CN106076334A - Activated carbon aerogel carried copper catalyst fast preparation method and application thereof - Google Patents
Activated carbon aerogel carried copper catalyst fast preparation method and application thereof Download PDFInfo
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- CN106076334A CN106076334A CN201610414318.3A CN201610414318A CN106076334A CN 106076334 A CN106076334 A CN 106076334A CN 201610414318 A CN201610414318 A CN 201610414318A CN 106076334 A CN106076334 A CN 106076334A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000010949 copper Substances 0.000 title claims abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 43
- 239000004964 aerogel Substances 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004966 Carbon aerogel Substances 0.000 claims abstract description 16
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 230000006315 carbonylation Effects 0.000 claims abstract description 5
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000008187 granular material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 208000036758 Postinfectious cerebellitis Diseases 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical class [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000035899 viability Effects 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
- B01J23/72—Copper
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to material with carbon element catalytic field, specifically a kind of activated carbon aerogel carried copper catalyst fast preparation method and application thereof.Preparation method through the following steps that realize: (1) prepares carbon aerogels；(2) activated carbon aeroge is prepared；(3) activated carbon aeroge and copper nitrate is used to prepare activated carbon aerogel carried copper catalyst precursor body；(4) process activated carbon aerogel carried copper catalyst precursor body and obtain the aerogel carried copper catalyst of activated carbon.The present invention is compared with prior art, there is obvious advance, aiming to the drawback that new carbon preparation technology is loaded down with trivial details, cost is high, this preparation method technique is advanced, and data are the most full and accurate, low cost, product is black powder, powder granule diameter 100nm, and reactivity is high, catalytic performance reaches 99.99%, and described activated carbon aerogel carried copper catalyst first Application prepares Synthesis of dimethyl carbonate in catalysis methanol gas-phase oxidation/carbonylation.
Description
Technical field
The present invention relates to material with carbon element catalytic field, the specifically a kind of aerogel carried copper catalyst of activated carbon quickly side of preparation
Method and application thereof.
Background technology
Material with carbon element is widely used in catalytic field due to the characteristic of himself, at present, uses more material with carbon element to have carbon
Fiber, activated carbon, Graphene etc..Carbon aerogels (CAs) is also the one of material with carbon element, and the material with carbon element of this loose structure has relatively
Big specific surface area, relatively low density and good mechanical performance, generally prepared by sol-gel process, can be by changing
Become presoma and carry out modulation carbon aerogels structure with the mol ratio of catalyst, drying condition, pH value etc..Furthermore, it is possible to pass through physics
Activation and chemical activation process the pore-size distribution regulating carbon aerogels so that it is be converted into the porous thing with hierarchical structure
Matter activated carbon aeroge (ACAs), this material has bigger specific surface and more stable physical property.
At present, various carbon materials has been widely studied and has been applied to reality, but the new carbon such as such as Graphene prepare work
Skill is numerous and diverse and relatively costly, but, the advantages such as carbon aerogels has low cost as material with carbon element, and preparation technology is simple, so tool
There is potential using value.Nowadays it is used for ultracapacitor etc., less in catalytic field application, therefore still in research rank
Section.
Summary of the invention
The present invention is in order to extend the range of application of material with carbon element, it is provided that a kind of aerogel carried copper catalyst of activated carbon is quick
Preparation method and applications.
The present invention is achieved by the following technical solutions: the quick preparation of the aerogel carried copper catalyst of a kind of activated carbon
Method, through the following steps that realize:
(1) carbon aerogels is prepared；
(2) activated carbon aeroge is prepared；
(3) activated carbon aeroge and copper nitrate is used to prepare activated carbon aerogel carried copper catalyst precursor body；
(4) process activated carbon aerogel carried copper catalyst precursor body and obtain the aerogel carried copper catalyst of activated carbon.
Gel, the thinking of rear gel supported catalyst are first prepared in the breakthrough employing of fast preparation method of the present invention,
The technology combined with metal relative to existing activated carbon aeroge, activated carbon aeroge has the advantage of Heat stability is good, urges
Agent active component has that particle diameter is little and the advantage (as illustrated in fig. 1 and 2) such as be uniformly dispersed.
