CN106582763A - Catalyst, preparation method thereof and application in preparation of oxalate - Google Patents
Catalyst, preparation method thereof and application in preparation of oxalate Download PDFInfo
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- CN106582763A CN106582763A CN201611158283.8A CN201611158283A CN106582763A CN 106582763 A CN106582763 A CN 106582763A CN 201611158283 A CN201611158283 A CN 201611158283A CN 106582763 A CN106582763 A CN 106582763A
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- catalyst
- palladium
- nanometer sheet
- oxalate
- graphene nanometer
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 44
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005859 coupling reaction Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 31
- 238000000034 method Methods 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
- 239000000203 mixture Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 230000009467 reduction Effects 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
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 230000008569 process Effects 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
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000002826 nitrites Chemical class 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
- 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 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
- 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
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- -1 graphite Alkene Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000010970 precious metal Substances 0.000 abstract description 3
- 239000004480 active ingredient Substances 0.000 abstract 3
- 230000008878 coupling Effects 0.000 abstract 2
- 238000010168 coupling process Methods 0.000 abstract 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- 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
- 238000002604 ultrasonography Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 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
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 235000013339 cereals Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 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
- 239000007788 liquid Substances 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
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 150000002835 noble gases Chemical class 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
- 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
- 238000001291 vacuum drying Methods 0.000 description 2
- JRMAQQQTXDJDNC-UHFFFAOYSA-M 2-ethoxy-2-oxoacetate Chemical compound CCOC(=O)C([O-])=O JRMAQQQTXDJDNC-UHFFFAOYSA-M 0.000 description 1
- 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 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
- 150000001875 compounds Chemical class 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
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 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
- 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
- 238000005984 hydrogenation reaction Methods 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
- 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
- 235000013599 spices Nutrition 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 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
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
-
- B01J35/393—
-
- 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
-
- 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
Abstract
The invention discloses a catalyst, a preparation method thereof and application in preparation of oxalate. The catalyst comprises a carrier and an active ingredient, and is characterized in that the carrier comprises nitrogen doped graphene nano-sheets, and the active ingredient comprises nano-palladium. The content of the active ingredient palladium in the catalyst is 0.03-2wt%, and the defects of high loading capacity of precious metals, low space time yield of oxalate and the like in production of an oxalate catalyst through CO coupling in the prior art are overcome when the catalyst is used in a CO coupling oxalate production technology.
Description
Technical field
The application is related to a kind of catalyst, its preparation method and the application in prepared by oxalate, belongs to chemical neck
Domain.
Background technology
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, hydrogenation can prepare ethylene glycol.CO gaseous oxidations are coupled producing oxalic ester (2CO+
2RONO → (COOR) 2+2NO) it is committed step in " coal-ethylene glycol ", with important industrial application value.In addition, should
Technique also has important application prospect in industrial tail gas process.Contain substantial amounts of CO in many industrial tail gas, it is main at present
It is burn processing, if the CO in tail gas to be collected the oxalate for being converted into high added value, energy-saving and emission-reduction not only can be realized, also
Resource can be made full use of and environmental problem is solved.
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 synthesiss, pharmacy, spice 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, the technology path production
Ethylene glycol is relatively costly, and main cause is the scarcity 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 worth.
CO is coupled the committed step that producing oxalic ester is that coal-ethylene glycol technology realizes that inorganic C1 is converted to organic C 2.The technical process it have
Have the advantages that Atom economy, reaction condition are gentle, energy consumption is low, environmental friendliness, equipment investment be low and good product quality.Palladio is urged
Agent has proved to be the active catalyst of this process.The catalyst of report is mostly using α-A1 at present2O3Or other metals
Oxide is used as carrier, and the efficient palladium-based catalyst prepared with material with carbon element carrier is then seldom reported.The catalysis for industrially using
Agent Pd/ α-A12O3The load capacity higher (about 2wt%) of middle Pd so that the catalyst cost of production ethylene glycol is significantly increased.
Therefore, using the carrier with large specific surface area, strengthen 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.
