CN106582763B - A kind of catalyst, preparation method and preparing the application in oxalate - Google Patents
A kind of catalyst, preparation method and preparing the application in oxalate Download PDFInfo
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- CN106582763B CN106582763B CN201611158283.8A CN201611158283A CN106582763B CN 106582763 B CN106582763 B CN 106582763B CN 201611158283 A CN201611158283 A CN 201611158283A CN 106582763 B CN106582763 B CN 106582763B
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- palladium
- oxalate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 26
- 238000005859 coupling reaction Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 30
- 239000012298 atmosphere Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- -1 graphite Alkene Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 4
- 238000002848 electrochemical method Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 238000010574 gas phase reaction Methods 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 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
- 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
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- 235000013339 cereals Nutrition 0.000 description 7
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 6
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 6
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 6
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical group CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 2
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 2
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 108091006230 SLC7A3 Proteins 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- LOMVENUNSWAXEN-NUQCWPJISA-N dimethyl oxalate Chemical group CO[14C](=O)[14C](=O)OC LOMVENUNSWAXEN-NUQCWPJISA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
This application discloses a kind of catalyst, preparation method and preparing the application in oxalate.The catalyst includes carrier and active component, which is characterized in that the carrier includes nitrogen-doped graphene nanometer sheet, and the active component includes Technique of Nano Pd.The content of active component palladium is 0.03~2wt% in the catalyst, in CO preparing oxalate by coupling reaction technique, overcoming in the prior art CO preparing oxalate by coupling reaction catalyst disadvantages such as noble-metal-supported amount is high, oxalate space-time yield is low.
Description
Technical field
This application involves a kind of catalyst, preparation method and the applications in oxalate preparation, belong to chemical neck
Domain.
Background technique
Oxalate is important Organic Chemicals, is widely used in preparing various important chemical products, such as oxalic acid
Ester hydrolysis can obtain oxalic acid, ammonification can obtain oxamides plus hydrogen can prepare ethylene glycol.CO gaseous oxidation is coupled producing oxalic ester (2CO+
2RONO → (COOR) 2+2NO) it is committed step in " coal-ethylene glycol ", there is important industrial application value.In addition, should
Technique also has important application prospect in industrial tail gas processing.Contain a large amount of CO in many industrial tail gas, it is main at present
It is burning processing, if converting the CO collection in tail gas to the oxalate of high added value, energy-saving and emission-reduction not only may be implemented, also
Resource can be made full use of and solve environmental problem.
Ethylene glycol is important Organic Chemicals and strategic materials, mainly for the production of polyester, fiber, explosive, and can
As antifreezing agent, plasticizer and solvent etc., there is extensive use in fields such as organic synthesis, pharmacy, fragrance and coating.It is global
More than 2,500 ten thousand tons of ethylene glycol annual requirement.Traditional ethylene glycol production method is mainly petroleum path, technology path production
Ethylene glycol higher cost, main cause are the scarcities of higher oil price and petroleum resources.Coal resources in China relative abundance, oil starvation
The national conditions of few gas determine that coal-ethylene glycol technology path and industrial applications have important strategic importance and economic value.
CO coupling producing oxalic ester is the committed step that coal-ethylene glycol technology realizes that inorganic C1 is converted to organic C 2.Its tool of the technical process
Have the advantages that Atom economy, reaction condition are mild, low energy consumption, environmental-friendly, equipment investment is low and good product quality.Palladium base is urged
Agent has proved to be the active catalyst of this process.The catalyst reported at present is mostly using α-A12O3Or other metals
Oxide is then seldom reported as carrier with efficient palladium-based catalyst prepared by carbon material carrier.The catalysis industrially used
Agent Pd/ α-A12O3The load capacity of middle Pd is higher (about 2wt%), so that the catalyst cost of production ethylene glycol is significantly increased.
Therefore, using the carrier with large specific surface area, enhance the interaction of carrier and catalyst, improve catalyst
Performance, reduce noble-metal-supported amount for improve oxalate production efficiency, reduce coal-ethylene glycol cost have it is important
Meaning.
Summary of the invention
According to the one aspect of the application, a kind of nitrogen-doped graphene nanometer sheet load palladium effective catalyst, the catalysis are provided
The content of active component palladium is 0.03~2wt% in agent, in CO preparing oxalate by coupling reaction technique, CO conversion per pass to be up to
68%, for oxalate selectivity up to 97%, oxalate space-time yield reaches 1.46gg-1(cat)·h-1(air speed 3Lg-1·h-1), when overcoming the catalyst used in prior art CO preparing oxalate by coupling reaction technique using Alpha-alumina as carrier, your gold
Belong to the disadvantages such as load capacity is high, oxalate space-time yield is low.
The catalyst, including carrier and active component, which is characterized in that the carrier includes nitrogen-doped graphene nanometer
Piece, the active component include Technique of Nano Pd.
Preferably, the mass percentage of the Technique of Nano Pd in the catalyst is 0.03~2wt%.It is further preferred that
The mass percentage of the Technique of Nano Pd in the catalyst is 0.18~0.71wt%.
Preferably, the average grain diameter of the Technique of Nano Pd is 1~9nm.It is further preferred that the average grain diameter of the Technique of Nano Pd
For 1~5nm.
Preferably, the atomicity percentage composition of nitrogen is 1~7at% in the nitrogen-doped graphene nanometer sheet.Into one
Preferably, the atomicity percentage composition of nitrogen is 2~7at% to step in the nitrogen-doped graphene nanometer sheet.
Preferably, the nitrogen-doped graphene nanometer sheet with a thickness of 0.8~30nm.
According to the another aspect of the application, the method for preparing above-mentioned any catalyst is provided, is at least included the following steps:
A) graphene nanometer sheet is placed in NH3In atmosphere, is kept at 400~800 DEG C no less than 3 hours, obtain nitrogen and mix
Miscellaneous graphene nanometer sheet；
B) the nitrogen-doped graphene nanometer sheet that step a) is obtained is placed in the solution containing palladium element, by ultrasonic treatment
Afterwards, isolated solid phase；
C) solid phase obtained by step b) it is washed, it is dry, roast after, be placed in the atmosphere containing reducibility gas in 150~
After restoring at least 2 hours under 450 DEG C of reduction temperature, room temperature is down in the atmosphere containing reducibility gas to get described in
Catalyst.
Graphene nanometer sheet can derive from commercially available in step a), can also be prepared using electrochemical method.
As an implementation, the graphene nanometer sheet is prepared using electrochemical method.Preferably, described to adopt
Graphene nanometer sheet is electrochemically prepared, is at least included the following steps:
Using graphitic source as anode and cathode, sulfuric acid and/or sulfate liquor are electrolyte, in a manner of square wave, AC and DC, are led to
Cross and apply 5~60V voltage, the graphitic source as electrode is subjected to electrochemical milling, further ultrasound, be filtered, washed, vacuum it is dry
Dry graphene nanometer sheet to obtain the final product.
As an implementation, the graphitic source is selected from graphite rod and/or graphite paper.
As a preferred embodiment, the sulfate in lithium sulfate, sodium sulphate, ammonium sulfate at least one
Kind.
As a preferred embodiment, described prepare graphene nanometer sheet using electrochemical method, include at least with
Lower step:
(1) use two electrode systems, using high purity graphite paper as anode and cathode, successively with 0.1mol/L hydrochloric acid, acetone, ethyl alcohol,
Ultrapure water etc. is cleaned.
(2) using the ammonium sulfate of 0.5~3mol/L as electrolyte.
(3) square-wave potential method is used, 5~60V of the upper limit, lower limit -60~-5V, 0.1~50Hz of frequency will be as electrodes
Graphite paper electrolysis expands removing by sulfate radical intercalation and obtains graphene nanometer sheet suspension.
(4) further by graphene nanometer sheet suspension ultrasound, be filtered, washed, be dried in vacuo up to graphene nanometer sheet.
Preferably, step a) is that graphene nanometer sheet is placed in tube furnace, in NH3Under atmosphere, at 400~800 DEG C
It is kept for 3~5 hours, obtains nitrogen-doped graphene nanometer sheet.
Preferably, ultrasonic treatment is to stir 2~18 hours in ultrasound in step b).
Preferably, the solution containing palladium element described in step b) is that the dissolution of palladium source obtains in a solvent.Further preferably
Ground, the palladium source are selected from palladium chloride, palladium acetate, potassium chloropalladite, sodium chloropalladite, potassium chloropalladate, dichloro diamino palladium, dichloro four
At least one of ammonia palladium, palladium nitrate, palladium acetylacetonate.It is further preferred that the solvent is selected from water, acetone, dichloromethane
At least one of alkane, chloroform, methanol, ethyl alcohol, hexamethylene, dimethylformamide, benzene, toluene.
Preferably, step c) is placed in for step b) gained solid phase after washed, dry, roasting containing reducibility gas
Room is down in the atmosphere containing reducibility gas behind reductase 12~8 hour under 150~450 DEG C of reduction temperature in atmosphere
Temperature to get arrive the catalyst.
Preferably, the atmosphere described in step c) containing reducibility gas is selected from the mixing of hydrogen, hydrogen and inert gas
Object.It is further preferred that the inert gas is nitrogen and/or argon gas.
According to the another aspect of the application, a kind of method for preparing oxalate is provided, which is characterized in that using above-mentioned any
At least one of catalyst and/or at least one of the catalyst being prepared according to above-mentioned any means, pass through an oxygen
Change carbon gaseous oxidation preparing oxalate by coupling reaction.
Preferably, the carbon monoxide gaseous oxidation preparing oxalate by coupling reaction is to contain an oxygen in fixed bed reactors
The unstripped gas for changing carbon and nitrous acid ester is contacted with the catalyst, reaction pressure is normal pressure, reaction temperature is 90~150 DEG C
Under the conditions of gas phase reaction prepare oxalate；
In the unstripped gas, the volume ratio of carbon monoxide and nitrous acid ester is 1.1~1.8；
The gas phase air speed of the unstripped gas is 2~5Lg-1·h-1。
Preferably, the nitrous acid ester is methyl nitrite and/or nitrous ether (ethyl nitrite)；The oxalate is dimethyl oxalate
And/or diethy-aceto oxalate.
The beneficial effect of the application includes but is not limited to:
1, catalyst provided herein using electrochemical stripping and carries out the graphene nanometer sheet of N doping as carrying
Body, the carrier have many advantages, such as large specific surface area, good thermal conductivity；In addition the modification of nitrogen changes the electricity of graphene nanometer sheet
Minor structure enhances the alkalinity of graphene nanometer sheet, enhances the interaction of carrier and active component, improves supported catalyst
Performance.
2, it is 0.03~2wt% that precious metal palladium load capacity is lower in catalyst provided herein, low under normal conditions
In the 0.8wt% of carrier quality, a large amount of noble metals can be saved, significantly reduce the cost of catalyst.
3, the preparation method of catalyst provided herein, it is active in catalyst without using any surfactant
Component palladium nano-particles clean surface, small-sized, particle diameter distribution is uniform, is highly dispersed at carrier graphene nanometer sheet surface,
Significantly enhance CO oxidative coupling catalytic performance.
4, the method for preparing oxalate provided herein passes through carbon monoxide gas using herein described catalyst
Phase oxidation preparing oxalate by coupling reaction；CO conversion per pass is up to 68%, and up to 97%, oxalate space-time yield reaches oxalate selectivity
1.46g·g-1(cat)·h-1(air speed 3Lg-1·h-1)。
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of graphene nanometer sheet GNP.
Fig. 2 is the transmission electron microscope picture of catalyst sample CAT-1.
Fig. 3 is the transmission electron microscope picture of Pd/GNP catalyst prepared by comparative example 1.
Specific embodiment
The application is described in detail below with reference to embodiment and attached drawing, but the application is not limited to these embodiments.
In embodiment, stereoscan photograph is shot using the JEOL-6700F type instrument of Hitachi, Ltd.
In embodiment, transmission electron microscope is shot using the TECNAI F20 type instrument of FEI Co., the U.S..
In embodiment, N content uses the ESCA-LAB type x-ray photoelectron spectroscopy of Britain VG Scienta company in sample
(being abbreviated as XPS) measurement；Pd content emits light using the Ultima2 type inductively coupled plasma body of Jobin Yvon company, France
Compose (being abbreviated as ICP) measurement.
In embodiment, graphite paper is purchased from lucky prosperous peace Trade Co., Ltd..
In embodiment, catalyst is evaluated by being monitored analysis to unstripped gas and the online gas-chromatography of product, in Japan
It is carried out on the GC2014 type gas chromatograph of Shimadzu Corporation.
Unless otherwise specified, reagent employed in embodiment comes from commercially available, without any processing；Instrument parameter is adopted
It is arranged with manufacturer's recommended.
The preparation of 1 catalyst sample of embodiment
The preparation of graphene nanometer sheet
Using two electrode systems, using high purity graphite paper as anode and cathode, successively with 0.1mol/L hydrochloric acid, acetone, ethyl alcohol, ultrapure
Water is cleaned；Using the ammonium sulfate of 1mol/L as electrolyte.With square-wave potential method, upper limit 9V, lower limit -9V, frequency 10Hz,
Graphite electrode is electrolysed, removing is expanded by sulfate radical intercalation and obtains graphene nanometer sheet suspension, graphene nanometer sheet is hanged
Turbid ultrasound, be filtered, washed, be dried in vacuo after to get graphene nanometer sheet, be denoted as GNP.
The preparation of nitrogen-doped graphene nanometer sheet
The graphene nanometer sheet GNP of above-mentioned acquisition is placed in tube furnace, at a temperature of N doping, is passed through ammonia, is kept
(N doping time) for a period of time, then in N2It is cooled to room temperature under atmosphere to get the graphene nanometer sheet of N doping is arrived, is denoted as
N-GNP。
The sample number into spectrum of the graphene nanometer sheet of gained N doping and the relationship of doping temperature are as shown in table 1.
Table 1
The preparation of catalyst sample
In solution containing palladium, when solvent is organic solvent: weighing the graphene nano of the N doping of the above-mentioned preparation of 1g
Piece is as carrier impregnation into solution containing palladium, and for a period of time, then heating is simultaneously ultrasonic to solvent at 50 DEG C for ultrasonic disperse
Until volatilization is dry, solid phase is obtained.Further in N2400 DEG C of roasting 3h, are finally containing reproducibility under reduction temperature in atmosphere
A period of time is restored in the atmosphere of gas, obtains the catalyst sample.
When containing water in solution containing palladium, in solvent: weighing the graphene nanometer sheet of the N doping of the above-mentioned preparation of 1g
As carrier impregnation into solution containing palladium, ultrasonic disperse for a period of time, stirs 8h, is centrifugally separating to obtain solid phase, deionization
Water washing 3 times, 80 DEG C are dried in vacuo 8 hours.Further in N2400 DEG C of roasting 3h, are finally containing under reduction temperature in atmosphere
Have and restore a period of time in the atmosphere of reducibility gas, obtains the catalyst sample.
It is the number of gained catalyst sample and the graphene nanometer sheet sample number into spectrum of selected N doping, containing palladium molten
Liquid, ultrasonic disperse time, the atmosphere composition containing reducibility gas, reduction temperature, the relationship of recovery time are as shown in table 2.
Table 2
Comparative example 1
It prepares catalyst Pd/GNP: weighing GNP carrier impregnation that 1g is prepared by embodiment 1 to 23.4mg palladium acetate and 20mL
In the solution that acetone is made into, ultrasonic disperse 2h, then simultaneously it is mixed to obtain solid until acetone volatilization is dry for ultrasound for heating at 50 DEG C
Close object.Further in N2400 DEG C of roasting 3h in atmosphere finally lead to hydrogen reducing 2h under the conditions of 300 DEG C, obtain catalyst
Pd/GNP.It is 0.62wt% by the load capacity that ICP measures palladium.
2 sample characterization of embodiment
The N doping amount in graphene nanometer sheet sample N-GNP-1~N-GNP-3 of N doping is surveyed using XPS
Fixed, the results are shown in Table 1.
The palladium load capacity in catalyst sample CAT-1~CAT-7 is determined using ICP, the results are shown in Table 2.
The stereoscan photograph of graphene nanometer sheet GNP is as shown in Figure 1；As seen from the figure, GNP be thickness 0.8~
The nanometer sheet of 30nm, size between 1~15 μm.
Catalyst sample CAT-1~CAT-7 is characterized using transmission electron microscope, the results show that N doping greatly improves
The dispersion degree of active component palladium, palladium grain diameter is uniform, average grain diameter is between 1~9nm.It is typical generation with sample CAT-1
Table, transmission electron microscope photo is as shown in Fig. 2, as seen from Figure 2, the graphene that palladium nano-particles are highly dispersed at N doping is received
Rice piece surface, Pd particle size distribution is uniform, average grain diameter 3.6nm.
Comparative example Pd/GNP is characterized using transmission electron microscope, as a result as shown in Figure 3.As seen from the figure, Pd
Nano particle is highly dispersed at carrier surface, and compared with sample CAT-1, nanoparticle size is larger (average grain diameter 6.2nm), grain
Diameter distribution is more inhomogenous.
3 catalyst sample of embodiment is used to prepare the reaction evaluating of oxalate
Catalyst sample CAT-1~CAT-7, comparative example Pd/GNP are respectively placed in fixed bed reactors, applied
It is reacted in CO gaseous oxidation preparing oxalate coupling reaction, includes CO and methyl nitrite in unstripped gas, CO and methyl nitrite flow
Volume ratio is 1.4, and the gas phase air speed of unstripped gas is 3Lg-1·h-1, reaction temperature is 130 DEG C, reaction pressure 0.1Mpa, former
Expect that gas and product are monitored analysis by online gas-chromatography, reaction result is shown in Table 3.
Table 3
Comparative example is compared with the catalyst sample that technical scheme provides it can be seen from data in table 3, when
In the approximate situation of palladium load capacity (compared with CAT-4), CO conversion per pass is far below CAT-4, even lower than Pd load capacity
The only CAT-3 of 0.18wt%.It can be seen that according to the catalyst of technical scheme preparation precious metal palladium dosage can be being saved
Meanwhile greatly improving CO conversion per pass and oxalate yield.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (9)
1. a kind of catalyst, including carrier and active component, which is characterized in that the carrier includes nitrogen-doped graphene nanometer
Piece, the active component include Technique of Nano Pd；
The catalyst is used to prepare oxalate；
The mass percentage of the Technique of Nano Pd in the catalyst is 0.03~2wt%.
2. catalyst according to claim 1, which is characterized in that the average grain diameter of the Technique of Nano Pd is 1~9nm.
3. catalyst according to claim 1, which is characterized in that the original of nitrogen in the nitrogen-doped graphene nanometer sheet
Subnumber percentage composition is 1~7at%.
4. catalyst according to claim 3, which is characterized in that the nitrogen-doped graphene nanometer sheet with a thickness of 0.8
~30nm.
5. the method for preparing any one of the Claims 1-4 catalyst, at least includes the following steps:
A) graphene nanometer sheet is placed in NH3In atmosphere, is kept at 400~800 DEG C no less than 3 hours, obtain N doping graphite
Alkene nanometer sheet；
B) the nitrogen-doped graphene nanometer sheet that step a) is obtained is placed in the solution containing palladium element, after ultrasonic treatment,
Isolated solid phase；
C) solid phase obtained by step b) it is washed, it is dry, roast after, be placed in the atmosphere containing reducibility gas in 150~450 DEG C
Reduction temperature under restore at least 2 hours after, room temperature is down in the atmosphere containing reducibility gas to get to the catalysis
Agent.
6. according to the method described in claim 5, it is characterized in that, the graphene nanometer sheet is prepared into using electrochemical method
It arrives.
7. according to the method described in claim 5, it is characterized in that, the solution containing palladium element is that palladium source is dissolved in solvent
In obtain；
The palladium source is selected from palladium chloride, palladium acetate, potassium chloropalladite, sodium chloropalladite, potassium chloropalladate, dichloro diamino palladium, dichloro
At least one of four ammonia palladiums, palladium nitrate, palladium acetylacetonate；
The solvent is in water, acetone, methylene chloride, chloroform, methanol, ethyl alcohol, hexamethylene, dimethylformamide, benzene, toluene
At least one.
8. a kind of method for preparing oxalate, which is characterized in that using in the described in any item catalyst of Claims 1-4
It is at least one and/or according at least one of the catalyst that any one of claim 5 to 7 the method is prepared, pass through
Carbon monoxide gaseous oxidation preparing oxalate by coupling reaction.
9. according to the method described in claim 8, it is characterized in that, the carbon monoxide gaseous oxidation preparing oxalate by coupling reaction is
In fixed bed reactors, the unstripped gas containing carbon monoxide and nitrous acid ester is contacted with the catalyst, is in reaction pressure
Gas phase reaction prepares oxalate under conditions of normal pressure, reaction temperature are 90~150 DEG C；
In the unstripped gas, the volume ratio of carbon monoxide and nitrous acid ester is 1.1~1.8；
The gas phase air speed of the unstripped gas is 2~5Lg-1·h-1。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691451A (en) * | 2014-01-07 | 2014-04-02 | 中国科学院福建物质结构研究所 | Catalyst for synthesizing methyl formate by virtue of gas-phase methanol carbonylation as well as preparation method and application of catalyst |
| CN104174393A (en) * | 2014-09-05 | 2014-12-03 | 中国科学院福建物质结构研究所 | Pd/ZnO efficient nano catalyst for producing oxalate by CO gas phase oxidative coupling as well as preparation method and application of Pd/ZnO efficient nano catalyst |
| CN104028293B (en) * | 2014-06-24 | 2016-08-03 | 常州大学 | A kind of preparation method of cryogenic nitrogen doped graphene load nano Pd particle hydrogenation catalyst |
| CN105903466A (en) * | 2016-05-03 | 2016-08-31 | 中国科学院福建物质结构研究所 | Catalyst for dimethyl oxalate synthesis and preparation method of catalyst for dimethyl oxalate synthesis |
-
2016
- 2016-12-15 CN CN201611158283.8A patent/CN106582763B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691451A (en) * | 2014-01-07 | 2014-04-02 | 中国科学院福建物质结构研究所 | Catalyst for synthesizing methyl formate by virtue of gas-phase methanol carbonylation as well as preparation method and application of catalyst |
| CN104028293B (en) * | 2014-06-24 | 2016-08-03 | 常州大学 | A kind of preparation method of cryogenic nitrogen doped graphene load nano Pd particle hydrogenation catalyst |
| CN104174393A (en) * | 2014-09-05 | 2014-12-03 | 中国科学院福建物质结构研究所 | Pd/ZnO efficient nano catalyst for producing oxalate by CO gas phase oxidative coupling as well as preparation method and application of Pd/ZnO efficient nano catalyst |
| CN105903466A (en) * | 2016-05-03 | 2016-08-31 | 中国科学院福建物质结构研究所 | Catalyst for dimethyl oxalate synthesis and preparation method of catalyst for dimethyl oxalate synthesis |
Non-Patent Citations (1)
| Title |
|---|
| "Electroreduction of oxygen on palladium nanoparticles supported on nitrogen-doped graphene nanosheets";Kristel Jukk et al.;《Electrochimica Acta》;20140610;第137卷;第206-212页 * |
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