CN114345348A - Catalyst for preparing isopropanol by acetone hydrogenation and preparation method thereof - Google Patents
Catalyst for preparing isopropanol by acetone hydrogenation and preparation method thereof Download PDFInfo
- Publication number
- CN114345348A CN114345348A CN202011084639.4A CN202011084639A CN114345348A CN 114345348 A CN114345348 A CN 114345348A CN 202011084639 A CN202011084639 A CN 202011084639A CN 114345348 A CN114345348 A CN 114345348A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- precipitation
- temperature
- acetone
- preparing
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing isopropanol by acetone hydrogenation and a preparation method thereof, wherein the mass content of CuO is 10-20%, the mass content of NiO is 1-5%, and ZrO is ZrO25-10% of SiO265-84% of mass content, and preparing the isopropanol catalyst by adopting a fractional precipitation mode. The invention has the advantages of simple preparation method, low price, high activity and selectivity, simple operation and the like, and is easy to industrially popularize and apply.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for preparing isopropanol by acetone gas-phase hydrogenation and a preparation method thereof.
Background
Isopropyl alcohol (IPA for short) is an important organic chemical raw material and organic solvent, and has wide application. The demand of the isopropanol is continuously increased in China, and the isopropanol has wide development prospect. However, the current situation of insufficient production in China is that the 'half-wall Jiangshan' of the isopropanol market in China needs to be imported. The main processes for producing isopropanol at present are the direct hydration process of propylene and the indirect hydration process of propylene.
In recent years, the yield of acetone has been increasing, but the production method of methyl methacrylate has C4The trend of distillation, direct oxidation instead of acetone cyanohydrin, and the continuous reduction of the amount of acetone used as solvent, narrow the application range of acetone, and thus the conversion of acetone into isopropanol fine chemicals is of great significance.
The catalyst for preparing isopropanol by acetone hydrogenation comprises Raney-Ni catalyst, Ru/C catalyst, Ru/Al catalyst2O3Catalyst, copper chromium catalyst. Acetone is hydrogenated on the above type of catalyst, generally a fixed bed reactor is adopted, acetone and hydrogen enter a catalyst bed layer in a certain proportion under the condition of liquid phase or gas phase, and isopropanol is generated by hydrogenation under proper temperature and pressure.
Japanese patent application Hei 3-41038 describes a method for hydrogenating acetone by using a Cu-Cr catalyst, and Russian patent RU2047590 uses NiO-CuO-Cr2O3The catalyst is used for preparing isopropanol by acetone hydrogenation. The use of the catalysts described in the above patents all has the disadvantage of not high conversion and selectivity, resulting in a low yield of isopropanol. In addition Cr in the catalyst2O3Is easy to pollute the environment and is unfavorable for the environment. Chinese patent CN1962588A reports a method for preparing isopropanol by gas phase continuous reaction using acetone as raw material and Ni-Co/Al as catalyst, and the high purity isopropanol for pharmaceutical and cosmetic industries can be obtained by the method through subsequent processing. However, the nickel and cobalt content in the supported nickel catalyst in the method is higher, so that the preparation cost of the catalyst is higher, and the economy of preparing isopropanol by hydrogenating acetone is reduced.
Disclosure of Invention
Aiming at the defects in the background technology, the invention provides a scientific and reasonable catalyst applied in the process of preparing isopropanol by directly hydrogenating acetone, and provides a preparation method of the catalyst and an application of the catalyst in the process of preparing isopropanol by directly hydrogenating acetone.
The catalyst for preparing isopropanol by acetone hydrogenation comprises the components of oxides of Cu, Ni, Zr and Si, wherein the mass content of CuO is 10-20%, the mass content of NiO is 1-5%, and ZrO is ZrO25-10% of SiO2The mass content is 65-84 percent
The catalyst for preparing isopropanol by acetone hydrogenation is prepared by a fractional precipitation method.