The content of the invention
According to the one side of the application, there is provided a kind of nitrogen-doped graphene nanometer sheet carries palladium effective catalyst, the catalysis
In agent the content of active component palladium be 0.03～2wt%, for CO preparing oxalate by coupling reaction techniques in, CO conversion per pass is up to
68%, up to 97%, oxalate space-time yield reaches 1.46gg to oxalate selectivity-1(cat)·h-1(air speed is 3Lg-1·h-1), when the catalyst adopted in overcoming prior art CO preparing oxalate by coupling reaction technique is using Alpha-alumina as carrier, your gold
Category load capacity is high, the low shortcoming of oxalate space-time yield.
The catalyst, including carrier and active component, it is characterised in that the carrier includes nitrogen-doped graphene nanometer
Piece, the active component include Technique of Nano Pd.
Preferably, Technique of Nano Pd weight/mass percentage composition in the catalyst is 0.03～2wt%.It is further preferred that
Technique of Nano Pd weight/mass percentage composition in the catalyst is 0.18～0.71wt%.
Preferably, the mean diameter of the Technique of Nano Pd is 1～9nm.It is further preferred that the mean diameter of the Technique of Nano Pd
For 1～5nm.
Preferably, in the nitrogen-doped graphene nanometer sheet, the atomic number percentage composition of nitrogen is 1～7at%.Enter one
Preferably, in the nitrogen-doped graphene nanometer sheet, the atomic number percentage composition of nitrogen is 2～7at% to step.
Preferably, the thickness of the nitrogen-doped graphene nanometer sheet is 0.8～30nm.
According to the another aspect of the application, there is provided the method for preparing above-mentioned any catalyst, at least comprise the following steps：
A) graphene nanometer sheet is placed in into NH3In atmosphere, keep 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 for obtaining step a) is placed in the solution containing palladium element, through supersound process
Afterwards, isolated solid phase；
C) solid phase obtained by step b) is scrubbed, dry, after roasting, be placed in the atmosphere containing reducibility gas in 150～
After at least 2 hours are reduced under 450 DEG C of reduction temperature, room temperature is down in the atmosphere containing reducibility gas, that is, obtains described
Catalyst.
In step a), graphene nanometer sheet can be from commercially available, it would however also be possible to employ electrochemical method is prepared.
Used as a kind of embodiment, the graphene nanometer sheet is prepared using electrochemical method.Preferably, it is described to adopt
Graphene nanometer sheet is electrochemically prepared, is at least comprised the following steps：
With graphitic source as anode and cathode, sulphuric acid and/or sulfate liquor are electrolyte, with square wave, AC and DC mode, are led to
Applying 5～60V voltages are crossed, the graphitic source as electrode is carried out into electrochemical milling, further ultrasound, filtration, washing, vacuum are done
It is dry to obtain final product graphene nanometer sheet.
Used as a kind of embodiment, the graphitic source is selected from graphite rod and/or graphite paper.
As one kind preferred embodiment, the sulfate in lithium sulfate, sodium sulfate, ammonium sulfate at least one
Kind.
Preferred embodiment the employing electrochemical method prepares graphene nanometer sheet as a kind of, at least include with
Lower step：
(1) using two electrode systems, with high purity graphite paper as anode and cathode, successively with 0.1mol/L hydrochloric acid, acetone, ethanol,
Ultra-pure water etc. is cleaned.
(2) ammonium sulfate with 0.5～3mol/L is as electrolyte.
(3) square-wave potential method, 5～60V of the upper limit, -60～-5V of lower limit, 0.1～50Hz of frequency, using as electrode are used
Graphite paper is electrolysed, and is peeled off by the expansion of sulfate radical intercalation and obtains graphene nanometer sheet suspension.
(4) graphene nanometer sheet suspension ultrasound, filtration, washing, vacuum drying are obtained final product into graphene nanometer sheet further.
Preferably, step a) is that graphene nanometer sheet is placed in tube furnace, in NH3Under atmosphere, at 400～800 DEG C
Kept for 3～5 hours, obtain nitrogen-doped graphene nanometer sheet.
