CN103962130A - Catalyst for oxalate ester synthetic reaction and preparation method of catalyst - Google Patents
Catalyst for oxalate ester synthetic reaction and preparation method of catalyst Download PDFInfo
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Abstract
The invention discloses a catalyst for the oxalate ester synthetic reaction and a preparation method of the catalyst. The catalyst uses a zirconia-aluminium oxide composite oxide as a carrier, wherein the zirconia in the composite oxide mainly exists in a square crystal form, and the aluminium oxide in the composite oxide mainly exists in a delta-aluminium oxide form. After being subjected to hydro-thermal treatment by a urea solution, the carrier is subjected to active load in the next step. A main active component of the catalyst is palladium, and an assistant is selected from one of zinc, nickel and iron. Based on the weight of the carrier, the content of the palladium is 0.03-0.3%, and the content of the assistant is 0.01-0.5%. By the adoption of the method, the prepared catalyst is uniform in active component distribution, can show the advantages of good catalytic activity and high stability when being used in the oxalate ester synthetic reaction by using gas-phase carbonic oxide and nitrous acid ester, can resist influence of industrial raw material gas impurities such as nitric oxide and methyl alcohol steam, and is more suitable for an industrialized production process.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method for oxalate synthetic reaction, be specially the catalyst and the preparation method that are suitable for carbon monoxide and the reaction of nitrites synthesis of oxalate.
Background technology
Oxalate is the important Organic Chemicals of a class, can be used for preparing oxalic acid, oxalyl chloride, oxamides, ethylene glycol etc., is the important basic industrial chemicals of a class.
Find under palladium catalytic action from people such as nineteen sixty-five U.S. Fenton, can there is coupling reaction oxalic ester in carbon monoxide, opened up the new direction of C-1 chemistry in alcohol medium.The feature of China's energy resources is that coal resources are relatively abundant, oil starvation, weak breath; Utilize synthesis gas to prepare industrial chemicals significant for rationally utilizing of the energy.
Domestic Duo Jia R&D institution has carried out the research that utilizes carbon monoxide coupling synthesis of oxalate successively.In the research that utilizes carbon monoxide synthesis of oxalate of report, adopt Alpha-alumina as carrier more, palladium is main active component, adds different auxiliary agents and prepares oxalate synthesis catalyst.
Also have successively report for the other forms of carrier of oxalate synthetic reaction, Liu Juntao etc. (CN101993361B) have reported a class lamellar composite carrier, by α-Al
2o
3, at least one inert carrier in SiC, spinelle, mullite or cordierite is as kernel, by α-Al
2o
3, θ-Al
2o
3, δ-Al
2o
3, λ-Al
2o
3or at least one porous coating material in molecular sieve is as shell, the weight ratio of its housing and kernel is 0.005 ~ 0.6:1.The preparation more complicated of lamellar composite carrier, is unfavorable for extensive expanding production and the cost that reduces catalyst.
Ma Xinbin etc. (CN101850273A) disclose a kind of regular catalyst and method for making thereof, taking ceramic honeycomb or metal beehive as skeleton carrier, the novel carriers material taking aluminium oxide, silica, titanium oxide as carrier coating, coating with aluminium oxide for well.Meter poplars etc. (CN102784640A) disclose a kind of metallic framework catalyst, and taking woven wire as skeleton, surperficial coated carrier coating, floods active component afterwards.The change of new carrier format needs the change of respective reaction device design, and in order to adapt to existing industrialization oxalate synthesizer, the reservation of traditional catalyst form is necessary.
Guo Junhuai etc. (CN1150992C) find to adopt δ-aluminium oxide as carrier, and owing to having higher specific activity surface, prepared catalyst shows and is better than activity and the life-span that Alpha-alumina is the catalyst prepared of carrier.
In existing disclosed technology, catalyst carrier is taking the simple aluminium oxide crystal formation such as Alpha-alumina or δ-aluminium oxide as main, and lower specific surface and mechanical strength be poor makes actual less stable.We find zirconia to introduce the stability that can strengthen carrier structure, adopt zirconium aluminium complex carrier can effectively improve simple aluminium oxide as easily the run off problem of poor stability of carrier active component in conjunction with specific post processing mode, effectively improved the tolerance of catalyst for actual industrial unstripped gas simultaneously.
Summary of the invention
The object of this invention is to provide a kind of Catalysts and its preparation method for the synthesis of oxalate reaction, be intended to solve the problem of loss of active component less stable in actual application.
