CN105903466A - Catalyst for dimethyl oxalate synthesis and preparation method of catalyst for dimethyl oxalate synthesis - Google Patents
Catalyst for dimethyl oxalate synthesis and preparation method of catalyst for dimethyl oxalate synthesis Download PDFInfo
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- CN105903466A CN105903466A CN201610284395.1A CN201610284395A CN105903466A CN 105903466 A CN105903466 A CN 105903466A CN 201610284395 A CN201610284395 A CN 201610284395A CN 105903466 A CN105903466 A CN 105903466A
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- dimethyl oxalate
- zinc
- palladium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title abstract description 5
- 238000001308 synthesis method Methods 0.000 title 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 49
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 18
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 230000002194 synthesizing effect Effects 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- IKIWQIUJLIJZJB-UHFFFAOYSA-N [N].O=[C] Chemical compound [N].O=[C] IKIWQIUJLIJZJB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 150000002940 palladium Chemical class 0.000 claims description 4
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 2
- 229940005991 chloric acid Drugs 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000005859 coupling reaction Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 2
- 238000004140 cleaning Methods 0.000 abstract 2
- 239000012752 auxiliary agent Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 10
- 230000008878 coupling Effects 0.000 description 9
- 238000010168 coupling process Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 239000010970 precious metal Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000003556 assay Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for dimethyl oxalate synthesis and a preparation method of the catalyst for dimethyl oxalate synthesis. The catalyst takes palladium as an active component and a-Al2O3 as a carrier, wherein a mass fraction of the active component Pd is 0.01-0.5%, and a mass fraction of a small quantity of residual Zn is 0.01-0.08. The catalyst is prepared by impregnating, calcining and acid cleaning; due to addition of the additive Zn in the preparation process, the active component can be well dispersed on the surface of the carrier, and consumption of the active component is reduced; most of the additive is removed by acid cleaning, so that a spatial distribution structure of the active component of the catalyst is further changed to optimize performances of the catalyst to a greater extent. According to experiments, the catalyst shows better catalytic activity in gas-phase CO coupling reaction for synthesis of dimethyl oxalate, CO conversion per pass is up to 63%, dimethyl oxalate selectivity is higher than 96%, and space time yield of dimethyl oxalate is larger than 1100g.L<-1>.h<-1> (air speed being 3000h<-1>).
Description
Technical field
The present invention relates to the preparation method of a kind of catalyst for the reaction of Oxidation of Carbon Monoxide coupling synthesizing dimethyl oxalate, mainly
Including the Pd/Al using acid washing method to prepare2O3The correlation technique of loaded catalyst.
Technical background
Dimethyl oxalate. is a kind of important industrial chemicals, is various important fine chemistry industry dyestuff, the solvent of medicine, extractant
And intermediate.Particularly by preparing extremely important industrial chemicals ethylene glycol under the effect of hydrogenation catalyst.
According to the resource situation of the few oil of the many coals of China, the synthetic method of Coal Chemical Industry is utilized to produce the route of dimethyl oxalate. and ethylene glycol
Gradually it is in full swing in the whole nation, compared with traditional ethylene route, the dependence to oil and ethylene can be alleviated to a certain extent
For the pressure that amount is not enough.Dimethyl oxalate. synthesis technique in " coal-ethylene glycol " route achieves inorganic C1(carbon monoxide)
To organic C2The transformation of (dimethyl oxalate .), is the reaction of a kind of Atom economy, and simultaneously synthesizing catalyst rises in whole reaction
The effect of key, therefore the research to the catalyst of synthesizing dimethyl oxalate has great importance.
Patent in terms of report CO gaseous oxidation coupling synthesizing dimethyl oxalate method for preparing catalyst continues to bring out the most both at home and abroad.