Preferably, in step b), supersound process is to stir 2～18 hours in ultrasound.
Preferably, the solution containing palladium element described in step b) is that the dissolving of palladium source is obtained in a solvent.Further preferably
Ground, the palladium source are selected from Palladous chloride., palladium, potassium chloropalladite, sodium chloropalladite, potassium chloropalladate, dichloro diamino palladium, dichloro four
At least one in ammonia palladium, Palladous nitrate., palladium acetylacetonate.It is further preferred that the solvent is selected from water, acetone, dichloromethane
At least one in alkane, chloroform, methanol, ethanol, hexamethylene, dimethylformamide, benzene, toluene.
Preferably, step c) solid phases obtained by step b) are scrubbed, dry, after roasting, be placed in containing reducibility gas
In atmosphere behind reductase 12～8 hour under 150～450 DEG C of reduction temperature, room is down in the atmosphere containing reducibility gas
Temperature, that is, obtain the catalyst.
Preferably, mixing of the atmosphere containing reducibility gas described in step c) selected from hydrogen, hydrogen and noble gases
Thing.It is further preferred that the noble gases are nitrogen and/or argon.
According to the another aspect of the application, there is provided a kind of method for preparing oxalate, it is characterised in that using above-mentioned any
At least one in catalyst and/or at least one in the catalyst that prepared according to above-mentioned any means, by an oxygen
Change carbon gaseous oxidation preparing oxalate by coupling reaction.
Preferably, the carbon monoxide gaseous oxidation preparing oxalate by coupling reaction is in fixed bed reactors, containing an oxygen
The unstripped gas for changing carbon and nitrites contact with the catalyst, reaction pressure be normal pressure, reaction temperature be 90～150 DEG C
Under the conditions of gas phase reaction prepare oxalate；
In the unstripped gas, carbon monoxide is 1.1～1.8 with the volume ratio of nitrites；
The gas phase air speed of the unstripped gas is 2～5Lg-1·h-1。
Preferably, the nitrites is methyl nitrite and/or nitrous ether (ethyl nitrite)；The oxalate is dimethyl oxalate.
And/or ethyl oxalate.
The beneficial effect of the application is included but is not limited to：
1st, catalyst provided herein, using electrochemical stripping and carries out the graphene nanometer sheet of N doping as load
Body, the carrier have the advantages that big, the good heat conductivity of specific surface area；The modification of nitrogen in addition changes the electricity of graphene nanometer sheet
Minor structure, enhances the alkalescence of graphene nanometer sheet, strengthens the interaction of carrier and active component, improves supported catalyst
Performance.
2nd, it is 0.03～2wt% that in catalyst provided herein, precious metal palladium load capacity is relatively low, low under normal circumstances
In the 0.8wt% of carrier quality, a large amount of noble metals can be saved, significantly reduce the cost of catalyst.
3rd, the preparation method of catalyst provided herein, without using any surfactant, activity in catalyst
Component palladium nano-particles clean surface, small-sized, particle diameter distribution is homogeneous, be highly dispersed at carrier graphene nanometer sheet surface,
Significantly enhance CO oxidative coupling catalytic performances.
4th, the provided herein method for preparing oxalate, using herein described catalyst, by carbon monoxide gas
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 is 3Lg-1·h-1)。
Description of the drawings
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
With reference to embodiment and detailed description the application, but the application is not limited to these embodiments.
In embodiment, stereoscan photograph is shot using the JEOL-6700F types instrument of Hitachi, Ltd.
In embodiment, transmission electron microscope is shot using the TECNAI F20 types instrument of FEI Co. of the U.S..
In embodiment, ESCA-LAB type x-ray photoelectron power spectrum of the N content using VG Scienta companies of Britain in sample
(being abbreviated as XPS) determines；Ultima2 type inductively coupled plasma launching light of the Pd contents using Jobin Yvon companies of France
Spectrum (being abbreviated as ICP) is determined.
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 chromatogram of product, in Japan
Carry out on the GC2014 type gas chromatograpies of Shimadzu Corporation.
If no special instructions, the reagent employed in embodiment is from commercially available, without any process；Instrument parameter is adopted
Arranged with manufacturer's recommended.
It is prepared by 1 catalyst sample of embodiment
The preparation of graphene nanometer sheet
Using two electrode systems, with high purity graphite paper as anode and cathode, successively with 0.1mol/L hydrochloric acid, acetone, ethanol, ultrapure
Water is cleaned；Ammonium sulfate with 1mol/L is as electrolyte.With square-wave potential method, upper limit 9V, lower limit -9V, frequency 10Hz,
Graphite electrode is electrolysed, is peeled off by the expansion of sulfate radical intercalation and is obtained graphene nanometer sheet suspension, graphene nanometer sheet is hanged
Turbid liquid ultrasound, filter, washing, after vacuum drying, obtain final product graphene nanometer sheet, be designated 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, ammonia is passed through, is kept
For a period of time (N doping time), then in N2Room temperature is cooled under atmosphere, that is, is obtained the graphene nanometer sheet of N doping, is designated as
N-GNP。
The sample number into spectrum of the graphene nanometer sheet of gained N doping is as shown in table 1 with the relation of doping temperature.
Table 1
The preparation of catalyst sample
When in the solution containing palladium, when solvent is organic solvent：Weigh the graphene nano of the N doping of the above-mentioned preparations of 1g
, as carrier impregnation in the solution containing palladium, for a period of time, then at 50 DEG C, heating is simultaneously ultrasonic to solvent for ultrasonic disperse for piece
Till volatilization is dry, solid phase is obtained.Further in N2400 DEG C of roasting 3h in atmosphere, are finally containing reproducibility under reduction temperature
Reduction a period of time in the atmosphere of gas, that is, the catalyst sample is obtained.
When in the solution containing palladium, when containing water in solvent：Weigh the graphene nanometer sheet of the N doping of the above-mentioned preparations of 1g
As carrier impregnation in the 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 vacuum dried 8 hours.Further in N2400 DEG C of roasting 3h in atmosphere, are finally containing under reduction temperature
There is reduction a period of time in the atmosphere of reducibility gas, that is, the catalyst sample is obtained.
Numbering and the graphene nanometer sheet sample number into spectrum of selected N doping of gained catalyst sample, containing the molten of palladium
Liquid, ultrasonic disperse time, the composition of the atmosphere containing reducibility gas, reduction temperature, the relation of recovery time are as shown in table 2.
Table 2
Comparative example 1
Prepare catalyst Pd/GNP：GNP carrier impregnations that 1g prepared by embodiment 1 are weighed to 23.4mg palladium and 20mL
In the solution that acetone is made into, ultrasonic disperse 2h, then at 50 DEG C heating ultrasound to acetone volatilization it is dry, obtain solid and mix
Compound.Further in N2400 DEG C of roasting 3h in atmosphere, finally under the conditions of 300 DEG C lead to hydrogen reducing 2h, that is, catalyst are obtained
Pd/GNP.The load capacity that palladium is determined by ICP is 0.62wt%.
2 sample characterization of embodiment
Surveyed using the N doping amount in graphene nanometer sheet sample N-GNP-1～N-GNP-3 of the XPS to N doping
It is fixed, as a result as shown in table 1.
The palladium load capacity in catalyst sample CAT-1～CAT-7 is determined using ICP, as a result as 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, as a result shown, N doping is greatly improved
The dispersion of active component palladium, palladium grain diameter are uniform, and mean diameter is between 1～9nm.With sample CAT-1 as typical generation
Table, as shown in Fig. 2 as seen from Figure 2, palladium nano-particles are highly dispersed at the Graphene of N doping and receive its transmission electron microscope photo
Rice piece surface, Pd particle size distributions are homogeneous, mean diameter is 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, compared with sample CAT-1, nanoparticle size larger (mean diameter 6.2nm), and grain
Footpath is distributed compared with heterogeneity.
3 catalyst sample of embodiment is used for the reaction evaluating for preparing oxalate
Catalyst sample CAT-1～CAT-7, comparative example Pd/GNP are respectively placed in fixed bed reactors, are applied
React in CO gaseous oxidations preparing oxalate coupling reaction, unstripped gas includes CO and methyl nitrite, 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, and reaction pressure is 0.1Mpa, former
Material gas and product are monitored analysis by online gas chromatogram, and reaction result is shown in Table 3.
Table 3
Comparative example be can be seen that compared with the catalyst sample that technical scheme is provided by data in table 3, when
In the case that palladium load capacity is approximate (compared with CAT-4), its CO conversion per pass is far below CAT-4, even below Pd load capacity
The only CAT-3 of 0.18wt%.It can be seen that precious metal palladium consumption can be being saved according to catalyst prepared by technical scheme
Meanwhile, greatly improve CO conversion per pass and oxalate yield.
The above, is only several embodiments of the application, any type of restriction is not done to the application, although this Shen
Please disclosed as above with preferred embodiment, but and be not used to limit the application, any those skilled in the art are not taking off
In the range of technical scheme, a little variation is made using the technology contents of the disclosure above or modification is equal to
Effect case study on implementation, belongs in the range of technical scheme.
Claims (10)
1. a kind of catalyst, including carrier and active component, it is characterised in that the carrier includes nitrogen-doped graphene nanometer
Piece, the active component include Technique of Nano Pd.
2. catalyst according to claim 1, it is characterised in that Technique of Nano Pd weight/mass percentage composition in the catalyst
For 0.03～2wt%.
3. catalyst according to claim 1, it is characterised in that the mean diameter of the Technique of Nano Pd is 1～9nm.
4. catalyst according to claim 1, it is characterised in that the original of nitrogen in the nitrogen-doped graphene nanometer sheet
Subnumber percentage composition is 1～7at%.
5. method according to claim 4, it is characterised in that the thickness of the nitrogen-doped graphene nanometer sheet is 0.8～
30nm。
6. the method for preparing catalyst described in any one of claim 1 to 5, at least comprises the following steps：
A) graphene nanometer sheet is placed in into NH3In atmosphere, keep at 400～800 DEG C no less than 3 hours, obtain N doping graphite
Alkene nanometer sheet；
B) the nitrogen-doped graphene nanometer sheet for obtaining step a) is placed in the solution containing palladium element, after supersound process,
Isolated solid phase；
C) solid phase obtained by step b) is scrubbed, dry, after roasting, be placed in the atmosphere containing reducibility gas in 150～450 DEG C
Reduction temperature under reduce at least 2 hours after, room temperature is down in the atmosphere containing reducibility gas, that is, obtains the catalysis
Agent.
7. method according to claim 4, it is characterised in that the graphene nanometer sheet is prepared into using electrochemical method
Arrive.
8. method according to claim 4, it is characterised in that the solution containing palladium element is dissolved in solvent for palladium source
In obtain；
The palladium source is selected from Palladous chloride., palladium, potassium chloropalladite, sodium chloropalladite, potassium chloropalladate, dichloro diamino palladium, dichloro
At least one in four ammonia palladiums, Palladous nitrate., palladium acetylacetonate；
The solvent is in water, acetone, dichloromethane, chloroform, methanol, ethanol, hexamethylene, dimethylformamide, benzene, toluene
At least one.
9. a kind of method for preparing oxalate, it is characterised in that using in the catalyst described in any one of claim 1 to 5
At least one at least one and/or catalyst that prepared according to claim 6 to 8 any one methods described, passes through
Carbon monoxide gaseous oxidation preparing oxalate by coupling reaction.
10. method according to claim 9, it is characterised in that the carbon monoxide gaseous oxidation preparing oxalate by coupling reaction
It is that, in fixed bed reactors, the unstripped gas containing carbon monoxide and nitrites is contacted with the catalyst, in reaction pressure
Oxalate is prepared for gas phase reaction under conditions of 90～150 DEG C for normal pressure, reaction temperature；
In the unstripped gas, carbon monoxide is 1.1～1.8 with the volume ratio of nitrites；
The gas phase air speed of the unstripped gas is 2～5Lg-1·h-1。
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