CN101773836A - Method for synthesizing dimethyl ether catalyst by hydrogenation of carbon dioxide under catalysis of CuO-ZnO-Al2O3/modified montmorillonite - Google Patents
Method for synthesizing dimethyl ether catalyst by hydrogenation of carbon dioxide under catalysis of CuO-ZnO-Al2O3/modified montmorillonite Download PDFInfo
- Publication number
- CN101773836A CN101773836A CN201010046321A CN201010046321A CN101773836A CN 101773836 A CN101773836 A CN 101773836A CN 201010046321 A CN201010046321 A CN 201010046321A CN 201010046321 A CN201010046321 A CN 201010046321A CN 101773836 A CN101773836 A CN 101773836A
- Authority
- CN
- China
- Prior art keywords
- dimethyl ether
- zno
- cuo
- catalyst
- carbon dioxide
- 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
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for synthesizing dimethyl ether catalyst by the hydrogenation of carbon dioxide under the catalysis of CuO-ZnO-Al2O3/modified montmorillonite. According to the method, CuO-ZnO-Al2O3/modified montmorillonite compound catalyst is prepared by the steps of (1) synthesis of methanol catalyst; (2) preparation of dehydrating agent; and (3) preparation of catalyst. Using montmorillonite as methanol dehydrating agent for the first time, the invention provides a method for directly synthesizing dimethyl ether by the hydrogenation of carbon dioxide under the catalysis of CuO-ZnO-Al2O3/modified montmorillonite, which is simple in preparing catalyst, low in preparation cost and good in activity.
Description
Technical field
The present invention relates to the Preparation of catalysts method, exactly, is a kind of CuO-ZnO-Al
2O
3The method of/modified montmorillonoid catalysis hydrogenation of carbon dioxide synthesizing dimethyl ether catalyst.
Background technology
CO
2The hydrogenation preparing dimethy ether is one of effective way of rationally utilizing carbon dioxide.(dimethylether DME) is a kind of important chemical material to dimethyl ether, in industries such as medicine, agricultural chemicals, dyestuff, household chemicals purposes is widely arranged.In recent years, along with the progress of dimethyl ether synthetic technology and the reduction of production cost, it is that the replacement liquid gasification is made domestic fuel and alternative diesel oil is made motor vehicle fuel that dimethyl ether is the most directly used.Because Application of dimethyl ether is more and more wider, particularly dimethyl ether has huge market potential as clean fuel, and there is important practical sense aspects such as the adjustment of energy resource structure, environmental protection, therefore both at home and abroad its research is more and more paid attention to.At present, CO
2The hydrogenation catalyst agent method mainly contains the co-precipitation infusion process, and (Tan Jingpin is etc. hydrogenation of carbon dioxide dimethyl ether synthesis CuO-ZnO-Al for Liu Zhijian, Liao Jianjun
2O
3The research [J] of/HZSM-5 type catalyst. Industrial Catalysis, 2002,10 (2): 46-49), precipitation of joint sedimentation (Zhao Yanqiao, Chen Jixiang, Zhang Jiyan. precipitation temperature is to the influence [J] of hydrogenation of carbon dioxide synthesizing dimethyl ether catalyst. Chemical Reaction Engineering and technology, 2007,23 (5): 456-461) with even gel method (Davis S C, Klabunde K J.Unsupported small metal particles:preparation, reactivity, and characterization[J] .Chem Rev, 1982,82:153-208) etc., and the simplest with the operation of coprecipitation infusion process.The synthesizing methanol by hydrogenating carbon dioxide catalyst is a major catalyst with the Cu-Zn base mainly, and adds auxiliary agent such as Al
2O
3, SiO
2, MgO, TiO
2, ZrO
2, Ga
2O
3Wait and improve catalytic activity.Imvite is a kind of alumino-silicate clays mineral with layer structure, and its reserves is abundant, distribution is wide, cheap.Because the imvite through modification can be made various well behaved functional materials, and multi-field playing a significant role such as environmental protection, catalysis, medicine, but the research of modified montmorillonoid and metal oxide acting in conjunction catalysis hydrogenation of carbon dioxide synthesizing dimethyl ether catalyst does not appear in the newspapers as yet.
Summary of the invention
In view of the foregoing, the object of the present invention is to provide a kind of new cheap CuO-ZnO-Al
2O
3The method of/modified montmorillonoid catalysis hydrogenation of carbon dioxide synthesizing dimethyl ether catalyst.
