CN107686105A - A kind of efficiently preparation method of nitrogen-doped carbon nanometer pipe and its application of nitrogen-doped carbon nanometer pipe - Google Patents
A kind of efficiently preparation method of nitrogen-doped carbon nanometer pipe and its application of nitrogen-doped carbon nanometer pipe Download PDFInfo
- Publication number
- CN107686105A CN107686105A CN201710799634.1A CN201710799634A CN107686105A CN 107686105 A CN107686105 A CN 107686105A CN 201710799634 A CN201710799634 A CN 201710799634A CN 107686105 A CN107686105 A CN 107686105A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- catalyst
- doped carbon
- nanometer pipe
- carbon nanometer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 41
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 17
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 77
- 239000010949 copper Substances 0.000 claims description 65
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 46
- 229910052802 copper Inorganic materials 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 33
- 239000011148 porous material Substances 0.000 claims description 28
- 238000007254 oxidation reaction Methods 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000005832 oxidative carbonylation reaction Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- 238000002604 ultrasonography Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 239000006004 Quartz sand Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000004080 punching Methods 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000007792 gaseous phase Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- LYVWMIHLNQLWAC-UHFFFAOYSA-N [Cl].[Cu] Chemical compound [Cl].[Cu] LYVWMIHLNQLWAC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 93
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 32
- 239000007864 aqueous solution Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000010453 quartz Substances 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000002041 carbon nanotube Substances 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 8
- 238000013019 agitation Methods 0.000 description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 description 8
- 239000012018 catalyst precursor Substances 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 8
- 238000002309 gasification Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000009257 reactivity Effects 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 241000894007 species Species 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000006315 carbonylation Effects 0.000 description 4
- 238000005810 carbonylation reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- -1 based on micropore Chemical compound 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000011156 evaluation Methods 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
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/01—Preparation of esters of carbonic or haloformic acids from carbon monoxide and oxygen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
A kind of preparation method of efficiently nitrogen-doped carbon nanometer pipe is will be in multi-walled carbon nanotube addition salpeter solution and closed in autoclave, is forced into 0.4 1.0MPa, stirs, it is then heated to 120 200 DEG C and keeps 1 4h, last autoclave is cooled to room temperature, washed to neutrality, filter, dry；CNT is with melamine solid using mass ratio as 1:14 mix and are ground well with mortar, are calcined in nitrogen high temperature, are dried after being washed till neutrality, obtain nitrogen-doped carbon nanometer pipe.N doping amount of the present invention is 4.6wt% 10.3wt%.
Description
Technical field
The present invention relates to a kind of efficiently preparation method of nitrogen-doped carbon nanometer pipe and its application of nitrogen-doped carbon nanometer pipe.
Background technology
Carbon Materials are because the features such as pore passage structure is abundant, surface is easily modified, is widely used in catalytic field, such as carbon is born
Copper-loaded catalyst is commonly applied to Synthesis of dimethyl carbonate, and particularly activated carbon supported copper catalysis methanol gas-phase oxidation/carbonylation is anti-
Should, such as patent CN102600843A and CN102872879A.Although activated carbon supported copper catalyst shows higher initial
Activity, but activated carbon, based on micropore, copper species mostly dropping place is in the outer surface of activated carbon, in catalyst preparation process and reaction
During easily reunite and cause dispersiveness to reduce so as to causing catalytic activity rapid decrease.And work can be regulated and controled by modified activated carbon
Property carbon surface chemical property, so as to strengthen the interaction between copper species and absorbent charcoal carrier, and then promote metal dispersion.Increase
Although adding the oxygen-containing functional group of activated carbon surface can promote the scattered of copper species to a certain extent and improve its anti-agglomeration energy
Power, so as to slow down the deactivation rate of catalyst (Zhang G.Appl.Catal, B, 179 (2015), 95-105), but reacting
Cheng Zhong, copper species still can reunite, so as to cause catalyst inactivation.
