CN1338332A - Catalyst for preparing dimethyl ether and its preparing process - Google Patents
Catalyst for preparing dimethyl ether and its preparing process Download PDFInfo
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- CN1338332A CN1338332A CN 00121542 CN00121542A CN1338332A CN 1338332 A CN1338332 A CN 1338332A CN 00121542 CN00121542 CN 00121542 CN 00121542 A CN00121542 A CN 00121542A CN 1338332 A CN1338332 A CN 1338332A
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Abstract
A catalyst for preparing dimethylether by hydrogenating CO2 is prepared from active component (copper oxdie, zinc oxide, and activated carbon and/or alumine and/or zirconium oxide) and zeolite carrier which may be H beta zeolite or one of P-contained HZSM-5, HY and H beta zeolites through mixing the suspension solution of zeolite, assistant and alcohol with the alcohol solution of soluble copper slat, zinc salt, aluminium salt and/or zirconium salt, adding alcohol solution of oxalic acid, ageing, filtering, drying and calcining. Its advantages are high convert rate of CO2 and high selectivity of dimethylether.
Description
The invention relates to a kind of hydrogenation catalyst and preparation thereof, be used for catalyst and the preparation thereof that hydrogenation of carbon dioxide is produced dimethyl ether about a kind of more precisely.
Dimethyl ether is a kind of purposes chemical products very widely.Its both alternative CFC is made aerosol, refrigerant and blowing agent, and alternative again liquefied gas is made fuel, still produces the important source material of multiple chemical products simultaneously.
" Journal of Molecular Catalysis, 1993,7 (2), 156 " have reported the research that carbon dioxide and hydrogen are produced oxygenatedchemicals, and wherein used catalyst prepares with the following method: Cu (NO
3)
2-Zn (NO
3)
2Solution and NH
4The Cu-Zn powder that the OH co-precipitation obtains mixes with Y zeolite, drying, shaping and roasting.At reactor feed gas is H
2/ CO
2=3.3 gaseous mixture, 260 ℃ of temperature, pressure 3.0MPa, gas space velocity 2200h
-1Reaction condition under, CO
2Conversion ratio be 13.7%, the dimethyl ether selectivity is 50.22%.
" Cu-MnO/Al
2O
3CO on the catalyst
2/ H
2The low research that is pressed into methyl ether " reported the Cu-Mn series CO that adopts the coprecipitation preparation in (the 9th national catalysis academic meeting paper collection, the 203rd～204 page)
2The hydrogenation synthesizing dimethyl ether catalyst is at H
2/ CO
2=3, pressure 2.0MPa, under 300 ℃ of reaction conditions of temperature, CO
2Conversion ratio is up to 30.89%, and the dimethyl ether selectivity is up to 31.4%.
Be entitled as at one piece in the thesis for the doctorate (Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences, 1998) of " the preparation chemistry of directed preparing dimethyl ether by synthetic gas bifunctional catalyst ", reported Cu-Zn-ZrO
2/ HZSM-5 catalyst, it be with contain the nitrate solution and the sodium carbonate liquor of copper, zinc, zirconium and flow co-precipitation in, fill in the flask of distilled water, treat that precipitation finishes, after stirring, filter, washing, again sediment is added in the HZSM-5 aaerosol solution stirring, filtration, dry, the roasting preparation.This catalyst is produced in the dimethyl ether reaction at carbon dioxide, and 240 ℃, 3.5MPa, 6000h
-1Under the condition, CO
2Conversion ratio is 29.5%, and the dimethyl ether selectivity is 40.8%.
In sum, existing catalyst is used for hydrogenation of carbon dioxide one step during dimethyl ether synthesizing reaction, CO
2Conversion ratio and dimethyl ether selectivity are all lower.
The purpose of this invention is to provide a kind of catalyst, can be used for carbon dioxide one-step and produce in the reaction of dimethyl ether, make reaction have higher carbon dioxide conversion and dimethyl ether selectivity, two of purpose of the present invention provides this Preparation of catalysts method.
Catalyst provided by the invention is made up of the active component of the heavy % of 5-50 and the Zeolite support of surplus, active component is that copper zinc atom ratio is 1: the cupric oxide of 0.5-5.0 and zinc oxide and with the atomic ratio of copper be 1: (a) auxiliary agent of 0.4-10.0 or (b) auxiliary agent, wherein (a) auxiliary agent is for being selected from active carbon, a kind of in aluminium oxide or the zirconia, (b) be 1 for the zirconium al atomic ratio: the zirconia of 0.25-20.0 and the mixture of aluminium oxide, Zeolite support is H β zeolite or is selected from phosphorus and the zeolite weight ratio is 1: 5～100 phosphorous HZSM-5, HY, a kind of in three kinds of zeolites of H β
In catalyst provided by the invention, the preferable range of the copper zinc atom ratio of active component cupric oxide and zinc oxide is 1: 1-3; When active component contains (b) auxiliary agent, the zirconium al atomic ratio preferred 1 in the mixture of zirconia and aluminium oxide: 1-10; When Zeolite support was phosphorous HZSM-5, HY or H β zeolite, the weight ratio of phosphorus and zeolite preferred 1 in the carrier: 20-70.
Preparation of catalysts process provided by the invention may further comprise the steps: (1) becomes liquid volume and solid weight than the suspension that is 50～1000 with H β zeolite or phosphorous HZSM-5, HY, a kind of zeolite and active carbon among the H β or aluminium oxide and/or zirconia with the alcoholic solution preparation; (2) soluble copper salt and zinc salt are mixed with mixed solution with alcohol; (3) be 100-300 according to the ml volumes of alcohol and the gram weight of oxalic acid: 1 ratio, the alcoholic solution of preparation oxalic acid; (4) step (1) and step (2) gained two solution are mixed, in room temperature, stir under, add the oxalic acid alcoholic solution that step (3) is prepared, dropwise, aging 10～60 minutes, after filtration, dry, roasting forms.
And when aluminium oxide and/or zirconia be with its precursor, for example the form of solubility zirconates, aluminum soluble salt adds fashionablely, and Preparation of catalysts process provided by the invention may further comprise the steps: (1) becomes liquid volume and solid weight than being the suspension of 50-1000 with H β zeolite or phosphorous HZSM-5, HY, a kind of zeolite among the H β with the alcoholic solution preparation; (2) soluble copper salt, zinc salt, aluminium salt and/or zirconates are mixed with mixed solution with alcohol; (3) be 100-300 according to the ml volumes of alcohol and the gram weight of oxalic acid: 1 ratio, preparation oxalic acid
Alcoholic solution; (4) step (1) and step (2) gained two solution are mixed, in room temperature, stir under, add the oxalic acid alcoholic solution that step (3) is prepared, dropwise, aging 10～60 minutes, after filtration, dry, roasting forms.
Among the preparation method provided by the invention, said phosphorous Zeolite support component can be to obtain through following method: behind phosphorus-containing compound solution-treated HZSM-5, HY such as ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP) or H β zeolite, 400～600 ℃ of following roastings.
Said mantoquita and zinc salt are meant nitrate, sulfate or the chloride of copper or zinc, wherein preferably nitrate.
The mixture of described zirconia or zirconia and aluminium oxide, except adopting the commercial goods, also can adopt supercritical drying, following method preparation: with mixed solution and ammoniacal liquor co-precipitation under room temperature, pH value 8-10 of zirconium salt solution or zirconates and aluminium salt, sediment is through being washed to no chlorion, again after the alcohol compound washing, in the alcohol compound medium, handle more than 30 minutes down through 260 ℃, 7.5MPa, obtain ZrO
2Or ZrO
2With Al
2O
3Mixture.
Preferred zirconyl chloride of said solubility zirconates or zirconyl nitrate, the preferred aluminum nitrate of aluminum soluble salt.
Said alcohol is anhydrous alcohol solution, can be anhydrous ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol etc., wherein preferred absolute ethyl alcohol.
Catalyst provided by the invention under than low reaction pressure, has the higher and dimethyl ether selectivity height of carbon dioxide conversion, characteristics that the oxygenatedchemicals yield is high, for example consists of CuO-ZnO-Al
2O
3/ P-HZSM-5, active component accounts for 30 heavy %, and copper zinc atom ratio is 1: 1, Al: Cu=1: 1 catalyst (seeing example 30), at 3.0MPa, 245 ℃, air speed 1200h
-1, H
2/ CO
2Under=2.8 the condition, CO
2Conversion ratio is 33.94%, and the dimethyl ether selectivity is 68.25%, and the methyl alcohol selectivity is 11.46%.
This Preparation of catalysts method provided by the invention, process is simple, need not washing.
Below will the present invention is further illustrated with example.
In an embodiment, employed Na β zeolite and H β zeolite are Fushun No.3 Petroleum Factory's product, silica alumina ratio 30, Na in the Na β zeolite
2O content 1.6 (weight) %, Na in the H β zeolite
2O content＜0.1 (weight) %; Na-ZSM-5 is a Chang Ling oil plant catalyst plant product, silica alumina ratio 80, Na
2O content 2.0 (weight) %; NaY is a Qilu Petrochemical company catalyst plant product, silica alumina ratio 4.9, Na
2O content 14 (weight) %; Other reagent is the chemical pure product that the Beijing Chemical Plant produces as not specifying.
When investigating activity of such catalysts and selectivity, the pretreatment condition of catalyst is: be broken into 20～40 purpose particles behind the 30MPa lower sheeting, 280～320 ℃ of hydrogen atmospheres reduced 4 hours down.
Reaction condition is: 245 ℃ of temperature, pressure 3.0MPa, air speed 1200h
-1, reaction gas H
2/ CO
2Be 2.8.Product is made up of the gas chromatograph analysis, is detector with the conductance cell.
Example 1～10th is the Preparation of catalysts process of carrier with H β zeolite.
Example 1
Take by weighing H β zeolite 8.5 grams after the grinding and activated carbon (Qingdao Red Star chemical industry group company product) 0.17 gram and place to burn and cherish, add 500 milliliters of ethanolic solutions and make suspension.
Than 1: 2, C: Cu=1: 0.4 ratio took by weighing quantitative Cu (NO according to the copper zinc atom
3)
2, Zn (NO
3)
2Be dissolved in 500 milliliters of ethanolic solutions, this mixed solution is joined in the above-mentioned suspension.
Take by weighing 1.49 gram oxalic acid in burning the bosom, add the ethanolic solution that 300 milliliters of alcohol solvents are made into oxalic acid.
Under room temperature, stirring, at above-mentioned H β zeolite, activated carbon, the Cu (NO of containing
3)
2, Zn (NO
3)
2Aaerosol solution in, drip the ethanolic solution of oxalic acid fast, through aging 30 minutes, filter, 120 ℃ of oven dry, 350 ℃ of roastings, obtain catalyst, numbering Cl consists of CuO-ZnO-C/H β, its active component accounts for 15 heavy %, and the copper zinc atom is than 1: 2, C: Cu=1: 0.4.
Its activity and selectivity see Table 1.
Example 2
Take by weighing H β zeolite 7 grams after the grinding and activated carbon 0.06 gram and place to burn and cherish, add 500 milliliters of ethanolic solutions and make suspension.
Than 1: 3, C: Cu=1: 2 ratio took by weighing quantitative Cu (NO according to the copper zinc atom
3)
2, Zn (NO
3)
2Be dissolved in 500 milliliters of ethanolic solutions, this mixed solution is joined in the above-mentioned suspension.
Take by weighing 3.28 gram oxalic acid in burning the bosom, add the ethanolic solution that 500 milliliters of alcohol solvents are made into oxalic acid.
Under room temperature, stirring, at above-mentioned H β zeolite, activated carbon, the Cu (NO of containing
3)
2, Zn (NO
3)
2Aaerosol solution in, drip the ethanolic solution of oxalic acid fast, through aging 30 minutes, filter, 120 ℃ of oven dry, 350 ℃ of roastings obtain catalyst C2, consist of CuO-ZnO-C/H β, its active component accounts for 30 heavy %, the copper zinc atom is than 1: 3, C: Cu=1: 2.
Its activity and selectivity see Table 1.
Example 3
Take by weighing H β zeolite 7 grams after the grinding and activated carbon 0.03 gram and place to burn and cherish, add 500 milliliters of ethanolic solutions and make suspension.
Than 1: 1, C: Cu=1: 5 ratio took by weighing quantitative Cu (NO according to the copper zinc atom
3)
2, Zn (NO
3)
2Be dissolved in 500 milliliters of ethanolic solutions, this mixed solution is joined in the above-mentioned suspension.
Take by weighing 3.3 gram oxalic acid in burning the bosom, add the ethanolic solution that 500 milliliters of alcohol solvents are made into oxalic acid.
Under room temperature, stirring, at above-mentioned H β zeolite, activated carbon, the Cu (NO of containing
3)
2, Zn (NO
3)
2Aaerosol solution in, drip the ethanolic solution of oxalic acid fast, through aging 30 minutes, filter, 120 ℃ of oven dry, 350 ℃ of roastings obtain catalyst C3, consist of CuO-ZnO-C/H β, its active component accounts for 30 heavy %, the copper zinc atom is than 1: 1, C: Cu=1: 5.
Its activity and selectivity see Table 1.
Example 4
Take by weighing H β zeolite 7 grams after the grinding and activated carbon 0.01 gram and place to burn and cherish, add 500 milliliters of ethanolic solutions and make suspension.
Than 1: 2.5, C: Cu=1: 10 ratio took by weighing quantitative Cu (NO according to the copper zinc atom
3)
2, Zn (NO
3)
2Be dissolved in 500 milliliters of ethanolic solutions, this mixed solution is joined in the above-mentioned suspension.
Take by weighing 3.33 gram oxalic acid in burning the bosom, add the ethanolic solution that 500 milliliters of alcohol solvents are made into oxalic acid.
Under room temperature, stirring, at above-mentioned H type β zeolite, activated carbon, the Cu (NO of containing
3)
2, Zn (NO
3)
2Aaerosol solution in, drip the ethanolic solution of oxalic acid fast, through aging 30 minutes, filter, 120 ℃ of oven dry, 350 ℃ of roastings obtain catalyst C4, consist of CuO-ZnO-C/H β, its active component accounts for 30 heavy %, the copper zinc atom is than 1: 2.5, C: Cu=1: 10.
Its activity and selectivity see Table 1.
Example 5
Take by weighing H β zeolite 7 gram and the Al after the grinding
2O
3Burn the bosom 0.72 gram places, the ethanolic solution that adds 500 milliliters is made suspension.
Take by weighing the Cu (NO of 2.66 grams
3)
2With 2.67 gram Zn (NO
3)
2Be dissolved in 500 milliliters of ethanolic solutions, this mixed solution is joined in the above-mentioned suspension.
Take by weighing 2.55 gram oxalic acid in burning the bosom, add the ethanolic solution that 500 milliliters of alcohol solvents are made into oxalic acid.
Under room temperature, stirring, at above-mentioned H β zeolite, the Al of containing
2O
3, Cu (NO
3)
2, Zn (NO
3)
2Aaerosol solution in, drip the ethanolic solution of oxalic acid fast, through aging 30 minutes, filter, 120 ℃ of oven dry, 350 ℃ of roastings obtain catalyst C5, consist of CuO-ZnO-Al
2O
3/ H β, its active component accounts for 30 heavy %, and the copper zinc atom is than 1: 1, Al: Cu=1: 1.
Its activity and selectivity see Table 1.
Example 6
Take by weighing H β zeolite 7 gram and the Al after the grinding
2O
3Burn the bosom 0.34 gram places, the ethanolic solution that adds 500 milliliters is made suspension.
Take by weighing the Cu (NO of 3.11 grams
3)
2With 3.13 gram Zn (NO
3)
2Be dissolved in 500 milliliters of ethanolic solutions, this mixed solution is joined in the above-mentioned suspension.
Take by weighing 2.98 gram oxalic acid in burning the bosom, add the ethanolic solution that 500 milliliters of alcohol solvents are made into oxalic acid.
Under room temperature, stirring, at above-mentioned H β zeolite, the Al of containing
2O
3, Cu (NO
3)
2, Zn (NO
3)
2Aaerosol solution in, drip the ethanolic solution of oxalic acid fast, through aging 30 minutes, filter, 120 ℃ of oven dry, 350 ℃ of roastings obtain catalyst C6, consist of CuO-ZnO-Al
2O
3/ H β, its active component accounts for 30 heavy %, and the copper zinc atom is than 1: 1, Al: Cu=1: 2.5.
Its activity and selectivity see Table 1.
Example 7
Take by weighing H β zeolite 7 gram and the ZrO after the grinding
2Burn the bosom 1.3 gram places, the ethanolic solution that adds 500 milliliters is made suspension.
Take by weighing the Cu (NO of 1.99 grams
3)
2With 2.0 gram Zn (NO
3)
2Be dissolved in 500 milliliters of ethanolic solutions, this mixed solution is joined in the above-mentioned suspension.
Take by weighing 1.9 gram oxalic acid in burning the bosom, add the ethanolic solution that 500 milliliters of alcohol solvents are made into oxalic acid.Under room temperature, stirring, at above-mentioned H β zeolite, the ZrO of containing
2, Cu (NO
3)
2, Zn (NO
3)
2Aaerosol solution in, drip the ethanolic solution of oxalic acid fast, through aging 30 minutes, filter, 120 ℃ of oven dry, 350 ℃ of roastings obtain catalyst C7, consist of CuO-ZnO-ZrO
2/ H β, its active component accounts for 30 heavy %, and the copper zinc atom is than 1: 1, Zr: Cu=1: 1.
Its activity and selectivity see Table 1.
Example 8
The explanation of this example is with the ZrO of supercritical drying preparation
2The process for preparing catalyst for auxiliary agent.
At ZrOCl
2In (Liu Lidian chemical plant, Beijing is analyzed pure) aqueous solution, stir under the room temperature and add ammoniacal liquor and reach about 10 to PH, obtain ZrO
2Hydrogel wears out them 2 hours in mother liquor, and suction filtration is washed to no Cl
-, get ZrO with the water in the ethanol exchanged water gel then
2Alcogel.Alcogel is placed autoclave, add absolute ethyl alcohol, at 260 ℃, 7.5MPa handled down after 30 minutes, and logical nitrogen flooding is removed ethanol and residual water, is chilled to room temperature and gets ZrO
2Powder.
Take by weighing H β zeolite 7 grams after the grinding and the ZrO of above-mentioned preparation
2Burn the bosom 0.65 gram places, add 500 milliliters of ethanolic solutions and make suspension;
Take by weighing 2.97 gram Cu (NO
3)
2, 2.81 gram Zn (NO
3)
2Be dissolved in 500 milliliters of ethanolic solutions, this mixed solution is joined in the above-mentioned suspension;
Take by weighing 2.67 gram oxalic acid in burning the bosom, add the ethanolic solution that 500 milliliters of alcohol solvents are made into oxalic acid.Then, under room temperature, stirring, at above-mentioned H β zeolite, the ZrO of containing
2, Cu (NO
3)
2, Zn (NO
3)
2Aaerosol solution in, drip the ethanolic solution of oxalic acid fast, through aging 30 minutes, filter, 120 ℃ of oven dry, 350 ℃ of roastings obtain catalyst C8, consist of CuO-ZnO-ZrO
2/ H β, its active component accounts for 30 heavy %, and the copper zinc atom is than 1: 1, Zr: Cu=1: 3.
Its activity and selectivity see Table 1.
Example 9
The explanation of this example is with the ZrO of supercritical drying preparation
2And Al
2O
3The process for preparing catalyst for auxiliary agent.
Take by weighing 0.23 gram ZrOCl
2, 0.69 gram Al (NO
3)
3Soluble in water, stir under the room temperature and add ammoniacal liquor and reach about 10 to PH, obtain ZrO
2, Al
2O
3Hydrogel wears out them 2 hours in mother liquor, and suction filtration is washed to no Cl
-1, obtain ZrO with the water in the ethanol exchanged water gel then
2And Al
2O
3Alcogel.Alcogel is placed autoclave, add absolute ethyl alcohol, at 260 ℃, 7.5MPa handled down after 30 minutes, and logical nitrogen flooding is removed ethanol and residual water, is chilled to room temperature and gets ZrO
2/ Al
2O
3Powder.
Take by weighing H β zeolite 7 grams after the grinding and the ZrO of above-mentioned preparation
2, Al
2O
3Place beaker, add 500 milliliters of ethanolic solutions and make suspension.
Take by weighing 2.93 gram Cu (NO
3)
2, 2.95 gram Zn (NO
3)
2Be dissolved in 500 milliliters of ethanolic solutions, this mixed solution is joined in the above-mentioned suspension.
Take by weighing 2.81 gram oxalic acid in burning the bosom, add the ethanolic solution that 500 milliliters of alcohol solvents are made into oxalic acid.Under room temperature, stirring, at above-mentioned H β zeolite, the ZrO of containing
2, Al
2O
3, Cu (NO
3)
2, Zn (NO
3)
2Aaerosol solution in, drip the ethanolic solution of oxalic acid fast, through aging 30 minutes, filter, 120 ℃ of oven dry, 350 ℃ of roastings obtain catalyst C9, consist of CuO-ZnO-Al
2O
3-ZrO
2/ H β, its active component accounts for 30 heavy %, and the copper zinc atom is than 1: 1, Zr+Al: Cu=1: 2, Zr: Al=1: 2.5.
Its activity and selectivity see Table 1.
Example 10
Preparation process when the precursor of this example explanation auxiliary agent zirconia and aluminium oxide is solubility zirconates and aluminium salt.
Take by weighing H β zeolite 7 grams after the grinding, add 500 milliliters of ethanolic solutions and make suspension;
Take by weighing 2.76 gram Cu (NO
3)
2, 2.77 gram Zn (NO
3)
2, 0.63 gram ZrO (NO
3)
2(Liu Lidian chemical plant, Beijing is analyzed pure), 0.39 gram Al (NO
3)
3Be dissolved in 500 milliliters of ethanolic solutions, this mixed ethanol solution is joined in the above-mentioned suspension.
Take by weighing 3.14 gram oxalic acid in burning the bosom, add the ethanolic solution that 500 milliliters of alcohol solvents are made into oxalic acid.Under room temperature, stirring, at above-mentioned H β zeolite, the Cu (NO of containing
3)
2, Zn (NO
3)
2, ZrO (NO
3)
2And Al (NO
3)
3Aaerosol solution in, drip the ethanolic solution of oxalic acid fast, through aging 30 minutes, filter, 120 ℃ of oven dry, 350 ℃ of roastings obtain catalyst C10, consist of CuO-ZnO-Al
2O
3-ZrO
2/ H β, active component accounts for 27 heavy %, and the copper zinc atom is than 1: 1, Zr+Al: Cu=1: 4, Zr: Al=2: 1.
Its activity and selectivity see Table 1.
Table 1
| Catalyst | Form | ??CO 2Conversion ratio (%) | Selectivity (%) | |||
| ??CH 3OCH 3 | ??CH 3OH | ????CO | ??CH 4 | |||
| C1 | CuO-ZnO-C/Hβ | 27.16 | 38.11 | 18.13 | 43.12 | 0.64 |
| C2 | CuO-ZnO-C/Hβ | 28.05 | 39.27 | 19.28 | 40.87 | 0.58 |
| C3 | CuO-ZnO-C/Hβ | 28.90 | 41.15 | 19.27 | 39.12 | 0.46 |
| C4 | CuO-ZnO-C/Hβ | 28.12 | 40.03 | 19.55 | 40.04 | 0.38 |
| C5 | CuO-ZnO-Al 2O 3/Hβ | 29.82 | 53.25 | 21.0 | 25.28 | 0.47 |
| C6 | CuO-ZnO-Al 2O 3/Hβ | 29.15 | 52.11 | 22.49 | 24.88 | 0.52 |
| C7 | CuO-ZnO-ZrO 2/Hβ | 28.07 | 40.07 | 19.18 | 40.29 | 0.46 |
| C8 | CuO-ZnO-ZrO 2/Hβ | 28.74 | 41.56 | 18.87 | 39.15 | 0.42 |
| C9 | CuO-ZnO-Al 2O 3-ZrO 2/Hβ | 29.19 | 42.73 | 19.25 | 37.41 | 0.61 |
| C10 | CuO-ZnO-Al 2O 3-ZrO 2/Hβ | 28.45 | 40.18 | 19.00 | 40.43 | 0.39 |
Example 11～23rd is the Preparation of catalysts process of carrier with phosphorous H β.
Example 11
According to phosphorus and zeolite weight ratio is 1: 20 ratio, is that the ammonium dihydrogen phosphate (ADP) of 1N and the ammonium chloride mixed solution exchange of 1N are prepared into the NH that contains P with Na β zeolite through concentration
4The β zeolite 500 ℃ of following roastings 4 hours, obtains phosphorous H β zeolite (brief note is P-H β).
Substitute H β zeolite with P-H β zeolite, other preparation condition makes catalyst with example 3, is numbered C11, consists of CuO-ZnO-C/P-H β, and its active component accounts for 30 heavy %, and the copper zinc atom is than 1: 1, C: Cu=1: 5.
Activity and selectivity see Table 2.
Example 12
Press the same processing method of example 11, preparation phosphorus and 1: 50 P-H β zeolite of zeolite weight ratio, other preparation condition is constant, obtain catalyst, be numbered C12, consist of CuO-ZnO-C/P-H β, its active component accounts for 30 heavy %, and the copper zinc atom is than 1: 1, C: Cu=1: 5.
Its activity and selectivity see Table 2.
Example 13
Press the same processing method of example 11, preparation phosphorus and 1: 70 P-H β zeolite of zeolite weight ratio, other preparation condition is constant, obtain catalyst, be numbered C13, consist of CuO-ZnO-C/P-H β, its active component accounts for 30 heavy %, and the copper zinc atom is than 1: 1, C: Cu=1: 5.
Its activity and selectivity see Table 2.
Example 14
According to phosphorus and zeolite weight ratio is 1: 20 ratio, is that the ammonium dihydrogen phosphate exchange of 1N is prepared into the NH that contains P with H β zeolite through concentration
4The β zeolite 500 ℃ of following roastings 4 hours, obtains phosphorous H β zeolite (brief note is P-H β).
Substitute H β zeolite with P-H β zeolite, other preparation condition makes catalyst with example 1, is numbered C14, consists of CuO-ZnO-C/P-H β, and its active component accounts for 15 heavy %, and wherein the copper zinc atom is than 1: 2, C: Cu=1: 0.4.
Activity and selectivity see Table 2.
Example 15～23
Press the same processing method of example 11, preparation phosphorus and 1: 50 P-H β zeolite of zeolite weight ratio.The preparation condition of example 15～23 is corresponding to example 2-10, and the gained catalyst is numbered C15～C23, forms corresponding to C2-C10, and carrier becomes P-H β.
Its activity and selectivity see Table 2.
Table 2
| Catalyst | Form | ??CO 2Conversion ratio (%) | Selectivity (%) | |||
| CH 3OCH ???3 | CH 3OH | ????CO | ????CH 4 | |||
| C11 | CuO-ZnO-C/P-Hβ | 29.11 | 50.06 | 18.99 | 30.48 | 0.47 |
| C12 | CuO-ZnO-C/P-Hβ | 30.35 | 53.48 | 19.15 | 27.05 | 0.32 |
| C13 | CuO-ZnO-C/P-Hβ | 29.87 | 51.13 | 19.42 | 28.92 | 0.53 |
| C14 | CuO-ZnO-C/P-Hβ | 29.55 | 54.30 | 18.77 | 26.65 | 0.28 |
| C15 | CuO-ZnO-C/P-Hβ | 30.58 | 55.14 | 18.85 | 25.64 | 0.37 |
| C16 | CuO-ZnO-C/P-Hβ | 31.18 | 56.95 | 17.13 | 25.53 | 0.39 |
| C17 | CuO-ZnO-C/P-Hβ | 30.66 | 55.52 | 18.16 | 25.77 | 0.55 |
| C18 | CuO-ZnO-Al 2O 3/P-Hβ | 32.56 | 60.54 | 15.19 | 24.08 | 0.19 |
| C19 | CuO-ZnO-Al 2O 3/P-Hβ | 31.88 | 58.87 | 16.44 | 24.35 | 0.34 |
| C20 | CuO-ZnO-ZrO 2/P-Hβ | 30.47 | 55.01 | 19.00 | 25.59 | 0.40 |
| C21 | CuO-ZnO-ZrO 2/P-Hβ | 30.89 | 55.33 | 19.27 | 24.98 | 0.42 |
| C22 | CuO-ZnO-Al 2O 3-ZrO 2/P-Hβ | 31.86 | 58.85 | 16.46 | 24.41 | 0.28 |
| C23 | CuO-ZnO-Al 2O 3-ZrO 2/P-Hβ | 30.91 | 56.10 | 17.74 | 25.84 | 0.32 |
Example 24～35th is the Preparation of catalysts process of carrier with phosphorous H-ZSM-5.
Example 24
According to phosphorus and zeolite weight ratio is 1: 20 ratio, is that the ammonium dihydrogen phosphate (ADP) of 1N and the ammonium chloride mixed solution exchange of 1N are prepared into the NH that contains P with the Na-ZSM-5 zeolite through concentration
4-ZSM-5 zeolite 500 ℃ of following roastings 4 hours, obtains phosphorous HZSM-5 zeolite (brief note is P-HZSM-5).
Substitute H β zeolite with the P-HZSM-5 zeolite, other preparation condition makes catalyst and is numbered C24 with example 3, consists of CuO-ZnO-C/P-HZSM-5, and its active component accounts for 30 heavy %, and the copper zinc atom is than 1: 1, C: Cu=1: 5.
Activity and selectivity see Table 3.
Example 25
Press the same processing method of example 24, preparation phosphorus and 1: 50 P-HZSM-5 zeolite of zeolite weight ratio, other preparation condition is constant, obtain catalyst, be numbered C25, consist of its active component of CuO-ZnO-C/P-HZSM-5 and account for 30 heavy %, the copper zinc atom is than 1: 1, C: Cu=1: 5.
Activity and selectivity see Table 3.
Example 26
Press the same processing method of example 24, the P-HZSM-5 zeolite of preparation phosphorus and zeolite weight ratio 1.70, other preparation condition is constant, obtain catalyst, be numbered C26, consist of CuO-ZnO-C/P-HZSM-5, its active component accounts for 30 heavy %, and the copper zinc atom is than 1: 1, C: Cu=1: 5.
Activity and selectivity see Table 3.
Example 27～35
Carrier is phosphorus and 1: 50 P-HZSM-5 zeolite of zeolite weight ratio in the example 27～35, and Zeolite support is that the processing method by example 25 obtains.
Other preparation condition of example 27～35 is corresponding to example 2～10, and the gained catalyst is numbered C27～C35, forms corresponding and C2-C1O, and carrier becomes P-HZSM-5.
Its activity and selectivity see Table 3.
Table 3
| Catalyst | Form | ??CO 2Conversion ratio (%) | Selectivity (%) | |||
| CH 3OCH 3 | CH 3OH | ?CO | CH 4 | |||
| C24 | CuO-ZnO-C/P-HZSM-5 | 30.45 | 59.21 | 15.96 | 23.16 | 1.67 |
| C25 | CuO-ZnO-C/P-HZSM-5 | 31.78 | 32.01 | 14.01 | 22.42 | 1.56 |
| C26 | CuO-ZnO-C/P-HZSM-5 | 31.56 | 61.75 | 15.56 | 21.05 | 1.64 |
| C27 | CuO-ZnO-C/P-HZSM-5 | 30.88 | 58.64 | 18.56 | 21.02 | 1.78 |
| C28 | CuO-ZnO-C/P-HZSM-5 | 32.56 | 64.18 | 12.77 | 21.23 | 1.82 |
| C29 | CuO-ZnO-C/P-HZSM-5 | 30.97 | 59.78 | 17.48 | 20.79 | 1.95 |
| C30 | CuO-ZnO-Al 2O 3/P-HZSM-5 | 33.94 | 68.25 | 11.46 | 18.38 | 1.91 |
| C31 | CuO-ZnO-Al 2O 3/P-HZSM-5 | 32.73 | 64.33 | 12.85 | 20.79 | 2.03 |
| C32 | CuO-ZnO-ZrO 2/P-HZSM-5 | 31.25 | 60.42 | 16.18 | 21.28 | 2.12 |
| C33 | CuO-ZnO-ZrO 2/P-HZSM-5 | 31.52 | 58.04 | 18.91 | 20.68 | 2.37 |
| C34 | CuO-ZnO-Al 2O 3-ZrO 2/P- HZSM-5 | 32.74 | 64.78 | 12.19 | 20.54 | 2.49 |
| C35 | CuO-ZnO-Al 2O 3-ZrO 2/P- HZSM-5 | 31.85 | 62.13 | 13.47 | 22.55 | 1.85 |
Example 36～47th is the Preparation of catalysts process of carrier with phosphorous HY zeolite.
Example 36
According to phosphorus and zeolite weight ratio is 1: 20 ratio, is that the ammonium dihydrogen phosphate (ADP) of 1N and the ammonium chloride mixed solution exchange of 1N are prepared into the NH that contains P with the NaY zeolite through concentration
4The Y zeolite 500 ℃ of following roastings 4 hours, obtains phosphorous HY zeolite (brief note is P-HY).
Substitute H β zeolite with the P-HY zeolite, other preparation condition makes catalyst and is numbered C36 with example 1, consists of CuO-ZnO-C/P-HY, and its active component accounts for 15 heavy %, and wherein the copper zinc atom is than 1: 2, C: Cu=1: 0.4.
Activity and selectivity see Table 4.
Example 37
Press the same processing method of example 36, preparation phosphorus and 1: 50 P-HY zeolite of zeolite weight ratio, other preparation condition is constant, obtain catalyst, be numbered C37, consist of CuO-ZnO-C/P-HY, its active component accounts for 15 heavy %, and the copper zinc atom is than 1: 2, C: Cu=1: 0.4.
Activity and selectivity see Table 4.
Example 38
Press the same processing method of example 36, preparation phosphorus and 1: 70 P-HY zeolite of zeolite weight ratio, other preparation condition is constant, obtain catalyst, be numbered C38, consist of CuO-ZnO-C/P-HY, its active component accounts for 15 heavy %, and wherein the copper zinc atom is than 1: 2, C: Cu=1: 0.4.
Activity and selectivity see Table 4.
Example 39～47
Carrier is phosphorus and 1: 50 P-HY zeolite of zeolite weight ratio in the example 39～47, and the P-HY zeolite obtains by the processing method of example 36.
Other preparation condition of example 39～47 is corresponding to example 2～10, and the gained catalyst is numbered C39～C47, forms corresponding to C2-C10, and carrier becomes P-HY.
Its activity and selectivity see Table 4.
Table 4
| Catalyst | Form | ????CO 2Conversion ratio (%) | Selectivity (%) | |||
| ??CH 3OCH 3 | ??CH 3OH | ????CO | ????CH 4 | |||
| C36 | CuO-ZnO-C/P-HY | 28.74 | 49.44 | 19.56 | 29.1 | 1.90 |
| C37 | CuO-ZnO-C/P-HY | 29.86 | 52.15 | 19.73 | 26.09 | 2.03 |
| C38 | CuO-ZnO-C/P-HY | 29.25 | 50.32 | 20.59 | 27.23 | 1.86 |
| C39 | CuO-ZnO-C/P-HY | 29.13 | 52.48 | 20.58 | 25.19 | 1.75 |
| C40 | CuO-ZnO-C/P-HY | 30.99 | 55.23 | 18.17 | 24.97 | 1.63 |
| C41 | CuO-ZnO-C/P-HY | 29.87 | 53.46 | 19.65 | 25.01 | 1.88 |
| C42 | CuO-ZnO-Al 2O 3/P-HY | 31.93 | 59.54 | 14.17 | 24.34 | 1.95 |
| C43 | CuO-ZnO-Al 2O 3/P-HY | 30.87 | 56.13 | 15.86 | 26.25 | 1.76 |
| C44 | CuO-ZnO-ZrO 2/P-HY | 30.08 | 50.49 | 20.84 | 26.84 | 1.83 |
| C45 | CuO-ZnO-ZrO 2/P-HY | 30.24 | 48.56 | 21.95 | 27.82 | 1.67 |
| C46 | CuO-ZnO-Al 2O 3-ZrO 2/P-HY | 31.16 | 56.72 | 16.38 | 25.15 | 1.75 |
| C47 | CuO-ZnO-Al 2O 3-ZrO 2/P-HY | 30.12 | 54.35 | 17.86 | 25.81 | 1.98 |
Claims (13)
1, a kind ofly be used for the catalyst that hydrogenation of carbon dioxide is produced dimethyl ether, it is characterized in that this catalyst weighs the active component of % by 5～50 and the Zeolite support of surplus is formed, active component is that copper zinc atom ratio is 1: 0.5～5.0 cupric oxide and zinc oxide, and with the atomic ratio of copper be 1: (a) auxiliary agent of 0.4-10.0 or (b) auxiliary agent, wherein (a) auxiliary agent is for being selected from active carbon, a kind of in aluminium oxide or the zirconia, (b) be 1 for the zirconium al atomic ratio: the zirconia of 0.25-20.0 and the mixture of aluminium oxide, Zeolite support is H β zeolite or is selected from phosphorus and the zeolite weight ratio is 1: the phosphorous HZSM-5 of 5-100, HY, a kind of in three kinds of zeolites of H β
2,, it is characterized in that the copper zinc atom ratio of said active component cupric oxide and zinc oxide is 1: 1-3 according to the described catalyst of claim 1.
3,, it is characterized in that the zirconium al atomic ratio is 1 in the auxiliary agent (b): 1-10.0 according to the described catalyst of claim 1.
4,, it is characterized in that in the wherein said P-contained zeolite carrier, phosphorus and zeolite weight ratio are 1: 20-70 according to the described catalyst of claim 1.
5, claim 1 Preparation of catalysts method is characterized in that preparation process comprises the steps:
(1) H β zeolite or phosphorous HZSM-5, HY, a kind of zeolite and active carbon among the H β or aluminium oxide and/or zirconia are become liquid volume and solid weight than the suspension that is 50～1000 with the alcoholic solution preparation;
(2) soluble copper salt and zinc salt are mixed with mixed solution with alcohol;
(3) be 100-300 according to the ml volumes of alcohol and the gram weight of oxalic acid: 1 ratio, the alcoholic solution of preparation oxalic acid;
(4) step (1) and step (2) gained two solution are mixed, in room temperature, stir under, add the oxalic acid alcoholic solution that step (3) is prepared, dropwise, aging 10～60 minutes, after filtration, dry, roasting forms.
6, claim 1 Preparation of catalysts method when active component auxiliary agent aluminium oxide and/or zirconia are to add fashionablely with its soluble-salt, is characterized in that preparation process comprises the steps:
(1) H β zeolite or phosphorous HZSM-5, HY, a kind of zeolite among the H β are become liquid volume and solid weight than the suspension that is 50～1000 with the alcoholic solution preparation;
(2) soluble copper salt, zinc salt, aluminium salt and/or zirconates are mixed with mixed solution with alcohol;
(3) be 100-300 according to the ml volumes of alcohol and the gram weight of oxalic acid: 1 ratio, the alcoholic solution of preparation oxalic acid;
(4) step (1) and step (2) gained two solution are mixed, in room temperature, stir under, add the oxalic acid alcoholic solution that step (3) is prepared, dropwise, aging 10～60 minutes, after filtration, dry, roasting forms.
7, according to the described catalyst of claim 1, it is characterized in that said phosphorous HZSM-5, HY, H β zeolite is with behind a kind of phosphorus-containing compound solution-treated HZSM-5, the HY or H β that are selected from ammonium phosphate, ammonium phosphite, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), the diammonium hydrogen phosphate, 400～600 ℃ of following roastings.
8,, it is characterized in that said soluble copper salt and soluble zinc salt are nitrate, sulfate or the chlorides of copper or zinc according to claim 5 or 6 described methods.
9, in accordance with the method for claim 8, it is characterized in that said soluble copper salt and soluble zinc salt are the nitrate of copper or zinc.
10, in accordance with the method for claim 6, it is characterized in that said solubility zirconates is zirconyl chloride or zirconyl nitrate, aluminum soluble salt is an aluminum nitrate.
11, the described Preparation of catalysts method of claim 5 is characterized in that auxiliary agent ZrO
2Or ZrO
2With Al
2O
3Mixture be to adopt following method preparation: with the mixed solution and the ammoniacal liquor co-precipitation of zirconium salt solution or zirconates and aluminium salt, sediment after alcohol compound washs, in the alcohol compound medium, obtains ZrO through supercritical drying again through being washed to no chlorion
2Or ZrO
2With Al
2O
3Mixture.
12, according to claim 5 or 6 described methods, it is characterized in that said alcohol is the anhydrous alcohol solution that comprises absolute ethyl alcohol, propyl alcohol, isopropyl alcohol, butanols, isobutanol,
13, in accordance with the method for claim 12, it is characterized in that said alcohol is absolute ethyl alcohol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008071059A1 (en) * | 2006-12-14 | 2008-06-19 | Taiyuan University Of Technology | A slurry catalyst and the preparation thereof |
| CN103725331A (en) * | 2013-12-13 | 2014-04-16 | 济南开发区星火科学技术研究院 | Method for producing ether gasoline |
| CN106140288A (en) * | 2015-04-03 | 2016-11-23 | 中国科学院青岛生物能源与过程研究所 | A kind of dimethyl ether directly catalyst preparing hexamethylbenzene and its preparation method and application |
| CN118162194A (en) * | 2024-05-14 | 2024-06-11 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336589C (en) * | 2004-04-16 | 2007-09-12 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether from synthetic gas by one step |
-
2000
- 2000-08-11 CN CNB001215426A patent/CN1137783C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008071059A1 (en) * | 2006-12-14 | 2008-06-19 | Taiyuan University Of Technology | A slurry catalyst and the preparation thereof |
| US8779014B2 (en) | 2006-12-14 | 2014-07-15 | Taiyuan University Of Technology | Slurry catalyst and the preparation thereof |
| CN103725331A (en) * | 2013-12-13 | 2014-04-16 | 济南开发区星火科学技术研究院 | Method for producing ether gasoline |
| CN106140288A (en) * | 2015-04-03 | 2016-11-23 | 中国科学院青岛生物能源与过程研究所 | A kind of dimethyl ether directly catalyst preparing hexamethylbenzene and its preparation method and application |
| CN106140288B (en) * | 2015-04-03 | 2018-11-13 | 中国科学院青岛生物能源与过程研究所 | A kind of dimethyl ether directly prepares the catalyst and its preparation method and application of hexamethylbenzene |
| CN118162194A (en) * | 2024-05-14 | 2024-06-11 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation and preparation method and application thereof |
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