Patent CN102962060A is open reports a kind of employing precious metal palladium loaded catalyst, by changing the kind of auxiliary agent and helping
The content of agent obtains the catalyst performance of optimum, and wherein the load capacity of palladium is 1% (in terms of vehicle weight), CO and nitrous acid
Space-time yield during methyl ester synthesizing dimethyl oxalate is 977g L-1H-1(space velocities is 3000h-1), life-span investigation is catalyzed
Agent shows good stability.It is different with by adding that other relevant patents also report different method for preparing catalyst
Auxiliary agent improves selectivity of catalyst and space-time yield, but these catalyst are primarily present following two problem:
1. the load capacity (in terms of carrier quality) of precious metals pd is the most higher, as patent CN101791555A is reported
Pd-La-Re/a-Al2O3Catalyst Pd load capacity reaches 1.5%；The Pd-Zr/a-Al of patent CN1148589 report2O3Catalyst
The content of middle Pd reaches 1%.Pd is the limited price of a kind of reserves and high noble metal, and the load capacity of high Pd causes catalysis
The cost of agent is high, is unfavorable for industrialized economy.
The space-time yield of 2.CO gaseous oxidation coupling synthesizing dimethyl oxalate product is on the low side, such as urging of patent CN1148589 report
Agent space-time yield is at 450g L-1H-1Left and right, the Pd-Mo/Al of patent US4384433 report2O3And Pd-Ni/Al2O3Two
The space-time yield planting catalyst is only 400g L-1H-1。
Therefore, how to prepare a kind of suitably catalyst and be applied in the reaction of CO gaseous oxidation coupling synthesizing dimethyl oxalate, right
The composition of the space-time yield improving dimethyl oxalate. further, the load capacity reducing precious metals pd and further optimized product has weight
The meaning wanted.
Summary of the invention
It is an object of the invention to provide a kind of synthesizing dimethyl oxalate catalyst and preparation method thereof, the catalyst that the present invention provides
In CO gaseous oxidation coupling synthesizing dimethyl oxalate reacts, there is more preferable catalytic performance.
Synthesizing dimethyl oxalate catalyst provided by the present invention, this catalyst is with palladium as active component, a-Al2O3For carrying
Body, wherein the mass fraction of active component Pd be 0.01-0.5%, preferably mass fraction be 0.2-0.4%；Carrier a-Al2O3
Specific surface area be 1-10m2/ g, specific pore volume is 0.01-1cm3/ g, average pore size is 5-30nm；Wherein there is the auxiliary agent of a small amount of residual,
Its mass fraction is 0.01～0.08%.
The preparation method of catalyst of the present invention, specifically comprises the following steps that
A. solubility palladium salt and zinc salt being dissolved and prepare impregnation liquid in the solution, in impregnation liquid, palladium ion concentration is 0.001-0.025
Mol/L, zinc ion concentration is 0.002-0.1mol/L；Described solution is the one in hydrochloric acid, nitric acid, acetic acid or sulfuric acid solution,
And the pH of solution is 0～6.
Described solubility palladium salt be in palladium, Palladous chloride., Palladous nitrate., chloric acid palladium ammonium or palladium acetylacetonate any one or
Two kinds；Soluble zinc salt is any one in zinc nitrate, zinc chloride, zinc acetate or zinc sulfate.
B. by a-Al2O3Carrier joins in the impregnation liquid in step A, stands 1-2 days, filters off solution, at 70-80 DEG C
It is dried 12～24h；Fully it is dried then at 140-150 DEG C；After put into 250-300 DEG C of roasting 5-6h of Muffle furnace；Wherein a-Al2O3's
Addition is that the mass fraction according to palladium ion concentration in impregnation liquid and the palladium of prepared catalyst requires and determines.
Described a-Al2O3The specific surface area of carrier is 1-10m2/ g, specific pore volume is 0.01-1cm3/ g, average pore size is 5-30nm.
C. by dried catalyst precarsor reductase 12-10 hours under reducing atmosphere, reduction temperature is 200-600 DEG C, reducing gases
Air speed is 500-6000h-1, in reducing atmosphere, then it is cooled to room temperature, obtains catalyst, wherein the mass fraction of Pd is
0.01-0.5%, the mass fraction of zinc is 0.1～0.6%；Described reducing gases is pure hydrogen or carbon monoxide-nitrogen mixed gas.