CNT (CNT) is due to its good heat endurance, mechanical stability and electronic conductivity energy and in recent years
It is wide concerned.These ducts may provide a special confinement environment for metallic catalyst and catalytic reaction, can prevent gold
Metal particles are reunited, so as to promote scattered and anti-agglomeration ability the raising of active specy.And because bending graphene wall is unique
Electronic structure, the performance of metallic catalyst may also be modified, so as to be advantageous to improve catalytic performance.
It can strengthen institute's gold-supported to a greater degree compared to oxygen-containing functional group in charcoal material surface increase nitrogen-containing functional group
Interaction between species and carrier, so as to significantly improve the anti-agglomeration ability of the decentralization of metal and catalyst, and then
Strengthen catalytic activity and stability.Meanwhile N doping amount and the performance of N doping Carbon Materials are closely related.Mixed using one-step method nitrogen
Miscellaneous CNT, N doping amount is relatively low, no more than 4.05% (L.M.Ombaka.J.Solid State Chem, 235 (2016),
202-211), so as to influenceing its performance.
The content of the invention
For the situation of background technology, it is an object of the invention to provide a kind of high efficient nitrogen-doped carbon nanometer of N doping amount
The preparation method and its nitrogen-doped carbon nanometer pipe of pipe are copper-based catalysts prepared by carrier and copper-based catalysts in methanol vapor phase oxygen
Change carbonylation Synthesis of dimethyl carbonate.
Specific technical scheme of the invention is implemented by following steps：
The present invention provides a kind of preparation method of efficiently nitrogen-doped carbon nanometer pipe, comprises the following steps：
(1) hydrothermal oxidization CNT
By multi-walled carbon nanotube：Salpeter solution is 1-2g：50-100mL, it is 0.05- by multi-walled carbon nanotube addition concentration
In 0.5mol/L salpeter solution, said mixture is transferred to the height equipped with temperature controller and propeller system
Press in kettle, autoclave is closed, and the oxygen dissolved three times to drain in solution is put with nitrogen punching, and system is further forced into 0.4-
1.0MPa, stirred with 100-300r/min speed, be then heated to 120-200 DEG C and keep 1-4h, last autoclave cooling
Pressure release after to room temperature, with ion water washing to neutrality, filter, be placed in baking oven in 80-100 DEG C of dry 8-12h；
(2) CNT after step (1) hydrothermal oxidization and melamine solid are using mass ratio as 1:1-4 is mixed and used and grinds
Alms bowl is ground well, and 600 DEG C of -900 DEG C of high-temperature roasting 2h-4h, dry after being washed to neutrality with distillation after the completion of roasting, obtain in nitrogen
Nitrogen-doped carbon nanometer pipe.
As above the CNT (CNT) described in step (1) is multi-walled carbon nanotube, specific surface area 180-260m2/ g, hole
Hold for 0.70-0.98ml/g, average pore size 7.6-12.8nm.
As above the nitrogen content of nitrogen-doped carbon nanometer pipe is 4.6wt%-10.3wt%, specific surface area 134-180m2/ g, hole
Hold for 0.60-0.80ml/g, average pore size 12.6-15.2nm.
The catalyst of the present invention is made up of active ingredient copper and nitrogen-doped carbon nanometer pipe, wherein Cu3.0-10.0wt%,
Nitrogen-doped carbon nanometer pipe 90-97wt%.
The catalyst of the present invention is prepared by following preparation method：
(1) formed by catalyst, be that the soluble non-chlorine copper salt solutions of 0.156-0.52mol/L are added dropwise to by concentration
In nitrogen-doped carbon nanometer pipe, 30-60min is stirred in ultrasound reactor, 8-15h is then dried at 30-50 DEG C, is done
Dry presoma；
(2) dry presoma under an inert atmosphere, rise to 300-450 DEG C with 2-10 DEG C/min speed, constant temperature calcining 180-
240min, room temperature taking-up is naturally cooled to, that is, obtains nitrogen-doped carbon nanometer pipe copper-loading catalyst.
