CN102513101A - Nano Pd catalyst used for preparing oxalic ester by CO gas phase oxidation coupling and its preparation method - Google Patents
Nano Pd catalyst used for preparing oxalic ester by CO gas phase oxidation coupling and its preparation method Download PDFInfo
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Abstract
The invention belongs to the oxalic ester preparation technical field, and provides a nano Pd catalyst used for preparing oxalic ester by CO gas phase oxidation coupling in coal glycol, its preparation method and its purpose. According to the invention, the catalyst takes alpha-alumina as a carrier, precious metal Pd nano particles are taken as an active component, by referring the weight of the catalyst carrier, the weight percentage content of the active ingredient Pd is 0.05-2%. The catalyst is prepared by using a nano metal in-situ loading method. The preparation method has the advantages of simple process and low energy consumption, and enables accurate regulation and control on the size and bare crystal face of the Pd nano particles. The catalyst with the bare crystal face of (lll) surface has the advantages of high Pd dispersiveness of active components, small size and narrow distribution, and can catalyze CO gas phase oxidation coupling to oxalic ester with high efficiency under low precious metal load capacity.
Description
Technical field
The present invention relates to the synthetic of oxalate, relate in particular in a kind of coal-ethylene glycol CO gaseous oxidation coupling producing oxalic ester with nanometer Pd Catalysts and its preparation method and purposes.
Background technology
Coal-ethylene glycol mainly divided for three steps, the first step: the CO dehydrogenation purifies after the coal based synthetic gas process transformation adsorbing separation; Second step: CO gaseous oxidation coupling producing oxalic ester; The 3rd step: hydrogenation of oxalate for preparing ethylene glycol.Wherein, CO gaseous oxidation coupling producing oxalic ester is to realize the committed step that inorganic CO transforms to the organic chemicals oxalate in the middle of the coal-ethylene glycol.Oxalate is a kind of important Organic Chemicals, can be used for preparing the intermediate of ethylene glycol, oxalic acid, oxalyl chloride, oxamides, 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.Patent JP8242.656 openly speciallys permit communique and has reported a kind of employing load type palladium catalyst, utilizes the technological process of CO and methyl nitrite normal pressure synthesizing dimethyl oxalate.This technology Atom economy is good, reaction condition is gentle, less energy consumption, three-waste free discharge, good product quality.The catalyst space-time yield of this patent report is 432gL
-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 in succession subsequently and in catalyst, add Zr (CN95116136.9), Ce (CN02111624.5), Ti (CN200710061392.2), La (CN200810114383.X), Ir (CN200810035248.6), Ni (CN200910307543.7), Cu (CN200910060087.0), MO
x(CN200910061854.X) etc. auxiliary agent improves the space-time yield of oxalate.The space-time yield of oxalate improves to some extent behind the adding auxiliary agent, but the consumption of major catalyst Pd is still than higher.At present, the actual negative carrying capacity of Pd is about 2% on the commercial plant.In addition, the catalyst of having reported in patent and the document all adopts traditional immersion process for preparing, and this method need experience steps such as dipping, drying, roasting, high temperature reduction, and the cycle is long, energy consumption is high, and can't carry out accuracy controlling to the size and the exposed crystal face of Pd particle.And the size of Pd particle and exposed crystal face are two very important parameters that influence catalytic activity.Therefore, develop a kind of easy fast method prepare CO gaseous oxidation coupling producing oxalic ester with low noble metal load capacity, size and exposed crystal face controlled, the high-activity nano catalyst has great economy and is worth.
Summary of the invention
The object of the present invention is to provide a kind of nanometer Pd catalyst and application in the reaction of CO gaseous oxidation coupling producing oxalic ester thereof of adopting the preparation of nano metal original position load method.Compare with existing catalyst; The pattern of this catalyst activity component Pd nano particle is mainly the non-spherical polyhedron of (111) for exposed crystal face; Can catalysis CO gaseous oxidation coupling efficiently become oxalate under than low noble metal load capacity (as 0.37%), CO conversion ratio, oxalate selectivity and space-time yield are all than higher.
Another object of the present invention is to provide the nano metal original position load preparation method of nanometer Pd catalyst.Compare with existing Preparation of catalysts method, it is easy fast that this method prepares process, only needs a step can accomplish Preparation of catalysts, and energy consumption is lower, and size and exposed crystal face that can accuracy controlling Pd particle.
