CN102527377B - 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
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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 to CO gas phase carbonylation producing oxalic ester efficient nano Pd catalyst in the two-step method coal-ethylene glycol.
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 approximately 1,500,000 tons of production capacity of China, approximately 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 few oily country that is a rich coal, thereby the Development of Coal preparing 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, as wherein important coal-ethylene glycol intermediate product, is significant for the strategic objective that realizes coal-ethylene glycol.In addition, oxalate is also 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, domesticly still adopt oxalic acid and alcohol to take the method that toluene or benzene is dehydrating agent esterification dehydration to produce oxalate.The method production technology cost is high, energy consumption is large, 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, 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 technique has that Atom economy is good, the advantages such as reaction condition is gentle, less energy consumption, three-waste free discharge, good product quality, and is subject to generally paying attention to both at home and abroad.The catalyst space-time yield of the emerging product report of space section is 432 g L
-1h
-1, through 480 hours successive reactions, yield did not reduce.But its noble metal use amount is large, the catalyst cost is higher, and space-time yield is lower.Have subsequently a lot of patents to report for work and add Zr(CN95116136.9 in catalyst), Ce(CN02111624.5), Ti(CN200710061392.2), La(CN200810114383.X), Ir(CN200810035248.6), Ni(CN200910307543.7), MO
xEtc. (CN200910061854.X) auxiliary agent improves the space-time yield of oxalate.At present, the highest 1000g L that reached of catalyst space-time yield
-1h
-1Above, but air speed is all very high, and the consumption of major catalyst Pd is still higher, and reaction temperature is also higher in addition.The catalyst for CO gas phase carbonylation producing oxalic ester of now having reported all adopts traditional infusion process preparation, and finally all adopts high-temperature hydrogen or carbon monoxide reduction activation.The tradition infusion process, due to the impact of the cluster effect of the solvation effect that is subject to immersion solvent and active component, is difficult for making active group high degree of dispersion, and in follow-up roasting and high temperature reduction process, active component may the crystallite coalescence, causes catalytic activity to reduce.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.With existing catalyst, compare, this catalyst can lower temperature with under the low noble metal load capacity efficiently catalysis CO gas phase carbonylation become oxalate, CO conversion ratio, oxalate are selective and space-time yield is all 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 diethy-aceto oxalate.
Another purpose of the present invention is to provide the dipping of efficient nano Pd catalyst-ultrasonic-controlled reducing preparation method of alkali-free liquid phase.
The objective of the invention is to be realized 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 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 Alpha-alumina, and its surface area is 1 – 10m
2/ g, process 2 – through 800 ℃ of 400 – in advance and obtain in 10 hours.
The preparation method of efficient nano Pd catalyst of the present invention, comprise the steps:
(1) the carrier Alpha-alumina is impregnated in Pd precursor solution, stirs:
During actual preparation: the Pd precursor wiring solution-forming that takes certain mass, make its concentration remain on 0.001 – 0.1mol/L, the carrier Alpha-alumina is placed in to Pd precursor solution, and stirring at room 1 – 20 hours, be distributed in Pd precursor solution Alpha-alumina equably;
(2) ultrasonic dispersion under heating condition:
The mixed liquor of Pd precursor in step (1) and Alpha-alumina ultrasonic solvent evaporates to solution under heating condition is dry, make the Pd precursor be adsorbed onto equably the Alpha-alumina surface;
(3) dry, roasting:
The sample that step (2) is obtained to absorption dry 1-20 hour under 200 ℃ of 100 – in baking oven, then 600 ℃ of roastings of 200 –, 1 – is 20 hours;
(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 to carry out the controlled reduction of liquid phase under the condition without alkaline additive, prepare and be of a size of 2 – 10nm, pattern is the nano Pd catalyst that spherical, cube or polyhedron and exposed crystal face are (111), (100) or (110);
(5) vacuum drying:
The sample that step (4) is obtained after filtration, washing, put into dry 1 – of vacuum drying chamber 20 hours, just obtain efficient nano Pd catalyst of the present invention.
In described preparation method's step (1), the Pd precursor is following any one or more any proportioning combination: palladium nitrate, palladium, palladium bichloride, potassium chloropalladite, potassium chloropalladate, ammonium chloropalladate, palladium acetylacetonate, dichloro diamino palladium, dichloro four ammonia palladiums.
In described preparation method's step (1), for the solvent that dissolves the Pd precursor, be to be selected from the following any combination 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.
In described preparation method's step (2), heating-up temperature is 100 ℃ of 20 –, and preferably 30 – is 60 ℃; The ultrasonic energy dispersive of every gram catalyst is 10 – 500W, preferably 150 – 350W.
In described preparation method's step (4), the reducing agent of the controlled reduction of alkali-free liquid phase adopts at least one in strong reductant, middle strong reductant or weak reductant, described strong reductant is selected from sodium borohydride or hydrazine hydrate, described middle strong reductant is selected from least one in ascorbic acid, formic acid, sodium formate, sodium acetate, and described weak reductant is selected from least one in citric acid, glucose, 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; 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 protective agent can be 1:(1 – 5), be preferably 1:2; Reduction temperature is 150 ℃ of 40 –, and preferably 80 – is 120 ℃, with the conventional high-temperature hydrogen reducing, compares, and has greatly reduced reduction temperature, has avoided sintering and the reunion of metallic particles.
Efficient nano Pd catalyst of the present invention is applied in the reaction of CO gas phase carbonylation producing oxalic ester, and wherein oxalate is any in dimethyl oxalate or diethy-aceto oxalate.
CO gas phase carbonylation producing oxalic ester provided by the invention comprises the steps: with the application process of efficient nano Pd catalyst
Reaction is carried out in the miniature evaluating catalyst system of normal pressure, adopts fixed bed reactors, and catalyst amount is 0.2 – 2mL, N in unstripped gas
2: CO:RONO=(30 – 70): (20 – 40): (10 – 30) (volume ratio), the gas phase air speed is 2000 – 5000h
-1, preferred 2500 – 4000h
-1, reaction temperature is 160 ℃ of 90 –, reaction pressure is 0.01 – 0.2Mpa, by the gas-chromatography on-line monitoring, analyzes raw material and product.
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%, is only generally 0.5% of carrier quality, can greatly reduce the noble metal use amount.
Can lower temperature with under the low noble metal load capacity efficiently catalysis CO gas phase carbonylation become oxalate, the CO conversion per pass reaches 48%, oxalate selectively 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, is conducive to realize industrialization.
The accompanying drawing explanation
0.5% Pd/ α-Al that Fig. 1 is embodiment 1 preparation
2O
3The transmission electron microscope photo of nanocatalyst.
0.5% Pd/ α-Al that Fig. 2 is embodiment 2 preparations
2O
3The transmission electron microscope photo of nanocatalyst.
0.5% Pd/ α-Al that Fig. 3 is embodiment 3 preparations
2O
3The transmission electron microscope photo of nanocatalyst.
0.5% Pd/ α-Al that Fig. 4 is embodiment 4 preparations
2O
3The transmission electron microscope photo of nanocatalyst.
0.5% Pd/ α-Al that Fig. 5 is embodiment 1 preparation
2O
3The chromatography figure of nanocatalyst.
0.5% Pd/ α-Al that Fig. 6 is embodiment 2 preparations
2O
3The chromatography figure of nanocatalyst.
0.5% Pd/ α-Al that Fig. 7 is embodiment 3 preparations
2O
3The chromatography figure of nanocatalyst.
0.5% Pd/ α-Al that Fig. 8 is embodiment 4 preparations
2O
3The chromatography figure of nanocatalyst.
The specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1:
Take the K that the 1g Alpha-alumina is impregnated into 1.25mL 37.6mmol/L
2PdCl
4-In the aqueous solution, then add 4mL ethanol, stir 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 ℃ are reduced 30 minutes, 60 ℃ of dryings of vacuum 10 hours.Transmission electron microscope photo is shown in Fig. 1, and Pd is dispersed in carrier surface as seen from the figure, and particle is mainly spherical, and a small amount of irregular polyhedrons is arranged, and average-size is 6 – 7nm.
Evaluating catalyst: the catalyst in the embodiment of the present invention is applied in the reaction of CO gas phase carbonylation producing oxalic ester, and catalyst amount is 1mL, N in unstripped gas
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, by the GC on-line monitoring, analyzes raw material and product.Fig. 5 is shown in chromatography, and reaction result is in Table 1.
Embodiment 2:
Take the Pd (NO that the 1g Alpha-alumina is impregnated into 1.25mL 37.6mmol/L
3)
2-In the aqueous solution, add again 4mL acetone, stir 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 ℃ are reduced 15 hours, and then add the 0.018g ascorbic acid to continue 90 ℃ of reduction 30 minutes, 60 ℃ of dryings of vacuum 10 hours.Transmission electron microscope photo is shown in Fig. 2, and Pd is dispersed in carrier surface as seen from the figure, and particle is mainly spherical, and a small amount of irregular polyhedrons is arranged, and average-size is 4 – 6nm.Fig. 6 is shown in chromatography, and reaction result is in Table 1.
Embodiment 3:
Take the Pd (OAc) that the 1g Alpha-alumina is impregnated into 1.25mL 37.6mmol/L
2-In acetone soln, add again 4mL acetone, stir 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 ℃ are reduced 30 minutes, 60 ℃ of dryings of vacuum 10 hours.Transmission electron microscope photo is shown in Fig. 3, and Pd is dispersed in carrier surface as seen from the figure, and particle is mainly spherical, and a small amount of irregular polyhedrons is arranged, and average-size is 4 – 6nm.Fig. 7 is shown in chromatography, and reaction result is in Table 1.