Soluble non-chlorine mantoquita as described above is copper nitrate or copper acetate.
Inert atmosphere as described above is nitrogen or argon gas.
The present invention catalyst be used for Oxidative Carbonylation Synthesis of DMC reaction, its reactions steps and
Process conditions are as follows：
The mixture of catalyst and quartz sand is fitted into fixed bed reactors, in a nitrogen atmosphere, by reactor
Reaction bed temperature is heated to 120-140 DEG C；Reacting gas volume flow ratio composition is CO：O2：Methanol=8:1:0.01-
11:1:The 0.01 preheated device of raw material is heated to 110-130 DEG C；The material that preheater comes out enters tubular type from the upper end of reactor
Reactor, material gaseous phase volume air speed are 4980-16600h-1, in temperature be 120-140 DEG C and pressure is normal pressure -2.0MPa
Under the conditions of react, obtain reaction product after the material condensed device condensation come out from reactor.
The addition between catalyst and quartz sand is catalyst as described above and quartz sand mass ratio is catalyst：Stone
Sand=1:2-5.
The technical advantage of the present invention is as follows：
The breakthrough first hydrothermal oxidization CNT of use of the catalyst of preparation of the present invention, the load of rear high temperature N doping
The thinking of copper catalyst, has that simple to operate, technique is advanced, N doping amount is high, copper nano particles particle diameter is small and is uniformly dispersed, is living
Property centric quantity it is more and the advantages that anti-agglomeration ability is strong, catalytic activity and stability are good.
CNT after first hydrothermal oxidization after high temperature nitrating has good physical and chemical performance, CNT table
Face nitrogen content significantly improves, that is, first passes through the nitrogenous function that high temperature nitrogen doping treatment after hydrothermal oxidization adds carbon nano tube surface
Group, including pyridine nitrogen, pyrroles's nitrogen and quaternary nitrogen etc..
The present invention has obvious advance compared with background technology, is the disadvantage prepared for Carbon Materials copper-loading catalyst
End, the CNT of high nitrogen-containing, nitrogen content 4.6%- are made using the method for high temperature N doping after first hydrothermal oxidization
10.3%, then copper nitrate solution is introduced into CNT cavity through ultrasonic wave added incipient impregnation and dried, finally in inert atmosphere
Middle protective roast, CNT confinement copper nanocatalyst is made, this preparation method is simple to operate, and technique is advanced, and data are accurate
It is full and accurate, copper nano particles is uniformly dispersed (4nm or so) by the way that copper species are dispersed in nitrogen-doped carbon nanometer pipe pipe cavity, and
The confinement effect and N doping of CNT cause the anti-agglomeration ability of active ingredient copper to increase, obtained carried copper
Catalyst shows preferably catalytic activity and steady in the reaction of catalysis methanol gas-phase oxidation/carbonylation Synthesis of dimethyl carbonate
It is qualitative.Methanol conversion is 8.5%-20%, and DMC space-time yield reaches 300-550mgg-1·h-1, DMC is selectively
86%-99%, stability 30h-60h.
High temperature nitrogen-doped carbon nanometer pipe supported copper is prepared for carried copper-base after the embodiment of the present invention uses first hydrothermal oxidization
Catalyst, and be applied in catalysis methanol gas-phase oxidation/carbonylation Synthesis of dimethyl carbonate (DMC) reaction.With not passing through
The comparative example of the Combined Processing is compared, and has N doping amount high, and methanol conversion is high, and DMC space-time yields and selectivity are high, and surely
The advantages that qualitative good.