CO gaseous oxidation coupling producing oxalic ester of the present invention comprises the active component on carrier and the carrier with nanometer Pd catalyst, and carrier is an Alpha-alumina; Active component is the Pd nano particle, and wherein, the average-size of said Pd nano particle is 1-25nm; Be preferably 2-3nm, be shaped as non-spherical polyhedron, the polyhedral exposed crystal face of said non-sphere is mainly (111) face; Particularly, the polyhedral exposed crystal face of said non-sphere is (111) face more than 50%; In the weight of catalyst carrier, the degree that active component Pd accounts for vehicle weight is 0.05-2%.
High-dispersion nano Pd Preparation of catalysts method of the present invention is following: the carrier Alpha-alumina is joined in Pd precursor, reducing agent, structure directing reagent and the protectant mixed solution, the nano metal Pd original position of generation is loaded on the carrier.
The Pd precursor is a kind of or any several kinds of combination of compounds in palladium nitrate, palladium acetate, the palladium halide among the said preparation method.
The instance of the reducing agent described in the said preparation method includes but not limited to a kind of or any several kinds of combination of compounds in sodium borohydride, hydrazine hydrate, ascorbic acid, formaldehyde, formic acid, sodium formate, sodium acetate, citric acid, glucose, the ethylene glycol, and the reducing agent consumption is 1-10 a times of Pd precursor.The effect of reducing agent is to make palladium cation in the precursor be reduced to the palladium of zeroth order, selects for use the reducing agent of varying strength can control reduction rate, thereby controls the nanocrystalline speed of growth.
Described structure directing reagent is selected from the compound that contains citrate or oxalate, and consumption is 1-10 a times of Pd precursor.The effect of structure directing reagent is the speed of growth of the different crystal faces of control, thus the controllably synthetic nano particle that exposes different crystal faces.Citrate or oxalate can optionally cover on Pd (111) face, suppress the growth of Pd (111) face, thereby make exposed (111) face of final synthetic Pd nano particle.No matter compound is acid or salt, and no matter cation is inorganic or organic ion, as long as anionicsite contains citrate or oxalate, and the purpose that just can implementation structure leads.If changing structure directing reagent is halide ion, then will obtain the nanometer Pd cube of exposed crystal face for (100).The non-spherical polyhedron of Pd that the exposed crystal face of the activity of this nanometer Pd cube catalysis CO gaseous oxidation coupling producing oxalic ester is mainly (111) (table 2 is seen in the catalytic activity data contrast) far short of what is expected, exposed (111) face of this explanation Pd is the active crystal face of CO gaseous oxidation coupling producing oxalic ester.
Described protective agent is selected from organic polymer; Like polyvinylpyrrolidone or polyethylene oxygen-polypropylene oxygen-polyethylene oxygen etc.; Or the chain alkyl ammonium salt, like softex kw or hexadecyltrimethylammonium chloride etc., consumption is 1-100 a times of Pd precursor.Protectant effect is the reunion that suppresses nano particle.
Heating-up temperature is 50-200 ℃ among the said preparation method, preferred 80-150 ℃.
Nanometer Pd catalyst applications of the present invention is in the reaction of CO gaseous oxidation coupling producing oxalic ester, and wherein oxalate is any in dimethyl oxalate or the diethy-aceto oxalate.
CO gaseous oxidation coupling producing oxalic ester provided by the invention comprises the steps: that with nanometer Pd Application of Catalyst method CO contacts with described nanometer Pd catalyst with nitrites under the 90-160 ℃ of condition; Obtain the oxalate product, analyze raw material and product through the gas-chromatography on-line monitoring.
Description of drawings
Fig. 1 is the 0.37%Pd/ α-Al of embodiment 1 preparation
2O
3The transmission electron microscope photo of nanocatalyst.
Fig. 2 is the 0.93%Pd/ α-Al of comparative example 1 preparation
2O
3The transmission electron microscope photo of nanocatalyst.
Fig. 3 is the 0.39%Pd/ α-Al of embodiment 2 preparations
2O
3The transmission electron microscope photo of nanocatalyst.
Fig. 4 is the 0.2%Pd/ α-Al of embodiment 3 preparations
2O
3The transmission electron microscope photo of nanocatalyst.
Fig. 5-Fig. 8 is the 0.37%Pd/ α-Al of embodiment 1 preparation
2O
3The high-resolution-ration transmission electric-lens photo of nanocatalyst.
Fig. 9, Figure 10 are the 0.93%Pd/ α-Al of comparative example 1 preparation
2O
3The high-resolution-ration transmission electric-lens photo of nanocatalyst.
Figure 11-Figure 14 is the 0.39%Pd/ α-Al of embodiment 2 preparations
2O
3The high-resolution-ration transmission electric-lens photo of nanocatalyst.
Figure 15-Figure 18 is the 0.2%Pd/ α-Al of embodiment 3 preparations
2O
3The high-resolution-ration transmission electric-lens photo of nanocatalyst.
The specific embodiment
Below in conjunction with specific embodiment and comparative example the present invention is described further, but the present invention is not limited to following examples.
The instrument model of using in catalyst characterization and the evaluation:
Transmission electron microscope, high-resolution-ration transmission electric-lens: NEC (JEOL), JEM-2010,200kV; Plasma emission spectrum: French HORIBA Jobin Yvon, Ultima2; Miniature catalyst test apparatus: Beijing Wei Kendu Science and Technology Ltd., customized; Gas-chromatography: day island proper Tianjin (Shimadzu), GC-2014.
Explanation about spacing of lattice, gas phase air speed and space-time yield:
Spacing of lattice: refer in the nanocrystalline high resolution transmission electron microscopy image of Pd the distance between two lattice fringes.In the middle of face-centered cubic Pd was nanocrystalline, the spacing of lattice of (111) crystal face was 0.226nm, and the spacing of lattice of (200) crystal face is 0.197nm.Therefore, as long as spacing of lattice equals or near 0.226nm, just can explain Pd nanocrystalline exposed be (111) face.Gas phase air speed: refer to that the unit interval passes through the volume of the reactant of per volume of catalyst (unit: h
-1).Space-time yield: refer to that under given reaction condition in the unit interval, unit volume (or weight) catalyst can obtain a certain product amount (unit: gL
-1h
-1).It is one of sign of weighing catalyst activity size and reactor assembly production capacity.
Embodiment
Embodiment 1:
Taking by weighing the 1g Alpha-alumina joins and contains Pd (OAc)
20.010g, in the 20mL aqueous solution of ascorbic acid 0.016g, sodium oxalate 0.054g, polyvinylpyrrolidone (PVP) 0.111g, 100 ℃ were stirred 0.5 hour, with acetone, water, washing with alcohol three times, 60 ℃ of dryings of vacuum 2 hours.The transmission electron microscope photo of gained sample is seen Fig. 1, can observe Pd by figure and be dispersed in carrier surface, and particle performance is non-spherical polyhedron, and average-size is 2-3nm.The high-resolution-ration transmission electric-lens photo of this sample is seen Fig. 5-Fig. 8, can know that by figure the spacing of lattice of this non-spherical polyhedron particle is 0.226nm, and is consistent with the spacing of lattice of Pd face-centered cubic (111) face, and visible its exposed crystal face is (111) face.Can know according to the analysis result of many high-resolution-ration transmission electric-lens photos statistics, the polyhedral exposed crystal face of this non-sphere be (111) face more than 50%.The actual negative carrying capacity that records Pd through plasma emission spectrum is 0.37%.
Evaluating catalyst: in the reaction of CO gaseous oxidation coupling producing oxalic ester, catalyst amount is 1mL, N in the unstripped gas with the catalyst applications of embodiment 1
2: CO: RONO=48: 28: 20 (volume ratio), gas phase air speed are 3000h
-1, reaction temperature is 90-160 ℃, reaction pressure is 0.1Mpa, analyzes raw material and product through the gas-chromatography on-line monitoring.Reaction result is seen table 1.
The catalytic performance of the catalyst of table 1: embodiment 1 in the reaction of CO gaseous oxidation coupling producing oxalic ester
Comparative example 1:
Taking by weighing the 1g Alpha-alumina joins and contains K
2PdCl
60.018g, PdCl
20.009g, in the 20mL aqueous solution of ascorbic acid 0.035g, KBr 0.179g, polyvinylpyrrolidone (PVP) 0.222g, 100 ℃ were stirred 0.5 hour, with acetone, water, washing with alcohol three times, 60 ℃ of dryings of vacuum 2 hours.The transmission electron microscope photo of gained sample is seen Fig. 2, can observe Pd by figure and be dispersed in carrier surface, and particle all is a cubic block, and average-size is 9-10nm.The high-resolution-ration transmission electric-lens photo of this sample is seen Fig. 9 and Figure 10, can know that by figure its spacing of lattice is 0.196nm, and is consistent with the spacing of lattice of Pd face-centered cubic (200) face, and visible its exposed crystal face is (100) face.The actual negative carrying capacity that records Pd through plasma emission spectrum is 0.93%.
With embodiment 1 identical mode the catalyst of comparative example 1 is estimated, wherein reaction temperature is 130 ℃.Reaction result is seen table 2.
The exposed crystal face of table 2:Pd is to the influence of catalytic activity
Can find that from table 2 data the Pd nano particle of exposed (111) face is high more a lot of than the cubical catalytic activity of the Pd of exposed (100) face.This explanation Pd (111) face is a CO gaseous oxidation coupling producing oxalic ester reactive activity crystal face, and preparation method of the present invention can controllably synthesize the non-spherical polyhedron of exposed (111) face.
Embodiment 2:
Taking by weighing the 1g Alpha-alumina joins and contains K
2PdCl
40.015g, in the 20mL aqueous solution of citric acid 0.084g, polyvinylpyrrolidone (PVP) 0.111g, when being heated to 60 ℃, add 1mL formaldehyde, stirred 3 hours, with acetone, water, washing with alcohol three times, 60 ℃ of dryings of vacuum 2 hours.Transmission electron microscope photo is seen Fig. 3, can know the Pd high degree of dispersion at carrier surface by figure, and particle performance is octahedra, and average-size is 20-22nm.The high-resolution-ration transmission electric-lens photo is seen Figure 11-Figure 14, can know that by figure the spacing of lattice of this octahedron particle is 0.226nm, and is consistent with the spacing of lattice of Pd face-centered cubic (111) face, and visible its exposed crystal face is (111) face.Can know according to the analysis result of many high-resolution-ration transmission electric-lens photos statistics, this octahedral exposed crystal face be (111) face more than 50%.The actual negative carrying capacity that records Pd through plasma emission spectrum is 0.39%.
Embodiment 3:
Taking by weighing the 1g Alpha-alumina joins and contains Pd (OAc)
20.004g, in the 20mL aqueous solution of sodium formate 0.007g, citric acid 0.084g, polyvinylpyrrolidone (PVP) 0.111g, 100 ℃ were stirred 0.5 hour, with acetone, water, washing with alcohol three times, 60 ℃ of dryings of vacuum 2 hours.Transmission electron microscope photo is seen Fig. 4, can know the Pd high degree of dispersion at carrier surface by figure, and particle performance is non-spherical polyhedron, and average-size is 2-3nm.The high-resolution-ration transmission electric-lens photo is seen Figure 15-Figure 18, can know that by figure the spacing of lattice of this non-spherical polyhedron particle is 0.226nm, and is consistent with the spacing of lattice of Pd face-centered cubic (111) face, and visible its exposed crystal face is (111) face.Can know according to the analysis result of many high-resolution-ration transmission electric-lens photos statistics, the polyhedral exposed crystal face of this non-sphere be (111) face more than 50%.
Embodiment 4:
Pd (OAc) as the Pd presoma
2Consumption is 0.020g, and all the other steps are identical with embodiment 3.
Embodiment 5:
Pd (OAc) as the Pd presoma
2Consumption is 0.040g, and all the other steps are identical with embodiment 3.
With embodiment 1 identical mode the catalyst of embodiment 2-5 is estimated, wherein reaction temperature is 130 ℃.Reaction result is seen table 4.
Table 4:
Can find out that from table 4 data the catalyst of low load capacity can be realized high catalytic activity equally.This explains that Pd nano particle high degree of dispersion is not reunited at carrier surface in the nanometer Pd catalyst of the present invention, and this point can be confirmed through transmission electron microscope photo among the embodiment 1.
Embodiment 6:
K as the Pd presoma
2PdCl
4Consumption be 0.015g, all the other steps are identical with embodiment 1.
Embodiment 7:
Pd (NO as the Pd presoma
3)
2Consumption be 0.010g, all the other steps are identical with embodiment 1.
The catalyst of observing embodiment 6,7 from transmission electron microscope photo and high-resolution-ration transmission electric-lens photo has the performance similar with embodiment 1.And with embodiment 1 identical mode the catalyst of embodiment 6,7 is estimated, wherein reaction temperature is 130 ℃.Reaction result is seen table 5.
Table 5: different Pd precursors are to the influence of catalytic performance
Can find out that from table 5 data the type of Pd precursor is little to the catalytic performance influence, the performance of the catalyst of three kinds of precursor acquisitions is very approaching.
Comparative example 2:
Alpha-alumina is replaced by gama-alumina, and all the other steps are identical with embodiment 1.
Carrier is seen table 6 to the influence of catalytic performance, and reaction temperature is 130 ℃.
Table 6: carrier is to the influence of catalytic performance
Data can be found out from table, when adopting gamma-aluminium oxide carrier, have no activity, but when adopting alpha-alumina supports, activity is very high.This explanation Alpha-alumina is the effective carrier of CO gaseous oxidation coupling producing oxalic ester reaction.
Beneficial effect of the present invention:
1. the pattern that can control the Pd nano particle through nano metal original position load method is mainly the non-spherical polyhedron of (111) for exposed crystal face, and exposed (111) face of Pd is the active crystal face of CO gaseous oxidation coupling producing oxalic ester.
2. the Pd nano particle high degree of dispersion in the catalyst is at carrier surface.
3. catalyst can catalysis CO gaseous oxidation coupling efficiently become oxalate under than low noble metal load capacity (as 0.37%).
4. the Preparation of Catalyst cycle is short, energy consumption is low.
Claims (9)
1. a CO gaseous oxidation coupling producing oxalic ester is with nanometer Pd catalyst; Comprise carrier and the active component on said carrier; Said carrier is an Alpha-alumina; Said active component is the Pd nano particle, it is characterized in that: said Pd nano particle is non-spherical polyhedron, the polyhedral exposed crystal face of said non-sphere be (111) face more than 50%.
2. nanometer Pd catalyst according to claim 1 is characterized in that: the average-size of described Pd nano particle is 1-25nm, is preferably 2-3nm.
3. nanometer Pd catalyst according to claim 1 and 2 is characterized in that: in the weight of catalyst carrier, the degree that described Pd nano particle accounts for vehicle weight is 0.05-2%.
4. each described nanometer Pd Preparation of catalysts method among the claim 1-3; It is characterized in that: the carrier Alpha-alumina is joined in Pd precursor, reducing agent, structure directing reagent and the protectant mixed solution, under heating-up temperature is 50-200 ℃, stirring condition, the nano metal Pd original position of generation is loaded on the carrier then.
5. nanometer Pd Preparation of catalysts method according to claim 4 is characterized in that: described Pd precursor comprises a kind of or any several kinds of combination of compounds in palladium nitrate, palladium acetate, the palladium halide; Described reducing agent comprises a kind of or any several kinds of combination of compounds in sodium borohydride, hydrazine hydrate, ascorbic acid, formaldehyde, formic acid, sodium formate, sodium acetate, citric acid, glucose, the ethylene glycol; Described structure directing reagent is selected from the compound that contains citrate or oxalate; Described protective agent is selected from the organic polymer that comprises polyvinylpyrrolidone or polyethylene oxygen-polypropylene oxygen-polyethylene oxygen, or comprises the chain alkyl ammonium salt of softex kw or hexadecyltrimethylammonium chloride.
6. according to claim 4 or 5 described nanometer Pd Preparation of catalysts methods, it is characterized in that: described heating-up temperature is 80-150 ℃.
In the claim 1 to 3 each described nanometer Pd catalyst as CO gaseous oxidation coupling catalyst in order to the preparation oxalate application.
8. nanometer Pd Application of Catalyst according to claim 7 is characterized in that: described oxalate is dimethyl oxalate or diethy-aceto oxalate.
9. nanometer Pd Application of Catalyst according to claim 7, the reaction temperature of said CO gaseous oxidation coupling is 90-160 ℃.
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| CN106391000B (en) * | 2016-10-10 | 2018-12-21 | 中国科学院福建物质结构研究所 | CO dehydrogenation purification reaction Pd (111)/γ-Al2O3Catalyst and preparation method thereof |
| CN107456999A (en) * | 2017-07-17 | 2017-12-12 | 中国科学院福建物质结构研究所 | A kind of nano Pd catalyst of porous manganese organic frame load and preparation method thereof |
| 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 |
| CN112295580A (en) * | 2020-11-04 | 2021-02-02 | 福州大学 | Sodium carbonate supported palladium-copper nano catalyst and application thereof in preparation of olefin by catalytic hydrogenation of alkyne |
| CN112295580B (en) * | 2020-11-04 | 2022-04-01 | 福州大学 | Sodium carbonate supported palladium-copper nano catalyst and application thereof in preparation of olefin by catalytic hydrogenation of alkyne |
| CN114433081A (en) * | 2022-02-25 | 2022-05-06 | 中国科学院福建物质结构研究所 | Preparation method of catalyst for CO-production of carbonic ester and formic ester by synthesizing oxalate with CO |
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