D the catalyst of step C is placed on concentration be 1～5% acid solution in soak 1～4h, then 60～80 DEG C of conditions
Under be washed with deionized catalyst to neutral, place into the abundant drying to obtain of 140-150 DEG C of baking oven except the catalyst after zinc, its
The mass fraction of middle Pd is 0.01-0.5%, and zinc mass fraction is 0.01～0.08%；Described solution be hydrochloric acid, nitric acid, acetic acid or
One in sulfuric acid solution.
The present invention introduces auxiliary agent in preparation process, and the addition of this auxiliary agent can make active component more disperse at carrier surface, subtracts simultaneously
Lack the consumption of active component.Wash away major part auxiliary agent by pickling processes again, change the space of catalyst activity component further
Distributed architecture, optimizes the performance of catalyst to a greater degree.
Test catalyst obtained above and be applied to the catalytic performance of CO gaseous oxidation coupling synthesizing dimethyl oxalate reaction: will urge
Agent fills in (device for testing) in fixed bed reactors, and catalyst amount is 2ml, unstripped gas CO and methyl nitrite stream
Amount ratio is 1.5, and gas phase air speed is 3000h-1, unstripped gas contacts at normal pressure, under conditions of 140 DEG C with described catalyst, it is thus achieved that
Dimethyl oxalate. product.Unstripped gas and product are to be analyzed by gas chromatogram on-line monitoring.Result shows, urging through peracid treatment
The catalytic performance of agent sample is substantially better than the catalyst without acid treatment.
Fig. 1～6 gives the TEM photo situation of each embodiment and comparative example catalyst sample, as seen from the figure, after peracid treatment
The size of Pd granule of catalyst be significantly less than the catalyst without acid treatment, and the Pd dispersion of the catalyst through peracid treatment
It is more uniformly distributed.
Fig. 7 gives the composition of the product after catalytic reaction and the ratio situation of each component, by the change of each component before and after reaction
Change can calculate CO conversion per pass, oxalate selectivity and oxalate space-time yield.
The present invention compared with prior art, has a following remarkable result:
1., compared with tradition infusion process, the catalyst of the present invention is owing to using preparation process to introduce auxiliary agent, then removes auxiliary agent with pickling,
Prepare the catalyst that precious metal palladium load capacity is relatively low and catalytic performance is higher.
2. the catalyst that prepared by the catalyst of the present invention is in CO gaseous oxidation coupling synthesizing dimethyl oxalate reacts, and CO one way turns
Rate is up to 63%, and dimethyl oxalate. selectivity is more than 96%, and dimethyl oxalate. space-time yield is more than 1100g L-1H-1(empty
Speed is 3000h-1).The similar catalyst prepared far above tradition infusion process.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the catalyst of preparation in embodiment 1.
Fig. 2 is the transmission electron microscope photo of the catalyst of preparation in comparative example 1.
Fig. 3 is the transmission electron microscope photo of the catalyst of preparation in embodiment 2.
Fig. 4 is the transmission electron microscope photo of the catalyst of preparation in comparative example 2.
Fig. 5 is the transmission electron microscope photo of the catalyst of preparation in embodiment 3.
Fig. 6 is the transmission electron microscope photo of the catalyst of preparation in comparative example 3.
Fig. 7 is the chromatography figure of the catalyst of embodiment 1 in test case.
It is embodied as example mode
Embodiment 1:
One. preparation process: 0.075g Palladous chloride. and 0.48g auxiliary agent zinc nitrate are dissolved in the hydrochloric acid that pH=1.3 volume is 15ml
In buffer, the 15g alumina balls (diameter 2mm, rotating disc type rolling ball method obtains) through 1300 DEG C of calcination process are added slow
Rush in liquid；First standing 12h at 60 DEG C, put into baking oven and be dried 24h at 80 DEG C, in baking oven, 150 DEG C are fully dried,
It is finally putting into 300 DEG C of roasting 6h of Muffle furnace；By dried catalyst precarsor at reducing gases (nitrogen-carbon mono oxide mixture) gas
In atmosphere, reduction 6h at 200 DEG C, wherein reducing gases air speed is 3000h-1.Being tested by ICP, wherein Pd content is carrier matter
The 0.29% of amount, auxiliary agent Zn content is the 0.57% of carrier quality.
