CN106378128B - A kind of CO synthesis of oxalate Pd/Al2O3The preparation method of catalyst - Google Patents
A kind of CO synthesis of oxalate Pd/Al2O3The preparation method of catalyst Download PDFInfo
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- CN106378128B CN106378128B CN201610870602.1A CN201610870602A CN106378128B CN 106378128 B CN106378128 B CN 106378128B CN 201610870602 A CN201610870602 A CN 201610870602A CN 106378128 B CN106378128 B CN 106378128B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
- C07C69/36—Oxalic acid esters
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Abstract
The present invention provides a kind of CO synthesis of oxalate Pd/Al2O3The preparation method of catalyst, specific method is that palladium salt is dissolved in diluted acid to prepare dipping mother liquor, by α-Al2O3Activated alumina ball is impregnated in the dipping mother liquor, is taken out, sufficiently dry at 100~150 DEG C；500-800 DEG C and constant temperature 1-5h is risen to by the heating rate of 50-100 DEG C/h under nitrogen protection to get Pd/Al is arrived2O3Catalyst.The load capacity of the preparation method simple process, prepared catalyst noble metal palladium is low, and active component high degree of dispersion on carrier, and the load capacity of the catalyst is only the 0.05-0.15% of vehicle weight.The catalyst is shown in CO synthesis of oxalate applicating evaluating, is up to 98% to the selectivity of oxalate, the space-time yield of dimethyl oxalate can reach 800g/L under the reaction condition of analoging industrial devicecat/ h or more (2000~3000h of air speed‑1), the catalyst using the Pd dosage prepared in the prior art higher than 0.3% is met or exceeded comprehensively.
Description
Technical field
The invention belongs to the preparation technical fields of dimethyl oxalate, and in particular to carbon monoxide gas-phase catalytic coupling synthesis grass
Dimethyl phthalate Pd/Al2O3The preparation method of catalyst.
Background technique
Carbon monoxide gas-phase catalytic coupling synthesizing dimethyl oxalate is environmental-friendly, Atom economy a green chemical industry
Production process meets the current resources situation of China's oil starvation, few gas, rich coal very much.The process success Key of Implementation is to be catalyzed
The research and development of agent.Temperature is burnt in active component and the impregnation sequence of auxiliary agent, the auxiliary agent difference of selection, roasting in the preparation process of catalyst
Degree, maceration extract pH value, selected carrier etc. can all seriously affect the performance and stability of catalyst.High work in order to obtain
Property, the long-life oxo catalyst, domestic many scientists the preparation condition of catalyst, carrier effect, auxiliary agent sieve
A lot of research work has been done in choosing etc..Such as: Wang Wei et al. [α-Al in dimethyl oxalate preparation process2O3Carrier is to palladium chtalyst
The influence of agent performance, gas chemical industry, 2009,34:21-24] use different preparation methods to obtain Different Pore Structures and ratio
α-the Al on surface2O3, as a result, it has been found that Pd/ α-Al2O3The activity of catalyst has the tendency that increase, total pore volume with the increase of specific surface
It is unobvious on the influence of the performance of catalyst, and pore-size distribution influences significantly the performance of catalyst.Liu Xiu virtue et al. [eggshell type
Pd/α-Al2O3The preparation and activity of catalyst are catalyzed journal, 2009,30 (3): 213-217] by the pH value of adjusting maceration extract
Carry out distribution of the regulation activity component on carrier, investigates influence of the active layer thickness to catalyst activity energy, the results showed that right
It is prepared for dimethyl oxalate in carbon monoxide coupling reaction, in the case where identical activity component load quantity, active component is got over
Surface layer is concentrated on, catalytic activity is higher.Also there are many patent reports in the catalyst by adding different metal promoters
(Fe, Mo, Ni, Ce, Ti, Si, Cu) improves active component dispersion degree on carrier, so as to reaching raising catalyst activity
And stability.For the catalyst reported at present, mostly using palladium as active component, α-Al2O3For carrier, and with γ-Al2O3、
SiO2When with active carbon as carrier, since its surface acidity is better than α-Al2O3, catalyst all shows poor catalytic performance
(USP 4229591,1980).But with α-Al2O3As the catalyst of carrier, that there is also active components is easy to reunite, stability is poor
The defects of.In order to overcome drawbacks described above, we develop a kind of preparation CO synthesis of oxalic acid being more simple and efficient by a large number of experiments
The method of dimethyl ester catalyst.