The preparation method comprises the following specific steps:
1) Mixing a precursor of zirconium salt with silica sol, carrying out concurrent flow precipitation with an alkaline precipitator, and stirring and keeping the temperature at 40-50 ℃ and the pH =9-10 in the precipitation process; after the reaction is finished, the reaction is carried out for 50-70 min;
2) dissolving precursors of Cu and Ni elements in deionized water according to a certain ratio, carrying out parallel-flow precipitation on a Cu and Ni solution and an aqueous solution of an alkaline precipitator at the temperature of 60-70 ℃, and stirring and keeping the pH =7-8 in the precipitation process;
3) mixing the precipitates obtained in the step 1) and the step 2), and continuously stirring for 20-40 min;
4) washing the precipitate obtained in the step 3) to be neutral by using deionized water, drying at the temperature of 100-350 ℃, and roasting at the temperature of 300-350 ℃ for 3-5 h; and granulating and forming to obtain the required catalyst.
According to the preparation method of the catalyst for preparing isopropanol by acetone hydrogenation, copper salt, nickel salt and zirconium salt used for preparing the catalyst are respectively nitrates of the copper salt, the nickel salt and the zirconium salt.
The alkaline precipitator used in the preparation method of the catalyst for preparing isopropanol by acetone hydrogenation is one of KOH, NaOH, K2CO3 and Na2CO 3.
According to the preparation method of the catalyst for preparing isopropanol by acetone hydrogenation, the used silica sol is SW-25 type silica sol.
According to the preparation method of the catalyst for preparing isopropanol by acetone hydrogenation, the average particle size of the used silica sol is 10 nm-20 nm.
The catalyst is used for the reaction of preparing isopropanol by hydrogenating acetone.
The application of the catalyst of the invention is that the catalyst is loaded into a fixed bed reactor, before being used, the catalyst is reduced in 5% hydrogen atmosphere, the reduction temperature is 160-180 ℃, the reduction time is 3-5h, then the temperature is increased to 270-290 ℃ and the reduction time is 3-6 h.
The catalyst is applied, the reaction temperature is 90-110 ℃, and the hourly space velocity of acetone feeding liquid is 0.3h < -1 > to 0.5h < -1 >.
The invention has the beneficial effects that:
noble metal does not need to be loaded, so that the production cost is greatly reduced;
the whole preparation process is simple and convenient, a good catalytic effect can be obtained without an additional impregnation cocatalyst, the production cost is low, and industrial large-scale production is easy to realize;
the reaction process has mild condition, high acetone conversion rate, high isobutanol selectivity and stable performance.
Detailed Description
The following examples are intended to further illustrate the invention and are not intended to limit the invention.
Example 1
According to the weight percentage of 10 percent CuO, 2 percent NiO and 7 percent ZrO2， 81%SiO2Dissolving nitrate of Zr in deionized water, mixing with silica sol, performing cocurrent flow precipitation with NaOH at 50 ℃, fully stirring and keeping pH =10 in the precipitation process, aging for 50min after the reaction is finished after the precipitation is finished, and aging the nitrate solution of Cu and Ni and Na at 60 DEG2CO3And (3) continuing to precipitate, after the precipitation is finished, aging for 30Min, adding the precipitates of the silica sol and the Zr into the precipitates of the Cu and the Ni, continuing stirring for 30Min, washing the obtained precipitates to be neutral by deionized water, drying, roasting for 4 hours at 350 ℃, granulating and tabletting to obtain the required catalyst, which is marked as A1.
Loading catalyst A150 ml in fixed bed reactor, reducing the catalyst for 4h at 180 deg.C under 5% hydrogen concentration, heating the reactor to 280 deg.C under pure hydrogen atmosphere, deeply reducing for 4h, vaporizing in 110 deg.C vaporizing furnace, and controlling liquid hourly space velocity of acetone at 0.3h-1The reaction temperature is controlled at 110 DEG CThe reaction pressure was controlled at about 0.3 MPa. After the reaction, the product was condensed, and the liquid phase was sampled and analyzed, and the reaction results are shown in Table 1.