Brief description of the drawings
Fig. 1 is the full elemental analysis XPS figures of nitrogen-doped carbon nanometer pipe prepared by the embodiment of the present invention 3；
Fig. 2 is the N1sXPS figures of nitrogen-doped carbon nanometer pipe prepared by the embodiment of the present invention 3；
Fig. 3 is the nitrogen adsorption desorption curve map of nitrogen-doped carbon nanometer pipe prepared by the embodiment of the present invention 3；
Fig. 4 is the TEM shape appearance figures of nitrogen-doped carbon nanometer pipe confinement copper catalyst prepared by the embodiment of the present invention 3.Can by Fig. 4
To find out, the copper nano particles being prepared are well dispersed, and decentralization is high；
Fig. 5 is the nitrogen-doped carbon nanometer pipe confinement copper catalyst of the preparation of the embodiment of the present invention 3 after activity rating 60h
TEM shape appearance figures, as seen from Figure 5, nitrogen-doped carbon nanometer pipe can effectively limit the migration and reunion of copper nano particles.
Embodiment
The ultrasonic wave added equi-volume impregnating of comparative example 1 prepares original carbon nanotubes CNT loaded Cu catalyst, and Cu/CNT is specific
Step is as follows：
1., weigh 0.113g Cu (NO3)2·3H2O, 3mL deionized waters are measured, added in beaker, magnetic agitation 10min,
Into 0.156mol/L copper nitrate aqueous solution；
2., to weigh specific surface area be 195m2/ g, pore volume 0.90ml/g, average pore size are 12.8nm original more wall carbon
Nanotube 1g, it is added in above-mentioned solution, is placed in ultrasound reactor and stirs 60min, ultrasonic frequency 60KHz；
3., the mixture after supersound process stood into 24h at room temperature；
4., stand after beaker placed in baking oven dried, 40 DEG C, drying time 8h of drying temperature, into original carbon after drying
Nanotube confinement copper catalyst precursor body；
5., dried presoma lead to 30ml/min nitrogen in tube furnace, rise to 350 DEG C with 2 DEG C/min speed, it is permanent
Temperature roasting 240min, naturally cools to room temperature taking-up, Cu/CNT catalyst is obtained, consisting of Cu-3wt%, CNT-97wt%.
The specific reactions steps that catalyst is evaluated in Oxidative Carbonylation Synthesis of DMC reactivity are such as
Under：
The homogeneous mixture of 0.3g catalyst and 0.6g quartz sands is fitted into stainless steel tubular reactor, heating journey is set
Sequence, preheating furnace is opened, when temperature rises to 140 DEG C, open CO and O2, methanol squeezed into by the type micro-sampling pumps of Series III,
Preheating gasification furnace gasified and with CO and O2Tow channel gas are sufficiently mixed, and then when temperature rises to required temperature, timing starts,
Gas chromatographic analysis, methanol feed rate 0.02ml/min, CO and O are carried out every 1h2Charging rate is respectively 22ml/min
And 2.0ml/min, material gaseous phase volume air speed are 7040h-1, reaction pressure is normal pressure.Original carbon nanotubes confinement copper catalyst
Catalysis methanol oxidative carbonylation synthesizes DMC space-time yield STYDMCOnly 86.2mgg-1·h-1, methanol conversion is
2.4%, DMC are selectively 70.3%, and the rapid deactivation in 5h.
Comparative example 2, hydrothermal oxidization CNT
1., measure nitric acid 2.34mL, deionized water 72.66mL, add in beaker, stir 10min, be made into 0.5mol/L's
Aqueous solution of nitric acid；
2., to weigh specific surface area be 220m2/ g, pore volume 0.78ml/g, average pore size are 8.7nm original carbon nanotubes
2g, it is added in above-mentioned aqueous solution of nitric acid；
3., said mixture is transferred to equipped with temperature controller and the autoclave of propeller system, it is high
Press kettle closed, the oxygen dissolved three times to drain in solution is put with nitrogen punching, system is further forced into 0.8MPa, with 100r/
Min speed stirring, is then heated to 140 DEG C and keeps 3h, last autoclave is cooled to pressure release after room temperature, with ion water washing
To neutrality, filter, be placed in baking oven and dry, 100 DEG C, drying time 10h of drying temperature, obtain the carbon nanometer after hydrothermal oxidization
Pipe, specific surface area 230m2/ g, pore volume 0.76ml/g, average pore size 9.2nm, elementary analysis atomic percent are carbon member
Cellulose content is 90.8%, and oxygen element content is 8.4%, nitrogen element content 0.8%.