Embodiment 4:
Take the Pd (OAc) that the 1g Alpha-alumina is impregnated into 1.25mL 37.6mmol/L
2-In acetone soln, add again 4mL acetone, stir 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 ℃ are reduced 30 minutes, 60 ℃ of dryings of vacuum 10 hours.Transmission electron microscope photo is shown in Fig. 4, and Pd is dispersed in carrier surface as seen from the figure, and particle is mainly spherical, and a small amount of irregular polyhedrons is arranged, and average-size is 3 – 5nm.Fig. 8 is shown in chromatography, and reaction result is in Table 1.
Table 1: the catalytic performance of embodiment catalyst in the reaction of CO gas phase carbonylation producing oxalic ester
Claims (4)
1. the preparation method of an efficient nano Pd catalyst, this catalyst activity component is the Pd nano particle, and carrier is Alpha-alumina, and in the quality of catalyst carrier, the weight percent content of Pd is 0.05 – 2%, and the method comprises the steps:
(1) by carrier impregnation in Pd precursor solution, stir, carrier is distributed in Pd precursor solution equably;
The solvent of described Pd precursor solution is any combination that is selected from following any or following two or more solvents: water, methyl alcohol, ethanol, propyl alcohol, butanols, acetone, chloroform, toluene, acetonitrile, benzene, cyclohexane, pyridine, ethylene glycol, ethyl acetate, ether; The concentration of described Pd precursor solution is 0.001 – 0.1mol/L;
(2) ultrasonic dispersion under heating condition:
The mixed liquor of Pd precursor in step (1) and Alpha-alumina ultrasonic solvent evaporates to solution under heating condition is dry, make the Pd precursor be adsorbed onto equably the Alpha-alumina surface;
Described heating-up temperature is 100 ℃ of 20 –; The ultrasonic energy dispersive of every gram catalyst is 10 – 500W;
(3) dry, roasting:
The adsorption sample that step (2) is obtained dry 1 – 20 hours under 200 ℃ of 100 – in baking oven, then 600 ℃ of roastings of 200 –, 1 – is 20 hours;
(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 to carry out the controlled reduction reaction of alkali-free liquid phase, prepare and be of a size of 2 – 10nm, pattern is spherical or polyhedron and the exposed crystal face nano Pd catalyst that is (111), (100) or (110);
Described reducing agent adopts at least one in strong reductant, middle strong reductant or weak reductant, described strong reductant is selected from sodium borohydride or hydrazine hydrate, described middle strong reductant is selected from least one in ascorbic acid, formic acid, sodium formate, sodium acetate, and described weak reductant is selected from least one in citric acid, glucose, ethylene glycol; Described structure directing reagent has a kind of sodium chloride, potassium chloride, sodium bromide, KBr, sodium iodide, KI, 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; 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 protective agent is 1:1 – 5; Reduction temperature is 150 ℃ of 40 –.
(5) vacuum drying:
The sample that step (4) is obtained after filtration, washing, put into dry 1 – of vacuum drying chamber 20 hours, just obtain efficient nano Pd catalyst.
2. preparation method according to claim 1 is characterized in that: the combination that in described step (1), the Pd precursor is following any material or following two or more materials: palladium nitrate, palladium, palladium bichloride, potassium chloropalladite, potassium chloropalladate, ammonium chloropalladate, palladium acetylacetonate, dichloro diamino palladium, dichloro four ammonia palladiums.
3. an efficient nano Pd catalyst, active component is the Pd nano particle, carrier is Alpha-alumina, quality in catalyst carrier, the weight percent content of Pd is 0.05 – 2%, it is characterized in that: described Pd nanoparticle size is 2 – 10nm, and pattern is spherical or polyhedron and exposed crystal face are (111), (100) or (110); And described nano Pd catalyst adopts the described method preparation of claim 1 or 2.
4. the application of efficient nano Pd catalyst claimed in claim 3 in the reaction of CO gas phase carbonylation producing oxalic ester, its application process comprises the steps: to adopt fixed bed reactors, the consumption of described efficient nano Pd catalyst is 0.2 – 2mL, in N in the volume ratio unstripped gas
2: CO:RONO=30 – 70:20 – 40:10 – 30, the gas phase air speed is 2000 – 5000h
-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.
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| 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 |
| 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 |
| 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 |
| CN104190414B (en) * | 2014-08-29 | 2016-03-23 | 中国科学院福建物质结构研究所 | A kind of sodium borohydride reduction that adopts prepares Pd/ α-Al 2o 3the preparation method of 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 |
| US20200061585A1 (en) * | 2017-05-01 | 2020-02-27 | Dsm Ip Assets B.V. | Improved process to deposit pd- nanoparticles |
| 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 |
| CN108993475B (en) * | 2018-08-16 | 2021-01-22 | 南京工业大学 | Ternary composite material heterogeneous light Fenton catalyst and preparation and application thereof |
| 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 |
| CN113121345B (en) * | 2021-02-20 | 2022-06-10 | 北京单原子催化科技有限公司 | Application of monatomic Pd catalyst in CO gas-phase carbonylation |
| CN113786833B (en) * | 2021-09-29 | 2023-05-16 | 重庆市生态环境科学研究院 | Preparation method of monometal or bimetallic nano-supported catalyst |
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| 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 |