The object of the present invention is achieved like this:
A kind of CuO-ZnO-Al
2O
3The method of/modified montmorillonoid catalysis hydrogenation of carbon dioxide synthesizing dimethyl ether catalyst the steps include:
(1) catalst for synthesis of methanol: the copper zinc-aluminium nitrate of certain mass ratio is dissolved in an amount of distilled water dissolves, in temperature is the sodium carbonate liquor that adds a certain amount of 1mol/L under the 343K, stir 10min, keep 343K to leave standstill certain hour, be filtered to neutrality, dry by the fire 12h at a certain temperature, with the product roasting at a certain temperature 4 hours of oven dry, catalst for synthesis of methanol;
(2) preparation of dehydrating agent: a certain amount of original montmorillonoid soil is added in a certain amount of distilled water, stir, the turbid solution of getting the upper strata filters, and the imvite of filtering gained is dried at a certain temperature, places round-bottomed flask, add certain density HCl solution, room temperature leaves standstill 24h, suction filtration, and washing is to neutral, the solid of gained is dried by the fire 12h at a certain temperature, get dehydrating agent;
(3) Preparation of catalysts: the catalst for synthesis of methanol of described step (1) gained is mixed by a certain percentage with (2) prepared dehydrating agent, be ground to 40～60 orders, get CuO-ZnO-Al
2O
3/ modified montmorillonoid composite catalyst.
The quality of copper zinc-aluminium nitrate is 6: 3: 1 according to its oxide mass ratio in the above-mentioned steps (1).
Imvite mixes by 1: 10 with water in the above-mentioned steps (2).
Catalyst for methanol mixes by mass ratio with imvite at 7: 3 in the above-mentioned steps (3).
It is generally acknowledged that dimethyl ether comes from the CO hydrogenation.CO
2At first become CO by hydrogen reducing, generate methyl alcohol by the CO hydrogenation again, methanol dehydration obtains dimethyl ether, and the reaction mechanism mechanism of reaction is as follows:
CO
2→CO→CH
3OH→CH
3OCH
3
This kind reaction mechanism can explain preferably that catalyst is to the relation between unstripped gas absorption property and the product distribution, i.e. CO
2With H
2Occur on the different catalytic sites CO at the adsorption activation on the catalyst
2The surface intermediate that forms behind the adsorption activation directly decomposes generation CO, if there is the hydrogen of suitable adsorption strength to exist nearby, this intermediate obtains methyl alcohol with further hydrogenation, dehydrating agent acid montmorillonite of the present invention provides a H proton for methanol molecules, thereby the formation leaving group, and form carbonium ion CH
3 +, ADSORPTION STATE methanol molecules and carbonium ion generation nucleophilic substitution generate dimethyl ether then.
CuO-ZnO-Al
2O
3The physicochemical property of/modified montmorillonoid composite catalyst:
Color form: black powder;
Particle diameter 150-250 μ m;
BET is 185.667m
2/ g;
Pore volume is 1.033cm
3/ g.
Advantage of the present invention:
1. the imvite raw material is easy to get, and is cheap.
World's montmorillonite resource is very abundant, is widely distributed.Statistics shows that world's montmorillonite gross reserves is about 2,500,000,000 tons, and wherein the reserves of the U.S., the former Soviet Union and China account for 3/4 of world saving, secondly are Italy, Greece, Australia and German.China's montmorillonite rich in mineral resources, proved reserves are more than 2,000,000,000 tons, and reserves should occupy first place in the world greater than 7,000,000,000 tons, and the ultra-large type mineral deposit is arranged.China's montmorillonite 90% is a ca-montmorillonite.Known montmorillonite resource distribution is in 23 provinces and regions, found that the ore deposit puts 400 many places, verifies nearly hundred places, mine.Large ore deposit more than 20, most of mineral deposits concentrate on provinces such as three provinces in the northeast of China and Xinjiang, Gansu, Guangxi.
2. the preparation method is simple.
Only need simple acidification is carried out in imvite, just can make imvite never dehydration property to higher dehydration property has been arranged.The XRD of imvite before and after the acidifying is compared, and as can be seen from Figure 1, the intensity of acidifying postpeak obviously reduces, and illustrates that the acidifying rear impurity reduces.
3. the selectivity of dimethyl ether and productive rate are higher.
Table 1 shows that the selectivity of dimethyl ether synthesis of the present invention and productive rate are all than higher.And than other the Catalysts Cu O-ZnO-Al of dimethyl ether synthesis
2O
3-Cr
2O
3/ modified paligorskite has more excellent performance.