For achieving the above object, the technical solution used in the present invention is as follows:
Catalyst for oxalate synthetic reaction of the present invention, adopt Zirconia-alumina composite oxide as carrier, wherein the zirconia in complex carrier mainly exists with tetragonal structure, aluminium oxide mainly exists with δ-aluminium oxide form, palladium and metal promoter are active component, prepare the reaction of oxalate after reduction for carbon monoxide coupling.
Adopt Zirconia-alumina composite oxide as carrier, zirconia accounts for 5% ~ 20% of carrier quality in mass.
The content of active component palladium is 0.03 % ~ 0.3 % of vehicle weight; Metal promoter is chosen one from zinc, nickel and iron, and metal promoter content is vehicle weight 0.01% ~ 0.5%.
Preparation method for the synthetic catalyst of oxalate is as follows: (1) adopts coprecipitation to prepare zirconia-alumina composite oxide, and wherein zirconia content accounts for 5% ~ 20% of composite oxides by mass, and carrier is before use through two rank temperature-programmed calcination; Roasting process comprises from room temperature with the heating rate temperature programming to 300 of 2-5 DEG C/min DEG C ~ 500 DEG C roasting 1 ~ 3 hour, is then warming up to 850 DEG C ~ 1100 DEG C roastings 3 ~ 5 hours with the heating rate of 2-5 DEG C/min; Zirconia after roasting in complex carrier mainly exists with tetragonal structure, and aluminium oxide mainly exists with δ-aluminium oxide or θ-aluminium oxide form, has a small amount of Alpha-alumina to exist; After roasting, the specific area of complex carrier is at 50 m
2/ g ~ 100m
2between/g;
(2) complex carrier adopts urea liquid processing before dipping active component, utilizes the urea gas that slowly decomposition produces while intensification to dredge the duct of complex carrier, the surface acid alkalescence of carrier is carried out to modification simultaneously; Concrete grammar is that zirconium aluminium complex carrier is put into water heating kettle, and adding mass fraction is 1% ~ 5% urea liquid, seals latter 100 DEG C ~ 150 DEG C and processes 1 ~ 5 hour, filters after washing dry;
(3) adopt organic solvent methyl alcohol or ethanol that the soluble compound of palladium and metal promoter is prepared into maceration extract, adopt ultrasonic immersing method to be incorporated on the carrier after surface treatment, flood latter 50 DEG C ~ 100 DEG C and be dried, 350 DEG C ~ 650 DEG C roastings 3 ~ 8 hours.
The activated processing of palpus before oxalate synthesis catalyst of the present invention uses, activation method can adopt the mode of liquid-phase reduction, also can adopt reducibility gas to reduce to catalyst.After catalyst activation for the reaction of carbon monoxide and nitrites synthesis of oxalate.Catalyst service condition is: reaction pressure is between 0 ~ 1MPa.Reaction temperature is that between 100 DEG C ~ 150 DEG C, reaction velocity is at 2000 h
-1~ 20000h
-1between.
It is carrier that oxalate synthesis catalyst of the present invention adopts the zirconia-alumina composite oxide after modification, the zirconic introducing of square has strengthened the stability of carrier, can stand washing away of actual complex raw material of industry gas and long-time thermal current with pressure, the zirconia of carrier surface itself is also good structural promoter simultaneously.Temperature programming technique makes the structure of complex carrier meet the special aperture requirement of ester synthesis reaction; The method of urea liquid hydrothermal treatment consists is further dredged the duct of carrier, and the load after the soda acid modification on surface simultaneously makes it becomes more firm.Adopt the catalyst of preparation in this way, catalytic activity is good, selectively high, and good stability, to the NO in unstripped gas, CO
2, the foreign gas tolerance such as methanol steam is high, can tolerate high-speed reaction, is more appropriate to the reaction of actual industrial unstripped gas.Meanwhile, coprecipitation is as a kind of traditional catalyst preparation process, simple, is beneficial to industrialization and amplifies.
Zinc, iron and nickel are good coagent, introduce in ester synthesis reaction catalyst and can effectively improve the activity of catalyst, but selectively often have loss.Method for preparing catalyst disclosed by the invention adopts complex carrier and the pretreated method of urea, and the crystal grain having caused while effectively having avoided active constituent loading is excessive, the selective problem declining very soon.
