CN110523412A - It is coupled synthesizing dimethyl oxalate palladium catalyst and preparation method thereof - Google Patents
It is coupled synthesizing dimethyl oxalate palladium catalyst and preparation method thereof Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 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 17
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000008878 coupling Effects 0.000 claims abstract description 6
- 238000010168 coupling process Methods 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 239000011258 core-shell material Substances 0.000 claims abstract description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- -1 carrier Chemical compound 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 6
- 230000001133 acceleration Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910020785 La—Ce Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010792 warming 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
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B01J35/396—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
-
- 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
Abstract
A kind of coupling synthesizing dimethyl oxalate palladium catalyst and preparation method thereof, especially with a-Al2O3For the catalyst of carrier loaded active component palladium, including carrier, active component Pd and auxiliary agent；The auxiliary agent is one or both of titanium, zirconium, cerium, lanthanum, nickel or copper；Carrier is a-Al2O3；Its specific surface area is 6~18m2·g‑1, 0.015~0.050mLg of Kong Rongwei‑1, for average pore size in 3~30nm, catalyst is core-shell catalyst, and active component is evenly distributed on carrier with the thickness of 0.2~1.5mm.Active component Pb, auxiliary agent are distributed in the shell of catalyst in preparation, significantly reduce Pd dosage, act synergistically and optimize between carrier, improve catalytic activity and target product selectivity.
Description
Technical field
The present invention relates to a kind of coupling synthesizing dimethyl oxalate palladium catalyst and preparation method thereof, in particular to it is a kind of with
a-Al2O3For the catalyst of carrier loaded active component palladium, belong to catalyst technical field.
Background technique
Dimethyl oxalate is important industrial chemicals, can be used for manufacturing oxalic acid, oxamide, ethylene glycol and some drugs and dye
The intermediate of material, wherein the technology of preparation of ethanediol by dimethyl oxalate hydrogenation is alternative uses nonrenewable resources petroleum next life
The technology of ethylene glycol is produced, there is important strategy and economic significance.
U.S. D.M.Fenton in 1966 et al. discovery, with a-Al2O3For carrier loaded active component palladium catalyst, can make
Carbon monoxide carries out coupling reaction in alcohol medium and synthesizes dimethyl oxalate.Company, Ube Industries Ltd. and U.S. ARCO later
Company has carried out research and development in this field in succession, and wherein Yu Buxingchan Ube company just mentions in last century late nineteen seventies
The method for using carbon monoxide and nitrous acid ester synthesis of oxalic ester by gaseous catalysis out, and propose the recycling work of reaction end gas
Skill.
China's richness coal few oil, therefore replace existing petroleum path preparing ethylene glycol to meet national conditions with coal-ethylene glycol.From
The research of domestic Efforts To Develop in terms of synthesis of oxalate since last century the eighties, especially in catalyst preparation side
Face.Chinese Academy of Sciences's Fujian object structure Chen Yi shield professor began one's study from 1979 CO preparing oxalate coupling reaction, in patent of invention
Use Al2O3As carrier.University Of Tianjin professor Xu Genhui has found a-Al2O3The catalyst activity of carrier preparation is better than γ-
Al2O3The catalyst of carrier preparation, it is believed that the reason is that CO and RONO are during the reaction, ask production in reactant RONO, generation
Object Pd(OR)2With product (COOR)2Needing biggish aperture just can enter and leave out of duct.a-Al2O3Although specific surface
It is smaller, but its aperture is big, and reactant and product can freely enter and leave its duct, and inner surface is using sufficiently.Japanese Ube company
Think that alumina catalyst support specific surface is less than 90m2/ g is advisable.UCC company is proposed with specific surface less than 10m2The nonacid load of/g
Body, i.e. a-Al2O3Carrier.
Separately there is more patent to mention used additives to improve the performance of catalyst, as used δ-Al in CN1415414A2O3For
Carrier, using Fe and La as auxiliary agent, loads the active component system of two kinds and two or more metals using Pd as active component in this way
Standby catalyst can effectively improve its catalytic activity and service life in synthesizing dimethyl oxalate reaction.
The load capacity of catalyst noble metal Pd is generally higher in most of patent, as Chinese patent CN101791555A is reported
Pd-La-Ce/ Al2O3The content of Pd is all 1.5% or so in catalyst；The Pd-La/Al of CN1055492A report2O3Catalysis
The Pd-Ti-Ce/Al that agent, CN101138722A are reported2O3Pd-La/Al of catalyst and CN101596455A report2O3Catalysis
The content of Pd is 1% or so in agent.Pd is a kind of noble metal, and expensive, reserves are limited, and high load capacity causes catalyst
It is at high cost, influence its use in the industry.
The efficiently low expensive full research and development for belonging to load capacity nanocatalyst of exploitation Novel series can save a large amount of expensive full categories,
To solving, expensive full category resource consumption is excessive, implements the strategy of sustainable development and is of great significance.
Summary of the invention
The purpose of the present invention is to provide one kind for CO coupling gas-phase dimethyloxalate synthesis catalyst and its preparation side
Method, the catalyst have preferable activity, higher space-time yield, higher selectivity under low temperature, lower pressure, can effectively drop
Low by-product generates, and process route is environmental-friendly, realizes that coal base industrializes synthesizing dimethyl oxalate.Catalysis provided by the present invention
Agent is coreshell type structure, has the characteristics that efficient, low noble metal dosage.
A kind of coupling synthesizing dimethyl oxalate palladium catalyst of the present invention, including carrier, active component Pd and auxiliary agent；It is described
Auxiliary agent is one or both of titanium, zirconium, cerium, lanthanum, nickel or copper；The carrier is a-Al2O3；Its specific surface area is 6~18m2·
g-1, 0.015~0.050mLg of Kong Rongwei-1, average pore size is in 3~30nm, it is characterized in that: the catalyst is hud typed urges
Agent, active component are evenly distributed on carrier with the thickness of 0.2~1.5mm.
Generally, the content of the active component Pd is the 0.1%~0.5% of vehicle weight, preferably 0.2%~0.4%.
The content of the auxiliary agent is respectively the 0.05%~0.20% of vehicle weight.
A kind of preparation method for being coupled synthesizing dimethyl oxalate palladium catalyst of the present invention, comprising the following steps:
(1) a-Al that weighs that treated2O3Carrier is placed in bulge, prepares dipping；
(2) according to a-Al2O3Carrier water absorption rate and target components content prepare isometric Pd and promoter metal solion；
(3) on the spray solution to the carrier of (1) for preparing step (2), the rotary container in sprinkling, dip time is controlled 10
~ 30 minutes；
(4) continue rotation container 10 ~ 30 minutes, after fully absorbing, take out drying, roasting obtains catalyst.
The presoma of the auxiliary agent and Pd are selected from the soluble salt of promoter metal and Pd.
In step (1), treated the a-Al2O3Carrier, be boil, dry by one of water and ammonium hydroxide heat, calcination process
Obtained from.
In step (2), the Pd ion concentration is 3.5 ~ 17.5g/L；The promoter metal ion concentration is 1.5 ~ 3.5g/
L。
In step (4), the drying temperature is 60 ~ 120 DEG C, and the time is 6 ~ 24 hours, and the atmosphere of the roasting is air,
Temperature is 350 ~ 500 DEG C, and the time is 2 ~ 10 hours.
The beneficial effects of the present invention are: the catalyst of CO coupling gas-phase dimethyloxalate synthesis of the present invention leads to
It crosses addition metal promoter and modification improvement is carried out to catalyst structure, improve the stability of active metal palladium and to target product oxalic acid
The selectivity of dimethyl ester.By dipping process control, drying time control, in calcination process, especially preparation process with catalysis
The isometric metal promoter of agent carrier period water absorption rate and metal Pd solion sprinkling dipping, may be implemented active component Pb,
Auxiliary agent is distributed in the shell of catalyst, significantly reduces Pd dosage, acts synergistically and optimizes between carrier, improve catalytic activity and
Target product selectivity.
Specific embodiment
Following embodiment is the further explanation to technical solution of the present invention and effect, is not to the technology of the present invention and effect
The limitation of fruit.
Embodiment 1
(1) 100 grams of a-Al are weighed2O3Carrier, 10 minutes water absorption rates of carrier are 29%；(2) palladium nitrate 0.257g is weighed, is measured
The Cu of 200g/L2+The copper nitrate 5mL of content prepares 29mL solution, is heated to 40 DEG C of acceleration dissolutions；(3) by step (2) configuration
On spray solution to the carrier of (1), the rotary container in sprinkling guarantees on solion homogeneous impregnation to carrier, dip time
Control was at 10 minutes；Continue rotation container 10 minutes, after fully absorbing, takes out carrier 12 0 DEG C of drying 6h, 450 DEG C of roasting 2h
Up to 0.1% palladium content, the catalyst of shell thickness 1.0mm.
50mL catalyst manufactured in the present embodiment is taken, is fitted into the fixed bed reactors of φ 3.2cm, is warming up to 200 DEG C, is led to
Hydrogen reducing 6 hours, cool to 115 DEG C；Charging reaction, unstripped gas are through nitrogen or the diluted CO of carbon dioxide and nitrous acid first
Ester gaseous mixture, in 0.2MPa, unstripped gas air speed is 4000h for reaction pressure control-1, the volume content of CO is 30% in unstripped gas,
The volume content of methyl nitrite is 20%.It collects dimethyl oxalate and weighs simultaneously purity assay.
Embodiment 2
Step (2) weighs palladium chloride 0.35g, measures the Cu of 200g/L2+The copper nitrate 5mL of content prepares 29mL solution, heating
It is dissolved to 40 DEG C of acceleration；0.2% palladium content, the catalyst of shell thickness 1.0mm is made with embodiment 1 in remaining.
Embodiment 3
(1) 100 grams of a-Al are weighed2O3Carrier, 15 minutes water absorption rates of carrier are 30%；Step (2) weighs palladium nitrate 0.51g, measures
The Cu of 200g/L2+The copper nitrate 8mL of content prepares 30mL solution, is heated to 40 DEG C of acceleration dissolutions；Remaining is made with embodiment 1
0.2% palladium content, the catalyst of shell thickness 1.2mm.
Embodiment 4
(1) 100 grams of a-Al are weighed2O3Carrier, 20 minutes water absorption rates of carrier are 32%；Step (2) weighs palladium nitrate 1g, measures
The Cu of 200g/L2+The copper nitrate 20mL of content prepares 32mL solution, is heated to 40 DEG C of acceleration dissolutions；Remaining is the same as embodiment 1, system
Obtain 0.4% palladium content, the catalyst of shell thickness 1.5mm.
Embodiment 5
Step (2) weighs palladium nitrate 1.26g, weighs 0.32g Ce (NO3)3·6H2O prepares 32mL solution, is heated to 40 DEG C and adds
Instant solution；0.5% palladium content, the catalyst of shell thickness 1.5mm is made with embodiment 4 in remaining.
Embodiment 6
(1) 100 grams of a-Al are weighed2O3Carrier, after ammonium hydroxide heat treatment drying, 20 minutes water absorption rates of carrier are 30%；Step (2) claims
Palladium nitrate 1.26g is taken, 0.32g Ce (NO is weighed3)3·6H2O prepares 30mL solution；Remaining is made 0.5% palladium and contains with embodiment 5
Amount, the catalyst of shell thickness 1.5mm.
Embodiment 7
(1) 100 grams of a-Al are weighed2O3Carrier, after hydro-thermal process drying, 20 minutes water absorption rates of carrier are 30%；Step (2) weighs
Palladium nitrate 1g measures the Cu of 100g/L2+The copper nitrate 20mL of content prepares 30mL solution, is heated to 40 DEG C of acceleration dissolutions；Remaining
With embodiment 1,0.4% palladium content, the catalyst of shell thickness 1.5mm is made.
Comparative example
The 0.5% equally distributed a-Al of palladium content active component2O3Carried catalyst.
Table 1, embodiment performance evaluation
Claims (10)
1. a kind of coupling synthesizing dimethyl oxalate palladium catalyst, including carrier, active component Pd and auxiliary agent；The auxiliary agent is
One or both of titanium, zirconium, cerium, lanthanum, nickel or copper；The carrier is a-Al2O3；Its specific surface area is 6~18m2·g-1, hole
Holding is 0.015~0.050mLg-1, average pore size is in 3~30nm, it is characterized in that: the catalyst is core-shell catalyst, it is living
Property component is evenly distributed on carrier with the thickness of 0.2~1.5mm.
2. catalyst as described in claim 1, it is characterised in that the content of the active component Pd is the 0.1% of vehicle weight
~0.5%.
3. catalyst as described in claim 1, it is characterised in that the content of the active component Pd is the 0.2% of vehicle weight
~0.4%.
4. catalyst as described in claim 1, it is characterised in that the content of the auxiliary agent be vehicle weight 0.05%~
0.20%.
5. a kind of preparation method for being coupled synthesizing dimethyl oxalate palladium catalyst, comprising the following steps:
(1) a-Al that weighs that treated2O3Carrier is placed in bulge, prepares dipping；
(2) according to a-Al2O3Carrier water absorption rate and target components content prepare isometric Pd and promoter metal solion；
(3) on the spray solution to the carrier of (1) for preparing step (2), the rotary container in sprinkling, dip time is controlled 10
~ 30 minutes；
(4) continue rotation container 10 ~ 30 minutes, after fully absorbing, take out drying, roasting obtains catalyst.
6. the preparation method of catalyst as claimed in claim 5, it is characterised in that the presoma of auxiliary agent and Pd are selected from promoter metal
With the soluble salt of Pd.
7. the preparation method of catalyst as claimed in claim 6, it is characterised in that the soluble salt of promoter metal and Pd are nitrate.
8. the preparation method of catalyst as claimed in claim 5, it is characterised in that in step (1), treated the a-Al2O3
Carrier is boiled, is dried by one of water and ammonium hydroxide heat, obtained from calcination process.
9. the preparation method of catalyst as claimed in claim 5, it is characterised in that in step (2), the Pd ion concentration is 3.5
~17.5g/L；The promoter metal ion concentration is 1.5 ~ 3.5g/L.
10. the preparation method of catalyst as claimed in claim 5, it is characterised in that in step (4), the drying temperature be 60 ~
120 DEG C, the time is 6 ~ 24 hours, and the atmosphere of the roasting is air, and temperature is 350 ~ 500 DEG C, and the time is 2 ~ 10 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN114210325A (en) * | 2021-12-21 | 2022-03-22 | 商丘国龙新材料有限公司 | Catalyst for synthesizing dimethyl oxalate by gas-phase carbonylation and preparation method and application thereof |
| CN114210340A (en) * | 2021-12-21 | 2022-03-22 | 商丘国龙新材料有限公司 | High-activity gas-phase synthesis dimethyl carbonate catalyst and preparation method and application thereof |
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