When being embodied as, step (2) prepares inertia after carbon aerogels is mixed homogeneously in activated carbon aeroge with potassium hydroxide
750 DEG C of high-temperature roasting 2h in atmosphere, roasting complete after pickling drying, being placed in aqueous solution of nitric acid of drying, at 80 DEG C
Magnetic agitation 6h under environment, washing, sucking filtration, be dried, it is thus achieved that activated carbon aeroge.Use potassium hydroxide, aqueous solution of nitric acid and
Activated carbon aeroge after magnetic agitation processes has good physical property, if specific surface area is by 815 m2·g-1Increase to
1152 m2·g-1, total pore volume is by 0.4811 cm3·g-1Increase to 0.6406 cm3·g-1, additionally surface functional group quantity is also
Increased, i.e. nitric acid oxidation processes the oxygen-containing functional group adding activated carbon aeroge surface, including carboxyl, phenolic group etc..
It addition, the invention provides the aerogel carried copper catalyst of described activated carbon at catalysis methanol gas-phase oxidation/carbonylation
Prepare the application in Synthesis of dimethyl carbonate.
The present invention compared with prior art, has obvious advance, it is intended to loaded down with trivial details for new carbon preparation technology,
The drawback that cost is high, this preparation method technique is advanced, and data are the most full and accurate, low cost, and product is black powder, and powder granule is straight
Footpath 100nm, reactivity is high, and catalytic performance reaches 99.99%, and the aerogel carried copper catalyst of described activated carbon first should
Synthesis of dimethyl carbonate is prepared for catalysis methanol gas-phase oxidation/carbonylation.
Accompanying drawing explanation
Fig. 1 is the TEM shape appearance figure of the aerogel carried copper catalyst of activated carbon obtained by the specific embodiment of the invention.
Fig. 2 is the activated carbon aerogel carried copper catalyst copper nano particles obtained by the specific embodiment of the invention
Dispersibility schematic diagram.As seen from the figure, preferably, dispersion is high in the copper nano particles dispersion prepared.
Fig. 3 is the X-ray diffraction of the aerogel carried copper catalyst of activated carbon obtained by the specific embodiment of the invention
Collection of illustrative plates.In figure: vertical coordinate is diffracted intensity, abscissa is the angle of diffraction 2 θ, and figure Plays peak 43.169,50.455 is all simple substance
The base peak of copper, as can be seen from Figure, diffracted intensity is weak, shows that elemental copper dispersion is high.
Fig. 4 is that the reactivity of the aerogel carried copper catalyst of activated carbon obtained by the specific embodiment of the invention is commented
Valency figure.In figure: vertical coordinate is the space-time yield (STY of dimethyl carbonateDMC), abscissa is the response time, dimethyl carbonate in figure
Space-time yield be up to 414 (mg/g h), illustrate that the aerogel carried copper catalyst of activated carbon is to methanol gas-phase oxidation carbonyl
Base is prepared dimethyl carbonate and is had good catalytic action.
Detailed description of the invention
The present invention use chemical substance material be: resorcinol, formaldehyde (37%), natrium carbonicum calcinatum, copper nitrate, methanol,
Hydrochloric acid, nitric acid, potassium hydroxide, deionized water, nitrogen, hydrogen, carbon dioxide, oxygen, carbon monoxide, it is as follows that it prepares consumption:
With gram, milliliter, centimetre3For measurement unit
Resorcinol: C6H6O2Chip solid 10g ± 0.001g
Formaldehyde: CH2O (37%) liquid 14.6ml ± 0.01ml
Natrium carbonicum calcinatum: Na2CO3Solid 0.1g ± 0.001g
Copper nitrate: Cu (NO3)2•3H2O powder body 0.66g ± 0.001g
Methanol: CH4O, concentration >=99.5% liquid 200ml ± 10ml
Hydrochloric acid: HCl, concentration 19% liquid 200ml ± 10ml
Nitric acid: HNO3, concentration 18% liquid 200ml ± 10ml
Potassium hydroxide: KOH chip solid 8g ± 0.001g
Deionized water: H2O liquid 3000ml ± 50ml
Nitrogen: N2Gas 100000cm3±100cm3
Hydrogen: H2Gas 100000cm3±100cm3
Carbon dioxide: CO2Gas 100000cm3±100cm3
Oxygen: O2Gas 100000cm3±100cm3
Carbon monoxide: CO gas 100000cm3±100cm3
Preparation method is as follows:
(1) carbon aerogels is prepared
1., resorcinol solid is prepared
Weighing resorcinol 10g, measure 14.6ml ± 0.001ml deionized water, in the blue lid bottle of addition, magnetic agitation is to uniformly；
2. formalin (37%) and natrium carbonicum calcinatum, are got out
Measure formalin 12.6ml ± 0.001ml, weigh natrium carbonicum calcinatum 0.1g ± 0.001g, add and added resorcinol
Blue lid bottle in magnetic agitation to homogeneous phase solution；
3., sol-gel process
By stirring to putting into after homogeneous solution left standstill a period of time in 50 DEG C of water-baths 3 days, in acetone soln 3 days, every day was more
Change a fresh acetone；
4., high-temperature roasting processes
The organic aerogel prepared is placed the carbon airsetting obtaining carbonization in cupel in tube furnace after 850 DEG C of high-temperature roasting 4h
Glue (in inert atmosphere).
(2) activated carbon aeroge is prepared
1., configuration hydrochloric acid solution
Measure hydrochloric acid (68%, wt) solution 33.33ml ± 0.001ml, deionized water 166.67ml ± 0.001ml, add beaker
Middle stirring 5min, is configured to the aqueous hydrochloric acid solution of 2mol/L；
2., configuration salpeter solution
Measure salpeter solution 4ml ± 0.001ml, deionized water 26ml ± 0.001ml, add and beaker stirs 5min, be configured to
The aqueous solution of nitric acid of 2mol/L；
3., potassium hydroxide high-temperature activation carbon aerogels
Weighing 4g carbon aerogels, 16g potassium hydroxide, after mix homogeneously, in placement cupel, in tube furnace, 750 DEG C of high-temperature roastings are (lazy
In property atmosphere) 2h；
4., pickling
With the carbon aerogels after configured good 2mol/L HCl washing potassium hydroxide high-temperature activation, take out when solution is neutrality
Filter, takes out placement beaker 100 DEG C of drying in baking oven；
5., acid treatment
Will dry after carbon aerogels in the aqueous solution of nitric acid configured, magnetic agitation 6h in the water-bath of 80 DEG C；
6., wash, sucking filtration
When acid-treated product is cooled to room temperature, add deionized water wash extremely neutrality, take out with qualitative filter paper subsequently
Filter, retains filter cake, discards cleaning mixture；
7., it is dried
Washing, filter cake after sucking filtration are placed in beaker, are dried in dry case, baking temperature 100 DEG C, drying time 600min.
(3) activated carbon aerogel carried copper catalyst precursor body is prepared
1., copper nitrate, activated carbon aeroge are prepared
Weigh activated carbon aeroge 1g, weigh copper nitrate solid 0.6661g；
2., preparation mixed liquor
Measure 30ml ± 0.001ml methanol solution, add in the beaker having filled activated carbon aeroge and copper nitrate solid, stirring
10min, becomes mixed solution；
3., ultrasound wave dispersion
The beaker filling mixed liquor is placed in ultrasound wave separating apparatus, carries out ultrasonic disperse, ultrasonic frequency 60KHz, ultrasound wave
Jitter time 300min；
4., wet impregnation
Mixed liquor after being disperseed by ultrasound wave is placed in magnetic agitation 8h in 50 DEG C of water-baths；
5., it is dried
Beaker, to time dry, placed in baking oven and is dried by liquid to be mixed stirring, baking temperature 50 DEG C, drying time 720min；It is dried
Rear Viability carbon aerogel load copper catalyst precursor body.
(4) the aerogel carried copper catalyst of activated carbon is prepared
The preparation of the aerogel carried copper catalyst of activated carbon is carried out in tube type high-temperature furnace, be heating, cooling, nitrogen and
Complete under hydrogen shield；
The quartz container filling activated carbon aerogel carried copper catalyst precursor body is placed in adaptation add in heat pipe；
1., by nitrogen, hydrogen pipe stretches in quartz heating-pipe, and nitrogen input rate is 120cm3/ min, hydrogen input rate is
40cm3/ min, opens the escape pipe of quartz heating-pipe simultaneously, and in making stove, pressure reaches 20Pa；
2., open tube type high-temperature furnace resistance heater, the aerogel carried copper catalyst of heat-agglomerating activated carbon, heating-up temperature
350 DEG C ± 1 DEG C, 10 DEG C/min of heating rate, heat time heating time 120min；
3., after question response completes, stop heating, be down to 25 DEG C with stove natural cooling under nitrogen protection；
4., close resistance heater, stop defeated nitrogen, hydrogen, open quartz heating-pipe, take out quartz container and interior activity thereof
Carbon aerogel load copper catalyst product；
5., grind, sieve
Aerogel carried for activated carbon copper catalyst carbide agate mortar, pestle are ground, then sieves with 650 eye mesh screens；
Grind, sieve to be repeated and make activated carbon aerogel carried copper catalyst end-product.
(5) detect, analyze, characterize
The pattern of the aerogel carried copper catalyst of activated carbon prepared, color and luster, Chemical Physics performance, catalysis activity are examined
Survey, analyze, characterize；
With transmission electron microscope tem observation sample surface morphology；
Crystal phase analysis is carried out with X-ray powder diffractometer；
With high pressure fixed bed micro-trans-chromatogram arrangement, catalyst activity is analyzed.
(6) activated carbon aerogel carried copper catalyst activity rating
Activated carbon aerogel carried copper catalyst first Application prepares dimethyl carbonate in methanol gas-phase oxidation/carbonylation, is
The micro-trans-chromatogram arrangement of high pressure fixed bed is carried out；
1., weigh the aerogel carried copper catalyst of 0.3g activated carbon, 3g quartz sand, load stainless steel reaction pipe after mix homogeneously and enter
Row activity rating；
2., open CO, after pressure is risen to the 1.5Mpa of reaction desirable pressure, open O2, CO and O2Volume flow ratio set
For 11:1；
3., heating schedule is set, opens preheating furnace and recirculated water；
4., when temperature rises to 80 DEG C, methanol is squeezed into by Series III type micro-sampling pump, carries out gasifying also at preheating gasification furnace
With CO and O2Tow channel gas is sufficiently mixed, and subsequently when temperature rises to react temperature required, timing starts, and carries out gas every 2h sampling
Analysis of hplc；
5., product is analyzed, with capillary column (DB-5,30m × 0.320mm × 0.25mm) point in gas chromatogram
From, flame ionization ditector (FID) detects.
Conclusion: the aerogel carried copper catalyst of activated carbon is black powder, powder granule diameter≤100nm, product purity
Reaching 80%, reactivity is high, and catalytic performance is good, reaches 99.99%.
(7) product storage
Being stored in the aerogel carried copper catalyst of activated carbon of preparation in the glass container of amber transparent, airtight lucifuge stores,
Moistureproof, sun-proof, acid-alkali salt corrodes, storage temperature 20 DEG C, relative humidity≤10%.
Claims (3)
1. the fast preparation method of the aerogel carried copper catalyst of activated carbon, it is characterised in that through the following steps that real
Existing:
(1) carbon aerogels is prepared；
(2) activated carbon aeroge is prepared；
(3) activated carbon aeroge and copper nitrate is used to prepare activated carbon aerogel carried copper catalyst precursor body；
(4) process activated carbon aerogel carried copper catalyst precursor body and obtain the aerogel carried copper catalyst of activated carbon.
The fast preparation method of the aerogel carried copper catalyst of activated carbon the most according to claim 1, it is characterised in that step
Suddenly 750 DEG C of high-temperature roasting 2h in inert atmosphere after carbon aerogels is mixed homogeneously with potassium hydroxide during (2) prepare activated carbon aeroge,
Roasting complete after pickling drying, being placed in aqueous solution of nitric acid of drying, magnetic agitation 6h in the environment of 80 DEG C, washing,
Sucking filtration, be dried, it is thus achieved that activated carbon aeroge.
3. the aerogel carried copper catalyst of activated carbon described in claim 1 or 2 closes in the preparation of catalysis methanol gas-phase oxidation/carbonylation
Become the application in dimethyl carbonate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610414318.3A CN106076334A (en) | 2016-06-15 | 2016-06-15 | Activated carbon aerogel carried copper catalyst fast preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610414318.3A CN106076334A (en) | 2016-06-15 | 2016-06-15 | Activated carbon aerogel carried copper catalyst fast preparation method and application thereof |
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| CN106076334A true CN106076334A (en) | 2016-11-09 |
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| CN116673054A (en) * | 2023-06-04 | 2023-09-01 | 太原理工大学 | Preparation of peanut shell nitrogen-doped carbon-supported copper catalyst and application of peanut shell nitrogen-doped carbon-supported copper catalyst in synthesis of diethyl carbonate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110975864A (en) * | 2019-12-24 | 2020-04-10 | 西南大学 | Preparation method of carbon-doped or metal-loaded monatomic or metal cluster catalyst, product and application thereof |
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| CN114890417A (en) * | 2022-02-21 | 2022-08-12 | 江苏联兴成套设备制造有限公司 | Method for preparing activated carbon aerogel by sodium salt coupling organic matter catalytic activation |
| CN114890417B (en) * | 2022-02-21 | 2023-08-22 | 江苏联兴成套设备制造有限公司 | Method for preparing activated carbon aerogel by catalytic activation of sodium salt coupled organic matter |
| CN116673054A (en) * | 2023-06-04 | 2023-09-01 | 太原理工大学 | Preparation of peanut shell nitrogen-doped carbon-supported copper catalyst and application of peanut shell nitrogen-doped carbon-supported copper catalyst in synthesis of diethyl carbonate |
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