Prepare the carbon nanotube loaded copper catalyst Cu/OCNT of hydrothermal oxidization
1., weigh 0.189g Cu (NO3)2·3H2O, 3mL deionized waters are measured, added in beaker, magnetic agitation 10min,
Into 0.260mol/L copper nitrate aqueous solution；
2., weigh the multi-walled carbon nanotube 1g after hydrothermal oxidization, be added in above-mentioned solution, be placed in ultrasound reactor and stir
Mix 40min, ultrasonic frequency 50KHz；
3., the mixture after supersound process stood into 12h at room temperature,
4., stand after by beaker place baking oven in dry, 40 DEG C of drying temperature, drying time 10h；Into direct nitrogen after drying
Doped carbon nanometer pipe confinement copper catalyst precursor body；
5., dried presoma in tube furnace lead to 20ml/min nitrogen, 300 DEG C of perseverances are risen to 3 DEG C/min speed
Temperature roasting 240min, naturally cools to room temperature taking-up, Cu/OCNT catalyst is obtained, consisting of Cu-5wt%, OCNT-
95wt%.
The specific reactions steps that catalyst is evaluated in Oxidative Carbonylation Synthesis of DMC reactivity are such as
Under：
1., by 0.3g catalyst and 1.0g quartz sands it is well mixed after be fitted into stainless steel tubular reactor；
2., set heating schedule, when the reaction bed temperature in reactor is heated into 120 DEG C, open CO and O2, first
Alcohol is squeezed into by the type micro-sampling pumps of Series III, preheating gasification furnace gasified and with CO and O2Tow channel gas are sufficiently mixed, and are adopted
With online gas chromatographic analysis, methanol feed rate 0.03ml/min, CO and O2Charging rate be respectively 30ml/min and
3.0ml/min, volume space velocity 9960h-1, reaction pressure 0.3MPa.Oxide/carbon nanometer tube confinement copper catalyst catalysis methanol
Oxidative carbonylation synthesizes DMC space-time yield STYDMCOnly 187.5mgg-1·h-1, methanol conversion 5.0%, DMC
Selectivity is 68.5%, and starts to inactivate in 10h and inactivate very fast.
Comparative example 3, direct nitrogen-doped carbon nanometer pipe
(1) it is 229m by 1.0g specific surface areas2/ g, pore volume 0.73ml/g, average pore size 8.5nm original carbon nanotubes and
2g melamine solids are placed in mortar grind well after be fitted into quartz boat；(2) quartz boat for filling mixture is placed in high temperature pipe
In formula stove, 20ml/min 700 DEG C of constant temperature calcining 240min of nitrogen are led in tube furnace, naturally cool to room temperature taking-up, washing
Filtered after to neutrality, be placed in baking oven and dry, 110 DEG C of drying temperature, drying time 10h, obtain the CNT of N doping, nitrogen
Doped carbon nanometer pipe specific surface area is 182m2/ g, pore volume 0.69ml/g, average pore size 12.6nm, elementary analysis atom hundred
It is that carbon element content is 97.0% to divide ratio, and oxygen element content is 1.6%, nitrogen element content 1.4%.
Prepare direct nitrogen-doped carbon nanometer pipe confinement copper catalyst
1., weigh 0.378g Cu (NO3)2·3H2O, 3mL deionized waters are measured, added in beaker, magnetic agitation 10min,
Into 0.520mol/L copper nitrate aqueous solution；
2., weigh N doping multi-walled carbon nanotube 1g, be added in above-mentioned solution, be placed in ultrasound reactor and stir
60min, ultrasonic frequency 50KHz；
3., the mixture after supersound process stood into 30h at room temperature；
4., stand after by beaker place baking oven in dry, 35 DEG C of drying temperature, drying time 12h；Into direct nitrogen after drying
Doped carbon nanometer pipe confinement copper catalyst precursor body；
5., dried presoma lead to 25ml/min 350 DEG C of nitrogen constant temperature calcining 240min in tube furnace, it is naturally cold
But taken out to room temperature, Cu/NCNT catalyst is obtained, consisting of Cu-10wt%, NCNT-90wt%.Catalyst is in methanol vapor phase
The specific reactions steps of oxidative carbonylation Synthesis of dimethyl carbonate reactivity evaluation are as follows：
1., by 0.3g catalyst and 1.5g quartz sands it is well mixed after be fitted into stainless steel tubular reactor；
2., set heating schedule, when the reaction bed temperature in reactor is heated into 130 DEG C, open CO and O2, first
Alcohol is squeezed into by the type micro-sampling pumps of Series III, preheating gasification furnace gasified and with CO and O2Tow channel gas are sufficiently mixed, and are adopted
With online gas chromatographic analysis, methanol feed rate 0.04ml/min, CO and O2Charging rate be respectively 36ml/min and
4.0ml/min, volume space velocity 12480h-1, reaction pressure is normal pressure.The nitrogen-doped carbon nanometer pipe confinement copper catalyst is catalyzed first
Alcohol oxidative carbonylation synthesizes DMC space-time yield STYDMCFor 164.2mgg-1·h-1, methanol conversion 4.5%, DMC choosings
Selecting property is 73.2%, and starts comparatively fast to inactivate in 7h.
Embodiment 1, hydrothermal oxidization CNT
1., measure nitric acid 0.23mL, deionized water 74.77mL, add in beaker, stir 10min, be made into 0.05mol/L
Aqueous solution of nitric acid；
2., to weigh specific surface area be 180m2/ g, pore volume 0.90ml/g, average pore size are 12.8nm original more wall carbon
Nanotube 2g, it is added in above-mentioned aqueous solution of nitric acid；
3., said mixture is transferred to equipped with temperature controller and the autoclave of propeller system, it is high
Press kettle closed, the oxygen dissolved three times to drain in solution is put with nitrogen punching, system is further forced into 0.4MPa, with 100r/
Min speed stirring, is then heated to 120 degree and keeps 1h, last autoclave is cooled to pressure release after room temperature, with ion water washing
To neutrality, filter, be placed in baking oven and dry, 90 DEG C of drying temperature, drying time 12h.
CNT after the oxidation of high temperature N doping
1., prepare oxidation after CNT and melamine
CNT 1.5g, melamine 3g are weighed respectively；
2., prepare mixture
The CNT weighed up and melamine solid are placed in mortar, grinding is uniform, is fitted into quartz boat；
3., high temperature N doping oxide/carbon nanometer tube
The quartz boat for filling mixture is placed in high temperature process furnances, 30ml/min 700 DEG C of nitrogen is led in tube furnace
Constant temperature calcining 240min, room temperature taking-up is naturally cooled to, is filtered after washing to neutrality, is placed in baking oven and dries, drying temperature 100
DEG C, drying time 10h obtains the CNT of N doping, and nitrogen-doped carbon nanometer pipe specific surface area is 171m2/ g, pore volume are
0.88ml/g, average pore size 14.1nm, elementary analysis atomic percent are that carbon element content is 92.2%, and oxygen element content is
3.2%, nitrogen element content 4.6%.
