CN104646049A - Preparation method of catalyst for directly synthesizing dimethyl ether from synthesis gas - Google Patents
Preparation method of catalyst for directly synthesizing dimethyl ether from synthesis gas Download PDFInfo
- Publication number
- CN104646049A CN104646049A CN201310590717.1A CN201310590717A CN104646049A CN 104646049 A CN104646049 A CN 104646049A CN 201310590717 A CN201310590717 A CN 201310590717A CN 104646049 A CN104646049 A CN 104646049A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- material liquid
- grams
- preparation
- dimethyl ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The present invention relates to a preparation method of a catalyst for directly synthesizing dimethyl ether from synthesis gas, wherein the problems of high catalyst synthesis cost and low dimethyl ether selectivity in the prior art are mainly solved through the preparation method of the present invention. According to the preparation method of the present invention, inorganic salts of Cu, Zn and Al are adopted as a methanol synthesis active component raw material, an HY molecular sieve, alpha-Al2O3, or an H-ZSM-5 molecular sieve is adopted as a methanol dehydration active component, a low carbon alcohol is adopted as a solvent, a silica sol, an alumina sol or white carbon black is adopted as a binder, a method selected from rotary evaporation, spray drying method and flash evaporation is adopted to dry, the obtained powder is calcined, then is added with graphite or cellulose ether and other processing aids, and is subjected to extrusion forming to prepare catalyst particles, and calcination is performed again so as to prepare the catalyst. According to the present invention, the catalyst production process is simple, the catalyst has characteristics of high activity, good selectivity, excellent activity at high space velocity, and high dimethyl ether time space yield, and the preparation method can be used for the industrial production of direct preparation of the dimethyl ether from the synthesis gas.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst of direct synthesis of dimethyl ether from synthesis gas.
Background technology
Dimethyl ether is a kind of simple organic ether compounds, is the colourless gas having mild flavor under normal temperature and pressure, at present main as spraying paint, hair jelly, air freshener and automobile-used Alevaire.In addition, dimethyl ether or a kind of clean energy resource, can use as automobile and domestic fuel.Dimethyl ether fuel has that efficiency is high, environmentally friendly, use safety and the advantage such as of many uses, has wide industrial prospect.
At present, the production method of dimethyl ether has two-step method and one-step method.Two-step method is methyl alcohol by Synthetic holography, then methanol dehydration is converted into dimethyl ether.And one-step synthesis method dimethyl ether is a kind of new technology developed in recent years, namely use a kind of bifunctional catalyst, it comprises methanol-fueled CLC component and methanol dehydration component, two reactions are carried out at same reactor.One-step method greatly enhances the conversion per pass of CO compared with two-step method.
At present, the patent of one-step synthesis method dimethyl ether catalyst is open a lot, such as US Patent No. 4098809, US 4177167, US 4375424, US 3894102, US 4417000, Japan Patent JP63254188, NKK house journal US 6147125, EP 1174408, and Chinese patent CN 1047105C, CN 1043739C, CN1131108C, CN 1176742C.Catalyst in these patents is bifunctional catalyst, namely using copper-based catalysts as methanol synthesis catalyst with using solid acid as methanol dehydration catalyst, combines respectively by mechanical mixture, co-precipitation, immersing hydrogels.But the poor catalyst activity of mechanical mixture, coprecipitation introduces Na
+ion, needs repeatedly to wash, and preparation process is complicated, poor repeatability.Immersing hydrogels method, with anhydrous ethanol, normal propyl alcohol or isopropyl alcohol for solvent, oxalic acid solubility in ethanol or propyl alcohol is low, and alcohol consumption is high, and precipitation need be filtered and be washed with alcohol, and then dry, process is complicated, and with high costs.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of direct synthesis of dimethyl ether from synthesis gas catalyst, the method is by revolving the dry or spraying dry of evaporate to dryness or flash distillation will precipitate and separated from solvent, obtain pressed powder, add the intensity that adhesive not only increases catalyst, and also improve catalytic performance, processing aid makes catalyst fines can be processed into any required form, to meet dissimilar reaction bed demand.In sum, the method not only simplify building-up process, improves the service efficiency of raw material, make catalyst production process simple, and reproducible, production cost reduces, and prepared catalyst has very high catalytic activity and dimethyl ether selectivity to direct synthesis of dimethyl ether from synthesis gas reaction.Low-carbon alcohols is reusable through condensation.