Example 2
According to 12 percent of CuO, 5 percent of NiO and 6 percent of ZrO2，77% SiO2The nitrate solution of Zr is dissolved in deionized water, then mixed with silica sol, and mixed with Na at 50 DEG C2CO3Performing parallel flow precipitation, fully stirring and keeping the pH =10 in the precipitation process, finishing the precipitation, and performing nitrate solution of Cu and Ni and Na at 60 DEG C2CO3Continuing to precipitate, aging for 30Min after precipitation, adding the precipitate of silica sol and Zr into the precipitate of Cu and Ni, continuing to stir for 30Min, washing the obtained precipitate with deionized water to neutrality, drying, roasting at 350 deg.C for 4 hr, adding K2CO3Mixing, granulating, and tabletting to obtain the desired catalyst, labeled as A2.
Catalyst A2 50ml of the catalyst was charged in a fixed bed reactor and reacted under the conditions of example 1, the results of which are shown in Table 1.
Example 3
According to 14 percent of CuO, 4 percent of NiO and 10 percent of ZrO2， 72% SiO2The nitrate solution of Zr is dissolved in deionized water, then mixed with silica sol, and mixed with Na at 50 DEG C2CO3Performing parallel flow precipitation, fully stirring and keeping the pH =10 in the precipitation process, finishing the precipitation, and performing nitrate solution of Cu and Ni and Na at 60 DEG C2CO3Continuing to precipitate, aging for 30Min after precipitation, adding the precipitate of silica sol and Zr into the precipitate of Cu and Ni, continuing to stir for 30Min, washing the obtained precipitate with deionized water to neutrality, drying, roasting at 350 deg.C for 4 hr, adding K2CO3Mixing, granulating, and tabletting to obtain the desired catalyst, labeled A3
Catalyst A3 50ml of the catalyst was charged in a fixed bed reactor and reacted under the conditions of example 1, the results of which are shown in Table 1.
Example 4
Based on 16% of CuO, 1% of NiO and 10% of ZrO2，73% SiO2The nitrate solution of Zr is dissolved in deionized waterMixing with silica sol, and mixing with Na at 50 deg.C2CO3Performing parallel flow precipitation, fully stirring and keeping the pH =10 in the precipitation process, finishing the precipitation, and performing nitrate solution of Cu and Ni and Na at 60 DEG C2CO3Continuing to precipitate, aging for 30Min after precipitation, adding the precipitate of silica sol and Zr into the precipitate of Cu and Ni, continuing to stir for 30Min, washing the obtained precipitate with deionized water to neutrality, drying, roasting at 350 deg.C for 4 hr, adding K2CO3Mixing, granulating, and tabletting to obtain the desired catalyst, labeled A4
Catalyst A450 ml was charged into a fixed bed reactor and reacted under the conditions of example 1, the results of which are shown in Table 1.
Example 5
According to 19 percent of CuO, 4 percent of NiO and 10 percent of ZrO2， 67% SiO2The nitrate solution of Zr is dissolved in deionized water, then mixed with silica sol, and mixed with Na at 50 DEG C2CO3Performing parallel flow precipitation, fully stirring and keeping the pH =10 in the precipitation process, finishing the precipitation, and performing nitrate solution of Cu and Ni and Na at 60 DEG C2CO3Continuing to precipitate, aging for 30Min after precipitation, adding the precipitate of silica sol and Zr into the precipitate of Cu and Ni, continuing to stir for 30Min, washing the obtained precipitate with deionized water to neutrality, drying, roasting at 350 deg.C for 4 hr, adding K2CO3Mixing, granulating, and tabletting to obtain the desired catalyst, labeled A5
Catalyst A550 ml was charged into a fixed bed reactor and reacted under the conditions of example 1, the results of which are shown in Table 1.
Example 6
According to 18 percent of CuO, 3 percent of NiO and 10 percent of ZrO2， 69% SiO2The nitrate solution of Zr is dissolved in deionized water, then mixed with silica sol, and mixed with Na at 50 DEG C2CO3Performing parallel flow precipitation, fully stirring and keeping the pH =10 in the precipitation process, finishing the precipitation, and performing nitrate solution of Cu and Ni and Na at 60 DEG C2CO3Continuing to precipitate, aging for 30Min after precipitation is finished, adding the precipitates of the silica sol and the Zr into the precipitates Cu and Ni for precipitationStirring for 30Min, washing the precipitate with deionized water to neutrality, oven drying, roasting at 350 deg.C for 4 hr, and adding K2CO3Mixing, granulating, and tabletting to obtain the desired catalyst, labeled as A6.
