexamethylene diamine+water+ethanol, splash into above-mentioned b) in step gained suspension, after mixing completely, then to add solution concentration be 1 ~ 20mol/L, the aluminum nitrate solution that consumption is 5 ~ 40mL; Aging after splashing into completely, suction filtration obtains catalyst precursor; The solution of Ludox, hexamethylene diamine and the addition sequence of aluminum nitrate solution can be adjusted;
D) span-80 that is 0.1 ~ 1mL by gained catalyst precursor and volume joins in the atoleine of 300 ~ 400mL and heat-treats, and obtains the target catalyst of pulpous state.
On the basis of technique scheme, additional technical scheme is as follows.
Described surfactant is PEG200, PEG400 or PVP, and its consumption is 1 ~ 5g.
Described Ludox is SW-20,25,30, JN-25,30,40, and JX-15, JA-25, ZA-25 and JK-25 model, consumption is 5 ~ 60mL.
The volume ratio of described each component of hexamethylene diamine solution is: Ji bis-An ﹕ Shui ﹕ ethanol=5 ~ 15mL ﹕ 1 ~ 10mL ﹕ 5 ~ 15mL.
Described steps d) in, add after span-80, be warming up to 250 ~ 400 ℃ and heat-treat 3 ~ 10 hours.
For starching an application for the catalyst that the preparation method of state bed synthesis gas catalyst for producing dimethyl ether obtains, described in it, application conditions is: reaction temperature is 250 ~ 350 ℃, and pressure is 3 ~ 5MPa, CO/H
2=1, flow is 40 ~ 400ml/min.
Technique scheme of the present invention, a kind of for starching state bed synthesis gas catalyst for producing dimethyl ether and its preparation method and application, compared with prior art, there is following outstanding substantive distinguishing features and marked improvement:
Method for preparing catalyst provided by the present invention is simple to operate, is raw materials usedly the market raw material that is easy to get, and low price, has good economic outlook.
Catalyst prepared by the present invention can increase substantially catalyst activity and dimethyl ether is selective, and its average CO conversion ratio can reach more than 58%, and DME selectively also can bring up to more than 80%.
The complete liquid phase method of catalyst utilization provided by the present invention, the problem of the organic media environment when having solved traditional catalyst surface state and can not fine adaptation using, thus high catalyst of life-span in slurry reactor is provided.The catalyst of preparing by method provided by the present invention still can maintain original high activity after evaluating 360h.Therefore be conducive to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is Catalyst for CO conversion ratio and the selective temporal evolution trend of DME of the embodiment of the present invention 8.
The specific embodiment
Below be only preferred embodiment of the present invention, can not limit scope of the present invention with this.The equalization of generally doing according to the present patent application the scope of the claims changes and modifies, and all should still remain within the scope of the patent.
Embodiment 1
Cu (the NO that is 2:1:4 by the certain proportion configuring
3)
2, Zn (NO
3)
2and Al (NO
3)
3the Na of mixed solution and 1mol/L
2cO
3solution under the condition of 50 ℃ of water-baths and vigorous stirring and drip add, and Flow Velocity is 1.0ml/min, is added dropwise to complete rear pH=7.0 ~ 7.2, continues to stir 2h, suction filtration, washing; Be distributed in ethanol under ultrasonic agitation condition with 1g PVP afterwards.After dispersion finishes, under room temperature and intense agitation, by 5mlJN-30 model Ludox and the hexamethylene diamine ethanolic solution (1mLH preparing
2o+5mL ethanol+5mL hexamethylene diamine) and drip enter wherein, after being added dropwise to complete, then the aluminum nitrate solution that is 1mol/L by concentration slowly splashes into, and then continues reaction and stirs 4h.Mixture suction filtration by gained, obtains catalyst precursor.Catalyst precursor and 0.1mLspan-80 are joined in 350mL atoleine, and low whipping speed is 400r/min and N
2under protective condition, be slowly warming up to after 250 ℃, maintain 8h, obtain slurried catalyst.
Prepared slurried catalyst is put into the reactor of 50ml, sample through 250 ℃ with containing 20%H
2and 80%N
2mist carry out, after temperature programmed reduction 10h, at reducing atmosphere, dropping to after 50 ℃, switch to synthesis gas, and be slowly forced into 3Mp, CO/H
2=1, total flow is 200ml/min.Temperature programming to 250 ℃ more afterwards.Product is by the on-line analysis of GC-950 type gas-chromatography.Acquired results is listed in table 1.
Embodiment 2
Cu (the NO that is 2:1:0.8 by the certain proportion configuring
3)
2, Zn (NO
3)
2and Al (NO
3)
3the Na of mixed solution and 1mol/L
2cO
3solution under the condition of 70 ℃ of water-baths and vigorous stirring and drip add, and Flow Velocity is 1.8ml/min, is added dropwise to complete rear pH=7.0 ~ 7.2, continues to stir 2h, suction filtration, washing; Be distributed in ethanol under ultrasonic agitation condition with the PVP of 5g afterwards.After dispersion finishes, all the other steps are identical with embodiment 1.Acquired results is listed in table 1.
Evaluating catalyst condition is identical with embodiment 1.
Embodiment 3
According to the mode Kaolinite Preparation of Catalyst of embodiment 2, difference be catalyst preparation process a) Ludox used be SW-25 model.
Prepared slurried catalyst is put into the reactor of 500ml, sample through 250 ℃ with containing 20%H
2and 80%N
2mist carry out, after temperature programmed reduction 10h, at reducing atmosphere, dropping to after 50 ℃, switch to synthesis gas, and be slowly forced into 4Mp, CO/H
2=1, total flow is 100ml/min.Temperature programming to 280 ℃ more afterwards.Product is by the on-line analysis of GC-950 type gas-chromatography.Acquired results is listed in table 1.
Embodiment 4
The certain proportion configuring is the Cu (NO of 4:3:3
3)
2, Zn (NO
3)
2and Al (NO
3)
3the Na of mixed solution and 1mol/L
2cO
3solution under the condition of 70 ℃ of water-baths and vigorous stirring and drip add, and Flow Velocity is 8.0ml/min, is added dropwise to complete rear pH=7.0 ~ 7.2, continues to stir 3h, suction filtration, washing; Be distributed in ethanol under ultrasonic agitation condition with 8.5g PEG200 afterwards.After dispersion finishes, under room temperature and intense agitation, by 15mlJX-15 model Ludox and the hexamethylene diamine ethanolic solution (5mLH preparing
2o+15mL ethanol+15mL hexamethylene diamine) and drip enter wherein, after being added dropwise to complete, then the aluminum nitrate solution that is 3mol/L by concentration slowly splashes into, and then continues reaction and stirs 4h.Mixture suction filtration by gained, obtains catalyst precursor.Catalyst precursor and 0.5mLspan-80 are joined in 300mL atoleine, and low whipping speed is 400r/min and N
2under protective condition, be slowly warming up to after 300 ℃, maintain 4h, obtain slurried catalyst.
Evaluating catalyst condition is identical with embodiment 3.
Embodiment 5
In preparation process, select ZA-25 model Ludox, and institute's consumption is 30mL, all the other preparations are consistent with embodiment 4.
Prepared slurried catalyst is put into the reactor of 500ml, sample through 280 ℃ with containing 20%H
2and 80%N
2mist carry out, after temperature programmed reduction 10h, at reducing atmosphere, dropping to after 50 ℃, switch to synthesis gas, and be slowly forced into 5Mp, CO/H
2=1, total flow is 400ml/min.Temperature programming to 280 ℃ more afterwards.Product is by the on-line analysis of GC-950 type gas-chromatography.Acquired results is listed in table 1.
Embodiment 6
The certain proportion configuring is the Cu (NO of 3:2:2
3)
2, Zn (NO
3)
2and Al (NO
3)
3the Na of mixed solution and 1mol/L
2cO
3solution under the condition of 80 ℃ of water-baths and vigorous stirring and drip add, and Flow Velocity is 11.0ml/min, is added dropwise to complete rear pH=10, continues to stir 3h, suction filtration, washing; Be distributed in ethanol under ultrasonic agitation condition with 8.5g PEG400 afterwards.After dispersion finishes, under room temperature and intense agitation, first 15mlJN-40 model Ludox is splashed into wherein, after dripping off completely, then by the hexamethylene diamine ethanolic solution (5mLH preparing
2o+5mL ethanol+8mL hexamethylene diamine) being 5mol/L with concentration, aluminum nitrate solution drip enter wherein, after being added dropwise to complete, then continuing reaction and stir 6h.Mixture suction filtration by gained, obtains catalyst precursor.Catalyst precursor and 1mLspan-80 are joined in liquid 320mL paraffin, and low whipping speed is 400r/min and N
2under protective condition, be slowly warming up to after 300 ℃, maintain 8h, obtain slurried catalyst.
Evaluating catalyst condition is identical with embodiment 5.Acquired results is listed in table 1.
Embodiment 7
In implementation step, first by the hexamethylene diamine ethanolic solution (3mLH preparing
2o+10mL ethanol+8mL hexamethylene diamine) splash into wherein, after mixing completely, the aluminum nitrate solution that is 5mol/L by concentration and 15mLJN-20 model Ludox drip enter wherein.All the other steps are identical with embodiment 6.
Evaluating catalyst condition is identical with embodiment 5.Acquired results is listed in table 1.
Embodiment 8
Cu (the NO that is 2:1:1 by the certain proportion configuring
3)
2, Zn (NO
3)
2and Al (NO
3)
3the Na of mixed solution and 1mol/L
2cO
3solution under the condition of 70 ℃ of water-baths and vigorous stirring and drip add, and Flow Velocity is 1.8.0ml/min, is added dropwise to complete rear pH=7.0 ~ 7.2, continues to stir 2h, suction filtration, washing; Be distributed in ethanol under ultrasonic agitation condition with 4g PVP afterwards.After dispersion finishes, under room temperature and intense agitation, by 45mlJN-30 model Ludox and the hexamethylene diamine ethanolic solution (5mLH preparing
2o+10mL ethanol+10mL hexamethylene diamine) and drip enter wherein, after being added dropwise to complete, then the aluminum nitrate solution that is 2mol/L by concentration slowly splashes into, and then continues reaction and stirs 6h.Mixture suction filtration by gained, obtains catalyst precursor.Catalyst precursor and 0.5mLspan-80 are joined in 350mL atoleine, and low whipping speed is 400r/min and N
2under protective condition, be slowly warming up to after 280 ℃, maintain 8h, obtain slurried catalyst.
Prepared slurried catalyst is put into the reactor of 500ml, sample through 280 ℃ with containing 20%H
2and 80%N
2mist carry out, after temperature programmed reduction 10h, at reducing atmosphere, dropping to after 50 ℃, switch to synthesis gas, and be slowly forced into 5Mp, CO/H
2=1, total flow is 100ml/min.Temperature programming to 280 ℃ more afterwards.Product is by the on-line analysis of GC-950 type gas-chromatography.Acquired results is listed in table 1
Embodiment 9
Cu (the NO that is 2:1:1 by the certain proportion configuring
3)
2, Zn (NO
3)
2and Al (NO
3)
3the Na of mixed solution and 1mol/L
2cO
3solution under the condition of 70 ℃ of water-baths and vigorous stirring and drip add, and Flow Velocity is 1.8.0ml/min, is added dropwise to complete rear pH=10, continues to stir 2h, suction filtration, washing; Be distributed in ethanol under ultrasonic agitation condition with 4g PEG200 afterwards.All the other steps are identical with embodiment 8.
Evaluating catalyst condition is identical with embodiment 8.Acquired results is listed in table 1.
Embodiment 10
According to the mode Kaolinite Preparation of Catalyst of embodiment 8, difference is that catalyst prepares Ludox and adopt to place expired Ludox.
Evaluating catalyst condition is identical with embodiment 8.Acquired results is listed in table 1.
Embodiment 11
Mode Kaolinite Preparation of Catalyst according to embodiment 8
Prepared slurried catalyst is put into the reactor of 50ml, sample through 350 ℃ with containing 20%H
2and 80%N
2mist carry out, after temperature programmed reduction 10h, at reducing atmosphere, dropping to after 50 ℃, switch to synthesis gas, and be slowly forced into 4Mp, CO/H
2=1, total flow is 80ml/min.Temperature programming to 300 ℃ more afterwards.Product is by the on-line analysis of GC-950 type gas-chromatography.Acquired results is listed in table 1.
Embodiment 12
Mode Kaolinite Preparation of Catalyst according to embodiment 6.
Evaluating catalyst condition is identical with embodiment 11.Acquired results is listed in table 1.
Embodiment 13
Using model instead is the Ludox 60mL of SW-30, and all the other steps are according to embodiment 4 preparations.
Evaluating catalyst condition is identical with embodiment 8.Acquired results is listed in table 1.
Embodiment 14
Cu (the NO that is 1.5:1:0.6 by the certain proportion configuring
3)
2, Zn (NO
3)
2and Al (NO
3)
3the Na of mixed solution and 1mol/L
2cO
3solution under the condition of 70 ℃ of water-baths and vigorous stirring and drip add, and Flow Velocity is 1.80 ml/min, is added dropwise to complete rear pH=10, continues to stir 2h, suction filtration, washing; Be distributed in ethanol under ultrasonic agitation condition with 4gPVP afterwards.In addition in heat treatment step: catalyst precursor and 0.5mLspan-80 are joined in atoleine, and low whipping speed is 400r/min and N
2under protective condition, be slowly warming up to after 280 ℃, maintain 5h, obtain slurried catalyst.All the other steps are identical with embodiment 8.
Evaluating catalyst condition is identical with embodiment 11.Acquired results is listed in table 1.
Table 1
Each embodiment catalyst performance index of table 1.
Claims (6)
1. for starching a method for state bed synthesis gas catalyst for producing dimethyl ether, described in it, catalyst is gained by the following method:
A) by the nitrate mixed solution of copper, zinc and aluminium and sodium carbonate liquor co-precipitation, gained precipitation solution to be carried out aging, gained precipitation is the presoma of methanol synthesis catalyst; It is characterized in that: in nitrate mixed solution used, the molal weight ratio of institute's cupric, zinc, aluminium is 1 ~ 6:1 ~ 5:0.5 ~ 3, bath temperature is 50 ~ 80 ℃, and Flow Velocity is 1.0mL/min ~ 13ml/min, pH=7 ~ 10 during titration end-point, obtain methanol synthesis catalyst presoma;
B) after gained precipitation filtering and washing, be distributed to ultrasonic agitation in ethanol and obtain suspension together with surfactant;
C) by Ludox with by the formulated hexamethylene diamine solution of hexamethylene diamine+water+ethanol, splash into above-mentioned b) in step gained suspension, after mixing completely, adding solution concentration is 1 ~ 20mol/L, the aluminum nitrate solution that consumption is 5 ~ 40mL; Splash into rear completely aging, suction filtration and obtain catalyst precursor; The solution of Ludox, hexamethylene diamine and the addition sequence of aluminum nitrate solution can be adjusted;
D) span-80 that is 0.1 ~ 1mL by gained catalyst precursor and volume joins in the atoleine of 300 ~ 400mL and heat-treats, and obtains the target catalyst of pulpous state.
2. preparation method according to claim 1, described in it, surfactant is PEG200, PEG400 or PVP, its consumption is 1 ~ 5g.
3. preparation method according to claim 1, described in it, Ludox is SW-20,25,30, JN-25,30,40, JX-15, JA-25, ZA-25 and JK-25 model, consumption is 5 ~ 60mL.
4. preparation method according to claim 1, described in it, the volume ratio of each component of hexamethylene diamine solution is: Ji bis-An ﹕ Shui ﹕ ethanol=5 ~ 15mL ﹕ 1 ~ 10mL ﹕ 5 ~ 15mL.
5. preparation method according to claim 1, steps d described in it), add after span-80, be warming up to 250 ~ 400 ℃ and heat-treat 3 ~ 10 hours.
6. an application for the catalyst that preparation method according to claim 1 obtains, described in it, application conditions is: reaction temperature is 250 ~ 350 ℃, pressure is 3 ~ 5MPa, CO/H
2=1, flow is 40 ~ 400ml/min.
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| CN110498738A (en) * | 2018-05-17 | 2019-11-26 | 中国科学院大连化学物理研究所 | A kind of method of direct preparation of dimethyl ether by using synthesis gas |
| CN113181897A (en) * | 2021-05-11 | 2021-07-30 | 太原理工大学 | Zn-Al slurry catalyst, preparation method thereof and application thereof in preparation of ethanol from synthesis gas |
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| CN103949258B (en) | 2016-08-17 |
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