CN103041826B - Bimetal nanometer catalyst as well as preparation and application method thereof - Google Patents
Bimetal nanometer catalyst as well as preparation and application method thereof Download PDFInfo
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Abstract
The invention discloses a bimetal nanometer catalyst used for preparing dimethyl oxalate through CO gas-phase oxidative coupling as well as preparation and an application method of the bimetal nanometer catalyst, and belongs to the technical field of preparation of the dimethyl oxalate. The bimetal nanometer catalyst is characterized in that a catalyst carrier is Alpha-aluminium oxide, an active component is Pd-Cu nanometer grains, the average size of the grain is 2-3nm, the Pd content of the active component is 0.01-2% and Cu content is 0.01-0.04% according to the mass of the catalyst carrier. The catalyst is prepared through a room temperature normal position load method, the preparation method is simple, the energy dissipation is low, the catalyst is suitable for industrial production, the active component Pd-Cu nanometer grains in the catalyst has high dispersity, large specific surface area, small size and uniformity in distribution; the catalyst provided by the invention adopts the Pd-Cu bimetal nanometer grains as the active component, and a bimetal component synergistic effect and a nanometer effect are utilized to reduce the content of the noble metal PD to 0.1% under the premise of keeping the high activity and stability of the catalyst, therefore and the cost of the catalyst is greatly reduced, and the partial substitution of the noble metal is realized.
Description
Technical field:
The invention belongs to dimethyl oxalate preparing technical field, relate to a kind of for CO gaseous oxidation coupling dimethyl oxalate bimetal nano catalyst and methods for making and using same thereof in coal-ethylene glycol.
Technical background:
Dimethyl oxalate is a kind of important Organic Chemicals, can be used for preparing oxalic acid, oxalyl chloride, oxamide, also can be used for fine chemistry industry and produces various dyestuff, medicine, important solvent, extractant and various intermediate.In addition, Hydrogenation of Dimethyl Oxalate can prepare extremely important chemical industry base stock ethylene glycol.Ethylene glycol purposes is very extensive, in a large number for the production of polyester and antifreezing agent.2011, whole world ethylene glycol demand more than 2,500 ten thousand tons, and wherein the demand of 40% in China.But the production capacity of China 3,100,000 tons, import is more than 7,000,000 tons.The production of usual ethylene glycol adopts oil ethene technology path, and China is the country that a rich coal lacks oil, therefore Development of Coal preparing ethylene glycol not only can alleviate the imbalance between supply and demand of ethylene glycol effectively, can also make up the deficiency of China's oil resource, have important strategic importance.
Coal-ethylene glycol technology comprises three key steps.They are respectively: 1) carbon monoxide dehydrogenation purification; 2) carbon monoxide gaseous oxidation coupling dimethyl oxalate; 3) preparing ethylene glycol by using dimethyl oxalate plus hydrogen.Wherein, carbon monoxide gaseous oxidation coupling dimethyl oxalate realizes the committed step that inorganic carbon monoxide transforms to organic chemicals dimethyl oxalate in coal-ethylene glycol.Although coal-ethylene glycol technology enters industrialization phase completely, and achieve good economic benefit, in coal-ethylene glycol the first two step, all adopt precious metals palladium catalyst, and the content of palladium all higher (> 1%).Since last century the eighties, report the New research progress of CO gaseous oxidation coupling producing oxalic ester both at home and abroad successively.The open Application Publication of patent JP8242.656 reports a kind of employing platinum group metal loaded catalyst, utilizes the technological process of CO and methyl nitrite atmospheric synthesis dimethyl oxalate.The catalyst space-time yield of this patent report is 432g L
-1h
-1, through 480 hours successive reactions, yield did not reduce.The catalyst adding the auxiliary agents such as Zr, Ce, Ti, Fe, La, Re, Ga in the catalyst and form in succession is reported subsequently by a lot of patent, be applied in the technique of CO and nitrites gas-phase synthesis of oxalate, but in the patent reported, the load capacity of catalyst noble metal Pd is generally higher.As the Pd-Zr/Al that Chinese patent CN95116136.9 reports
2o
3the Pd-La-Re/Al of catalyst and CN101791555A report
2o
3in catalyst, the content of Pd is all about 1.5%; The Pd-Ce/Al that Chinese patent CN1381310A reports
2o
3the Pd-Ga/Al of catalyst, CN1055492A report
2o
3the Pd-Ti-Ce/Al of catalyst, CN101138722A report
2o
3with the Pd-La/Al of CN101596455A report
2o
3in catalyst, the content of Pd is all about 1%.Pd is a kind of noble metal, and expensive, reserves are limited, and high load capacity causes catalyst cost high, affects its use in the industry.