Catalyst A650 ml was charged in a fixed bed reactor and reacted under the conditions of example 1, the results of which are shown in Table 1.
Example 7
According to 20 percent of CuO, 5 percent of NiO and 10 percent of ZrO2， 65% SiO2The nitrate solution of Zr is dissolved in deionized water, then mixed with silica sol, and mixed with Na at 50 DEG C2CO3Performing parallel flow precipitation, fully stirring and keeping the pH =10 in the precipitation process, finishing the precipitation, and performing nitrate solution of Cu and Ni and Na at 60 DEG C2CO3Continuing to precipitate, aging for 30Min after precipitation, adding the precipitate of silica sol and Zr into the precipitate of Cu and Ni, continuing to stir for 30Min, washing the obtained precipitate with deionized water to neutrality, drying, roasting at 350 deg.C for 4 hr, adding K2CO3Mixing, granulating, and tabletting to obtain the desired catalyst, labeled as A7.
Catalyst A750 ml was charged to a fixed bed reactor and reacted under the conditions of example 1, the results of which are shown in Table 1.
Example 8
10% of CuO, 1% of NiO and 5% of ZrO2，84% SiO2The nitrate solution of Zr is dissolved in deionized water, then mixed with silica sol, and mixed with Na at 50 DEG C2CO3Performing parallel flow precipitation, fully stirring and keeping the pH =10 in the precipitation process, finishing the precipitation, and performing nitrate solution of Cu and Ni and Na at 60 DEG C2CO3Continuing to precipitate, aging for 30Min after precipitation, adding the precipitate of silica sol and Zr into the precipitate of Cu and Ni, continuing to stir for 30Min, washing the obtained precipitate with deionized water to neutrality, drying, roasting at 350 deg.C for 4 hr, adding K2CO3Mixing, granulating, and tabletting to obtain the desired catalyst, labeled A8
Catalyst A850 ml was charged to a fixed bed reactor and reacted under the conditions of example 1, the results of which are shown in Table 1.
Example 9
Loading catalyst A150 ml into a fixed bed reactor, reducing the catalyst for 5h at 160 deg.C under 5% hydrogen concentration, heating the reactor to 270 deg.C under pure hydrogen atmosphere for deep reduction for 4h, vaporizing in a vaporizing furnace at 110 deg.C, and controlling liquid hourly space velocity of acetone at 0.3h-1The reaction temperature is controlled at 90 ℃ and the reaction pressure is controlled at 0.3 MPa. After the reaction, the product was condensed, and the liquid phase was sampled and analyzed, and the reaction results are shown in Table 1.
Example 10
Loading catalyst A150 ml into a fixed bed reactor, reducing the catalyst for 4h at 170 deg.C under 5% hydrogen concentration, heating the reactor to 280 deg.C under pure hydrogen atmosphere for deep reduction for 3h, vaporizing in a vaporizing furnace at 110 deg.C, and controlling liquid hourly space velocity of acetone at 0.4h-1The reaction temperature was controlled at 100 ℃ and the product was condensed, the liquid phase was sampled and analyzed, and the reaction results are shown in Table 1.
Example 11
Loading catalyst A150 ml into a fixed bed reactor, reducing the catalyst for 5h at 180 deg.C under 5% hydrogen concentration, heating the reactor to 280 deg.C under pure hydrogen atmosphere, deeply reducing for 6h, vaporizing in a vaporizing furnace at 110 deg.C, and controlling liquid hourly space velocity of acetone at 0.5h-1The reaction temperature is controlled at 110 ℃ and the reaction pressure is controlled at 0.3 MPa. After the reaction, the product was condensed, and the liquid phase was sampled and analyzed, and the reaction results are shown in Table 1.