Detailed description of the invention
Below by embodiment, Catalysts and its preparation method of the present invention is described further.
Embodiment 1
The catalyst for oxalate synthetic reaction of the present embodiment, adopts Zirconia-alumina composite oxide as carrier, and zirconia accounts for 5% of carrier quality in mass.The content of active component palladium is 0.2 % of vehicle weight;
Metal promoter is zinc, and zinc content is vehicle weight 0.3%.
Its preparation method is as follows:
(1) adopt coprecipitation to prepare zirconia-alumina composite oxide, wherein zirconia content accounts for 5%% of composite oxides by mass, and carrier is before use through two rank temperature-programmed calcination; Roasting process comprises from room temperature with heating rate temperature programming to the 300 DEG C DEG C roasting of 2-5 DEG C/min 3 hours, is then warming up to 850 DEG C of roastings 5 hours with the heating rate of 2 DEG C/min; Zirconia after roasting in complex carrier mainly exists with tetragonal structure, and aluminium oxide mainly exists with δ-aluminium oxide or θ-aluminium oxide form, has a small amount of Alpha-alumina to exist; After roasting, the specific area of complex carrier is at 50 m
2/ g ~ 100m
2between/g;
(2) complex carrier adopts urea liquid processing before dipping active component, utilizes the urea gas that slowly decomposition produces while intensification to dredge the duct of complex carrier, the surface acid alkalescence of carrier is carried out to modification simultaneously; Concrete grammar is that zirconium aluminium complex carrier is put into water heating kettle, and adding mass fraction is 1%% urea liquid, seals latter 100 DEG C DEG C and processes 5 hours, filters after washing dry;
(3) adopt organic solvent methyl alcohol or ethanol that the soluble compound of palladium and metal promoter is prepared into maceration extract, adopt ultrasonic immersing method to be incorporated on the carrier after surface treatment, flood latter 50 DEG C and be dried, 350 DEG C of roastings 8 hours.
By the catalyst P d/Zn/ZrO preparing
2-Al
2o
3in the hydrogen nitrogen mixture that is 3:7 in volume ratio, 200 DEG C are reduced 5 hours.Nitrogen protection drops to 120 DEG C, and (unstripped gas consists of: MN 15%, CO 30%, N to switch to reactor feed gas
230%, NO 10%, CO
210%, methyl alcohol trace), air speed is 8000h
-1, under normal pressure, to test 500 hours, space-time yield is basicly stable at 850g/L.h, and dimethyl oxalate is selective basicly stable more than 95%.
Embodiment 2
The catalyst for oxalate synthetic reaction of the present embodiment, adopts Zirconia-alumina composite oxide as carrier, and zirconia accounts for 16% of carrier quality in mass.
The content of active component palladium is 0.3 % of vehicle weight;
Metal promoter is nickel, and nickel metal promoter content is vehicle weight 0.01%%.
Its preparation method is as follows:
(1) adopt coprecipitation to prepare zirconia-alumina composite oxide, wherein zirconia content accounts for 16% of composite oxides by mass, and carrier is before use through two rank temperature-programmed calcination; Roasting process comprises from room temperature with heating rate temperature programming to the 500 DEG C roasting of 3 DEG C/min 1 hour, is then warming up to 1100 DEG C of roastings 3 hours with the heating rate of 3 DEG C/min; Zirconia after roasting in complex carrier mainly exists with tetragonal structure, and aluminium oxide mainly exists with δ-aluminium oxide or θ-aluminium oxide form, has a small amount of Alpha-alumina to exist; After roasting, the specific area of complex carrier is at 50 m
2/ g ~ 100m
2between/g;
(2) complex carrier adopts urea liquid processing before dipping active component, utilizes the urea gas that slowly decomposition produces while intensification to dredge the duct of complex carrier, the surface acid alkalescence of carrier is carried out to modification simultaneously; Concrete grammar is that zirconium aluminium complex carrier is put into water heating kettle, and adding mass fraction is 3% urea liquid, seals latter 150 DEG C and processes 1 hour, filters after washing dry;
(3) adopt organic solvent methyl alcohol or ethanol that the soluble compound of palladium and metal promoter is prepared into maceration extract, adopt ultrasonic immersing method to be incorporated on the carrier after surface treatment, flood latter 00 DEG C and be dried, 650 DEG C of roastings 3 hours.
By the catalyst P d/Ni/ZrO preparing
2-Al
2o
3first adopt hydrazine hydrate solution to carry out liquid-phase reduction, in the hydrogen nitrogen mixture that is 3:7 in volume ratio, 100 DEG C are reduced 0.5 hour, and (unstripped gas consists of: MN 10%, CO 30%, N to switch to reactor feed gas
225%, NO 10%, CO
210%, methyl alcohol trace), being forced into 0.3MPa, air speed is 15000h
-1, to test 500 hours, space-time yield is basicly stable at 780g/L.h, and dimethyl oxalate is selective basicly stable more than 95%.
Embodiment 3
The catalyst for oxalate synthetic reaction of the present embodiment, adopts Zirconia-alumina composite oxide as carrier, and zirconia accounts for 20% of carrier quality in mass.The content of active component palladium is 0.03 %% of vehicle weight;
Metal promoter is iron, and iron content is vehicle weight 0.5%.
Its preparation method is as follows:
(1) adopt coprecipitation to prepare zirconia-alumina composite oxide, wherein zirconia content accounts for 20% of composite oxides by mass, and carrier is before use through two rank temperature-programmed calcination; Roasting process comprises from room temperature with heating rate temperature programming to the 400 DEG C roasting of 5 DEG C/min 2 hours, is then warming up to 1000 DEG C of roastings 4 hours with the heating rate of 3 DEG C/min; Zirconia after roasting in complex carrier mainly exists with tetragonal structure, and aluminium oxide mainly exists with δ-aluminium oxide or θ-aluminium oxide form, has a small amount of Alpha-alumina to exist; After roasting, the specific area of complex carrier is at 50 m
2/ g ~ 100m
2between/g;
(2) complex carrier adopts urea liquid processing before dipping active component, utilizes the urea gas that slowly decomposition produces while intensification to dredge the duct of complex carrier, the surface acid alkalescence of carrier is carried out to modification simultaneously; Concrete grammar is that zirconium aluminium complex carrier is put into water heating kettle, and adding mass fraction is 1% ~ 5% urea liquid, seals latter 100 DEG C ~ 150 DEG C and processes 1 ~ 5 hour, filters after washing dry;
(3) adopt organic solvent methyl alcohol or ethanol that the soluble compound of palladium and metal promoter is prepared into maceration extract, adopt ultrasonic immersing method to be incorporated on the carrier after surface treatment, flood latter 80 DEG C and be dried, 500 DEG C of roastings 5 hours.
By the catalyst P d/Fe/ZrO preparing
2-Al
2o
3in the hydrogen nitrogen mixture that is 3:7 in volume ratio, 200 DEG C are reduced 5 hours.Nitrogen protection drops to 120 DEG C, and (unstripped gas consists of: MN 10%, CO 30%, N to switch to reactor feed gas
225%, NO 10%, CO
210%, methyl alcohol trace), being forced into 1MPa, air speed is 20000h
-1, to test 500 hours, space-time yield is basicly stable at 1050g/L.h, and dimethyl oxalate is selective basicly stable more than 97%.
Embodiment 4
It is 5% zirconium aluminium complex carrier that coprecipitation is prepared zirconia content, to the sesbania powder that adds 5% in the powder obtaining after dry, fully kneaded and formed with the nitric acid of concentration 2% after, dry.2 DEG C/min is warming up to 300 DEG C of roastings 1 hour, is warming up to 1100 DEG C of roastings 3 hours afterwards through 2 DEG C/min.Complex carrier after roasting is added in the water heating kettle of the urea liquid that fills 500mL5%, process 1h for 150 DEG C.Cooled and filtered, washing, dry.
The palladium bichloride measuring and iron chloride iron are dissolved in methyl alcohol and are configured to maceration extract, add carrier after treatment, ultrasonic immersing 0.5 hour, 80 DEG C dry 5 hours, 650 DEG C of roastings 4 hours.Be prepared into palladium content and iron content and be respectively 0.1% and 0.01% catalyst.
By the catalyst P d/Fe/ZrO preparing
2-Al
2o
3in the hydrogen nitrogen mixture that is 3:7 in volume ratio, 200 DEG C are reduced 5 hours.Nitrogen protection drops to 120 DEG C, and (unstripped gas consists of: MN 10%, CO 30%, N to switch to reactor feed gas
225%, NO 10%, CO
210%, methyl alcohol trace), being forced into 1MPa, air speed is 20000h
-1, to test 500 hours, space-time yield is basicly stable at 1050g/L.h, and dimethyl oxalate is selective basicly stable more than 97%.