Prepare nitrogen-doped carbon nanometer pipe confinement copper catalyst
1., weigh 0.113g Cu (NO3)2·3H2O, 3mL deionized waters are measured, added in beaker, magnetic agitation 10min,
Into 0.156mol/L copper nitrate aqueous solution；
2., weigh N doping multi-walled carbon nanotube 1g, be added in above-mentioned solution, be placed in ultrasound reactor and stir
60min, ultrasonic frequency 60KHz；
3., the mixture after supersound process stood into 24h at room temperature,
4., stand after by beaker place baking oven in dry, 30 DEG C of drying temperature, drying time 14h；Into N doping after drying
CNT confinement copper catalyst precursor body；
5., dried presoma in tube furnace lead to 30ml/min nitrogen, 350 DEG C of perseverances are risen to 5 DEG C/min speed
Temperature roasting 240min, naturally cools to room temperature taking-up, Cu/NCNT catalyst is obtained, consisting of Cu-3wt%, NCNT-
97wt%.
The specific reactions steps that catalyst is evaluated in Oxidative Carbonylation Synthesis of DMC reactivity are such as
Under：
1., by 0.3g catalyst and 1g quartz sands it is well mixed after be fitted into stainless steel tubular reactor；
2., set heating schedule, when the reaction bed temperature in reactor is heated into 140 DEG C, open CO and O2, first
Alcohol is squeezed into by the type micro-sampling pumps of Series III, preheating gasification furnace gasified and with CO and O2Tow channel gas are sufficiently mixed, and are adopted
With online gas chromatographic analysis, methanol feed rate 0.05ml/min, CO and O2Charging rate be respectively 50ml/min and
5.0ml/min, volume space velocity 16600h-1, reaction pressure is normal pressure.The nitrogen-doped carbon nanometer pipe confinement copper catalyst is catalyzed first
Alcohol oxidative carbonylation synthesizes DMC space-time yield STYDMC313.5mgg is reached-1·h-1, methanol conversion 8.5%,
DMC is selectively 86.0%, and starts slowly to decline in 30h.
Embodiment 2
Operation and step with embodiment 1 is identical, but the concentration of nitric acid used when aoxidizing is changed into 0.5mol/L, oxidation
Temperature is changed into 180 DEG C, and oxidative pressure is changed into 0.8MPa, and mixing speed is changed into 200r/min, and oxidization time is changed into 2h；High temperature nitrogen is mixed
When miscellaneous, the quality of melamine is changed into 4.5g, obtains high temperature N doping multi-walled carbon nanotube, nitrogen-doped carbon nanometer pipe specific surface area
For 171m2/ g, pore volume 0.87ml/g, average pore size 12.7nm, elementary analysis atomic percent are that carbon element content is
83.6%, oxygen element content is 6.8%, nitrogen element content 9.6%.
Prepare nitrogen-doped carbon nanometer pipe confinement copper catalyst
1., weigh 0.189g Cu (NO3)2·3H2O, 3mL deionized waters are measured, added in beaker, magnetic agitation 10min,
Into 0.260mol/L copper nitrate aqueous solution；
2., weigh N doping multi-walled carbon nanotube 1g, be added in above-mentioned solution, be placed in ultrasound reactor and stir
60min, ultrasonic frequency 40KHz；
3., the mixture after supersound process stood into 12h at room temperature,
4., stand after by beaker place baking oven in dry, 30 DEG C of drying temperature, drying time 15h；Into N doping after drying
CNT confinement copper catalyst precursor body；
5., dried presoma in tube furnace lead to 20ml/min nitrogen, 300 DEG C of perseverances are risen to 6 DEG C/min speed
Temperature roasting 240min, naturally cools to room temperature taking-up, Cu/NCNT catalyst is obtained, consisting of Cu-5wt%, NCNT-
95wt%.