Table 1 the present invention and CuO-ZnO-Al
2O
3-Cr
2O
3The comparison of/modified paligorskite catalyst
(reaction condition: pressure 3MPa, reaction temperature 545K, hydrogen-carbon ratio 3)
By table 1 more as can be seen, the methyl alcohol of gained of the present invention, the selectivity of dimethyl ether and productive rate are all than like product CuO-ZnO-Al
2O
3-Cr
2O
3The height of/modified paligorskite.
5. the good reproducibility of catalyst.
The catalyst of this experiment gained is carried out the secondary use, and the productive rate of its dimethyl ether and yield all do not have to reduce.
Description of drawings
The XRD figure of imvite before and after Fig. 1 acidifying is among the figure: a-original montmorillonoid soil, imvite after the b-1.0mol/LHCl acidifying.
Fig. 2 is the influence of reaction pressure to dimethyl ether.
Fig. 3 is H
2With CO
2Volume ratio is to the influence of dimethyl ether.
Fig. 4 is the influence of reaction temperature to dimethyl ether.
The specific embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described again:
Step 1: the electronic balance of the BS224S type of producing with Beijing Sai Duolisi instrument system Co., Ltd takes by weighing 9.11g Cu (NO
3)
2, 5.48g Zn (NO
3)
2, 1.84g Al (NO
3)
3Be dissolved in the 70ml distilled water, add in the 250ml round-bottomed flask, place DF-101S heat collecting type heated at constant temperature magnetic stirring apparatus (Great Wall, Zhengzhou science, industry and trade also Co., Ltd produce) to be heated to 343K round-bottomed flask,, add the NaCO of 1mol/L rapidly
3Solution 75ml, vigorous stirring 10min keeps 343K to leave standstill 4h.Filtering and washing is extremely neutral repeatedly to pour products obtained therefrom into husky star funnel, puts into baking oven, and 343K is baking 12h down, puts into chamber type electric resistance furnace, roasting 4h under the 623K.
Step 2:
(1) gets imvite 8g and add in the 1000ml beaker and add water 800ml, stir 1min, leave standstill 10min, go the upper strata turbid solution to pour husky star funnel suction filtration into, products obtained therefrom is put into baking oven, at 343K baking 12h with glass bar.
(2) imvite with (1) gained adds 0.2mol/L respectively, 0.5mol/L, and 1.0mol/L in the hydrochloric acid of 2.0mol/L, soaks 10h, is filtered to neutrality respectively, dries by the fire 8h under 343K.
Step 3: the catalst for synthesis of methanol CuO-ZnO-Al that takes by weighing the step 1 gained
2O
30.7g the prepared dehydrating agent imvite of step 2 0.3g puts into agate mortar and grinds 5min, forms CuO-ZnO-Al
2O
3/ modified montmorillonoid composite catalyst.
Acidifying concentration, reaction pressure, hydrogen-carbon ratio, reaction temperature are to the composite catalyst Effect on Performance
(1) with the CuO-ZnO-Al of step 3 gained
2O
3/ modified montmorillonoid composite catalyst differential high pressure the micro-reaction device (WR-04 type, Tianjin roc Xiang Science and Technology Ltd.) of packing into, at reaction pressure 3MPa, hydrogen-carbon ratio 3 is reacted data such as table 2 under the reaction temperature 545K.
Table 2 acid concentration is to the influence of catalytic performance
As can be seen from Table 2: can not catalytic synthesising dimethyl ether without the composite catalyst of superacidulated montmorillonite load, along with the increase of acid concentration, CO
2Conversion ratio along with increase, when acid concentration reached 1.0mol/L, it is maximum that the selectivity of dimethyl ether and productive rate reach.Along with acid concentration continues to increase CO
2Conversion ratio tends towards stability, and the selectivity of accessory substance CO obviously increases, and the selectivity and the productive rate of dimethyl ether all descend.Illustrate that catalytic effect was best when acid concentration was 1.0mol/L.Before and after Fig. 1 acidifying the XRD figure of imvite more as can be seen: imvite is lower than not-acidified imvite crest after the acidifying.
(2) Fig. 2 is that other condition is constant, the catalytic effect of composite catalyst under the differential responses pressure.As can be seen from the figure, reaction pressure raises and helps the generation of dimethyl ether.With improving constantly of reaction pressure, CO
2Conversion ratio improve constantly, but the selectivity of dimethyl ether and productive rate raise earlier, reaches maximum when 3MPa, reduces then.