Embodiment 5
Get zirconia content and be 10% zirconium aluminium complex carrier, to the sesbania powder that adds 5% in the powder obtaining after dry, fully kneaded and formed with the nitric acid of concentration 2% after, dry.5 DEG C/min is warming up to 300 DEG C of roastings 3 hours, is warming up to 1000 DEG C of roastings 3 hours afterwards through 5 DEG C/min.1200 DEG C of roastings 5 hours.Complex carrier after roasting is added in the water heating kettle of the urea liquid that fills 500mL1%, process 5h for 120 DEG C.Cooled and filtered, washing, dry.
The palladium bichloride measuring and nickel nitrate are dissolved in ethanol and are configured to maceration extract, add carrier after treatment, ultrasonic immersing 0.5 hour, 80 DEG C dry 5 hours, 500 DEG C of roastings 4 hours.Be prepared into palladium content and nickel content and be respectively 0.03% and 0.1% catalyst.
By the catalyst P d/Ni/ZrO preparing
2-Al
2o
3first adopt hydrazine hydrate solution to carry out liquid-phase reduction, in the hydrogen nitrogen mixture that is 3:7 in volume ratio, 100 DEG C are reduced 0.5 hour, and (unstripped gas consists of: MN 10%, CO 30%, N to switch to reactor feed gas
225%, NO 10%, CO
210%, methyl alcohol trace), being forced into 0.3MPa, air speed is 15000h
-1, to test 500 hours, space-time yield is basicly stable at 780g/L.h, and dimethyl oxalate is selective basicly stable more than 95%.
Embodiment 6
Get zirconia content and be 20% zirconium aluminium complex carrier, 3 DEG C/min is warming up to 500 DEG C of roastings 1 hour, is warming up to 800 DEG C of roastings 3 hours afterwards through 3 DEG C/min.1000 DEG C of roastings 5 hours.Complex carrier after roasting is added in the water heating kettle of the urea liquid that fills 500mL3%, process 1h for 150 DEG C.Cooled and filtered, washing, dry.
The palladium bichloride measuring and zinc nitrate are dissolved in ethanol and are configured to maceration extract, add carrier after treatment, ultrasonic immersing 0.5 hour, 80 DEG C dry 5 hours, 500 DEG C of roastings 4 hours.Be prepared into palladium content and zinc content and be respectively 0.3% and 0.5% catalyst.
By the catalyst P d/Zn/ZrO preparing
2-Al
2o
3in the hydrogen nitrogen mixture that is 3:7 in volume ratio, 200 DEG C are reduced 5 hours.Nitrogen protection drops to 120 DEG C, and (unstripped gas consists of: MN 15%, CO 30%, N to switch to reactor feed gas
230%, NO 10%, CO
210%, methyl alcohol trace), air speed is 8000h
-1, under normal pressure, to test 500 hours, space-time yield is basicly stable at 850g/L.h, and dimethyl oxalate is selective basicly stable more than 95%.
Claims (4)
1. the catalyst for oxalate synthetic reaction, it is characterized in that adopting Zirconia-alumina composite oxide as carrier, wherein the zirconia in complex carrier mainly exists with tetragonal structure, aluminium oxide mainly exists with δ-aluminium oxide form, palladium and metal promoter are active component, prepare the reaction of oxalate after reduction for carbon monoxide coupling.
2. the catalyst for oxalate synthetic reaction according to claim 1, is characterized in that adopting Zirconia-alumina composite oxide as carrier, and zirconia accounts for 5% ~ 20% of carrier quality in mass.
3. according to claim 1 for the synthetic catalyst of oxalate, 0.03 % ~ 0.3 % that the content that it is characterized in that active component palladium is vehicle weight; Metal promoter is chosen one from zinc, nickel and iron, and metal promoter content is vehicle weight 0.01% ~ 0.5%.
4. claim requires the preparation method for the synthetic catalyst of oxalate described in 1, it is characterized in that: (1) adopts coprecipitation to prepare zirconia-alumina composite oxide, wherein zirconia content accounts for 5% ~ 20% of composite oxides by mass, and carrier is before use through two rank temperature-programmed calcination; Roasting process comprises from room temperature with the heating rate temperature programming to 300 of 2-5 DEG C/min DEG C ~ 500 DEG C roasting 1 ~ 3 hour, is then warming up to 850 DEG C ~ 1100 DEG C roastings 3 ~ 5 hours with the heating rate of 2-5 DEG C/min; Zirconia after roasting in complex carrier mainly exists with tetragonal structure, and aluminium oxide mainly exists with δ-aluminium oxide or θ-aluminium oxide form, has a small amount of Alpha-alumina to exist; After roasting, the specific area of complex carrier is at 50 m
2/ g ~ 100m
2between/g;
(2) complex carrier adopts urea liquid processing before dipping active component, utilizes the urea gas that slowly decomposition produces while intensification to dredge the duct of complex carrier, the surface acid alkalescence of carrier is carried out to modification simultaneously; Concrete grammar is that zirconium aluminium complex carrier is put into water heating kettle, and adding mass fraction is 1% ~ 5% urea liquid, seals latter 100 DEG C ~ 150 DEG C and processes 1 ~ 5 hour, filters after washing dry;
(3) adopt organic solvent methyl alcohol or ethanol that the soluble compound of palladium and metal promoter is prepared into maceration extract, adopt ultrasonic immersing method to be incorporated on the carrier after surface treatment, flood latter 50 DEG C ~ 100 DEG C and be dried, 350 DEG C ~ 650 DEG C roastings 3 ~ 8 hours.
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| CN107175104A (en) * | 2016-03-11 | 2017-09-19 | 中国科学院大连化学物理研究所 | A kind of catalyst of gas-phase dimethyloxalate synthesis and its preparation method and application |
| CN108187691A (en) * | 2017-12-26 | 2018-06-22 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of preparation method and applications of filled composite structure catalyst for CO gas phase coupling synthesis of oxalate |
| CN109718789A (en) * | 2018-12-29 | 2019-05-07 | 万华化学集团股份有限公司 | A kind of core-shell structure loaded catalyst and preparation method thereof |
| CN110227488A (en) * | 2019-06-25 | 2019-09-13 | 河南能源化工集团研究总院有限公司 | A kind of maleic anhydride hydrogenation prepares catalyst of succinic anhydride and preparation method thereof |
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| CN114160125A (en) * | 2021-12-14 | 2022-03-11 | 河南能源化工集团研究总院有限公司 | Ultralow palladium catalyst for catalytically synthesizing dimethyl oxalate and preparation method thereof |
| CN115709089A (en) * | 2022-11-15 | 2023-02-24 | 国家能源集团宁夏煤业有限责任公司 | Fischer-Tropsch synthetic oil hydrofining catalyst and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107175104A (en) * | 2016-03-11 | 2017-09-19 | 中国科学院大连化学物理研究所 | A kind of catalyst of gas-phase dimethyloxalate synthesis and its preparation method and application |
| CN108187691A (en) * | 2017-12-26 | 2018-06-22 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of preparation method and applications of filled composite structure catalyst for CO gas phase coupling synthesis of oxalate |
| CN108187691B (en) * | 2017-12-26 | 2019-08-30 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A preparation method and application of a filled composite structure catalyst for CO gas-phase coupling synthesis of oxalate |
| CN109718789A (en) * | 2018-12-29 | 2019-05-07 | 万华化学集团股份有限公司 | A kind of core-shell structure loaded catalyst and preparation method thereof |
| CN109718789B (en) * | 2018-12-29 | 2022-02-15 | 万华化学集团股份有限公司 | Core-shell structure supported catalyst and preparation method thereof |
| CN110227488A (en) * | 2019-06-25 | 2019-09-13 | 河南能源化工集团研究总院有限公司 | A kind of maleic anhydride hydrogenation prepares catalyst of succinic anhydride and preparation method thereof |
| CN110227451A (en) * | 2019-06-25 | 2019-09-13 | 河南能源化工集团研究总院有限公司 | Dimethyl oxalate and dimethyl carbonate joint production process catalyst and preparation method thereof |
| CN114160125A (en) * | 2021-12-14 | 2022-03-11 | 河南能源化工集团研究总院有限公司 | Ultralow palladium catalyst for catalytically synthesizing dimethyl oxalate and preparation method thereof |
| CN115709089A (en) * | 2022-11-15 | 2023-02-24 | 国家能源集团宁夏煤业有限责任公司 | Fischer-Tropsch synthetic oil hydrofining catalyst and preparation method and application thereof |
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