In terms of practical technique development, the catalyst and reaction process is most important is embodied in coal-ethylene glycol skill at present
In art and as one of them very important technical unit.Fujian Inst. of Matter Structure, Chinese Academy of Sciences collected in 2007 with pelletization
Group's cooperation, which takes the lead in building up beating the world, covers 10,000 tons coal-ethylene glycol commerical test device, builds up 200,000 tons in Tongliao within 2009
Process units, then other research units and enterprise have also respectively carried out exploitation and industrialization, CO synthesis grass therein both at home and abroad
Dimethyl phthalate catalyst is similar from performance and preparation method, uses more traditional infusion process substantially, wherein Pd content is big
All 1% or more, the later period carries out various improvement to infusion process, including change and add auxiliary agent, ultrasonic treatment etc., but due to this
All unavoidably there is precipitating, the accumulation process of Pd component during a little preparation methods on a catalyst support, so not
The progress of making a breakthrough property, in the new oxo catalyst technology of Fujian Inst. of Matter Structure, Chinese Academy of Sciences's exploitation, Pd's contains
Amount is reduced to 0.3%, and catalytic performance also obtains larger improvement.But it can significantly improve in catalyst and live the present invention provides one
Property component dispersion degree, improve the method route of catalyst performance.
Summary of the invention
The purpose of the present invention is dispersed uneven primarily directed to existing industrialization oxalate synthesis catalyst active component palladium
Even, easy to reunite, the deficiencies of stability is poor, at high cost, provides a kind of new carbon monoxide gas-phase catalytic coupling synthesis of oxalic acid diformazan
The Pd/Al of ester2O3The load capacity of the preparation method of catalyst, the catalyst noble metal palladium is lower, and active component is uniform on carrier
Dispersion.
Carbon monoxide gas-phase catalytic coupling synthesizing dimethyl oxalate of the present invention Pd/ α-Al2O3The preparation side of catalyst
Method, the specific steps are as follows:
A. palladium salt is dissolved in diluted acid and is configured to dipping mother liquor, the diluted acid is the hydrochloric acid of 0.05-0.2mol/L, nitric acid
Or one of aqueous solution of glacial acetic acid, it is preferred that dilute hydrochloric acid；Palladium salt is one of palladium chloride, palladium nitrate, palladium acetate, it is preferred that chlorine
Change palladium；
B. carrier is immersed in the dipping mother liquor of step A, at 40~60 DEG C place 6~for 24 hours；Load after taking out dipping
Body, it is sufficiently dry at 100~150 DEG C；Wherein the additional amount of carrier is determined according to the design (calculated) load amount of palladium；The carrier is to live
Property alumina balls, specific surface area 1-20m2/ g, partial size are 2~5mm, are that alumina balls are obtained by 1300 DEG C of high-temperature roastings
α-Al2O3.The design (calculated) load amount of palladium is the 0.05-0.25wt%, preferably 0.05-0.15% that palladium accounts for vehicle weight.
Alumina balls of the above-mentioned steps after dry are put into atmosphere furnace, first displace the sky in boiler tube with nitrogen purging by C
Gas, then 500-800 DEG C and constant temperature 1-5h is risen to by the heating rate of 50-100 DEG C/h under nitrogen protection, in heating and constant temperature mistake
Nitrogen is continually fed into take away the multiple gases that catalyst generates at high temperature in journey, after constant temperature Temperature fall to room temperature,
Obtain Pd/Al2O3Catalyst.
The flow for being passed through nitrogen and catalyst single batch treating capacity are 3~10 times of boiler tube volume flows hourly.
Pd/Al is prepared according to the above method2O3Catalyst, wherein the load capacity of Metal Palladium is the 0.05- of vehicle weight
0.25wt%, preferably 0.05-0.15%.
It can be seen that the catalyst sample prepared in Fig. 1-3 using this method from Fig. 1-4 catalyst sample TEM photo,
Dispersion degree of the active component on carrier is apparently higher than the catalyst sample that Fig. 4 uses prior art preparation.
It can illustrate in conjunction with Tables 1 and 2 data, active component Pd is greatly improved using catalyst prepared by this method
Dispersion degree in the carrier, to there is the catalytic activity for relatively improving catalyst.
Catalyst prepared by the present invention compared with prior art, has the advantage that
(1) catalyst preparation process disclosed by the invention is simple, can reduce the components precipitate in solution phase and the shadow of aggregation
It rings, active component palladium is highly dispersed on carrier in catalyst, improves the utilization rate of active component palladium.