Comparative example 1
50ml of commercial copper hydrogenation catalyst is loaded in a fixed bed reactor, the catalyst is reduced for 4h under the concentration of 5 percent hydrogen gas at 170 ℃, then the reactor is heated to 230 ℃ and deeply reduced for 3h under the pure hydrogen atmosphere, the catalyst is vaporized in a vaporization furnace at 110 ℃, and the liquid hourly space velocity of acetone is controlled to be 0.5h-1The reaction temperature is controlled at 110 ℃ and the reaction pressure is controlled at 0.3 MPa. After the reaction, the product was condensed, and the liquid phase was sampled and analyzed, and the reaction results are shown in Table 1.
TABLE 1
| Examples | Acetone conversion rate,% of | Iso-propanol selectivity,% |
| Example 1 | 99.2 | 99.4 |
| Example 2 | 99.4 | 99.0 |
| Example 3 | 99.1 | 99.1 |
| Example 4 | 99.1 | 98.2 |
| Example 5 | 99.3 | 99.5 |
| Example 6 | 99.8 | 99.2 |
| Example 7 | 99.2 | 98.3 |
| Example 8 | 99.6 | 98.7 |
| Example 9 | 99.4 | 98.8 |
| Example 10 | 99.8 | 99.5 |
| Example 11 | 99.5 | 99.1 |
| Comparative example | 97.0 | 93.4 |
As can be seen from the data in Table 1, the catalyst for preparing isopropanol by hydrogenating acetone prepared by the method has the advantages of high conversion rate, high selectivity and stable performance.
Claims (9)
1. The catalyst for preparing isopropanol by acetone hydrogenation is characterized in that the catalyst comprises oxides of Cu, Ni, Zr and Si, wherein the mass content of CuO is 10-20%, the mass content of NiO is 1-5%, and ZrO is ZrO25-10% of SiO2The mass content is 65-84%.
2. The method of claim 1, wherein the catalyst is prepared by a fractional precipitation method comprising the steps of:
1) Mixing a precursor of zirconium salt with silica sol, carrying out concurrent flow precipitation with an alkaline precipitator, and stirring and keeping the temperature at 40-50 ℃ and the pH =9-10 in the precipitation process; after the reaction is finished, aging for 50-70 min;
2) dissolving precursors of Cu and Ni elements in deionized water according to a ratio, carrying out parallel-flow precipitation on a Cu and Ni solution and an aqueous solution of an alkaline precipitator at the temperature of 60-70 ℃, and stirring and keeping the pH =7-8 in the precipitation process;
3) mixing the precipitates obtained in the step 1) and the step 2), and continuously stirring for 20-40 min;
4) washing the precipitate obtained in the step 3) to be neutral by using deionized water, drying at the temperature of 100-350 ℃, and roasting at the temperature of 300-350 ℃ for 3-5 h; and granulating and forming to obtain the required catalyst.
3. The method of claim 2, wherein the copper salt, nickel salt and zirconium salt are nitrate.
4. The process for preparing the catalyst according to claim 2, wherein the alkaline precipitant is KOH, NaOH, K2CO3One kind of (1).
5. The method for preparing a catalyst according to claim 2, wherein the silica sol is a silica sol of the SW-25 type.
6. The method for preparing a catalyst according to claim 2 or 5, wherein the silica sol has an average particle diameter of 10 nm to 20 nm.
7. The use of the catalyst according to claim 1, wherein the catalyst is used in the reaction of hydrogenating acetone to produce isopropanol.
8. The application of the catalyst according to claim 7 is characterized in that the catalyst is loaded into a fixed bed reactor, before use, the catalyst is reduced in a 5% hydrogen atmosphere, the reduction temperature is 160-180 ℃, the reduction time is 3-5h, then the temperature is increased to 270-290 ℃, and the reduction is carried out in a pure hydrogen atmosphere, and the reduction time is 3-6 h.
9. Use of a catalyst according to claim 7, characterised in that the reaction temperature is 90 ℃ -Acetone feeding liquid hourly space velocity of 0.3h at 110 DEG C-1~0.5h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011084639.4A CN114345348A (en) | 2020-10-12 | 2020-10-12 | Catalyst for preparing isopropanol by acetone hydrogenation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011084639.4A CN114345348A (en) | 2020-10-12 | 2020-10-12 | Catalyst for preparing isopropanol by acetone hydrogenation and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114345348A true CN114345348A (en) | 2022-04-15 |
Family
ID=81089936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011084639.4A Pending CN114345348A (en) | 2020-10-12 | 2020-10-12 | Catalyst for preparing isopropanol by acetone hydrogenation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114345348A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927168A (en) * | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Nickel-based catalyst for preparing isopropyl alcohol by acetone hydrogenation and application thereof |
| CN103030526A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing isopropanol by gas phase hydrogenation of acetone |
-
2020
- 2020-10-12 CN CN202011084639.4A patent/CN114345348A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927168A (en) * | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Nickel-based catalyst for preparing isopropyl alcohol by acetone hydrogenation and application thereof |
| CN103030526A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing isopropanol by gas phase hydrogenation of acetone |
Non-Patent Citations (2)
| Title |
|---|
| 尹丽等: ""镍基催化剂上丙酮的常压气相加氢"", 《吉林工学院学报》, vol. 22, no. 3, pages 41 - 43 * |
| 钟顺和等: ""ZrO2-SiO2负载Cu-Ni催化剂的CO2加氢反应性能"", 《分子催化》, vol. 15, no. 3, pages 170 - 174 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101954288B (en) | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof | |
| CN110743544B (en) | Palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof | |
| CN111233626B (en) | Method for preparing benzhydrol by diphenyl ketone hydrogenation | |
| CN109529858B (en) | Modified nickel-silicon catalyst and application thereof in preparation of gamma-butyrolactone by catalyzing hydrogenation of maleic anhydride | |
| CN113061122B (en) | Preparation method of 2, 5-dihydroxymethyl tetrahydrofuran | |
| WO2021109611A1 (en) | Catalyst for hydrogenolysis and preparation method therefor | |
| CN110975882A (en) | Preparation method of catalyst for benzyl alcohol synthesis and catalytic hydrogenation system | |
| WO2016180000A1 (en) | Two-step ethylene glycol and 1,2-propylene glycol preparation method using cellulose | |
| CN114345348A (en) | Catalyst for preparing isopropanol by acetone hydrogenation and preparation method thereof | |
| CN114471638B (en) | Catalyst for synthesizing succinic acid (anhydride), preparation method and application | |
| CN107442134B (en) | Rhodium/nickel alloy nano catalyst and preparation method and application thereof | |
| CN107952473B (en) | Catalyst for preparing isopropanol by acetone hydrogenation | |
| CN112237937B (en) | Nitrogen-doped zirconia carrier, and preparation method and application thereof | |
| CN111250098B (en) | Water hydrogenation catalyst for Fischer-Tropsch synthesis reaction and preparation method and application thereof | |
| CN110624571B (en) | Catalyst for synthesizing 3, 5-dichloroaniline and preparation method and application thereof | |
| CN109603886B (en) | Fe3O4/g-C3N4Composite materials and their use as catalysts | |
| CN114073990A (en) | Preparation method of copper-based hydrogenation catalyst without roasting | |
| CN114618501B (en) | Copper-based catalyst for preparing neopentyl glycol by hydrogenation method and preparation method thereof | |
| CN111875497B (en) | Method for synthesizing ethyl glyoxylate by catalytic hydrogenation of diethyl maleate | |
| CN114602463B (en) | P-hydroxybenzoic acid ethyl ester hydrogenation catalyst and preparation method thereof | |
| CN110479259B (en) | Supported Ru-based catalyst with molybdenum oxide-zinc oxide-zirconium oxide composite oxide as carrier | |
| CN116459846B (en) | Hydroxy ester hydrogenation nano Cu-based catalyst and preparation method and application thereof | |
| CN115715982B (en) | Catalyst suitable for preparing VA and MMP, catalyst preparation method and catalysis method | |
| CN115894196B (en) | Method for continuously synthesizing cyclopentanone | |
| CN114433100B (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |