CN102527377A - High-efficiency nano Pd catalyst used in the process of preparing oxalate through CO carbonylation and prepared by dipping-controllable reduction method - Google Patents
High-efficiency nano Pd catalyst used in the process of preparing oxalate through CO carbonylation and prepared by dipping-controllable reduction method Download PDFInfo
- Publication number
- CN102527377A CN102527377A CN201110241453XA CN201110241453A CN102527377A CN 102527377 A CN102527377 A CN 102527377A CN 201110241453X A CN201110241453X A CN 201110241453XA CN 201110241453 A CN201110241453 A CN 201110241453A CN 102527377 A CN102527377 A CN 102527377A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- precursor
- oxalate
- alpha
- hours
- 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.)
- Granted
Links
Images
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a high-efficiency nano Pd catalyst used in the process of preparing oxalate through CO carbonylation. The catalyst comprises alpha-aluminum oxide serving as a carrier and 0.05 to 2 weight percent of noble metal Pd nanoparticles serving as active ingredients. The catalyst is prepared by a dipping-alkali-free liquid phase controllable reduction method. The catalyst is high in metal dispersion degree and narrow in dimensional distribution and can efficiently catalyze CO gas phase carbonylation to prepare the oxalate under the conditions of low temperature and low noble metal load, wherein the single-pass conversion ratio of the CO is 48 percent; the selectivity of the oxalate is over 99 percent; and the space time yield of the oxalate is more than 1,000 g.L<-1>.h<-1> (space velocity is 3,000 h<-1>).
Description
Technical field
The present invention relates to a kind of efficient nano Pd catalyst, relate in particular in the two-step method coal-ethylene glycol CO gas phase carbonylation producing oxalic ester with efficient nano Pd catalyst.
Technical background
Ethylene glycol is a kind of extremely important, strategic large chemical industry base stock, at present, more than 2,000 ten thousand tons of world's annual requirements, wherein 1/3rd the market demand is in China.The total output of whole world ethylene glycol surpasses 1,800 ten thousand tons, and about 1,500,000 tons of the production capacity of China, about 5,000,000 tons of breach, imbalance between supply and demand is very outstanding, a large amount of dependence on import.At present mainly by oil ethene route synthesizing glycol, and China is the country of the few oil of a rich coal, thereby the development coal-ethylene glycol not only can be alleviated the imbalance between supply and demand of ethylene glycol effectively, and can promote the level of coal resources high-efficiency cleaning trans-utilization.Oxalate is significant for the strategic objective that realizes coal-ethylene glycol as wherein important coal-ethylene glycol intermediate product.In addition, oxalate also is a kind of important Organic Chemicals, can be used for preparing the intermediate of oxalic acid, oxalyl chloride, oxamides, ethylene glycol, some drugs, dyestuff and solvent.
At present, domestic oxalic acid and the alcohol of still adopting is that dehydrating agent esterification dehydration method is produced oxalate with toluene or benzene.This method production technology cost is high, energy consumption is big, seriously polluted, prepared using is unreasonable.The sixties in 20th century, U.S. Fenton reported that the direct coupling of a kind of CO and alcohol becomes the method for oxalate, the new way of having opened up C1 chemical synthesis oxalate.But this reaction needed is carried out under pressurized conditions, and Ube Industries Ltd. has announced a kind of employing platinum group metal loaded catalyst subsequently, utilizes the technological process of CO and methyl nitrite normal pressure synthesizing dimethyl oxalate.This technology has good, the advantages such as reaction condition is gentle, less energy consumption, three-waste free discharge, good product quality of Atom economy, generally payes attention to and receive both at home and abroad.The catalyst space-time yield of the emerging product report of space portion is 432 g L
-1h
-1, through 480 hours successive reactions, yield did not reduce.But its noble metal use amount is big, the catalyst cost is higher, and space-time yield is lower.There are a lot of patents to report for work subsequently and in catalyst, add Zr (CN95116136.9), Ce (CN02111624.5), Ti (CN200710061392.2), La (CN200810114383.X), Ir (CN200810035248.6), Ni (CN200910307543.7), MO
x(CN200910061854.X) etc. auxiliary agent improves the space-time yield of oxalate.At present, the highest 1000g L that reached of catalyst space-time yield
-1h
-1More than, but air speed is all very high, and the consumption of major catalyst Pd is still than higher, reaction temperature is also than higher in addition.The catalyst of at present having reported that is used for CO gas phase carbonylation producing oxalic ester all adopts traditional immersion process for preparing, and all adopts high-temperature hydrogen or carbon monoxide reduction activation at last.The tradition infusion process is because the influence of group's cluster effect of solvation effect that receives immersion solvent and active component is difficult for making active group high degree of dispersion, and active component may the crystallite coalescence in follow-up roasting and high temperature reduction process, causes the catalytic activity reduction.Therefore, developing a kind of new method prepares CO gas phase carbonylation producing oxalic ester and has with high activity low noble metal load capacity nanocatalyst that great economy is worth and social effect.
Summary of the invention
The object of the present invention is to provide a kind of employing dipping-ultrasonic-controlled reducing process of alkali-free liquid phase to prepare efficient nano Pd catalyst.Compare with existing catalyst, this catalyst can be under lower temperature and low noble metal load capacity efficiently catalysis CO gas phase carbonylation become oxalate, CO conversion ratio, oxalate selectivity and space-time yield are all than higher.
Another object of the present invention is to provide the application of efficient nano Pd catalyst in the reaction of CO gas phase carbonylation producing oxalic ester, wherein oxalate can be any in dimethyl oxalate or the diethy-aceto oxalate.
Another purpose of the present invention is to provide the dipping-ultrasonic-controlled reducing preparation method of alkali-free liquid phase of efficient nano Pd catalyst.
The objective of the invention is to realize by following technical scheme; Efficient nano Pd catalyst of the present invention is characterized in that: the catalyst activity component is the Pd nano particle, and catalyst carrier is an Alpha-alumina; In the quality of carrier, wherein the weight percent content of Pd is 0.05 – 2%.
Catalyst carrier provided by the invention is an Alpha-alumina, and its surface area is 1 – 10m
2/ g handles 2 – through 800 ℃ of 400 – in advance and obtained in 10 hours.
Efficient nano Pd Preparation of catalysts method of the present invention comprises the steps:
(1) the carrier Alpha-alumina is impregnated in the Pd precursor solution, stirs:
During actual fabrication: the Pd precursor wiring solution-forming that takes by weighing certain mass; Make its concentration remain on 0.001 – 0.1mol/L; The carrier Alpha-alumina is placed Pd precursor solution, and stirring at room 1 – 20 hours is distributed in the Pd precursor solution Alpha-alumina equably;
(2) ultrasonic dispersion under heating condition:
Mixed liquor ultrasonic solvent evaporates to solution under heating condition of Pd precursor in the step (1) and Alpha-alumina is done, made the Pd precursor be adsorbed onto the Alpha-alumina surface equably;
(3) dry, roasting:
(4) the controlled reduction of alkali-free liquid phase:
The sample that step (3) is obtained adds reducing agent, structure directing reagent and protective agent and carries out the controlled reduction of liquid phase under the condition of no alkaline additive; Prepare and be of a size of 2 – 10nm, pattern is that sphere, cube or polyhedron and exposed crystal face are the nanometer Pd catalyst of (111), (100) or (110);
(5) vacuum drying:
The sample that step (4) is obtained through filter, washing, put into dry 1 – of vacuum drying chamber 20 hours, just obtain efficient nano Pd catalyst of the present invention.
The Pd precursor is following any or two or more any proportioning combination in said preparation method's the step (1): palladium nitrate, palladium, palladium bichloride, potassium chloropalladite, potassium chloropalladate, ammonium chloropalladate, palladium acetylacetonate, dichloro diamino palladium, dichloro four ammonia palladiums.
The solvent that is used to dissolve the Pd precursor in said preparation method's the step (1) is to be selected from the following combination in any that can dissolve any or following two or more solvents of Pd precursor solvent: water, methyl alcohol, ethanol, propyl alcohol, butanols, acetone, chloroform, toluene, acetonitrile, benzene, cyclohexane, pyridine, ethylene glycol, ethyl acetate, ether.
Heating-up temperature is 100 ℃ of 20 – in said preparation method's the step (2), 60 ℃ of preferred 30 –; The ultrasonic energy dispersive of every gram catalyst is 10 – 500W, preferred 150 – 350W.
The reducing agent of the controlled reduction of alkali-free liquid phase adopts at least a in strong reductant, middle strong reductant or the weak reductant in said preparation method's the step (4); Described strong reductant is selected from sodium borohydride or hydrazine hydrate; Strong reductant is selected from least a in ascorbic acid, formic acid, sodium formate, the sodium acetate in described, and described weak reductant is selected from least a in citric acid, glucose, the ethylene glycol; Described structure directing reagent has a kind of sodium chloride, potassium chloride, sodium bromide, KBr, sodium iodide, KI, citric acid, natrium citricum, potassium citrate, ammonium citrate of being selected from least; Described protective agent has a kind of polyvinylpyrrolidone (PVP), softex kw (CTAB), hexadecyltrimethylammonium chloride (CTAC), polyethylene oxygen-polypropylene oxygen-polyethylene oxygen (P123) of being selected from least; The above-mentioned reducing agent and the mol ratio of metallic precursor are (2 – 5): 1; The mol ratio of structure directing reagent and protective agent and metallic precursor is (5 – 20): 1, and the ratio between structure directing reagent and the protective agent can be 1: (1 – 5) is preferably 1:2; Reduction temperature is 150 ℃ of 40 –, and 120 ℃ of preferred 80 – compare with the conventional high-temperature hydrogen reducing, have greatly reduced reduction temperature, have avoided the sintering and the reunion of metallic particles.
Efficient nano Pd catalyst applications of the present invention is in the reaction of CO gas phase carbonylation producing oxalic ester, and wherein oxalate is any in dimethyl oxalate or the diethy-aceto oxalate.
CO gas phase carbonylation producing oxalic ester provided by the invention comprises the steps: with efficient nano Pd Application of Catalyst method
Be reflected in the miniature evaluating catalyst of the normal pressure system and carry out, adopt fixed bed reactors, catalyst amount is 0.2 – 2mL, N in the unstripped gas
2: CO:RONO=(30 – 70): (20 – 40): (10 – 30) (volume ratio), gas phase air speed are 2000 – 5000h
-1, preferred 2500 – 4000h
-1, reaction temperature is 160 ℃ of 90 –, reaction pressure is 0.01 – 0.2Mpa, analyzes raw material and product through the gas-chromatography on-line monitoring.
The present invention compared with prior art has following characteristics:
1. catalyst adopts the controlled reducing process preparation of dipping-ultrasonic-alkali-free liquid phase, and active component Pd high degree of dispersion is at carrier surface.
2. the weight percent content of active component Pd in catalyst is 0.05 – 2%, generally is merely 0.5% of carrier quality, can reduce the noble metal use amount greatly.
3. can be under lower temperature and low noble metal load capacity efficiently catalysis CO gas phase carbonylation become oxalate, the CO conversion per pass reaches 48%, the oxalate selectivity is greater than 99%, the oxalate space-time yield is greater than 1000g L
-1h
-1(air speed is 3000h-
-1).
4. catalyst preparation process is simple, cost is low, helps realizing industrialization.
Description of drawings
Fig. 1 is 0.5% Pd/ α-Al of embodiment 1 preparation
2O
3The transmission electron microscope photo of nanocatalyst.
Fig. 2 is 0.5% Pd/ α-Al of embodiment 2 preparations
2O
3The transmission electron microscope photo of nanocatalyst.
Fig. 3 is 0.5% Pd/ α-Al of embodiment 3 preparations
2O
3The transmission electron microscope photo of nanocatalyst.
Fig. 4 is 0.5% Pd/ α-Al of embodiment 4 preparations
2O
3The transmission electron microscope photo of nanocatalyst.
Fig. 5 is 0.5% Pd/ α-Al of embodiment 1 preparation
2O
3The chromatography figure of nanocatalyst.
Fig. 6 is 0.5% Pd/ α-Al of embodiment 2 preparations
2O
3The chromatography figure of nanocatalyst.
Fig. 7 is 0.5% Pd/ α-Al of embodiment 3 preparations
2O
3The chromatography figure of nanocatalyst.
Fig. 8 is 0.5% Pd/ α-Al of embodiment 4 preparations
2O
3The chromatography figure of nanocatalyst.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described further, but the present invention is not limited to following examples.
Embodiment 1:
Take by weighing the 1g Alpha-alumina and be impregnated into the K of 1.25mL 37.6mmol/L
2PdCl
4-In the aqueous solution, add 4mL ethanol again, stirred 3 hours, in 40 ℃ of water-baths with the ultrasonic dispersion of the energy of 200W 4 hours; 110 ℃ of dryings 4 hours, 400 ℃ of roastings 4 hours add the 0.070g ascorbic acid, 0.353g KBr; 0.444g PVP, 100 ℃ were reduced 60 ℃ of dryings of vacuum 10 hours 30 minutes.Transmission electron microscope photo is seen Fig. 1, can know that by figure Pd is dispersed in carrier surface, and particle is mainly sphere, and a small amount of irregular polyhedrons is arranged, and average-size is 6 – 7nm.
Evaluating catalyst: in the reaction of CO gas phase carbonylation producing oxalic ester, catalyst amount is 1mL, N in the unstripped gas with the catalyst applications in the embodiment of the invention
2: CO:RONO=48:28:20 (volume ratio), the gas phase air speed is 3000h
-1, reaction temperature is 130 ℃, reaction pressure is 0.1Mpa, analyzes raw material and product through the GC on-line monitoring.Fig. 5 is seen in chromatography, and reaction result is seen table 1.
Embodiment 2:
Take by weighing the 1g Alpha-alumina and be impregnated into the Pd (NO of 1.25mL 37.6mmol/L
3)
2-In the aqueous solution, add 4mL acetone again, stirred 3 hours; In 35 ℃ of water-baths with the ultrasonic dispersion of the energy of 200W 3 hours, 110 ℃ of dryings 4 hours, 400 ℃ of roastings 4 hours; Add the 0.105g citric acid, 0.353g KBr, 0.444g PVP; 90 ℃ were reduced 15 hours, and then added 90 ℃ of reduction of 0.018g ascorbic acid continuation 30 minutes, 60 ℃ of dryings of vacuum 10 hours.Transmission electron microscope photo is seen Fig. 2, can know that by figure Pd is dispersed in carrier surface, and particle is mainly sphere, and a small amount of irregular polyhedrons is arranged, and average-size is 4 – 6nm.Fig. 6 is seen in chromatography, and reaction result is seen table 1.
Embodiment 3:
Take by weighing the 1g Alpha-alumina and be impregnated into the Pd (OAc) of 1.25mL 37.6mmol/L
2-In the acetone soln, add 4mL acetone again, stirred 3 hours; In 35 ℃ of water-baths with the ultrasonic dispersion of the energy of 200W 3 hours, 110 ℃ of dryings 4 hours, 400 ℃ of roastings 2 hours; Add the 0.070g ascorbic acid, 0.353g KBr, 0.444g PVP; 100 ℃ were reduced 60 ℃ of dryings of vacuum 10 hours 30 minutes.Transmission electron microscope photo is seen Fig. 3, can know that by figure Pd is dispersed in carrier surface, and particle is mainly sphere, and a small amount of irregular polyhedrons is arranged, and average-size is 4 – 6nm.Fig. 7 is seen in chromatography, and reaction result is seen table 1.
Embodiment 4:
Take by weighing the 1g Alpha-alumina and be impregnated into the Pd (OAc) of 1.25mL 37.6mmol/L
2-In the acetone soln, add 4mL acetone again, stirred 3 hours; In 35 ℃ of water-baths with the ultrasonic dispersion of the energy of 200W 3 hours, 110 ℃ of dryings 4 hours, 400 ℃ of roastings 2 hours; Add 1mL 0.4mol/L solution of potassium borohydride, 0.353g KBr, 0.444g PVP; 100 ℃ were reduced 60 ℃ of dryings of vacuum 10 hours 30 minutes.Transmission electron microscope photo is seen Fig. 4, can know that by figure Pd is dispersed in carrier surface, and particle is mainly sphere, and a small amount of irregular polyhedrons is arranged, and average-size is 3 – 5nm.Fig. 8 is seen in chromatography, and reaction result is seen table 1.
Table 1: the catalytic performance of embodiment catalyst in the reaction of CO gas phase carbonylation producing oxalic ester
Claims (9)
1. efficient nano Pd catalyst, it is characterized in that: active component is the Pd nano particle, and carrier is an Alpha-alumina, and in the quality of catalyst carrier, the weight percent content of Pd is 0.05 – 2%.
2. catalyst according to claim 1 is characterized in that: catalyst carrier is an Alpha-alumina, and its surface area is 1 – 10m
2/ g handles 2 – through 800 ℃ of 400 – in advance and obtained in 4 hours.
3. catalyst according to claim 1 and 2; It is characterized in that: described catalyst carrier Alpha-alumina is impregnated in the Pd precursor solution; Stir and down the solvent evaporates of the ultrasonic Pd of being dispersed to precursor solution is dried in heating; Make the Pd precursor be adsorbed onto the Alpha-alumina surface equably, carry out drying, roasting then, the sample after the roasting adds reducing agent, structure directing reagent and protective agent and carries out the controlled reduction of alkali-free liquid phase; Prepare and be of a size of 2 – 10nm, pattern is that sphere, cube or polyhedron and exposed crystal face are the efficient nano Pd catalyst of (111), (100) or (110).
4. the described efficient nano Pd of claim 1 Preparation of catalysts method comprises the steps:
(1) with carrier impregnation in Pd precursor solution, stir, carrier is distributed in the Pd precursor solution equably;
(2) ultrasonic dispersion under heating condition:
Mixed liquor ultrasonic solvent evaporates to solution under heating condition of Pd precursor in the step (1) and Alpha-alumina is done, made the Pd precursor be adsorbed onto the Alpha-alumina surface equably;
(3) dry, roasting:
Adsorption sample 100 – in baking oven that step (2) is obtained descended dry 1 – 20 hours for 200 ℃, and 600 ℃ of roastings of 200 –, 1 – is 20 hours then;
(4) the controlled reduction of alkali-free liquid phase:
Sample adding reducing agent, structure directing reagent and protective agent that step (3) is obtained carry out the controlled reduction reaction of alkali-free liquid phase; Prepare and be of a size of 2 – 10nm, pattern is that sphere, cube or polyhedron and exposed crystal face are the nanometer Pd catalyst of (111), (100) or (110);
(5) vacuum drying:
The sample that step (4) is obtained through filter, washing, put into dry 1 – of vacuum drying chamber 20 hours, just obtain efficient nano Pd catalyst of the present invention.
5. preparation method according to claim 4 is characterized in that: the Pd precursor is the combination of following any material or following two or more materials in the step (1): palladium nitrate, palladium, palladium bichloride, potassium chloropalladite, potassium chloropalladate, ammonium chloropalladate, palladium acetylacetonate, dichloro diamino palladium, dichloro four ammonia palladiums.
6. according to claim 4 or 5 described preparation methods, it is characterized in that: the solvent that is used to dissolve the Pd precursor in the step (1) is to be selected from the following combination in any that can dissolve any or following two or more solvents of Pd precursor solvent: water, methyl alcohol, ethanol, propyl alcohol, butanols, acetone, chloroform, toluene, acetonitrile, benzene, cyclohexane, pyridine, ethylene glycol, ethyl acetate, ether; The concentration of the Pd precursor solution that Pd precursor and solvent are made into is 0.001 – 0.1mol/L.
7. according to claim 4 or 5 described preparation methods, it is characterized in that: heating-up temperature is 100 ℃ of 20 – in the step (2), 60 ℃ of preferred 30 –; The ultrasonic energy dispersive of every gram catalyst is 10 – 500W, preferred 150 – 350W.
8. according to claim 4 or 5 described preparation methods; It is characterized in that: the reducing agent of the controlled reduction of step (4) alkali-free liquid phase adopts at least a in strong reductant, middle strong reductant or the weak reductant; Described strong reductant is selected from sodium borohydride or hydrazine hydrate; Strong reductant is selected from least a in ascorbic acid, formic acid, sodium formate, the sodium acetate in described, and described weak reductant is selected from least a in citric acid, glucose, the ethylene glycol; Described structure directing reagent has a kind of sodium chloride, potassium chloride, sodium bromide, KBr, sodium iodide, KI, citric acid, natrium citricum, potassium citrate, ammonium citrate of being selected from least; Described protective agent has a kind of polyvinylpyrrolidone, softex kw, hexadecyltrimethylammonium chloride, polyethylene oxygen-polypropylene oxygen-polyethylene oxygen of being selected from least; The above-mentioned reducing agent and the mol ratio of metallic precursor are 2 – 5:1; The mol ratio of structure directing reagent and protective agent and metallic precursor is 5 – 20:1, and the ratio between structure directing reagent and the protective agent can be 1:1 – 5, is preferably 1:2; Reduction temperature is 150 ℃ of 40 –, 120 ℃ of preferred 80 –.
9. claim 1 – 4 arbitrary described efficient nano Pd catalyst are applied in the reaction of CO gas phase carbonylation producing oxalic ester, and its application process comprises the steps:
Adopt fixed bed reactors, claim 1 – 4 arbitrary described efficient nano Pd catalyst consumption are 0.2 – 2mL, in N in the volume ratio unstripped gas
2: CO:RONO=40: 10 – 30 of 70: 20 – of 30 –, the gas phase air speed is 2000 – 5000h
-1, preferred 2500 – 4000h
-1, reaction temperature is 160 ℃ of 90 –, and reaction pressure is 0.01 – 0.2Mpa, obtains the oxalate product, and wherein oxalate refers to dimethyl oxalate or diethy-aceto oxalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110241453XA CN102527377B (en) | 2011-05-27 | 2011-08-21 | High-efficiency nano Pd catalyst used in the process of preparing oxalate through CO carbonylation and prepared by dipping-controllable reduction method |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110142198.3 | 2011-05-27 | ||
| CN201110142198 | 2011-05-27 | ||
| CN201110241453XA CN102527377B (en) | 2011-05-27 | 2011-08-21 | High-efficiency nano Pd catalyst used in the process of preparing oxalate through CO carbonylation and prepared by dipping-controllable reduction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102527377A true CN102527377A (en) | 2012-07-04 |
| CN102527377B CN102527377B (en) | 2013-12-04 |
Family
ID=46336126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110241453XA Active CN102527377B (en) | 2011-05-27 | 2011-08-21 | High-efficiency nano Pd catalyst used in the process of preparing oxalate through CO carbonylation and prepared by dipping-controllable reduction method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102527377B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102600862A (en) * | 2012-02-09 | 2012-07-25 | 中国科学院福建物质结构研究所 | Preparation method of catalyst for synthesizing dimethyl oxalate from CO |
| CN103007929A (en) * | 2012-12-07 | 2013-04-03 | 上海华谊（集团）公司 | Pd-based catalyst prepared through colloid deposition, preparation method and application |
| WO2013086691A1 (en) * | 2011-12-14 | 2013-06-20 | 中国科学院福建物质结构研究所 | Nano pd catalyst for preparation of oxalate by gas phase co oxidative coupling, and preparation process thereof |
| CN104148088A (en) * | 2014-06-27 | 2014-11-19 | 中国科学院福建物质结构研究所 | Catalyst for synthesizing dimethyl oxalate from CO and ultrasonic dispersion preparation method of catalyst |
| CN104190414A (en) * | 2014-08-29 | 2014-12-10 | 中国科学院福建物质结构研究所 | Sodium borohydride reduction adopted method for preparing Pd/alpha-Al2O3 catalyst |
| CN105597743A (en) * | 2016-03-01 | 2016-05-25 | 中国科学院福建物质结构研究所 | Preparation method of catalyst for CO gas-phase catalyzed synthesis of dimethyl oxalate |
| CN106984320A (en) * | 2017-04-24 | 2017-07-28 | 北京化工大学 | A kind of high-dispersion loading type metallic catalyst and preparation method thereof |
| CN107497425A (en) * | 2017-07-05 | 2017-12-22 | 中国科学院福建物质结构研究所 | Two-part fluid bed CO dehydrogenations purify reaction technology and used catalyst |
| CN108014787A (en) * | 2017-12-18 | 2018-05-11 | 苏州铜宝锐新材料有限公司 | The preparation method of high dispersive ball shaped nano metallic catalyst |
| CN108993475A (en) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | Ternary composite material heterogeneous light Fenton catalyst and preparation and application thereof |
| CN109732096A (en) * | 2019-02-01 | 2019-05-10 | 东南大学 | A kind of preparation method of metal nanoparticle |
| CN109926066A (en) * | 2019-04-01 | 2019-06-25 | 北京化工大学 | Double auxiliary agent nano Pd catalyst Preparation method and uses |
| CN110612159A (en) * | 2017-05-01 | 2019-12-24 | 帝斯曼知识产权资产管理有限公司 | Improved method for depositing PD nanoparticles |
| CN113121345A (en) * | 2021-02-20 | 2021-07-16 | 北京单原子催化科技有限公司 | Application of monatomic Pd catalyst in CO gas-phase carbonylation |
| CN113786833A (en) * | 2021-09-29 | 2021-12-14 | 重庆市生态环境科学研究院 | Preparation method of single metal or double metal nano supported catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190884A (en) * | 2006-11-21 | 2008-06-04 | 上海焦化有限公司 | Method for synthesizing dimethyl oxalate and coproducing dimethyl carbonate |
| CN101589031A (en) * | 2007-01-24 | 2009-11-25 | 住友化学株式会社 | Method for producing propylene oxide |
-
2011
- 2011-08-21 CN CN201110241453XA patent/CN102527377B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190884A (en) * | 2006-11-21 | 2008-06-04 | 上海焦化有限公司 | Method for synthesizing dimethyl oxalate and coproducing dimethyl carbonate |
| CN101589031A (en) * | 2007-01-24 | 2009-11-25 | 住友化学株式会社 | Method for producing propylene oxide |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013086691A1 (en) * | 2011-12-14 | 2013-06-20 | 中国科学院福建物质结构研究所 | Nano pd catalyst for preparation of oxalate by gas phase co oxidative coupling, and preparation process thereof |
| US9463444B2 (en) | 2011-12-14 | 2016-10-11 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences | Preparation process of nanocatalysts with (111) crystal facet exposed and process for vapour-phase CO oxidative coupling to oxalate |
| CN102600862A (en) * | 2012-02-09 | 2012-07-25 | 中国科学院福建物质结构研究所 | Preparation method of catalyst for synthesizing dimethyl oxalate from CO |
| CN102600862B (en) * | 2012-02-09 | 2016-12-14 | 中国科学院福建物质结构研究所 | A kind of preparation method of CO synthesizing dimethyl oxalate catalyst |
| CN103007929B (en) * | 2012-12-07 | 2018-01-12 | 上海华谊（集团）公司 | The Pd bases catalyst of colloidal deposition method preparation, preparation method and application |
| CN103007929A (en) * | 2012-12-07 | 2013-04-03 | 上海华谊（集团）公司 | Pd-based catalyst prepared through colloid deposition, preparation method and application |
| CN104148088A (en) * | 2014-06-27 | 2014-11-19 | 中国科学院福建物质结构研究所 | Catalyst for synthesizing dimethyl oxalate from CO and ultrasonic dispersion preparation method of catalyst |
| CN104190414A (en) * | 2014-08-29 | 2014-12-10 | 中国科学院福建物质结构研究所 | Sodium borohydride reduction adopted method for preparing Pd/alpha-Al2O3 catalyst |
| CN105597743A (en) * | 2016-03-01 | 2016-05-25 | 中国科学院福建物质结构研究所 | Preparation method of catalyst for CO gas-phase catalyzed synthesis of dimethyl oxalate |
| CN106984320A (en) * | 2017-04-24 | 2017-07-28 | 北京化工大学 | A kind of high-dispersion loading type metallic catalyst and preparation method thereof |
| CN110612159A (en) * | 2017-05-01 | 2019-12-24 | 帝斯曼知识产权资产管理有限公司 | Improved method for depositing PD nanoparticles |
| CN107497425A (en) * | 2017-07-05 | 2017-12-22 | 中国科学院福建物质结构研究所 | Two-part fluid bed CO dehydrogenations purify reaction technology and used catalyst |
| CN107497425B (en) * | 2017-07-05 | 2019-07-30 | 中国科学院福建物质结构研究所 | Two-part fluidized bed CO dehydrogenation purification reaction technology and used catalyst |
| CN108014787A (en) * | 2017-12-18 | 2018-05-11 | 苏州铜宝锐新材料有限公司 | The preparation method of high dispersive ball shaped nano metallic catalyst |
| CN108993475A (en) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | Ternary composite material heterogeneous light Fenton catalyst and preparation and application thereof |
| CN109732096A (en) * | 2019-02-01 | 2019-05-10 | 东南大学 | A kind of preparation method of metal nanoparticle |
| CN109732096B (en) * | 2019-02-01 | 2022-01-28 | 东南大学 | Preparation method of metal nanoparticles |
| CN109926066A (en) * | 2019-04-01 | 2019-06-25 | 北京化工大学 | Double auxiliary agent nano Pd catalyst Preparation method and uses |
| CN113121345A (en) * | 2021-02-20 | 2021-07-16 | 北京单原子催化科技有限公司 | Application of monatomic Pd catalyst in CO gas-phase carbonylation |
| CN113786833A (en) * | 2021-09-29 | 2021-12-14 | 重庆市生态环境科学研究院 | Preparation method of single metal or double metal nano supported catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102527377B (en) | 2013-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102527377B (en) | High-efficiency nano Pd catalyst used in the process of preparing oxalate through CO carbonylation and prepared by dipping-controllable reduction method | |
| CN102553579B (en) | Preparation method of high-dispersity supported nano metal catalyst | |
| CN103041826B (en) | Bimetal nanometer catalyst as well as preparation and application method thereof | |
| CN105363436B (en) | Carbon monoxide gas phase coupling catalyst for synthesizing oxalic ester, preparation method and its usage | |
| CN102513101B (en) | Nano Pd catalyst used for preparing oxalic ester by CO gas phase oxidation coupling and its preparation method | |
| CN106064087A (en) | Method for preparing VOCs catalytic combustion catalyst | |
| CN107686105B (en) | Preparation method of high-efficiency nitrogen-doped carbon nano tube and application of nitrogen-doped carbon nano tube | |
| CN103691451A (en) | Catalyst for synthesizing methyl formate by virtue of gas-phase methanol carbonylation as well as preparation method and application of catalyst | |
| CN107684907B (en) | Noble metal catalyst for catalyzing wet oxidation of industrial wastewater, preparation method and application thereof | |
| CN108067220A (en) | A kind of hydrogen peroxide synthesis loaded catalyst and its preparation method and application | |
| CN110028382A (en) | A method of preparing sorbierite | |
| CN101642708B (en) | Non-noble metal catalyst, preparation thereof and application thereof | |
| CN106423161A (en) | Preparation method of hydrogenation catalyst and catalyst | |
| CN106944065A (en) | The preparation method and application of graphene-supported nickel hydrogenation catalyst | |
| CN111408392A (en) | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof | |
| CN107876097A (en) | A kind of CO catalytic oxidation use catalyst of high activity and high stability and preparation method thereof | |
| CN113058596A (en) | High-stability CO2Preparation and application of catalyst for preparing ethanol by hydrogenation | |
| CN104801299A (en) | Plant reduction preparation method of ruthenium-on-carbon catalyst, ruthenium-on-carbon catalyst and application | |
| CN101138720B (en) | Metallic-radicle integral catalyzer for direct catalytic conversion of methyl hydride and method of preparing the same | |
| CN110665546A (en) | Noble metal/amino MOFs selective hydrogenation catalyst, preparation method and application thereof | |
| CN108192057B (en) | Porous organic polymer and its solid catalyst for supporting gold nano grain；And it prepares and applies | |
| CN106807366B (en) | Core-shell catalyst for preparing lactic acid and pyruvic acid from glycerol, and preparation and application thereof | |
| CN115624988B (en) | Organic iron-SiO 2 Aerogel-like catalyst and preparation method thereof | |
| CN108069850A (en) | A kind of method for being catalyzed lactic acid oxidative dehydrogenation and preparing pyruvic acid | |
| CN101524647B (en) | Metal base monolithic catalyst for preparing low carbon hydrocarbons by using methane through oxidative coupling and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180103 Address after: 562300 Guizhou Province, Xingren Buyi and Miao Autonomous Prefecture Xingren County Economic Development Zone (Industrial Park) Patentee after: Guizhou Xin alcohol science and Technology Development Co., Ltd. Address before: Fuzhou City, Fujian province 350002 Yangqiao Road No. 155 Patentee before: Fujian Institute of Research on the Structure of Matter, Chinese Academy of Scie |
|
| TR01 | Transfer of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: High-efficiency nano Pd catalyst used in the process of preparing oxalate through CO carbonylation and prepared by dipping-controllable reduction method Effective date of registration: 20200525 Granted publication date: 20131204 Pledgee: Guizhou Xinchun Energy Co., Ltd Pledgor: Guizhou Xin alcohol science and Technology Development Co., Ltd. Registration number: Y2020110000003 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |