CN109569650A - One kind is for CO coupling catalyst for synthesizing oxalic ester and preparation method thereof - Google Patents
One kind is for CO coupling catalyst for synthesizing oxalic ester and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000002148 esters Chemical class 0.000 title claims abstract description 11
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 8
- 230000008878 coupling Effects 0.000 title claims abstract description 7
- 238000010168 coupling process Methods 0.000 title claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 4
- 239000010970 precious metal Substances 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 150000003624 transition metals Chemical class 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000002803 maceration Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 19
- 238000001179 sorption measurement Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 238000010129 solution processing Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 16
- 238000003786 synthesis reaction Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 13
- 238000007598 dipping method Methods 0.000 abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 25
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 15
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 241000282326 Felis catus Species 0.000 description 10
- 230000009102 absorption Effects 0.000 description 7
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910002666 PdCl2 Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- -1 nitrous acid Ester Chemical class 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002339 La(NO3)3 Inorganic materials 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- JKRZOJADNVOXPM-UHFFFAOYSA-N Oxalic acid dibutyl ester Chemical class CCCCOC(=O)C(=O)OCCCC JKRZOJADNVOXPM-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 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
- B01J23/70—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
- B01J23/8906—Iron and noble metals
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- 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
-
- 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)
- Catalysts (AREA)
Abstract
One kind belonging to the technical field of catalyst preparation for CO coupling catalyst for synthesizing oxalic ester and preparation method thereof.Catalyst is with α-Al2O3It is active component for carrier-supported precious metal palladium, one or more of addition transition-metal Fe, Co, Ce, Zr, La are used as auxiliary agent.The loading of active component Pd is 0.1 ~ 1 wt%(of carrier quality in terms of PdO), the additive amount of auxiliary agent is 0.1 ~ 3 wt%(of carrier quality in terms of oxide).The characteristics of catalyst, is prepared using a kind of microwave-assisted dipping process, and the catalyst of the method synthesis can significantly improve the degree of scatter of active metal, while reducing the dosage of noble metal, the effective activity and stability for improving catalyst.
Description
Technical field
The catalyst and preparation method thereof that the present invention relates to a kind of for oxalic acid Lipase absobed is related generally to using microwave-assisted
Prepare loading type Pd/Al of CO coupling synthesis of oxalate2O3The relevant technologies of catalyst.
Background technique
Oxalate can hydrolyze a variety of important chemical industry productions such as to obtain oxalic acid, be hydrogenated to ethylene glycol, ammonification generation oxamides
Product are a kind of highly important chemical raw materials.Traditional oxalate synthetic route, is mainly esterified by oxalic acid and alcohol
Reaction synthesis, the method production technology cost is high, energy consumption is high, seriously polluted, raw material availability is low.And CO gas phase coupling is utilized to close
At oxalate technique, have that Atom economy, reaction condition are mild, low energy consumption, environmental-friendly, equipment investment is low and product quality
The advantages that good, the development of alleviation and synthesis gas chemical industry to petroleum resources pressure have vital strategic importance and
Economic significance.
Early in nineteen sixty-five, Fenton et al. proposes that carbon monoxide can occur in alcohol medium under the catalysis of palladium
Coupling reaction generates oxalate.Union carbide corporation's joint development of company, Ube Industries Ltd. and U.S. liquid phase method on this basis
Dialkyl oxalate synthesis technology, and a set of industrial production equipment for producing 6000 tons of dibutyl oxalates per year was established in 1978.
Since the condition of liquid phase method synthesis of oxalate is harsher, reaction carries out under high pressure, while liquid-phase system is easy
Corrode catalyst in equipment and reaction process to be easy to be lost.Therefore, company, Ube Industries Ltd. and Italian Montedison
Company has carried out the research of vapor phase method in 1978 in succession.Ube Industries Ltd. patent JP8242.656 discloses special permission and reports
A kind of process flow of CO and methyl nitrite atmospheric synthesis dimethyl oxalate, patent use load type palladium catalyst, pass through
480 hours successive reactions, space-time yield average out to 432 g/L (cat) h of dimethyl oxalate.
Later, many researchs for CO atmospheric synthesis oxalate are unfolded in succession, by add in the catalyst Cu, Fe,
The auxiliary agents such as Ce, Zr, Ni, Ti, Mo, Ga, La, on the one hand reduce the dosage of noble metal, while also improving the activity of catalyst.
Patent CN201010128732.0 report it is a kind of use infusion process synthesize addition La, Re for the Pd/ α-of auxiliary agent
Al2O3Catalyst, in the reaction of CO synthesizing dimethyl oxalate, air speed is 3670 h-1, under conditions of reaction temperature is 135 DEG C,
The space-time yield of dimethyl oxalate is up to 1000 g/L (cat) h, and selectivity is up to 98% or more.But the dosage of its noble metal is very
Height, loading is average 1.5% or more, so that the cost of catalyst increases.
Patent CN201210028850.3 reports a kind of Pd-M/ of the CO gas-phase dimethyloxalate synthesis of dipping synthesis
Al2O3Catalyst, M auxiliary agent used are Mg, Ce, Co or Ni, 2400 h of air speed-1, reaction control temperature is 120 ~ 140oC, grass
The space-time yield of dimethyl phthalate is up to 917 g/L (cat) h；Patent CN201110323078.3 reports a kind of Pd/ α-Al2O3
Catalyst, catalyst use two kinds of auxiliary agent step impregnations, the first auxiliary agent be Ti, Si, V and Mo in any one, for pair
The modification of carrier, second of auxiliary agent are any one in Zr, La and Ce, with active component Pd co-impregnation on carrier, are catalyzed
Agent is 3000h in air speed-1, reaction control temperature 120oUnder the conditions of C, the space-time yield of dimethyl oxalate is 872 ~ 927 g/L
(cat) h, the selectivity of dimethyl oxalate are 97.8%.
The CO catalyst for synthesizing oxalic ester by gas-phase reported at present, most of is all to use traditional dipping means, and pass
For the infusion process of system since the solvation effect by maceration extract is influenced, active constituent is not easy high degree of dispersion, and in subsequent roasting and
Active component is easy to happen reunion in reduction process, and catalytic activity is caused to reduce.Therefore, to the improvement of catalyst synthesis processes,
While reducing noble metal dosage, preparation high dispersive, high stability, high activity CO catalyst for synthesizing oxalic ester by gas-phase be mesh
Preceding all circles' concerted effort direction.
Summary of the invention
It is an object of the invention in the preparation process of current catalyst for synthesizing oxalic ester, traditional dipping means exist
Defect, provide it is a kind of prepare CO catalyst for synthesizing oxalic ester by gas-phase using microwave-assisted dipping process, this method synthesis
Catalyst can significantly improve the degree of scatter of active metal, the effective activity and stability for improving catalyst.
To achieve the above object, The technical solution adopted by the invention is as follows:
Oxalate synthesis catalyst of the invention, with 1 ~ 8 mm of diameter, specific surface area for 1 ~ 20 m2Spherical α-the Al of/g2O3To carry
Body, carrier specific surface area preferably 5 ~ 10 m2/ g, supported precious metal palladium are active component, at the same add transition-metal Fe, Co, Ce,
One or more of Zr, La are used as auxiliary agent, and the loading of active component Pd is 0.1 ~ 1 wt%(of carrier quality in terms of PdO),
Preferred active component loading is 0.2 ~ 0.5 wt%(of carrier quality in terms of PdO), the additive amount of auxiliary agent is carrier quality
0.1 ~ 3 wt%(is in terms of oxide), preferred additive dosage is 0.3 ~ 0.8 wt%(of carrier quality in terms of oxide).
The Pd salt of solubility of the present invention is one kind of palladium chloride or palladium nitrate, promoter metal salt be Fe, Co,
The chloride or nitrate of Ce, Zr, La.
CO of the present invention is coupled catalyst for synthesizing oxalic ester, and preparation method includes the following steps:
(1) a certain amount of promoter metal salt is weighed in proportion, and hydrochloric acid solution is added or water is dissolved, is proportionally added into a certain amount of
The dissolution of soluble Pd salt, finally plus water is configured to the maceration extract of required concentration.According to carrier quality and saturated water absorption and
The load capacity of active metal Pd and promoter metal determine the dosage of Pd salt and promoter metal salt in required maceration extract, carry by every gram
Body prepares the maceration extract of 1.0 ~ 1.5 times of saturated water absorptions, determines solution total amount；
(2) a certain amount of carrier α-Al is weighed2O3Maceration extract is added dropwise in ball in proportion, guarantees maceration extract uniform adsorption on carrier；
(3) carrier after maceration extract is added using microwave treatment, microwave frequency 2459MHz, power is 500 ~ 2000 W, microwave
Processing 2 ~ 8 times, every time 10 ~ 80s, every 1 ~ 20min of minor tick；Catalyst after microwave treatment is transferred to 50 ~ 150oThe baking of C
In case, 2 ~ 15h is dried；
(4) it using the catalyst after 0.5 ~ 4 wt%NaOH solution processing drying of 1.0 ~ 1.5 times of carrier saturated water absorption amounts, protects
NaOH solution is demonstrate,proved in catalyst surface uniform adsorption, 10 ~ 20 h of closed processes；
(5) treated that catalyst is washed 2 ~ 8 times with the deionized water of 1 ~ 5 times of carrier quality for NaOH solution, then urging after washing
Agent is in 100 ~ 200oIn the baking oven of C, 2 ~ 12 h are dried；
(6) by the catalyst after drying 300 ~ 600 in airo2 ~ 8h is roasted under C to get the catalyst.
Catalyst of the present invention be mainly used for CO gas-phase synthesis of oxalate reaction, especially CO gas-phase dimethyloxalate synthesis,
Diethy-aceto oxalate.Reaction uses fixed bed reactors, 1 ~ 15 mL(heap volume of catalyst filling), 150 ~ 400oC prereduction 4 ~
10 h, reducing atmosphere are 20 ~ 100vol% hydrogen (nitrogen balance), restore 1000 ~ 3000 h of air speed-1.With nitrogen, CO, nitrous acid
Ester is raw material, and CO volume fraction is 10 ~ 50%, and methyl nitrite volume fraction is 5 ~ 30%, and reaction control temperature is 100 ~ 160oC, volume space velocity are 1000 ~ 6000h-1, reaction pressure is 0 ~ 1.0 MPa, and the selectivity of oxalate is greater than 97%, and space-time yield can
Up to 1300 g/L (cat) h or more, the yield of catalyst operation 600h dimethyl oxalate does not decline, illustrates the stability of catalyst
It can be preferably.
Catalyst of the invention and preparation method thereof compares existing catalyst, has the advantage that
(1) Microwave-assisted synthesis process can aggravate the moisture movement in maceration extract significantly, be more conducive to effects of ion
Dispersion, so that degree of scatter of the active component Pd on carrier is effectively increased, so that catalyst activity component contains lower
Under amount, still there is greater activity.
(2) there is temperature gradient from heat source position in regular heating process heat always, and the heat of Microwave-assisted firing leans on
Vibration and friction between heated medium itself hydrone generate, and the medium being heated is not limited by size and shape, temperature
Degree can the whole of " inertialess " change.For the catalyst of molding spherical alumina support dipping, heat distribution is equal on the whole
One, be conducive to drying process active component and be uniformly distributed on carrier.
(3) patent CN201010128732.0 report it is a kind of use infusion process synthesize addition La, Re for the Pd/ of auxiliary agent
α-Al2O3Catalyst, in the reaction of CO synthesizing dimethyl oxalate, air speed is 3670 h-1, reaction temperature is 135 DEG C of condition
Under, the space-time yield of dimethyl oxalate is up to 1000 g/L (cat) h.But the dosage of its noble metal is very high, and loading averagely exists
1.5% or more, so that the cost of catalyst increases；And its content in terms of PdO in the application is 0.2-0.5%, should control temperature
It is 120oC, volume space velocity 3500h-1, space-time yield up to 1130 g/L (cat) h or more, catalyst in the application
Catalytic performance is significantly larger than catalyst in the prior art.
Detailed description of the invention
Fig. 1 is to investigate figure in the service life for the catalyst that embodiment 1 synthesizes.
Specific embodiment
The present invention is described in further detail With reference to embodiment, but claim of the invention is not
It is limited only to following embodiments.
Embodiment 1
(1) catalyst synthesizes
Weigh FeCl3The dissolution of 20ml water is added in 0.8125g, takes PdCl2Powder 0.4348g, adds to FeCl3It dissolves, adds in solution
Water is settled to 50ml.Take the α-Al of high-temperature roasting2O34 ~ 5mm of balloon borne body 100g(diameter phi, 5 ~ 8 m of reference area2/ g, saturation are inhaled
Water rate 45%), the maceration extract prepared is added dropwise on carrier, makes maceration extract in carrier surface uniform adsorption.
Carrier after dipping uses frequency for microwave treatment 4 times that 2459 MHz, power are 600 W, every time 20 s, every time
It is spaced 2 min.
Catalyst after microwave treatment is transferred to 60oIn the baking oven of C, 12 h are dried.With the NaOH of 1 wt% after drying
Solution 60ml is added dropwise to catalyst surface, guarantees NaOH solution in catalyst surface uniform adsorption, closed processes 10h.NaOH is molten
After liquid processing, with 200ml deionized water washing catalyst 5 times, then by the catalyst after washing in 120oIn the baking oven of C, drying 5
H, the catalyst after drying is 500 in airo4 h are roasted under C.Gained catalyst activity component Pd content is carrier quality
0.3wt%(is in terms of PdO), Fe content is the 0.4wt%(of carrier quality with Fe2O3Meter).
(2) performance evaluation
Using fixed bed reactors, 10ml catalyst is loaded, 200oC prereduction 8 h, reducing atmosphere 30%H2-70%N2, also
Former 2000 h of air speed-1, 120 are cooled under reducing atmosphereoC。
Reaction is using nitrogen, CO, methyl nitrite as raw material, volume fraction, reaction control temperature, volume space velocity, reaction pressure
Power is as shown in table 1, and differential responses condition evaluation results are shown in Table 1.
The evaluation result of 1. embodiment of table, 1 catalyst at different conditions
Embodiment 2
(1) catalyst synthesizes
Weigh Ce (NO3)3•6H2The hydrochloric acid solution 20ml dissolution of 0.35mol/L is added in O1.2612g, takes PdCl2Powder 0.5797
G adds in above-mentioned solution and dissolves, water is added to be settled to 50ml.Take the α-Al of high-temperature roasting2O3Balloon borne body 100g(diameter phi 4 ~ 5
Mm, 5 ~ 8 m of reference area2/ g, saturated water absorption 45%), the maceration extract prepared is added dropwise on carrier, makes maceration extract in carrier
Surface uniform adsorption.
Carrier after dipping uses frequency for microwave treatment 5 times that 2459 MHz, power are 500 W, every time 30 s, every time
It is spaced 5 min.
Catalyst after microwave treatment is transferred to 80oIn the baking oven of C, 10 h are dried.It is molten with the NaOH of 2wt% after drying
Liquid 60ml is added dropwise to catalyst surface, guarantees NaOH solution in catalyst surface uniform adsorption, closed processes 15h.NaOH solution
After processing, with 250ml deionized water washing catalyst 5 times, then by the catalyst after washing in 120oIn the baking oven of C, 5 h are dried,
Catalyst after drying is 500 in airo4 h are roasted under C.Gained catalyst activity component Pd content is carrier quality
0.4wt%(is in terms of PdO), Ce content is the 0.5wt%(of carrier quality with CeO2Meter).
(2) performance evaluation
Using fixed bed reactors, 10ml catalyst is loaded, 200oC prereduction 8 h, reducing atmosphere 30%H2-70%N2, also
Former 2000 h of air speed-1, 120 are cooled under reducing atmosphereoC。
Reaction is using nitrogen, CO, methyl nitrite as raw material, and volume fraction is respectively 75%, 15%, 10%, reaction control temperature
It is 120oC, volume space velocity are 2500 h-1, reaction pressure is 0.3 MPa, and evaluation result is listed in Table 2 below.
Embodiment 3
(1) catalyst synthesizes
Weigh ZrOCl2•8H2The hydrochloric acid solution 20ml dissolution of 0.1mol/L is added in O 0.7845g, takes Pd (NO3)2Powder 0.3765
G adds in above-mentioned solution and dissolves, water is added to be settled to 50ml.Take the α-Al of high-temperature roasting2O3Balloon borne body 100g(diameter phi 4 ~ 5
Mm, 5 ~ 8 m of reference area2/ g, saturated water absorption 45%), the maceration extract prepared is added dropwise on carrier, makes maceration extract in carrier
Surface uniform adsorption.
Carrier after dipping uses frequency for microwave treatment 5 times that 2459 MHz, power are 600 W, every time 40 s, every time
It is spaced 10 min.
Catalyst after microwave treatment is transferred to 120oIn the baking oven of C, 10 h are dried.With the NaOH of 1 wt% after drying
Solution 60ml is added dropwise to catalyst surface, guarantees NaOH solution in catalyst surface uniform adsorption, closed processes 20h.NaOH is molten
After liquid processing, with 200ml deionized water washing catalyst 5 times, then by the catalyst after washing in 120oIn the baking oven of C, drying 5
H, the catalyst after drying is 450 in airo6 h are roasted under C.Gained catalyst activity component Pd content is carrier quality
0.2 wt%(is in terms of PdO), Zr content is 0.3 wt%(of carrier quality with ZrO2Meter).
(2) performance evaluation
With embodiment 2, evaluation result is listed in Table 2 below for evaluation procedure.
Embodiment 4
(1) catalyst synthesizes
Weigh Zr (NO3)4•5H2The hydrochloric acid solution 20ml dissolution of 0.45mol/L is added in O 1.0453g, takes PdCl2Powder 0.7247
G adds in above-mentioned solution and dissolves, water is added to be settled to 50ml.Take the α-Al of high-temperature roasting2O3Balloon borne body 100g(diameter phi 4 ~ 5
Mm, 5 ~ 8 m of reference area2/ g, saturated water absorption 45%), the maceration extract prepared is added dropwise on carrier, makes maceration extract in carrier
Surface uniform adsorption.
Carrier after dipping uses frequency for microwave treatment 5 times that 2459 MHz, power are 600 W, every time 20 s, every time
It is spaced 5 min.
Catalyst after microwave treatment is transferred to 150oIn the baking oven of C, 10 h are dried.With the NaOH of 1 wt% after drying
Solution 60ml is added dropwise to catalyst surface, guarantees NaOH solution in catalyst surface uniform adsorption, closed processes 15h.NaOH is molten
After liquid processing, with 200ml deionized water washing catalyst 5 times, then by the catalyst after washing in 120oIn the baking oven of C, drying 5
H, the catalyst after drying is 500 in airo6 h are roasted under C.Gained catalyst activity component Pd content is carrier quality
0.5wt%(is in terms of PdO), Zr content is 0.3 wt%(of carrier quality with ZrO2Meter).
(2) performance evaluation
With embodiment 2, evaluation result is listed in Table 2 below for evaluation procedure.
Embodiment 5
(1) catalyst synthesizes
Weigh Zr (NO3)4•5H2O 1.0453g、La(NO3)3•6H2The hydrochloric acid solution 20ml of O 0.2658g addition 0.35mol/L
Dissolution, takes PdCl2Powder 0.5797g adds in above-mentioned solution and dissolves, water is added to be settled to 50ml.Take the α-Al of high-temperature roasting2O3
Balloon borne 4 ~ 5 mm of body 100g(diameter phi, 5 ~ 8 m of reference area2/ g, saturated water absorption 45%), the maceration extract prepared is added dropwise to
On carrier, make maceration extract in carrier surface uniform adsorption.
Carrier after dipping uses frequency for microwave treatment 5 times that 2459 MHz, power are 600 W, every time 20 s, every time
It is spaced 5 min.
Catalyst after microwave treatment is transferred to 80oIn the baking oven of C, 12 h are dried.With the NaOH of 1 wt% after drying
Solution 60ml is added dropwise to catalyst surface, guarantees NaOH solution in catalyst surface uniform adsorption, closed processes 15h.NaOH is molten
After liquid processing, with 250ml deionized water washing catalyst 5 times, then by the catalyst after washing in 120oIn the baking oven of C, drying 5
H, the catalyst after drying is 500 in airo4 h are roasted under C.Gained catalyst activity component Pd content is carrier quality
0.4wt%(is in terms of PdO), Zr content is 0.3 wt%(of carrier quality with ZrO2Meter), La content is the 0.2wt% of carrier quality
(with La2O3Meter).
(2) performance evaluation
With embodiment 2, evaluation result is listed in Table 2 below for evaluation procedure.
The evaluation result of the different embodiment kind catalyst of table 2.
Using nitrogen, CO, nitrous acid ester as raw material, CO volume fraction is 15%, and methyl nitrite (MN) volume fraction is 10%, reaction
Controlled at 120oC, volume space velocity 3500h-1, reaction pressure is 0.3 MPa, and the selectivity of oxalate is greater than 97.8%,
Space-time yield is up to 1130 g/L (cat) h or more.And with the increase of Pd content in catalyst, space-time yield also gradually increases
Add.
Embodiment 6
Using fixed bed reactors, catalyst in 10ml embodiment 1 is loaded, 200o8 h of C prereduction, reducing atmosphere 30%
H2-70%N2, restore 2000 h of air speed-1, 120 are cooled under reducing atmosphereoC。
Using nitrogen, CO, nitrous acid ester as Material synthesis dimethyl oxalate, CO volume fraction is 25%, methyl nitrite volume
Score is 15%, reaction control temperature 120oC, volume space velocity 2500h-1, reaction pressure is 0.3 MPa；Runing time is
600h.The result is shown in Figure 1, the selective average out to 99.2% of dimethyl oxalate, and space-time yield is average up to 1354 g/L (cat)
H runs 600h average yield always in 1300 g/L (cat) h or more.Catalyst does not decline in operation 600h, illustrates its stabilization
Property is good.
Claims (3)
1. one kind is coupled catalyst for synthesizing oxalic ester for CO, with α-Al2O3It is active component for carrier-supported precious metal palladium,
It is characterized in that, which is the spherical α-Al of 1 ~ 8 mm of diameter2O3, specific surface area 5-10m2/g；Catalyst addition
One or more of transition-metal Fe, Co, Ce, Zr, La are used as auxiliary agent；The loading of active component Pd is calculated as carrier with PdO
0.2 ~ 0.5wt% of quality, the additive amount of auxiliary agent are calculated as 0.3 ~ 0.8wt% of carrier quality with oxide.
2. a kind of preparation method for CO coupling catalyst for synthesizing oxalic ester according to claim 1, which is characterized in that
The following steps are included:
(1) promoter metal salt is weighed in proportion, hydrochloric acid solution is added or water is dissolved, and the dissolution of solubility Pd salt is added, finally
Water is added to be configured to the maceration extract of required concentration；According to carrier quality and saturated water absorption and active metal Pd and promoter metal
Load capacity determines the dosage of solubility Pd salt and promoter metal salt in required maceration extract, prepares 1.0 ~ 1.5 times by every gram of carrier and satisfies
Solution total amount is determined with the maceration extract of water absorption rate；Soluble Pd salt is one kind of palladium chloride or palladium nitrate, promoter metal salt be Fe,
The chloride or nitrate of Co, Ce, Zr, La；
(2) carrier α-Al is weighed2O3Maceration extract is added dropwise in ball, guarantees maceration extract uniform adsorption on carrier；
(3) carrier after maceration extract, microwave frequency 2459MHz, by the catalyst after microwave treatment are added using microwave treatment
It is transferred to 50 ~ 150oIn the baking oven of C, 2 ~ 15h is dried；
(4) it using the catalyst after 0.5 ~ 4 wt%NaOH solution processing drying of 1.0 ~ 1.5 times of carrier saturated water absorption amounts, protects
Demonstrate,prove NaOH solution uniform adsorption on a catalyst, 10 ~ 20 h of closed processes；
(5) treated that catalyst is washed 2 ~ 8 times with the deionized water of 1 ~ 5 times of carrier quality for NaOH solution, then urging after washing
Agent is in 100 ~ 200oIn the baking oven of C, 2 ~ 12 h are dried；
(6) by the catalyst after drying 300 ~ 600 in airo2 ~ 8h is roasted under C to get the catalyst.
3. a kind of preparation method for CO coupling catalyst for synthesizing oxalic ester according to claim 2, which is characterized in that institute
Microwave power is 500 ~ 2000 W in the step of stating preparation method (3), is handled 2 ~ 8 times, every time 10 ~ 80s, every minor tick 1 ~
20min。
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