Two. acid pickling step: by gained Pd-Zn/Al2O3Catalyst be placed on volume be 15ml mass fraction be 1% hydrochloric acid molten
Liquid soaks 2h, then under the conditions of 60 DEG C, is washed with deionized catalyst 8 times, every minor tick 3h, until the inspection of pH reagent paper
Survey display neutrality, place into 150 DEG C of baking oven and be fully drying to obtain required catalyst.Being tested by ICP, wherein Pd content is for carrying
The 0.28% of weight, auxiliary agent Zn content is the 0.04% of carrier quality.
Comparative example 1:
The catalyst prepared according to " step one " in embodiment 1.
Embodiment 2:
One. preparation process: 0.098g Palladous nitrate. and 0.48g auxiliary agent zinc nitrate are dissolved in pH=1.2 volume is that 15ml nitric acid delays
Rush in liquid, the 15g alumina balls (diameter 2mm, rotating disc type rolling ball method obtains) through 1300 DEG C of calcination process are added buffering
In liquid；First standing 12h at 60 DEG C, put into baking oven and be dried 24h at 80 DEG C, in baking oven, 150 DEG C are fully dried,
After put into 300 DEG C of roasting 6h of Muffle furnace；By dried catalyst precarsor in reducing gases (nitrogen-carbon mono oxide mixture) atmosphere
In, reduction 6h at 200 DEG C, wherein reducing gases air speed is 3000h-1.Being tested by ICP, wherein Pd content is carrier quality
0.29%, auxiliary agent Zn content is the 0.57% of carrier quality.
Two. acid pickling step: by gained Pd-Zn/Al2O3Catalyst be placed on volume be 15ml mass fraction be 1.5% nitric acid molten
Liquid soaks 2h, then under the conditions of 60 DEG C, is washed with deionized catalyst 8 times, every minor tick 3h, until the inspection of pH reagent paper
Survey display neutrality, place into 150 DEG C of baking oven and be fully drying to obtain required Pd/Al2O3Catalyst.Tested by ICP, wherein Pd
Content is the 0.29% of carrier quality, and auxiliary agent Zn content is the 0.05% of carrier quality.
Comparative example 2:
The catalyst prepared according to " step one " in embodiment 2.
Embodiment 3:
One. preparation process: 0.095g palladium and 0.48g auxiliary agent zinc nitrate are dissolved in the acetic acid that pH=1 volume is 15ml and delay
Rush in liquid, the 15g alumina balls (diameter 2mm, rotating disc type rolling ball method obtains) through 1300 DEG C of calcination process are added buffering
In liquid；First standing 12h at 60 DEG C, put into baking oven and be dried 24h at 80 DEG C, in baking oven, 150 DEG C are fully dried,
After put into 300 DEG C of roasting 6h of Muffle furnace；By dried catalyst precarsor in reducing gases (nitrogen-carbon mono oxide mixture) atmosphere
In, reduction 6h at 200 DEG C, wherein reducing gases air speed is 3000h-1.Being tested by ICP, wherein Pd content is carrier quality
0.29%, auxiliary agent Zn content is the 0.57% of carrier quality.
Two. acid pickling step: by gained Pd-Zn/Al2O3Catalyst be placed on volume be 15ml mass fraction be 2.0% acetic acid molten
Liquid soaks 2h, then under the conditions of 60 DEG C, is washed with deionized catalyst 8 times, every minor tick 3h, until the inspection of pH reagent paper
Survey display neutrality, place into 150 DEG C of baking oven and be fully drying to obtain required Pd/Al2O3Catalyst.Tested by ICP, wherein Pd
Content is the 0.29% of carrier quality, and auxiliary agent Zn content is the 0.06% of carrier quality.
Comparative example 3:
The catalyst prepared according to " step one " in embodiment 3.
Test case:
By Catalyst packing in test fixed-bed reactor, catalyst amount is 2ml, unstripped gas CO and nitrous acid first
Ester flow-rate ratio is 1.5, and gas phase air speed is 3000h-1, unstripped gas is 0.1Mpa in reaction pressure, with described under conditions of 140 DEG C
Catalyst contacts, it is thus achieved that dimethyl oxalate. product.Changed by the composition of gas chromatogram on-line monitoring assay products and unstripped gas,
And calculate the catalyst property indices such as CO conversion per pass, oxalate selectivity, oxalate space-time yield.
The most respectively to embodiment 1, comparative example 1, embodiment 2, comparative example 2, embodiment 3 and comparative example 3
Catalyst performance is evaluated, and the results are shown in Table 1
Table 1: embodiment catalyst catalytic performance in CO gaseous oxidation coupling dimethyl oxalate. reacts
Having trace to run off from table 1 precious metals pd after pickling processes, auxiliary agent Zn removes substantially.With not at overpickling
The catalyst of reason is compared, and the catalyst of the present invention shows preferably in CO gaseous oxidation coupling synthesizing dimethyl oxalate reacts
Catalysis activity.
Claims (3)
1. a synthesizing dimethyl oxalate catalyst, this catalyst is with palladium as active component, a-Al2O3For carrier, wherein activity
The mass fraction of component Pd is 0.01-0.5%；Carrier a-Al2O3Specific surface area be 1-10m2/ g, specific pore volume is
0.01-1cm3/ g, average pore size is 5-30nm；Wherein having the Zn of a small amount of residual, its mass fraction is 0.01～0.08%.
Synthesizing dimethyl oxalate catalyst the most according to claim 1, is characterized in that the quality of active component Pd in catalyst
Mark is 0.2-0.4%.
3. the method preparing synthesizing dimethyl oxalate catalyst described in claim 1, specifically comprises the following steps that
A. solubility palladium salt and zinc salt being dissolved and prepare impregnation liquid in the solution, in impregnation liquid, palladium ion concentration is 0.001-0.025
Mol/L, zinc ion concentration is 0.002-0.1mol/L；Described solution is the one in hydrochloric acid, nitric acid, acetic acid or sulfuric acid solution,
And the pH of solution is 0～6；
Described solubility palladium salt be in palladium, Palladous chloride., Palladous nitrate., chloric acid palladium ammonium or palladium acetylacetonate any one or
Two kinds；Soluble zinc salt is any one in zinc nitrate, zinc chloride, zinc acetate or zinc sulfate；
B. by a-Al2O3Carrier joins in the impregnation liquid in step A, stands 1-2 days, filters off solution, at 70-80 DEG C
It is dried 12～24h；Fully it is dried then at 140-150 DEG C；After put into 250-300 DEG C of roasting 5-6h of Muffle furnace；Wherein a-Al2O3's
Addition is to determine according to palladium ion concentration in impregnation liquid and the mass fraction of the palladium of prepared catalyst；
Described a-Al2O3The specific surface area of carrier is 1-10m2/ g, specific pore volume is 0.01-1cm3/ g, average pore size is 5-30nm；
C. by dried catalyst precarsor reductase 12-10 hours under reducing atmosphere, reduction temperature is 200-600 DEG C, reducing gases
Air speed is 500-6000h-1, in reducing atmosphere, then it is cooled to room temperature, obtains catalyst, wherein the mass fraction of Pd is
0.01-0.5%, the mass fraction of zinc is 0.1～0.6%；Described reducing gases is pure hydrogen or carbon monoxide-nitrogen mixed gas；
D the catalyst of step C is placed on concentration be 1～5% acid solution in soak 1～4h, then 60～80 DEG C of conditions
Under be washed with deionized catalyst to neutral, place into the abundant drying to obtain of 140-150 DEG C of baking oven except the catalyst after zinc, its
The mass fraction of middle Pd is 0.01-0.5%, and zinc mass fraction is 0.01～0.08%；Described solution be hydrochloric acid, nitric acid, acetic acid or
One in sulfuric acid solution.
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