The present invention realizes above-mentioned purpose technical scheme:
First the inorganic salts of Cu, Zn, Al are dissolved in low-carbon alcohols and make raw material A.As the slurry preparing methanol-fueled CLC component.Then methanol dehydration component is directly joined in above-mentioned mixed solution A, stir and obtain material liquid B.In material liquid B, under agitation add the low-carbon alcohol solution material liquid C containing oxalic acid, add binding agent in the oxalate coprecipitation thing that reaction generates, drying obtains powder, after first time roasting, through extrusion molding after mixing with processing aid, obtained described catalyst after roasting again.
The inorganic salts of described Cu are one or more in copper nitrate, copper sulphate, copper chloride, and the inorganic salts of Zn are one or more in zinc nitrate, zinc sulfate, zinc chloride, and the inorganic salts of Al are one or two or more kinds in aluminum nitrate, aluminum sulfate, aluminium chloride.The mol ratio of each constituent atoms is Cu:Zn:Al=5 ~ 7:2 ~ 4:1, and that optimum is 5.5 ~ 6.5:2.5 ~ 3.5:1.
Described low-carbon alcohols is one or two or more kinds mixture of absolute methanol, absolute ethyl alcohol, anhydrous isopropyl alcohol, anhydrous normal butyl alcohol.
The total concentration of the described inorganic salts containing Cu, Zn, Al is 80 ~ 500g/L.
Described methanol dehydration component is HY molecular sieve, α-Al
2o
3, one or two or more kinds mixture in H-ZSM-5 molecular sieve, in methanol dehydration component and methanol-fueled CLC component, Cu, Zn, Al inorganic salts are converted to the mass ratio of the gross mass of metal oxide is 1:1 ~ 4, is 1:2 ~ 3.5 preferably.
The oxalic acid mass concentration of the described low-carbon alcohol solution containing oxalic acid is 10 ~ 30%, is 15 ~ 25% preferably.
The mass ratio of described oxalic acid and Cu inorganic salts is 0.7 ~ 1.2:1, is 0.9 ~ 1.1:1 preferably.
Described binding agent is one or two or more kinds in Ludox, Alumina gel, white carbon, and its addition is finally obtain catalyst quality 5 ~ 20%, is 10 ~ 15% preferably.
Described processing aid is one or two or more kinds mixture in graphite, CMC, hydroxyethylcellulose, methyl hydroxyethylcellulose, ethylhydroxyethylcellulose, methylhydroxypropylcellulose, xanthans, and the addition of processing aid is finally obtain catalyst fines quality 0 ~ 10%.
Described first time sintering temperature is 200 ~ 500 DEG C, and roasting time is 2 ~ 16 hours.Second time sintering temperature is 200 ~ 400 DEG C, and roasting time is 2 ~ 10 hours.
When described use H-ZSM-5 molecular sieve is as methanol dehydration component, its silica alumina ratio is 30 ~ 300.
Described drying means is that vacuum revolves that evaporate to dryness is dry, spraying dry, one in flash distillation.
Described catalyst was both applicable to fixed bed, or was also applicable to moving bed or fluidized-bed reaction.
Catalyst in the present invention can be used for the reaction of direct synthesis of dimethyl ether from synthesis gas, H in synthesis gas
2: CO=1 ~ 6:1(volume ratio), and can a certain amount of N be contained
2, CH
4, CO
2, reaction pressure is 3 ~ 6MPa, and reaction temperature is 200 ~ 350 DEG C, and synthesis gas air speed is 1500 ~ 7000h
-1, reactor both can be fixed bed, also can be fluid bed.
Advantage of the present invention is that process is simple, reduces Catalyst Production cost, and alcohol reclaims can avoid contaminated environment, improve speed of production, be easy to automation, obtained catalyst activity is high, selective good, under higher space velocity, there is excellent activity, improve the production efficiency of dimethyl ether.
Detailed description of the invention
Below by embodiment, the present invention will be described, but therefore the present invention is not subject to any restriction.
Catalyst activity evaluation method:
In continuous fixed bed reactor, load 2mL catalyst (20-40 order), use H
2and N
2gaseous mixture (H
2percentage by volume is 12%) reduce according to certain heating schedule at ambient pressure, with 1.5 DEG C/min from room temperature to 160 DEG C, then be warming up to 240 DEG C with 0.5 DEG C/min, keep constant temperature 8 hours at 240 DEG C.Then synthesis gas is passed into, H
2: CO=7:3(volume ratio), reaction pressure is 4MPa, and reaction temperature is 250 DEG C, and reaction velocity is 3000h
-1.
Embodiment 1
Taking copper nitrate 13.6 grams, zinc nitrate 6.7 grams, aluminum nitrate 4.2 grams, be dissolved in 60mL absolute methanol, is material liquid A.
Add 1.7 grams of HY molecular sieves to material liquid A, stir and form material liquid B.
9.5g oxalic acid is dissolved in 70mL absolute methanol, and forming clear solution, is material liquid C.
Material liquid C is joined in material liquid B, form light blue suspension, add after 1.5 grams of Ludox (quality solid content 30%) are uniformly mixed, pour in rotary evaporation bottle, rotary evaporation in vacuo is to dry, absolute methanol is reclaimed by condensation, and dry solid abrasive powdered, 350 DEG C of roastings 4 hours.
Get the powder after 9.000 grams of roastings and 0.009 gram of graphite through ground and mixed, by extrusion shaping machine extrusion molding, obtain 20 ~ 40 order particles, 300 DEG C of roastings 4 hours, as catalyst.Evaluation result is in table 1.
Embodiment 2
Taking 14.3 grams, copper sulphate, 7.1 grams, zinc sulfate, 5.5 grams, aluminum sulfate, be dissolved in 60mL absolute ethyl alcohol, is material liquid A.
6.7 grams of α-Al are added to material liquid A
2o
3, stir and form material liquid B
12.9g oxalic acid is dissolved in 70mL absolute ethyl alcohol, and forming clear solution, is material liquid C.
Material liquid C is joined in material liquid B, form light blue suspension, add 10 grams of Alumina gel (solid content 25%), be uniformly mixed, then pour in rotary evaporation bottle, rotary evaporation in vacuo is to dry, and absolute ethyl alcohol is reclaimed by condensation, dry solid abrasive powdered, 350 DEG C of roastings 4 hours.
Dry after 9.9 grams, powder after roasting mixes with the 5g CMC aqueous solution (mass fraction 2%), solid abrasive powdered, 300 DEG C of roastings 4 hours, by extrusion shaping machine extrusion molding, obtains 20 ~ 40 order particles, as catalyst.Evaluation result is in table 1.
Embodiment 3
Taking copper chloride 8.4 grams, zinc chloride 4.5 grams, 1.1 grams, aluminium chloride, be dissolved in 60mL anhydrous isopropyl alcohol, is material liquid A.
Add 2.9 grams of H-ZSM-5 molecular sieves (Si/Al=30) to material liquid A, stir and form material liquid B.
9.2g oxalic acid is dissolved in 70mL anhydrous isopropyl alcohol, and forming clear solution, is material liquid C.
Joined in material liquid B by material liquid C, form light blue suspension, add 1.1 grams of white carbons, be uniformly mixed, so spray-dried, obtain catalyst granules, dry solid abrasive powdered, 350 DEG C of roastings 4 hours.
Dry after 9.8 grams, powder after roasting mixes with the 10g CMC aqueous solution (mass fraction 2%), solid abrasive powdered, 300 DEG C of roastings 4 hours, by extrusion shaping machine extrusion molding, obtains 20 ~ 40 order particles, as catalyst.Evaluation result is in table 1.
Embodiment 4
Taking copper nitrate 13.1 grams, 7.8 grams, zinc sulfate, 1.2 grams, aluminium chloride, be dissolved in 60mL anhydrous normal butyl alcohol, is material liquid A.
Add 4.5 grams of H-ZSM-5 molecular sieves (Si/Al=100) to material liquid A, stir and form material liquid B.
16.2g oxalic acid is dissolved in 70mL anhydrous normal butyl alcohol, and forming clear solution, is material liquid C.
Material liquid C is joined in material liquid B, form light blue suspension, add Ludox (solid content is 30%) 2.0 grams, be uniformly mixed, then pour rotary evaporation bottle into, rotary evaporation in vacuo is to dry, and anhydrous normal butyl alcohol is reclaimed by condensation, dry solid abrasive powdered, 350 DEG C of roastings 4 hours.
Dry after 9 grams, powder after roasting mixes with the 50g CMC aqueous solution (mass fraction 2%), solid abrasive powdered, 300 DEG C of roastings 4 hours, by extrusion shaping machine extrusion molding, obtains 20 ~ 40 order particles, as catalyst.Evaluation result is in table 1.
Embodiment 5
Taking 15.7 grams, copper sulphate, zinc chloride 4.9 grams, aluminum nitrate 3.4 grams, be dissolved in 60mL absolute methanol, is material liquid A.
Add 2.9 grams of H-ZSM-5 molecular sieves (Si/Al=300) to material liquid A, stir and form material liquid B.
12.6g oxalic acid is dissolved in 70mL absolute methanol, and forming clear solution, is material liquid C.
Material liquid C is joined in material liquid AB, forms light blue suspension, add 2 grams of Alumina gel (solid content 25%), be uniformly mixed, then carry out flash distillation, to dry, absolute methanol is reclaimed by condensation, and dry solid abrasive powdered, 350 DEG C of roastings 4 hours.
Dry after 9.8 grams, powder after roasting mixes with the 5g CMC aqueous solution (mass fraction 2%), solid abrasive powdered, 300 DEG C of roastings 4 hours, by extrusion shaping machine extrusion molding, obtains 20 ~ 40 order particles, as catalyst.Evaluation result is in table 1.
Embodiment 6
Take copper chloride 9.2 grams, 7.8 grams, zinc sulfate, aluminum nitrate 3.36 grams, being dissolved in the methyl alcohol of 60mL recovery, is material liquid A.
Add 2.9 grams of H-ZSM-5 molecular sieves (Si/Al=30) to material liquid A, stir and form material liquid B.
10.1g oxalic acid is dissolved in the methyl alcohol that 60mL reclaims, and forming clear solution, is material liquid C.
Joined in material liquid B by material liquid C, form light blue suspension, after adding 0.5 gram of white carbon mixing, pour rotary evaporation bottle into, rotary evaporation in vacuo is to dry, and absolute methanol is reclaimed by condensation, and dry solid abrasive powdered, 350 DEG C of roastings 4 hours.
Dry after 9.9 grams, powder after roasting mixes with the 5g CMC aqueous solution (mass fraction 2%), solid abrasive powdered, 300 DEG C of roastings 4 hours, by extrusion shaping machine extrusion molding, obtains 20 ~ 40 order particles, as catalyst.Evaluation result is in table 1.
Embodiment 7
Taking copper nitrate 13.1 grams, zinc nitrate 8.1 grams, aluminum nitrate 3.4 grams, be dissolved in 60mL absolute methanol, is material liquid A.
Add 2.9 grams of H-ZSM-5 molecular sieves (Si/Al=30) to material liquid A, stir and form material liquid B.
13.1g oxalic acid is dissolved in 70mL absolute methanol, and forming clear solution, is material liquid C.
Material liquid C is joined in material liquid B, forms light blue suspension, add 3.6 gram of 30% Ludox, pour in rotary evaporation bottle after mixing, rotary evaporation in vacuo is to dry, and absolute methanol is reclaimed by condensation, dry solid abrasive powdered, 500 DEG C of roastings 2 hours.
Dry after 9.9 grams, powder after roasting mixes with 5 grams of xanthan gum solutions (mass fraction 2%), solid abrasive powdered, 400 DEG C of roastings 2 hours, by extrusion shaping machine extrusion molding, obtains 20 ~ 40 order particles, as catalyst.Evaluation result is in table 1.
Embodiment 8
Taking copper nitrate 13.1 grams, zinc nitrate 8.1 grams, aluminum nitrate 3.4 grams, be dissolved in 60mL absolute methanol, is material liquid A.
Add 2.9 grams of H-ZSM-5 molecular sieves (Si/Al=30) to material liquid A, stir and form material liquid B.
13.1g oxalic acid is dissolved in 70mL absolute methanol, and forming clear solution, is material liquid C.
Joined in material liquid B by material liquid C, form light blue suspension, add 5.6 gram of 30% Ludox (solid content 30%), carry out spraying dry after mixing, dry solid abrasive powdered, 450 DEG C of roastings 2 hours.
Dry after 9.5 grams, powder after roasting mixes with 25g hydroxyethyl cellulose aqueous solution (mass fraction 2%), solid abrasive powdered, 400 DEG C of roastings 2 hours, by extrusion shaping machine extrusion molding, obtains 20 ~ 40 order particles, as catalyst.Evaluation result is in table 1.
Embodiment 9
Taking copper nitrate 13.1 grams, zinc nitrate 8.1 grams, aluminum nitrate 3.4 grams, be dissolved in 60mL absolute methanol, is material liquid A.
Add 2.9 grams of H-ZSM-5 molecular sieves (Si/Al=30) to material liquid A, stir and form material liquid B.
13.1g oxalic acid is dissolved in 70mL absolute methanol, and forming clear solution, is material liquid C.
Joined in material liquid B by material liquid C, form light blue suspension, add 7.8 grams of Ludox (solid content 30%), carry out spraying dry after mixing, dry solid abrasive powdered, 400 DEG C of roastings 2 hours.
Dry after 9.5 grams, powder after roasting mixes with 25g hydroxyethyl cellulose aqueous solution (mass fraction 2%), solid abrasive powdered, 350 DEG C of roastings 2 hours, by extrusion shaping machine extrusion molding, obtains 20 ~ 40 order particles, as catalyst.Evaluation result is in table 1.
Embodiment 10
Taking copper nitrate 13.1 grams, zinc nitrate 8.1 grams, aluminum nitrate 3.4 grams, be dissolved in 60mL absolute methanol, is material liquid A.
Add 2.9 grams of H-ZSM-5 molecular sieves (Si/Al=30) to material liquid A, stir and form material liquid B.
13.1g oxalic acid is dissolved in 70mL absolute methanol, and forming clear solution, is material liquid C.
Joined in material liquid B by material liquid C, form light blue suspension, add 3.6 grams of Ludox (solid content 30%), carry out expansion drying after mixing, dry solid abrasive powdered, 350 DEG C of roastings 4 hours.
Dry after 9.5 grams, powder after roasting mixes with 25g hydroxyethyl cellulose aqueous solution (mass fraction 2%), solid abrasive powdered, 350 DEG C of roastings 2 hours, by extrusion shaping machine extrusion molding, obtains 20 ~ 40 order particles, as catalyst.Evaluation result is in table 1.
Embodiment 11
Taking copper nitrate 13.1 grams, zinc nitrate 8.1 grams, aluminum nitrate 3.4 grams, be dissolved in 60mL absolute methanol, is material liquid A.
Add 2.9 grams of H-ZSM-5 molecular sieves (Si/Al=50) to material liquid A, stir and form material liquid B.
13.1g oxalic acid is dissolved in 70mL absolute methanol, and forming clear solution, is material liquid C.
Joined in material liquid B by material liquid C, form light blue suspension, add 3.6 grams of Ludox (solid content 30%), carry out spraying dry after mixing, dry solid abrasive powdered, 300 DEG C of roastings 4 hours.
Dry after 9.5 grams, powder after roasting mixes with 25g hydroxyethyl cellulose aqueous solution (mass fraction 2%), solid abrasive powdered, 300 DEG C of roastings 4 hours, by extrusion shaping machine extrusion molding, obtains 20 ~ 40 order particles, as catalyst.Evaluation result is in table 1.
Embodiment 12
Taking copper nitrate 13.05 grams, zinc nitrate 8.04 grams, aluminum nitrate 3.36 grams, be dissolved in 60mL absolute methanol, is material liquid A.
Add 3.2 grams of H-ZSM-5 molecular sieves (Si/Al=50) to material liquid A, stir and form material liquid B.
12.5g oxalic acid is dissolved in 70mL absolute methanol, and forming clear solution, is material liquid C.
Joined in material liquid B by material liquid C, form light blue suspension, then carry out spraying dry, dry solid abrasive powdered, 350 DEG C of roastings 6 hours.
By extrusion shaping machine extrusion molding after powder after roasting mixes with 25g hydroxyethyl cellulose aqueous solution (mass fraction 2%), obtain 20 ~ 40 order particles, 350 DEG C of roastings 6 hours are as catalyst.Evaluation result is in table 1.
Table 1 evaluating catalyst result
| CO conversion ratio (/ %) | Dimethyl ether selectivity (/ %) | |
| Embodiment 1 | 55 | 67 |
| Embodiment 2 | 24 | 65 |
| Embodiment 3 | 40 | 70 |
| Embodiment 4 | 36 | 69 |
| Embodiment 5 | 52 | 67 |
| Embodiment 6 | 63 | 67 |
| Embodiment 7 | 30 | 67 |
| Embodiment 8 | 38 | 68 |
| Embodiment 9 | 44 | 67 |
| Embodiment 10 | 81 | 69 |
| Embodiment 11 | 53 | 67 |
| Embodiment 12 | 33 | 67 |
Catalyst production process technique of the present invention is simple, and catalyst activity is high, selective good, and under higher space velocity, have excellent activity, dimethyl ether space-time yield is high, can be used in the industrial production of direct preparation of dimethyl ether by using synthesis gas.
Claims (10)
1., by a preparation method for direct synthesis of dimethyl ether from synthesis gas catalyst, comprise the following steps:
The inorganic salts of Cu, Zn, Al are dissolved in low-carbon alcohols and make material liquid A, as the slurry preparing methanol-fueled CLC component by a;
Methanol dehydration component directly joins in above-mentioned mixed solution A by b, stirs and obtains material liquid B;
C under agitation adds the low-carbon alcohol solution material liquid C containing oxalic acid in material liquid B, binding agent is added in the oxalate coprecipitation thing that reaction generates, drying obtains powder, after first time roasting, mix with processing aid or do not mix with processing aid, directly through extrusion molding, obtained described catalyst after roasting again.
2. method according to claim 1, is characterized in that:
In step a: the inorganic salts containing Cu are one or two or more kinds in copper nitrate, copper sulphate, copper chloride; Inorganic salts containing Zn are one or two or more kinds in zinc nitrate, zinc sulfate, zinc chloride; Inorganic salts containing Al are one or two or more kinds in aluminum nitrate, aluminum sulfate, aluminium chloride;
The mol ratio of each constituent atoms is Cu:Zn:Al=5 ~ 7:2 ~ 4:1.
3. method according to claim 1 and 2, is characterized in that:
Low-carbon alcohols is one or two or more kinds mixture of absolute methanol, absolute ethyl alcohol, anhydrous isopropyl alcohol, anhydrous normal butyl alcohol;
In step a: the total concentration containing the inorganic salts of Cu, Zn, Al is 80 ~ 500g/L.
4. the method according to claim 1,2 or 3, is characterized in that:
In step b: methanol dehydration component is HY molecular sieve, α-Al
2o
3, one or two or more kinds mixture in H-ZSM-5 molecular sieve, in methanol dehydration component and methanol-fueled CLC component, Cu, Zn, Al inorganic salts are converted to the mass ratio of the gross mass of metal oxide is 1:1 ~ 4.
5. method according to claim 1, is characterized in that:
The oxalic acid mass concentration of the low-carbon alcohol solution containing oxalic acid is 10 ~ 30%;
In step c: the mass ratio of oxalic acid and Cu inorganic salts is 0.7 ~ 1.2:1.
6. method according to claim 1, is characterized in that:
Binding agent used is one or two or more kinds in Ludox, Alumina gel, white carbon, and it adds quality is finally obtain catalyst quality 5 ~ 20%;
Processing aid is one or two or more kinds mixture in graphite, CMC, hydroxyethylcellulose, methyl hydroxyethylcellulose, ethylhydroxyethylcellulose, methylhydroxypropylcellulose, xanthans, and addition is finally obtain catalyst fines quality 0 ~ 10%.
7. method according to claim 1, is characterized in that: sintering temperature is 200 ~ 500 DEG C for the first time, and roasting time is 2 ~ 16 hours; Second time sintering temperature is 200 ~ 400 DEG C, and roasting time is 2 ~ 10 hours.
8. method according to claim 4, is characterized in that: when using H-ZSM-5 molecular sieve as methanol dehydration component, its silica alumina ratio is 30 ~ 300.