Chinese patent CN101612580A discloses a kind of Pd-Cu/Al
2o
3catalyst application is in synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling reaction.Although catalyst of the present invention composition on similar with foregoing patent, component structure and content on have obvious difference.The nanometer granule be highly dispersed on carrier of catalyst activity component Pd-Cu of the present invention to be average-size be 2-3nm, and the content of Cu is lower than 0.05%, the target product of catalyst preparing of the present invention is also different, is for carbon monoxide and methyl nitrite gaseous oxidation coupling dimethyl oxalate.The small-size effect that catalyst of the present invention make use of nano particle significantly improves catalytic performance.There is nano particle small-size effect just and show good catalytic performance in multiple catalytic reaction in many carrier nanometer catalysts.Such as, document CATTECH, in 2002,6:102-115, author Haruta. M. finds that block gold is chemically inert, does not have catalytic activity, but in much reacting, shows surprised catalytic performance to when below 10nm when gold grain size is little.Therefore, the research and development of Novel series efficient low noble metal load capacity nanocatalyst can save a large amount of noble metal, overrun, implement the strategy of sustainable development significant to solution Precious Metals Resources.
Summary of the invention:
Main purpose of the present invention is: higher for the load capacity of catalyst noble metal Pd in CO gaseous oxidation coupling dimethyl oxalate technique in coal-ethylene glycol technology, catalyst high in cost of production is not enough, provides that a kind of noble-metal-supported amount is low, performance is high, the bimetal nano Catalysts and its preparation method for CO gaseous oxidation coupling dimethyl oxalate of good stability.
Another object of the present invention is to provide above-mentioned nanocatalyst preparing the application in dimethyl oxalate.
In order to solve above technical problem, the present invention is achieved by the following technical solutions:
A kind of CO gaseous oxidation coupling dimethyl oxalate bimetal nano catalyst, the carrier of catalyst is Alpha-alumina is that active component is Pd-Cu nano particle; The composition of catalyst is in the quality of carrier, and active component Pd content is 0.01 – 2%, Cu content is 0.01-0.04%.
The specific area of described alpha-alumina supports is 1 – 20m
2/ g, specific pore volume is 0.01-0.1cm
3/ g, average pore size is 10-50nm; The Size Distribution of described Pd-Cu nano particle, at 1 – 20nm, is preferably 1-5nm; Described Pd-Cu nanoparticulate dispersed degree is 15-60%, and specific area is 50-400m
2/ g
The preparation method of nanocatalyst of the present invention adopts the preparation of room temperature original position load method, comprises the following steps:
(1) precious metal palladium salt, mantoquita, organic complexing agent and surfactant are made into mixed aqueous solution;
Described palladium salt be selected from palladium nitrate, palladium bichloride, potassium chloropalladite, potassium chloropalladate or ammonium chloropalladate any one; Described mantoquita be selected from copper chloride, Schweinfurt green, copper nitrate or copper sulphate any one; Described organic complexing agent be selected from citric acid, natrium citricum, potassium citrate or ammonium citrate any one; Described surfactant be selected from polyvinylpyrrolidone, polyvinyl alcohol, lauryl sodium sulfate, neopelex or softex kw any one.
(2) alpha-alumina supports to be joined in the mixed aqueous solution of step (1) and to stir 0.5-2 hour;
(3) reducing agent wiring solution-forming is joined in the suspension of above-mentioned steps (2), and stirred at ambient temperature reduction 10-48 hour;
Described reducing agent be selected from ascorbic acid, glucose, formic acid or sodium formate any one, preferred ascorbic acid.
(4) the product isolated by filtration of step (3) is obtained filtrate and solids, then solids use water, absolute ethyl alcohol, acetone washing are repeatedly, vacuum 60-80 DEG C of drying 5 – 20 hours;
(5) by step (4) dried solids activation process 3-6 hour under pure hydrogen atmosphere, hydrogen flow rate 10-60 ml/min, activation temperature 250-450 DEG C, is then cooled to room temperature in pure hydrogen atmosphere, obtains described nanocatalyst.
The soluble copper salt added in the step (1) of described preparation method is excessive, Cu
2+ion serves significant effect in course of reaction, Cu
2+the introducing of ion can affect the coring and increment of Pd nano particle, effectively can improve the dispersion of Pd nano particle, and Cu
2+ion itself is at room temperature difficult to be reduced by more weak reducing agent, the only Cu of trace
2+ion is reduced into Cu nano particle owing to there is underpotential deposition effect on Pd surface, forms one of catalyst activity component.
In step (4) filtrate of described preparation method, unreacted palladium salt completely, can reuse.
The application process of CO gaseous oxidation coupling dimethyl oxalate bimetal nano catalyst provided by the invention comprises the steps: to adopt fixed bed reactors, catalyst amount is 0.2 – 2mL, unstripped gas CO and methyl nitrite flow-ratio control are between 1.2-1.6, and gas phase air speed is 2000 – 5000h
-1, unstripped gas contacts with described nanocatalyst under the condition of normal pressure, 90 – 150 DEG C, obtains dimethyl oxalate product.Unstripped gas and product are analyzed by gas-chromatography on-line monitoring.
The present invention compared with prior art, has following remarkable result:
1. bimetal nano catalyst of the present invention adopts Pd-Cu duplex metal nano granule as active component, and Pd-Cu nanoparticulate dispersed degree is high, specific area is large, size is little, be evenly distributed.
2. bimetal nano catalyst of the present invention utilizes bimetallic component synergistic effect and nano effect that the content of precious metals pd in catalyst is reduced to 0.1%, a large amount of noble metal can be saved, to the cost of catalyst be greatly reduced, achieve the Some substitute of noble metal.
3. bimetal nano catalyst of the present invention has good catalytic activity at low noble metal load capacity (about 0.1%) and reaction temperature 130 DEG C, and CO conversion per pass is up to 62%, and dimethyl oxalate selective 97%, dimethyl oxalate space-time yield is greater than 1300 g L
-1h
-1; And industrial catalyst noble metal Pd load capacity higher (about 2%), at reaction temperature 130 DEG C, CO conversion per pass is only 35%, and dimethyl oxalate space-time yield is 750 g L
-1h
-1.
4. bimetal nano catalyst of the present invention just has higher catalytic activity at compared with low reaction temperatures 100 DEG C, and CO conversion per pass reaches 42%, dimethyl oxalate selective 98%, and dimethyl oxalate space-time yield reaches 911 g L
-1h
-1, this will reduce industrial energy consumption greatly.
5. bimetal nano catalyst preparation process of the present invention is simple and easy to operate, energy consumption is low, cost is lower.
Accompanying drawing explanation
Fig. 1 is the chromatography figure that the nanocatalyst of embodiment 1 preparation gathers at reaction temperature 130 DEG C.
Fig. 2 is the chromatography figure that the nanocatalyst of comparative example 1 preparation gathers at reaction temperature 130 DEG C.
Fig. 3 is nanocatalyst Pd prepared by embodiment 1
3delement XPS spectrum figure.
Fig. 4 is nanocatalyst Cu prepared by embodiment 1
2pelement XPS spectrum figure.
Fig. 5 is nanocatalyst Pd prepared by comparative example 1
3delement XPS spectrum figure.
Fig. 6 is nanocatalyst transmission electron microscope photo prepared by embodiment 1.
Fig. 7 is nanocatalyst transmission electron microscope photo prepared by comparative example 1.
Fig. 8 is nanocatalyst transmission electron microscope photo prepared by embodiment 2.
Fig. 9 is nanocatalyst transmission electron microscope photo prepared by embodiment 3.
Figure 10 is nanocatalyst transmission electron microscope photo prepared by embodiment 4.
Figure 11 is nanocatalyst transmission electron microscope photo prepared by embodiment 5.
Figure 12 is nanocatalyst transmission electron microscope photo prepared by embodiment 6.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1:
Take in the 15ml aqueous solution that 1g Alpha-alumina joins containing 0.0163g potassium chloropalladite, 0.0170g copper chloride, 0.2220g polyvinylpyrrolidone (PVP), 0.2100g citric acid, stirring at room temperature 0.5 hour, then the 5ml aqueous solution containing 0.0700g ascorbic acid is added, at room temperature stir reduction 16 hours, product isolated by filtration obtains filtrate and solids, then solids water, absolute ethyl alcohol, acetone wash 6 times, vacuum 60 DEG C of dryings 8 hours.Dried solids 400 DEG C of activation process 3 hours under pure hydrogen (flow velocity 40ml/min) atmosphere, are then cooled to room temperature, i.e. obtained catalyst in pure hydrogen atmosphere.Catalyst XPS spectrum figure is shown in Fig. 3 and Fig. 4, is zeroth order by Pd and Cu element valence in the known catalyst of Pd3d and Cu2P electron binding energy.Catalyst electromicroscopic photograph is shown in Fig. 6, Pd-Cu nano particle on the known catalyst of electromicroscopic photograph is highly dispersed at carrier surface, nanoparticle size is distributed in 1-5nm, average-size is 2.7nm, the actual negative carrying capacity recording Pd in catalyst by plasma emission spectroscopy (ICP) is the actual negative carrying capacity of 0.13%, Cu is 0.014%.
Evaluating catalyst: by the catalyst application in the embodiment of the present invention in the reaction of CO gaseous oxidation coupling dimethyl oxalate, catalyst amount is 1mL, and unstripped gas CO and methyl nitrite flow-rate ratio are 1.4, and gas phase air speed is 3000h
-1, reaction temperature is 90-150 DEG C, and reaction pressure is 0.1Mpa, and unstripped gas and product are analyzed by gas-chromatography on-line monitoring, and Fig. 1 is shown in chromatography, and reaction result is in table 1.
Table 1: the catalytic performance of embodiment 1 catalyst in the reaction of CO gaseous oxidation coupling dimethyl oxalate
As can be seen from Table 1: catalyst of the present invention can under low noble metal load capacity and lower temperature the synthesis of oxalate of catalysis CO gaseous oxidation coupling efficiently, and this catalyst has good stability, at reaction temperature 130 DEG C, experienced by the successive reaction of 100 hours, catalyst activity and selectivity does not all decline.
Comparative example 1:
Take in the 15ml aqueous solution that 1g Alpha-alumina joins containing 0.0163g potassium chloropalladite, 0.2220g polyvinylpyrrolidone (PVP), 0.2100g citric acid, stirring at room temperature 0.5 hour, then the 5ml aqueous solution containing 0.0700g ascorbic acid is added, at room temperature stir reduction 16 hours, product isolated by filtration obtains filtrate and solids, then solids water, absolute ethyl alcohol, acetone wash 6 times, vacuum 60 DEG C of dryings 8 hours.Dried solids 400 DEG C of activation process 3 hours under pure hydrogen (flow velocity 40ml/min) atmosphere, are then cooled to room temperature, i.e. obtained catalyst in pure hydrogen atmosphere.Catalyst XPS spectrum figure is shown in Fig. 5, is zeroth order by Pd element valence in the known catalyst of Pd3d electron binding energy.Catalyst electromicroscopic photograph is shown in Fig. 7, and the comparatively large and skewness of the Pd nanoparticle size on the known catalyst of electromicroscopic photograph, reunite a little, nano particle average-size is 11.6nm.The actual negative carrying capacity being recorded Pd in catalyst by plasma emission spectroscopy (ICP) is 0.37%.
Evaluate the catalyst of comparative example 1 in the same manner as in example 1, wherein reaction temperature is 130 DEG C, and Fig. 2 is shown in chromatography, and reaction result is in table 2.
Table 2: embodiment 1 and the catalytic performance of comparative example 1 catalyst in the reaction of CO gaseous oxidation coupling dimethyl oxalate
Table 3: the different physical properties of embodiment 1 and comparative example 1 catalyst
Can find from table 2 data, although precious metals pd load capacity is 1/3rd of Pd load capacity in comparative example 1 catalyst in embodiment 1 catalyst, the catalytic activity of embodiment 1 catalyst is 2 times of comparative example 1 catalyst activity.Can illustrate from table 3 data, the main cause producing catalytic activity difference is that in embodiment 1 catalyst, active component Pd-Cu nano particle has less particle size, higher decentralization and larger specific area.
Embodiment 2:
Take in the filtrate that 1g Alpha-alumina joins in embodiment 1, stirring at room temperature 0.5 hour, then the 5ml aqueous solution containing 0.0700g ascorbic acid is added, at room temperature stir reductase 12 4 hours, product isolated by filtration obtains filtrate and solids, then solids water, absolute ethyl alcohol, acetone wash 6 times, vacuum 60 DEG C of dryings 8 hours.Dried solids 400 DEG C of activation process 3 hours under pure hydrogen (flow velocity 40ml/min) atmosphere, are then cooled to room temperature, i.e. obtained catalyst in pure hydrogen atmosphere.Catalyst transmission electron microscope photo is shown in Fig. 8, and the Pd-Cu nano particle on the known catalyst of electromicroscopic photograph is highly dispersed at carrier surface, and nanoparticle size is distributed in 1-5nm, and average-size is 2.7nm.The actual negative carrying capacity recording Pd in catalyst by plasma emission spectroscopy (ICP) is the actual negative carrying capacity of 0.121%, Cu is 0.019%.
Embodiment 3:
Take in the 15ml aqueous solution that 1g Alpha-alumina joins containing 0.0163g potassium chloropalladite, 0.0200g copper acetate, 0.2220g polyvinylpyrrolidone (PVP), 0.2100g citric acid, stirring at room temperature 0.5 hour, then the 5ml aqueous solution containing 0.0700g ascorbic acid is added, at room temperature stir reduction 16 hours, product isolated by filtration obtains filtrate and solids, then solids water, absolute ethyl alcohol, acetone wash 6 times, vacuum 60 DEG C of dryings 8 hours.Dried solids 400 DEG C of activation process 3 hours under pure hydrogen (flow velocity 40ml/min) atmosphere, are then cooled to room temperature, i.e. obtained catalyst in pure hydrogen atmosphere.Catalyst transmission electron microscope photo is shown in Fig. 9, and the Pd-Cu nano particle on the known catalyst of electromicroscopic photograph is highly dispersed at carrier surface, and nanoparticle size is distributed in 1-4nm, and average-size is 2.0nm.The actual negative carrying capacity recording Pd in catalyst by plasma emission spectroscopy (ICP) is the actual negative carrying capacity of 0.087%, Cu is 0.026%.
Embodiment 4:
Take in the filtrate that 1g Alpha-alumina joins in embodiment 3, stirring at room temperature 0.5 hour, then the 5ml aqueous solution containing 0.0700g ascorbic acid is added, at room temperature stir reductase 12 4 hours, product isolated by filtration obtains filtrate and solids, then solids water, absolute ethyl alcohol, acetone wash 6 times, vacuum 60 DEG C of dryings 8 hours.Dried solids 400 DEG C of activation process 3 hours under pure hydrogen (flow velocity 40ml/min) atmosphere, are then cooled to room temperature, i.e. obtained catalyst in pure hydrogen atmosphere.Catalyst transmission electron microscope photo is shown in Figure 10, and the Pd-Cu nano particle on the known catalyst of electromicroscopic photograph is highly dispersed at carrier surface, and nanoparticle size is distributed in 1-4nm, and average-size is 2.0nm.The actual negative carrying capacity recording Pd in catalyst by plasma emission spectroscopy (ICP) is the actual negative carrying capacity of 0.119%, Cu is 0.015%.
Embodiment 5:
Take in the 15ml aqueous solution that 1g Alpha-alumina joins containing 0.0163g potassium chloropalladite, 0.0242g copper nitrate, 0.2220g polyvinylpyrrolidone (PVP), 0.2100g citric acid, stirring at room temperature 0.5 hour, then the 5ml aqueous solution containing 0.0700g ascorbic acid is added, at room temperature stir reduction 16 hours, product isolated by filtration obtains filtrate and solids, then solids water, absolute ethyl alcohol, acetone wash 6 times, vacuum 60 DEG C of dryings 8 hours.Dried solids 400 DEG C of activation process 3 hours under pure hydrogen (flow velocity 40ml/min) atmosphere, are then cooled to room temperature, i.e. obtained catalyst in pure hydrogen atmosphere.Catalyst transmission electron microscope photo is shown in Figure 11, and the Pd-Cu nano particle on the known catalyst of electromicroscopic photograph is highly dispersed at carrier surface, and nanoparticle size is distributed in 1-5nm, and average-size is 2.9nm.The actual negative carrying capacity recording Pd in catalyst by plasma emission spectroscopy (ICP) is the actual negative carrying capacity of 0.118%, Cu is 0.027%.
Embodiment 6:
Take in the filtrate that 1g Alpha-alumina joins in embodiment 5, stirring at room temperature 0.5 hour, then the 5ml aqueous solution containing 0.0700g ascorbic acid is added, at room temperature stir reductase 12 4 hours, product isolated by filtration obtains filtrate and solids, then solids water, absolute ethyl alcohol, acetone wash 6 times, vacuum 60 DEG C of dryings 8 hours.Dried solids 400 DEG C of activation process 3 hours under pure hydrogen (flow velocity 40ml/min) atmosphere, are then cooled to room temperature, i.e. obtained catalyst in pure hydrogen atmosphere.Catalyst transmission electron microscope photo is shown in Figure 12, and the Pd-Cu nano particle on the known catalyst of electromicroscopic photograph is highly dispersed at carrier surface, and nanoparticle size is distributed in 1-5nm, and average-size is 2.7nm.The actual negative carrying capacity recording Pd in catalyst by plasma emission spectroscopy (ICP) is the actual negative carrying capacity of 0.106%, Cu is 0.019%.
Evaluate the catalyst of embodiment 2-6 in the same manner as in example 1, wherein reaction temperature is 130 DEG C, and reaction result is in table 4.
Table 4: the catalytic performance of embodiment catalyst in the reaction of CO gaseous oxidation coupling dimethyl oxalate
As can be seen from Table 4: catalyst of the present invention catalysis CO gaseous oxidation coupling efficiently can become dimethyl oxalate under low noble-metal-supported amount (about 0.1%), and CO conversion ratio, dimethyl oxalate are selective and space-time yield is all higher.This to illustrate in bimetal nano catalyst of the present invention that active component Pd-Cu nanoparticulate dispersed degree is high, specific area is large, size is little and is evenly distributed.This point can be confirmed by transmission electron microscope photo and size distribution histogram.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (2)
1. a CO gaseous oxidation coupling dimethyl oxalate bimetal nano catalyst, is characterized in that, this catalyst take Alpha-alumina as carrier, with Pd-Cu nano particle for active component; The composition of catalyst is in the quality of carrier, and active component Pd content is 0.01-2%, Cu content is 0.01-0.04%;
The specific area of described alpha-alumina supports is 1-20m
2/ g, specific pore volume is 0.01-0.1cm
3/ g, average pore size is 10-50nm;
The Size Distribution of described Pd-Cu nano particle is at 1-20nm;
The decentralization of described Pd-Cu nano particle is 15-60%, and specific area is 50-400m
2/ g;
This catalyst adopts the preparation of room temperature original position load method, comprises the following steps:
(1) precious metal palladium salt, mantoquita, organic complexing agent and surfactant are made into mixed aqueous solution;
(2) alpha-alumina supports to be joined in the mixed aqueous solution of step (1) and to stir 0.5-2 hour;
(3) reducing agent wiring solution-forming is joined in the suspension of above-mentioned steps (2), and stirred at ambient temperature reduction 10-48 hour;
(4) the product isolated by filtration of step (3) is obtained filtrate and solids, then solids use water, absolute ethyl alcohol, acetone washing are repeatedly, vacuum 60-80 DEG C of dry 5-20 hour;
(5) by step (4) dried solids activation process 3-6 hour under pure hydrogen atmosphere, hydrogen flow rate 10-60 ml/min, activation temperature 250-450 DEG C, is then cooled to room temperature in pure hydrogen atmosphere, i.e. obtained described nanocatalyst.
2., for the preparation of a preparation method for CO gaseous oxidation coupling dimethyl oxalate bimetal nano catalyst according to claim 1, it is characterized in that:
Described palladium salt be selected from palladium nitrate, palladium bichloride, potassium chloropalladite, potassium chloropalladate or ammonium chloropalladate any one;
Described mantoquita be selected from copper chloride, Schweinfurt green, copper nitrate or copper sulphate any one;
Described organic complexing agent be selected from citric acid, natrium citricum, potassium citrate or ammonium citrate any one;
Described surfactant be selected from polyvinylpyrrolidone, polyvinyl alcohol, lauryl sodium sulfate, neopelex or softex kw any one;
Described reducing agent be selected from ascorbic acid, glucose, formic acid or sodium formate any one.
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| CN102513101A (en) * | 2011-12-14 | 2012-06-27 | 中国科学院福建物质结构研究所 | Nano Pd catalyst used for preparing oxalic ester by CO gas phase oxidation coupling and its preparation method |
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Effective date of registration: 20171229 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: Yang Qiao Road, Gulou District of Fuzhou city of Fujian Province, No. 155 350002 Patentee before: Fujian Institute of Research on the Structure of Matter, Chinese Academy of Scie |
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Denomination of invention: Bimetal nanometer catalyst as well as preparation and application method thereof Effective date of registration: 20200525 Granted publication date: 20150415 Pledgee: Guizhou Xinchun Energy Co., Ltd Pledgor: Guizhou Xin alcohol science and Technology Development Co., Ltd. Registration number: Y2020110000003 |