CN1142021C - Catalyst for preparing dimethyl ether - Google Patents
Catalyst for preparing dimethyl ether Download PDFInfo
- Publication number
- CN1142021C CN1142021C CNB001215477A CN00121547A CN1142021C CN 1142021 C CN1142021 C CN 1142021C CN B001215477 A CNB001215477 A CN B001215477A CN 00121547 A CN00121547 A CN 00121547A CN 1142021 C CN1142021 C CN 1142021C
- Authority
- CN
- China
- Prior art keywords
- zeolite
- catalyst
- alcohol
- zinc
- solution
- 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.)
- Expired - Lifetime
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a catalyst for preparing dimethyl ether by CO2 hydrogenization, which is prepared from 5 to 50 wt% of active components and zeolite carriers as the rest, wherein the active components are copper oxide and zinc oxide in an atomic ratio of copper to zinc equal to 1: (0.5 to 5.0). The zeolite carriers are Hbeta zeolites or one of P-contained HZSM-5, HY and Hbeta zeolites. The catalyst is preapred the following steps: mixing the suspension solution of the zeolites and alcohol with the alcohol solution of soluble copper salts and zinc salts; adding the alcohol solution of oxalic acid; carrying out ageing, filtration, drying and calcination. Compared with the prior art, the catalyst has higher CO2 conversion rate and dimethyl ether selectivity.
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.OMPa, 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 is with containing the nitrate solution and the sodium carbonate liquor of copper, zinc, zirconium and flowing co-precipitation in the flask that fills 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 5～50 heavy % and the Zeolite support of surplus, wherein active component is that copper zinc atom ratio is 1: 0.5～5.0 cupric oxide and zinc oxide, and Zeolite support is H β zeolite or is selected from phosphorus and the zeolite weight ratio is a kind of in three kinds of zeolites of phosphorous HZSM-5, HY, H β of 1: 5～100.
In described active component cupric oxide and the zinc oxide, the preferable range of copper zinc atom ratio is 1: 1～3; In phosphorous HZSM-5, HY or the H β Zeolite support, the weight ratio of phosphorus and zeolite preferred 1: 20～70.
Preparation of catalysts process provided by the invention may further comprise the steps:
(1) H β zeolite or phosphorous HZSM-5, HY, a kind of zeolite among the H β are mixed with alcoholic solution,
Be mixed with liquid volume and solid weight than the suspension that is 50～1000;
(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, preparation grass
The alcoholic solution of acid;
(4) (1) and (2) two solution are mixed, under room temperature, stirring, adding (3) is prepared
The oxalic acid alcoholic solution dropwises, aging 10～60 minutes, after filtration, dry, roasting and
Become.
Among the preparation method provided by the invention, described phosphorous Zeolite support component can be to obtain through following method: with after being selected from one or more mixed solution in ammonium phosphate, ammonium hydrogen phosphate, ammonium phosphite, ammonium dihydrogen phosphate (ADP) or the diammonium hydrogen phosphate and handling HZSM-5, HY 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.
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, have carbon dioxide conversion height and dimethyl ether selectivity height, characteristics that the oxygenatedchemicals yield is high, for example consist of CuO-ZnO/P-HZSM-5, its active component 25 heavy %, the copper zinc atom was than 1: 4, phosphorus and zeolite weight ratio are 1: 50 catalyst (seeing example 10), at 3.0MPa, 245 ℃, air speed 1200h
-1, H
2/ CO
2Under=2.8 the condition, CO
2Conversion ratio is 31.46%, and the dimethyl ether selectivity is 58.73%.
This Preparation of catalysts method provided by the invention, it is simple to have process, the advantage that need not to wash.
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 chemical reagent is Beijing Chemical Plant's product, chemical pure.
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
After the 9.45 gram grindings of H β zeolite, add 500 milliliters of ethanolic solutions, make H β zeolite suspension;
Take by weighing 0.78 gram Cu (NO
3)
2With 0.39 gram Zn (NO
3)
2Be dissolved in 500 milliliters of ethanolic solutions, and this mixed solution is joined in the above-mentioned suspension that contains zeolite;
Take by weighing 0.67 gram oxalic acid in beaker, add the ethanolic solution that 100 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)
2Suspension in, drip the ethanolic solution of oxalic acid fast, filter after 30 minutes through aging reaction, 120 ℃ of oven dry, 350 ℃ of roastings obtain catalyst prod, numbering C1 consists of CuO-ZnO/H β, its active component is 5 heavy %, the copper zinc atom was than 1: 0.5.
Its activity and selectivity see Table 1.
Example 2
After the 9.0 gram grindings of H β zeolite, add 500 milliliters of ethanolic solutions, make H β zeolite suspension;
Take by weighing 0.78 gram Cu (NO
3)
2With 1.56 gram Zn (NO
3)
2Be dissolved in 500 milliliters of ethanolic solutions, and this mixed solution is joined in the above-mentioned suspension that contains zeolite;
Take by weighing 1.34 gram oxalic acid in beaker, add the ethanolic solution that 200 milliliters of alcohol solvents are made into oxalic acid.
Under room temperature, stirring, at above-mentioned H type β zeolite, the Cu (NO of containing
3)
2, Zn (NO
3)
2Suspension in, drip the ethanolic solution of oxalic acid fast, filter after 30 minutes through aging reaction, 120 ℃ of oven dry, 350 ℃ of roastings obtain catalyst prod, numbering C2 consists of CuO-ZnO/H β, its active component is 10 heavy %, the copper zinc atom was than 1: 2.
Its activity and selectivity see Table 1.
Example 3
After the 7.5 gram grindings of H β zeolite, add 500 milliliters of ethanolic solutions, make H β zeolite suspension;
Take by weighing 1.18 gram Cu (NO
3)
2With 4.67 gram Zn (NO
3)
2Be dissolved in 500 milliliters of ethanolic solutions, and this mixed solution is joined in the above-mentioned suspension that contains zeolite;
Take by weighing 3.4 gram oxalic acid in beaker, 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, the Cu (NO of containing
3)
2, Zn (NO
3)
2Suspension in, drip the ethanolic solution of oxalic acid fast, filter after 30 minutes through aging reaction, 120 ℃ of oven dry, 350 ℃ of roastings obtain catalyst prod, numbering C3 consists of CuO-ZnO/H β, its active component accounts for 25 heavy %, the copper zinc atom was than 1: 4.
Its activity and selectivity see Table 1.
Example 4
After the 5 gram grindings of H β zeolite, add 500 milliliters of ethanolic solutions, make H β zeolite suspension;
Take by weighing 1.96 gram Cu (NO
3)
2With 9.72 gram Zn (NO
3)
2Be dissolved in 500 milliliters of ethanolic solutions, and this mixed solution is joined in the above-mentioned suspension that contains zeolite;
Take by weighing 6.8 gram oxalic acid in beaker, add the ethanolic solution that 1000 milliliters of alcohol solvents are made into oxalic acid.
Under room temperature, stirring, at above-mentioned H type β zeolite, the Cu (NO of containing
3)
2, Zn (NO
3)
2Suspension in, drip the ethanolic solution of oxalic acid fast, filter after 30 minutes through aging reaction, 120 ℃ of oven dry, 350 ℃ of roastings obtain catalyst prod, numbering C4 consists of CuO-ZnO/H β, its active component accounts for 50 heavy %, the copper zinc atom was than 1: 5.
Its activity and selectivity see Table 1.
Example 5
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 C5, consists of CuO-ZnO/P-H β, and its active component accounts for 25 heavy %, and the copper zinc atom was than 1: 4.
Activity and selectivity see Table 1.
Example 6
Press the same processing method of example 5, preparation phosphorus and 1: 50 P-H β zeolite of zeolite weight ratio, other preparation condition is constant, obtains catalyst, is numbered C6, consists of CuO-ZnO/P-H β, and its active component accounts for 25 weight %, and the copper zinc atom was than 1: 4.
Its activity and selectivity see Table 1.
Example 7
Press the same processing method of example 5, preparation phosphorus and 1: 70 P-H β zeolite of zeolite weight ratio, other preparation condition is constant, obtains catalyst, is numbered C7, forms CuO-ZnO/P-H β, and its active component accounts for 25 weight %, and the copper zinc atom was than 1: 4.
Its activity and selectivity see Table 1.
Example 8
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 3, is numbered C8, consists of CuO-ZnO/P-H β, and its active component accounts for 25%, and the copper zinc atom was than 1: 4.
Activity and selectivity see Table 1.
Example 9～11st is the Preparation of catalysts process of carrier with phosphorous H-ZSM-5.
Example 9
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 NaZSM-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 C9 with example 3, consists of CuO-ZnO/P-HZSM-5, and its active component accounts for 25 heavy %, and the copper zinc atom was than 1: 4.
Activity and selectivity see Table 1.
Example 10
Press the same processing method of example 9, preparation phosphorus and 1: 50 P-HZSM-5 zeolite of zeolite weight ratio, other preparation condition is constant, obtains catalyst, is numbered C10, consists of its active component of CuO-ZnO/P-HZSM-5 and accounts for 25 weight %, and the copper zinc atom was than 1: 4.
Activity and selectivity see Table 1.
Example 11
Press the same processing method of example 9, preparation phosphorus and 1: 70 P-HZSM-5 zeolite of zeolite weight ratio, other preparation condition is constant, obtains catalyst, is numbered C11, consists of CuO-ZnO/P-HZSM-5, and its active component accounts for 25 weight %, and the copper zinc atom was than 1: 4.
Activity and selectivity see Table 1.
Example 12～14th is the Preparation of catalysts process of carrier with phosphorous HY zeolite.
Example 12
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 C12 with example 3, consists of CuO-ZnO/P-HY, its active component 25%, and the copper zinc atom was than 1: 4.
Activity and selectivity see Table 1.
Example 13
Press the same processing method of example 12, preparation phosphorus and 1: 50 P-HY zeolite of zeolite weight ratio, other preparation condition is constant, obtains catalyst, is numbered C13, consists of CuO-ZnO/P-HY, and its active component accounts for 25 weight %, and the copper zinc atom was than 1: 4.
Activity and selectivity see Table 1.
Example 14
Press the same processing method of example 12, preparation phosphorus and 1: 70 P-HY zeolite of zeolite weight ratio, other preparation condition is constant, obtains catalyst, is numbered C14, consists of CuO-ZnO/P-HY, and its active component accounts for 25 weight %, and the copper zinc atom was than 1: 4.
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/Hβ | 27.16 | 35.54 | 28.13 | 35.90 | 0.43 |
| C2 | CuO-ZnO/Hβ | 28.31 | 37.28 | 27.28 | 34.87 | 0.57 |
| C3 | CuO-ZnO/Hβ | 28.92 | 39.16 | 25.42 | 35.03 | 0.39 |
| C4 | CuO-ZnO/Hβ | 27.86 | 36.84 | 26.53 | 36.17 | 0.46 |
| C5 | CuO-ZnO/P-Hβ | 29.13 | 43.47 | 21.17 | 35.03 | 0.33 |
| C6 | CuO-ZnO/P-Hβ | 30.57 | 45.72 | 19.36 | 34.60 | 0.32 |
| C7 | CuO-ZnO/P-Hβ | 29.86 | 44.28 | 20.84 | 34.43 | 0.45 |
| C8 | CuO-ZnO/P-Hβ | 28.76 | 42.56 | 22.15 | 34.78 | 0.51 |
| C9 | CuO-ZnO/P-HZSM-5 | 30.25 | 55.12 | 17.36 | 25.68 | 1.84 |
| C10 | CuO-ZnO/P-HZSM-5 | 31.46 | 58.73 | 15.49 | 24.02 | 1.76 |
| C11 | CuO-ZnO/P-HZSM-5 | 30.89 | 56.91 | 16.75 | 24.59 | 1.75 |
| C12 | CuO-ZnO/P-HY | 29.03 | 42.85 | 23.78 | 31.39 | 1.98 |
| C13 | CuO-ZnO/P-HY | 30.12 | 45.13 | 22.43 | 30.57 | 1.87 |
| C14 | CuO-ZnO/P-HY | 29.35 | 43.56 | 23.56 | 31.09 | 1.79 |
Claims (9)
1, a kind ofly is 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, wherein active component is that copper zinc atom ratio is 1: 0.5～5.0 cupric oxide and zinc oxide, and Zeolite support is H β zeolite or is selected from phosphorus and the zeolite weight ratio is a kind of in three kinds of zeolites of phosphorous HZSM-5, HY, H β of 1: 5～100.
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 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.
4, 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 among the H β are mixed with alcoholic solution, be mixed with liquid volume (milliliter) and solid weight (gram) than the aaerosol solution that is 50～1000;
(2) soluble copper salt and soluble 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, under room temperature, stirring, the alcoholic solution of the oxalic acid that adding step (3) is prepared dropwises, and aging 10～60 minutes, filtration, dry, roasting.
5, according to the described preparation method of claim 4, it is characterized in that described P-contained zeolite carrier component obtains with following method: with after being selected from one or more mixed solution in ammonium phosphate, ammonium hydrogen phosphate, ammonium phosphite, ammonium dihydrogen phosphate (ADP) or the diammonium hydrogen phosphate and handling HZSM-5, HY or H β zeolite, 400～600 ℃ of following roastings.
6, in accordance with the method for claim 4, it is characterized in that said soluble copper salt and soluble zinc salt are nitrate, sulfate or the chlorides of copper or zinc.
7, in accordance with the method for claim 6, it is characterized in that said soluble copper salt and soluble zinc salt are the nitrate of copper or zinc.
8, in accordance with the method for claim 4, it is characterized in that said alcohol is the anhydrous alcohol solution that comprises absolute ethyl alcohol, propyl alcohol, isopropyl alcohol, butanols, isobutanol,
9, in accordance with the method for claim 8, it is characterized in that said alcohol is absolute ethyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001215477A CN1142021C (en) | 2000-08-11 | 2000-08-11 | Catalyst for preparing dimethyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001215477A CN1142021C (en) | 2000-08-11 | 2000-08-11 | Catalyst for preparing dimethyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1338331A CN1338331A (en) | 2002-03-06 |
| CN1142021C true CN1142021C (en) | 2004-03-17 |
Family
ID=4588867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001215477A Expired - Lifetime CN1142021C (en) | 2000-08-11 | 2000-08-11 | Catalyst for preparing dimethyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1142021C (en) |
Cited By (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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101934233B (en) * | 2010-09-13 | 2011-12-07 | 浙江大学 | Preparation method of catalyst Cu-ZnO/HZSM-5 for directly synthesizing dimethyl ether by using synthesis gas |
-
2000
- 2000-08-11 CN CNB001215477A patent/CN1142021C/en not_active Expired - Lifetime
Cited By (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1338331A (en) | 2002-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1046215C (en) | Selective hydrogen adding catalyst with metal in third main group and eighth group | |
| CN1154537C (en) | Prodn. of unsaturated acids or esters thereof and catalysts therefor | |
| CN106867565A (en) | A kind of preparation method of high density liquid hydrocarbon fuel | |
| CN1720208A (en) | Process for producing alcohol | |
| CN1091119A (en) | The preparation method of carboxylic acid | |
| CN106866589B (en) | A kind of preparation method of gamma-valerolactone | |
| CN103008001B (en) | Fischer-Tropsch synthesis catalyst comprising composite molecular sieve, and preparation method and application thereof | |
| CN110479258A (en) | A kind of high stability catalyst of levulic acid hydrogenation synthesis gamma-valerolactone and preparation method thereof | |
| CN1525887A (en) | Skeletal isomerization of fatty acids | |
| CN105713642B (en) | Method for synthesizing high density aviation fuel from lignocellulose | |
| CN1448480A (en) | Isomerization dewaxing catalyst and its prepn. | |
| CN1096496A (en) | With the diethylamine is the template synthesized silicon-aluminum phosphate molecular sieve | |
| CN1142021C (en) | Catalyst for preparing dimethyl ether | |
| CN1883798A (en) | Catalyst for direct preparation of dimethyl ether by using synthesis gas | |
| CN1827564A (en) | Process for polymerization preparation of diesel oil from C4 components containing butylene | |
| CN113976167A (en) | Preparation method and application of Pd/HY molecular sieve and method for selectively loading metal on hierarchical pore molecular sieve | |
| CN112058313B (en) | Composite catalyst, preparation method thereof and application thereof in citral synthesis | |
| CN1775734A (en) | Method for synthesizing diphenyl carbonate from phenol oxidation carbonylation by environment friendly solvent process | |
| CN103420816B (en) | Polyformaldehyde dimethyl ether preparation method | |
| CN1137783C (en) | Catalyst for preparing dimethyl ether and its preparing process | |
| CN103316705A (en) | Catalyst for removing mercaptan sulfur in catalytic gasoline at low temperature and preparation method of catalyst | |
| CN108579740B (en) | Preparation method and application of efficient catalyst for preparing aldehyde by olefin hydroformylation | |
| CN108144642B (en) | A kind of oil hydrogenation HC fuel catalyst and preparation and application | |
| CN1086509A (en) | The method for making of methyl-formiate | |
| CN100336589C (en) | Catalyst for preparing dimethyl ether from synthetic gas by one step |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040317 |