(2) dispersion degree of catalyst activity component palladium provided by the invention is higher, and load capacity is low, reduces the life of catalyst
Produce cost.
(3) selectivity of catalyst oxalate disclosed by the invention reaches 98%, in the reaction condition of analoging industrial device
The space-time yield of lower dimethyl oxalate can reach 800g/Lcat/ h or more (2000~3000h of air speed-1), it meets or exceeds and adopts comprehensively
It is higher than 0.3% catalyst with the Pd dosage prepared in the prior art.
(4) catalyst disclosed by the invention has high catalytic activity.
Detailed description of the invention
Fig. 1 is the TEM photo of catalyst prepared by embodiment 1
Fig. 2 is the TEM photo of catalyst prepared by embodiment 2
Fig. 3 is the TEM photo of catalyst prepared by embodiment 3
Fig. 4 is the TEM photo of catalyst prepared by comparative example 1
Specific embodiment
Embodiment 1
The hydrochloric acid for the 0.1mol/L for being dissolved in 20ml volume according to 0.1wt%Pd load capacity, the palladium chloride for weighing calculation amount is matched
At solution, then 20g carrier alpha-oxidation aluminium ball was soaked in this active component solution after 12 hours, transfers to 50 DEG C of baking ovens
In make liquid slow evaporation, be evaporated it is subsequent it is continuous be warming up to 150 DEG C and be cooled to room temperature after being kept for 6 hours, take out this sample, then
It is placed in high-temperature tubular atmosphere furnace, is warming up to 600 DEG C from room temperature with the rate of 50 DEG C/h under conditions of logical nitrogen protection, herein
At a temperature of stop 2 hours, then proceed to be cooled to 50 DEG C or so under nitrogen protection, taking out sample is obtained catalyst sample
Product.
It measures 10mL catalyst to be placed in plus the mixing of 10ml porcelain bead in the stainless steel reaction pipe that internal diameter is 14mm, nitrogen purging
Reaction tube temperature adds to 130 DEG C afterwards, is passed through reaction gas with following flow: 100mL/min methyl nitrite, 150mL/min mono-
Carbonoxide and 150mL/min nitrogen, start to be reacted, reaction pressure 0.05MPa, and reaction temperature is 130 DEG C, reaction result
It is listed in Table 1 below.
Embodiment 2
According to 0.1wt%Pd load capacity, weigh metering palladium nitrate be dissolved in the dust technology that 20ml concentration is 0.2M be made into it is molten
Then 20g carrier alpha-oxidation aluminium ball is soaked in this active component solution after 6 hours by liquid, transferring in 60 DEG C of baking ovens makes
Liquid is slowly evaporated, and is evaporated and subsequent continuous be warming up to 150 DEG C and kept for 24 hours.After being cooled to room temperature, this sample is taken out, is then set
In high-temperature tubular atmosphere furnace, 750 DEG C are warming up to from room temperature with the rate of 100 DEG C/h under conditions of logical nitrogen protection, herein
At a temperature of stop 2 hours, then proceed to be cooled to 50 DEG C or so under nitrogen protection, taking out sample is obtained catalyst sample
Product.
Catalyst is evaluated according to the evaluation condition of embodiment 1, reaction result is listed in Table 1 below.
Embodiment 3
According to 0.05wt%Pd load capacity, weigh metering palladium acetate be dissolved in the glacial acetic acid that 20ml concentration is 1M be made into it is molten
Then 20g carrier alpha-oxidation aluminium ball is soaked in this active component solution after 6 hours by liquid, transferring in 60 DEG C of baking ovens makes
Liquid is slowly evaporated, and is evaporated and subsequent continuous be warming up to 150 DEG C and kept for 24 hours.After being cooled to room temperature, this sample is taken out, is then set
In high-temperature tubular atmosphere furnace, 600 DEG C are warming up to from room temperature with the rate of 50 DEG C/h under conditions of logical nitrogen protection, it is warm herein
Degree is lower to stop 2 hours, then proceedes to be cooled to 50 DEG C or so under nitrogen protection, and taking out sample is obtained catalyst sample
Product.
Catalyst is evaluated according to the evaluation condition of embodiment 1, reaction result is listed in Table 1 below.
Comparative example 1
The hydrochloric acid for the 0.1mol/l for being dissolved in 20ml volume according to 0.1wt%Pd load capacity, the palladium chloride for weighing calculation amount is matched
At solution, then 20g carrier alpha-oxidation aluminium ball was soaked in this active component solution after 12 hours, transfers to 50 DEG C of baking ovens
In make liquid slow evaporation, be evaporated it is subsequent it is continuous be warming up to 150 DEG C and be cooled to room temperature after being kept for 6-12 hour, after taking-up sample,
The sodium hydroxide solution that 40mL 2mol/L is added stands 2 hours, falls lye after active component is completely fixed on carrier
Fall, then be washed with distilled water for several times, obtains required catalyst sample precursor after 6 hours dry at 150 DEG C.
Catalyst is evaluated according to the evaluation condition of embodiment 1, reaction result is listed in Table 1 below.
Comparative example 2
Proportionally 1 method prepares the catalyst that Pd load capacity is 0.3wt%.
The Evaluation results of 1 catalyst of table
Catalyst sample made above respectively takes 1g, high-resolution-ration transmission electric-lens observation is carried out after grinding sample preparation, due to this catalysis
Agent α-the Al more smooth using substrate2O3For carrier, the chip area large surface of carrier is smooth under transmission electron microscope, and Pd particle exists
State in larger particle size range on carrier basal plane can be observed clearly, therefore can be somebody's turn to do by transmission electron microscope photo visual evaluation
The dispersion degree of Pd on catalyst.
Above-mentioned sample has carried out the dispersion degree test of CO absorption on chemical adsorption instrument simultaneously, data such as table 2:
| Metal dispersity (%) | |
| Embodiment 1 | 29.36 |
| Embodiment 2 | 28.55 |
| Embodiment 3 | 32.55 |
| Comparative example 1 | 26.15 |
| Comparative example 2 | 24.85 |
As can be seen from Table 2, compared with existing catalyst sample prepared by infusion process, at high temperature of the present invention
The preparation method of reason can effectively improve dispersion degree of the active component palladium ion on carrier.
Claims (3)
1. a kind of CO synthesizing dimethyl oxalate Pd/ Al2O3The preparation method of catalyst, comprises the concrete steps that:
A. palladium salt is dissolved in diluted acid and is configured to dipping mother liquor, the diluted acid is the hydrochloric acid, nitric acid or ice of 0.05-0.2mol/L
One of aqueous solution of acetic acid；The palladium salt is one of palladium chloride, palladium nitrate, palladium acetate；
B. carrier is immersed in the dipping mother liquor of step A, at 40 ~ 60 DEG C place 6 ~ for 24 hours；Carrier after taking out dipping,
It is sufficiently dry at 100 ~ 150 DEG C；Wherein the additional amount of carrier is determined according to the design (calculated) load amount of palladium；The carrier is active oxidation
Aluminium ball passes through the α-Al that 1300 DEG C of high-temperature roastings obtain2O3, specific surface area is 1-20 m2/ g, partial size are 2 ~ 5mm；
C. alumina balls of the step B after dry are put into atmosphere furnace, first displace the air in boiler tube with nitrogen purging, then
500-800 DEG C and constant temperature 1-5h is risen to by the heating rate of 50-100 DEG C/h under nitrogen protection, the nitrogen in heating and thermostatic process
Gas is continually fed into take away the multiple gases that catalyst generates at high temperature, and Temperature fall is arrived to room temperature after constant temperature
Pd/ Al2O3Catalyst, wherein the load capacity of Metal Palladium is the 0.05-0.25wt%, specific surface area 1-20 of vehicle weight
m2/ g, partial size are 2 ~ 5mm.
2. CO synthesizing dimethyl oxalate Pd/Al according to claim 12O3The preparation method of catalyst, it is characterized in that step
Palladium salt described in rapid A is palladium chloride, and the diluted acid is dilute hydrochloric acid；The load capacity of the Metal Palladium for the catalyst that step C is obtained is
The 0.05-0.15% of vehicle weight.
3. CO synthesizing dimethyl oxalate Pd/Al according to claim 12O3The preparation method of catalyst, it is characterized in that step
The flow for being passed through nitrogen described in rapid C in heating and thermostatic process is 3 ~ 10 times of boiler tube volume flows hourly.
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| CN106902821A (en) * | 2017-04-17 | 2017-06-30 | 高化学（江苏）化工新材料有限责任公司 | A kind of preparation method of the loaded catalyst of yolk type |
| CN107456999B (en) * | 2017-07-17 | 2019-03-08 | 中国科学院福建物质结构研究所 | A kind of nano Pd catalyst and preparation method thereof of porous manganese organic frame load |
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