9. method according to claim 1, is characterized in that: drying means is that vacuum revolves that evaporate to dryness is dry, spraying dry, one in flash distillation.
10. method according to claim 1, is characterized in that: the catalyst of preparation was both applicable to fixed bed, or is also applicable to moving bed or fluidized-bed reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310590717.1A CN104646049A (en) | 2013-11-20 | 2013-11-20 | Preparation method of catalyst for directly synthesizing dimethyl ether from synthesis gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310590717.1A CN104646049A (en) | 2013-11-20 | 2013-11-20 | Preparation method of catalyst for directly synthesizing dimethyl ether from synthesis gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104646049A true CN104646049A (en) | 2015-05-27 |
Family
ID=53237981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310590717.1A Pending CN104646049A (en) | 2013-11-20 | 2013-11-20 | Preparation method of catalyst for directly synthesizing dimethyl ether from synthesis gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104646049A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363456A (en) * | 2015-11-05 | 2016-03-02 | 华东理工大学 | Copper-based catalyst and preparation method and application thereof |
| US20210046464A1 (en) * | 2019-08-15 | 2021-02-18 | Exxonmobil Research And Engineering Company | Acid/metal bifunctional catalyst produced by extrusion |
| US20210046460A1 (en) * | 2019-08-15 | 2021-02-18 | Exxonmobil Research And Engineering Company | Metal catalyst synthesis and acid/metal bifunctional catalyst systems thereof |
| US20210046461A1 (en) * | 2019-08-15 | 2021-02-18 | Exxonmobil Research And Engineering Company | Metal catalysts with low -alkali metal content and acid/metal bifunctional catalyst systems thereof |
| US20210046470A1 (en) * | 2019-08-15 | 2021-02-18 | Exxonmobil Research And Engineering Company | Acid/metal bifunctional catalyst systems produced with carbon coatings |
| WO2021056572A1 (en) * | 2019-09-24 | 2021-04-01 | 东北大学 | Aluminum shared metal-zeolite bifunctional catalyst, and preparation method and application |
| US11602734B2 (en) | 2019-08-15 | 2023-03-14 | ExxonMobil Technology and Engineering Company | Acid/metal bifunctional catalysts produced by slurry methods |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02280836A (en) * | 1989-04-21 | 1990-11-16 | Mitsubishi Heavy Ind Ltd | Preparation of catalyst for dimethyl ether synthesis |
| 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 |
| CN101722029A (en) * | 2008-10-30 | 2010-06-09 | 邹运湖 | Method for preparing catalyst for synthesizing dimethyl ether on fluidized bed |
| CN101940934A (en) * | 2009-07-09 | 2011-01-12 | 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 |
-
2013
- 2013-11-20 CN CN201310590717.1A patent/CN104646049A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02280836A (en) * | 1989-04-21 | 1990-11-16 | Mitsubishi Heavy Ind Ltd | Preparation of catalyst for dimethyl ether synthesis |
| 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 |
| CN101722029A (en) * | 2008-10-30 | 2010-06-09 | 邹运湖 | Method for preparing catalyst for synthesizing dimethyl ether on fluidized bed |
| CN101940934A (en) * | 2009-07-09 | 2011-01-12 | 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 |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363456A (en) * | 2015-11-05 | 2016-03-02 | 华东理工大学 | Copper-based catalyst and preparation method and application thereof |
| US20210046464A1 (en) * | 2019-08-15 | 2021-02-18 | Exxonmobil Research And Engineering Company | Acid/metal bifunctional catalyst produced by extrusion |
| US20210046460A1 (en) * | 2019-08-15 | 2021-02-18 | Exxonmobil Research And Engineering Company | Metal catalyst synthesis and acid/metal bifunctional catalyst systems thereof |
| US20210046461A1 (en) * | 2019-08-15 | 2021-02-18 | Exxonmobil Research And Engineering Company | Metal catalysts with low -alkali metal content and acid/metal bifunctional catalyst systems thereof |
| US20210046470A1 (en) * | 2019-08-15 | 2021-02-18 | Exxonmobil Research And Engineering Company | Acid/metal bifunctional catalyst systems produced with carbon coatings |