(3) other conditions are constant, change hydrogen-carbon ratio and obtain Fig. 3.As can be seen from the figure, hydrogen-carbon ratio increases, CO
2Conversion ratio improves constantly, and the selectivity of dimethyl ether constantly raises, but when hydrogen-carbon ratio increases to 3, CO
2Conversion ratio begins to descend, and the productive rate of dimethyl ether and methyl alcohol also begins to descend.So hydrogen-carbon ratio is that 3 o'clock catalytic effects are best.
(4) Fig. 4 is the catalytic effect figure of composite catalyst under the differential responses temperature.As can be seen from the figure, with the rising of reaction temperature, CO
2Conversion ratio is along with increase, but the selectivity of dimethyl ether and methyl alcohol raises earlier and afterwards descend, and when reaction temperature reached 545K, the selectivity of dimethyl ether and yield reached maximum, and catalytic effect was best when promptly reaction temperature was 545K.
Can obtain from (1)-(4), the prepared composite catalyst of crossing with the hcl acidifying of 1mol/L of imvite, at reaction temperature 545K, reaction pressure 3MPa, hydrogen-carbon ratio is that 3 o'clock catalytic effects are best.The selectivity of dimethyl ether and productive rate are respectively 16.7% and 4.4%.
Claims (4)
1. CuO-ZnO-Al
2O
3The method of/modified montmorillonoid catalysis hydrogenation of carbon dioxide synthesizing dimethyl ether catalyst may further comprise the steps:
(1) catalst for synthesis of methanol: the copper zinc-aluminium nitrate of certain mass ratio is dissolved in an amount of distilled water dissolves, in temperature is the sodium carbonate liquor that adds a certain amount of 1mol/L under the 343K, stir 10min, keep 343K to leave standstill certain hour, be filtered to neutrality, dry by the fire 12h at a certain temperature, with the product roasting at a certain temperature 4 hours of oven dry, catalst for synthesis of methanol;
(2) preparation of dehydrating agent: a certain amount of original montmorillonoid soil is added in a certain amount of distilled water, stir, get the upper strata turbid solution and filter, the imvite of filtering gained is dried at a certain temperature, place round-bottomed flask, add certain density HCl solution, room temperature leaves standstill 24h, suction filtration, and washing is to neutral, the solid of gained is dried by the fire 12h at a certain temperature, get dehydrating agent;
(3) Preparation of catalysts: the catalst for synthesis of methanol of described step (1) gained is mixed by a certain percentage with (2) prepared dehydrating agent imvite, be ground to 40～60 orders, get CuO-ZnO-Al
2O
3/ modified montmorillonoid composite catalyst.
2. a kind of CuO-ZnO-Al according to claim 1
2O
3The method of/modified montmorillonoid catalysis hydrogenation of carbon dioxide synthesizing dimethyl ether catalyst is characterized in that: the quality of copper zinc-aluminium nitrate is 6: 3: 1 by the mass ratio of its oxide in the step (1).
3. a kind of CuO-ZnO-Al according to claim 1
2O
3The method of/modified montmorillonoid catalysis hydrogenation of carbon dioxide synthesizing dimethyl ether catalyst is characterized in that: the mass ratio of original montmorillonoid soil and water is 1: 10 in the step (2).
4. a kind of CuO-ZnO-Al according to claim 1
2O
3The method of/modified montmorillonoid catalysis hydrogenation of carbon dioxide synthesizing dimethyl ether catalyst is characterized in that: catalyst for methanol mixes by mass ratio with imvite at 7: 3 in the step (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010046321A CN101773836A (en) | 2010-01-14 | 2010-01-14 | Method for synthesizing dimethyl ether catalyst by hydrogenation of carbon dioxide under catalysis of CuO-ZnO-Al2O3/modified montmorillonite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010046321A CN101773836A (en) | 2010-01-14 | 2010-01-14 | Method for synthesizing dimethyl ether catalyst by hydrogenation of carbon dioxide under catalysis of CuO-ZnO-Al2O3/modified montmorillonite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101773836A true CN101773836A (en) | 2010-07-14 |
Family
ID=42510500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010046321A Pending CN101773836A (en) | 2010-01-14 | 2010-01-14 | Method for synthesizing dimethyl ether catalyst by hydrogenation of carbon dioxide under catalysis of CuO-ZnO-Al2O3/modified montmorillonite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101773836A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614882A (en) * | 2012-03-07 | 2012-08-01 | 中国科学院山西煤炭化学研究所 | Low temperature methanol cracking catalyst for methanol-fueled automobiles as well as preparation method thereof and application thereof |
| CN105618088A (en) * | 2016-01-28 | 2016-06-01 | 中国科学院上海高等研究院 | Copper fluoride based hydrotalcite-like catalyst, method for preparing same and application of copper fluoride based hydrotalcite-like catalyst |
| CN114436773A (en) * | 2022-01-28 | 2022-05-06 | 湘潭大学 | Method for improving carbon dioxide hydrogenation conversion rate through coupling dehydration |
-
2010
- 2010-01-14 CN CN201010046321A patent/CN101773836A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614882A (en) * | 2012-03-07 | 2012-08-01 | 中国科学院山西煤炭化学研究所 | Low temperature methanol cracking catalyst for methanol-fueled automobiles as well as preparation method thereof and application thereof |
| CN102614882B (en) * | 2012-03-07 | 2013-10-30 | 中国科学院山西煤炭化学研究所 | Low temperature methanol cracking catalyst for methanol-fueled automobiles as well as preparation method thereof and application thereof |
| CN105618088A (en) * | 2016-01-28 | 2016-06-01 | 中国科学院上海高等研究院 | Copper fluoride based hydrotalcite-like catalyst, method for preparing same and application of copper fluoride based hydrotalcite-like catalyst |
| CN105618088B (en) * | 2016-01-28 | 2018-09-25 | 中国科学院上海高等研究院 | A kind of copper fluoride base class hydrotalcite catalyst and its preparation method and application |
| CN114436773A (en) * | 2022-01-28 | 2022-05-06 | 湘潭大学 | Method for improving carbon dioxide hydrogenation conversion rate through coupling dehydration |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102229520B (en) | Method for preparing alcohol by acetic acid gas phase hydrogenation | |
| CN103084178B (en) | Copper-contained hydrotalcite-based catalyst for preparing mixed alcohol by using synthesis gas as well as preparation method and application thereof | |
| CN105582935B (en) | A kind of copper zinc composite oxide, preparation method and the usage | |
| CN102716749B (en) | Auxiliary agent-modified catalyst for CO-CO2 co-hydrogenation synthesis of methanol | |
| CN106076346B (en) | Catalyst, preparation method and application for methanol steam catalytically reforming hydrogen producing | |
| CN103785418A (en) | Cobalt tin catalyst for preparing alcohol by carboxylic acid hydrogenation | |
| CN108586392A (en) | A kind of method that 5 hydroxymethyl furfural add in-place hydrogen prepares 2,5- dimethyl furans | |
| CN107586254B (en) | Method for synthesizing ethylene glycol by hydrogenating oxalate | |
| CN113198520B (en) | One-pot preparation method of molecular sieve supported palladium carbon catalyst and application of molecular sieve supported palladium carbon catalyst in synthesis of dimethyl carbonate by gas phase method | |
| CN108404918A (en) | Tumer ester through hydrogenation produces the copper zinc SiO 2 catalyst and preparation method thereof of ethyl alcohol | |
| Kong et al. | Production of liquid fuel intermediates from furfural via aldol condensation over La2O2CO3-ZnO-Al2O3 catalyst | |
| CN103464159B (en) | Copper-iron based catalyst and application thereof in preparing low mixed alcohols by catalyzing synthesis gas | |
| CN101972648A (en) | Modified Mn-Zr catalyst as well as preparation method and application thereof to preparing dimethyl ether | |
| CN101428229B (en) | Catalyst for synthesis of gas produced low-carbon mixed alcohol and production method thereof | |
| CN103613483B (en) | A kind of layering loading catalyst prepares the application in low-carbon alcohol at synthetic gas | |
| CN101773836A (en) | Method for synthesizing dimethyl ether catalyst by hydrogenation of carbon dioxide under catalysis of CuO-ZnO-Al2O3/modified montmorillonite | |
| CN104710282A (en) | Method for production of ethanol and co-production of methanol | |
| CN102863335A (en) | Preparation method of diethyl succinate | |
| CN101722001A (en) | Composite catalyst for dimethyl ether synthesis and preparation method and application thereof | |
| CN106810419A (en) | For graphene-supported metal composite in acetic acid preparation of ethanol through hydrogenation catalyst and preparation method thereof | |
| CN103408032B (en) | Method for supercritical hydrothermal synthesis of flyash zeolite | |
| CN101934232B (en) | Method for preparing catalyst for directly synthesizing dimethyl ether by biomass gasifiable synthesis gas | |
| CN100438979C (en) | Preparation of hydrocarbon molecular sieve catalyst by methanol transformation | |
| CN102319566A (en) | Copper cobalt Si catalyst of synthesis gas preparation low-carbon alcohols and preparation method thereof | |
| CN104841448B (en) | Organic silicon waste contact body borne nickel-based methanation catalyst and preparation method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20100714 |