| US11602734B2 (en) | 2019-08-15 | 2023-03-14 | ExxonMobil Technology and Engineering Company | Acid/metal bifunctional catalysts produced by slurry methods |
| US11638912B2 (en) | 2019-08-15 | 2023-05-02 | ExxonMobil Technology and Engineering Company | Metal catalyst synthesis and acid/metal bifunctional catalyst systems thereof |
| US11654421B2 (en) * | 2019-08-15 | 2023-05-23 | ExxonMobil Technology and Engineering Company | Metal catalysts with low-alkali metal content and acid/metal bifunctional catalyst systems thereof |
| US11691139B2 (en) * | 2019-08-15 | 2023-07-04 | ExxonMobil Technology and Engineering Company | Acid/metal bifunctional catalyst systems produced with carbon coatings |
| US11819818B2 (en) * | 2019-08-15 | 2023-11-21 | ExxonMobil Technology and Engineering Company | Acid/metal bifunctional catalyst produced by extrusion |
| WO2021056572A1 (en) * | 2019-09-24 | 2021-04-01 | 东北大学 | Aluminum shared metal-zeolite bifunctional catalyst, and preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104646049A (en) | Preparation method of catalyst for directly synthesizing dimethyl ether from synthesis gas | |
| Ji et al. | Conversion of CO 2 into cyclic carbonates by a Co (ii) metal–organic framework and the improvement of catalytic activity via nanocrystallization | |
| CN105170097A (en) | TiO2/ZIF-8 nanocomposite with core-shell structure and preparation method of TiO2/ZIF-8 nanocomposite | |
| CN102302934B (en) | Novel auxiliary-modified catalyst for preparing methanol by catalytic hydrogenation of carbon dioxide and preparation method of catalyst | |
| CN104624196B (en) | A kind of high-specific surface area fischer-tropsch synthetic catalyst and preparation method and application | |
| WO2022021506A1 (en) | Preparation of ultrathin porous carbon nitride nano-photocatalyst and applications thereof in photocatalytically oxidizing fructose to synthesize lactic acid | |
| MX2014009856A (en) | New generation kaolin based paint pigment extender. | |
| CN112403526A (en) | Ce-MOF/Bi2MoO6Heterojunction photocatalyst and preparation method and application thereof | |
| CN104785261B (en) | Oxalate hydrogenation catalyst synthesized by mixed silicon source method and preparation method thereof | |
| CN101983765B (en) | Catalyst for preparing methyl alcohol by catalytic hydrogenation on assistant modified carbon dioxide and preparation method thereof | |
| CN108499607A (en) | A kind of Preparation method and use of Quito aqueous acid medium alkali bifunctional MOFs pore catalyst | |
| CN101455976A (en) | Effective catalyst used in hydrogenation of dimethyl oxalate to synthesizing ethylene glycol and production method thereof | |
| CN112517012B (en) | CO (carbon monoxide)2Preparation method and application of catalyst for preparing methanol by hydrogenation | |
| CN105195156A (en) | Preparation method and application of high-dispersity copper-based catalyst | |
| CN112007637B (en) | Bimetallic alloy-halloysite composite catalyst and preparation method and application thereof | |
| CN107335446A (en) | A kind of cobalt-base catalyst and its preparation and application that mixed alcohol is produced for one-step method from syngas | |
| CN103212418A (en) | Dual-function catalyst for directly preparing dimethyl ether from synthesis gas and preparation method of dual-function catalyst | |
| CN105153058A (en) | Synthetic method of benzotriazoles compound | |
| CN109894140A (en) | A kind of preparation method and its catalytic applications of solid base hydrotalcite supported precious metal catalyst | |
| CN101269331A (en) | Process for producing high-stability central-hole material Cu-Zn-Al2O3, and application of the same in producing mellow wine dehydrogenating catalyst | |
| CN100567240C (en) | A kind of method of synthesizing 2-ethoxy-phenol | |
| CN109574798A (en) | A kind of method that synthesis gas directly produces ethyl alcohol | |
| CN103551154B (en) | Preparation methods and catalysis method of dimethyl maleate hydrogenation catalyst | |
| CN111286035B (en) | Zn (II) complex based on 4, 4' -dicarboxylic acid dimethyl azobenzene and adenine and synthetic method and application thereof | |
| CN115403782B (en) | Two-dimensional metal organic frame material containing sulfur and nitrogen groups, conjugated bimetal organic frame material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150527 |