The specific reactions steps that catalyst is evaluated in Oxidative Carbonylation Synthesis of DMC reactivity are such as
Under：
1., by 0.2g catalyst and 0.8g quartz sands it is well mixed after be fitted into stainless steel tubular reactor；
2., set heating schedule, when the reaction bed temperature in reactor is heated into 125 DEG C, open CO and O2, first
Alcohol is squeezed into by the type micro-sampling pumps of Series III, preheating gasification furnace gasified and with CO and O2Tow channel gas are sufficiently mixed, and are adopted
With online gas chromatographic analysis, methanol feed rate 0.01ml/min, CO and O2Charging rate be respectively 10ml/min and
1.0ml/min, volume space velocity 4980h-1, reaction pressure 0.5MPa.The nitrogen-doped carbon nanometer pipe confinement copper catalyst is catalyzed
Methanol oxidative carbonylation synthesizes DMC space-time yield STYDMC514.5mgg is reached-1·h-1, methanol conversion is
18.8%, DMC are selectively 90.5%, and start slowly to decline in 50h.
Embodiment 3
Operation and step with embodiment 1 is identical, but the concentration of hydrothermal oxidization aqueous solution of nitric acid is changed into 0.5mol/L,
Oxidizing temperature is changed into 200 DEG C, and oxidative pressure is changed into 1.0MPa, and mixing speed is changed into 300r/min, and oxidization time is changed into 3h；High temperature
During N doping, the quality of melamine is changed into 6g, obtains high temperature N doping multi-walled carbon nanotube, and nitrogen-doped carbon nanometer pipe compares surface
Product is 135m2/ g, pore volume 0.76ml/g, average pore size 15.1nm, elementary analysis atomic percent are that carbon element content is
82.3%, oxygen element content is 7.4%, nitrogen element content 10.3%.
Prepare nitrogen-doped carbon nanometer pipe confinement copper catalyst
1., weigh 0.265g Cu (NO3)2·3H2O, 3mL deionized waters are measured, added in beaker, magnetic agitation 10min,
Into 0.375mol/L copper nitrate aqueous solution；
2., weigh N doping multi-walled carbon nanotube 1g, be added in above-mentioned solution, be placed in ultrasound reactor and stir
60min, ultrasonic frequency 45KHz；
3., the mixture after supersound process stood into 14h at room temperature,
4., stand after by beaker place baking oven in dry, 30 DEG C of drying temperature, drying time 15h；Into N doping after drying
CNT confinement copper catalyst precursor body；
5., dried presoma lead to 25ml/min 350 DEG C of nitrogen constant temperature calcining 240min in tube furnace, it is naturally cold
But taken out to room temperature, Cu/NCNT catalyst is obtained, consisting of Cu-7wt%, NCNT-93wt%.
The specific reactions steps that catalyst is evaluated in Oxidative Carbonylation Synthesis of DMC reactivity are such as
Under：
1., by 0.3g catalyst and 1.5g quartz sands it is well mixed after be fitted into stainless steel tubular reactor；
2., set heating schedule, when the reaction bed temperature in reactor is heated into 130 DEG C, open CO and O2, first
Alcohol is squeezed into by the type micro-sampling pumps of Series III, preheating gasification furnace gasified and with CO and O2Tow channel gas are sufficiently mixed, and are adopted
With online gas chromatographic analysis, methanol feed rate 0.02ml/min, CO and O2Charging rate be respectively 16ml/min and
2.0ml/min, volume space velocity 5840h-1, reaction pressure 2.0MPa.The nitrogen-doped carbon nanometer pipe confinement copper catalyst is catalyzed
Methanol oxidative carbonylation synthesizes DMC space-time yield STYDMC547.7mgg is reached-1·h-1, methanol conversion is
20.0%, DMC are selectively 91.3%, and without obvious inactivation in 60h.
Embodiment 4
Operation and step with embodiment 1 is identical, but the concentration of hydrothermal oxidization aqueous solution of nitric acid is changed into 0.1mol/L,
Oxidizing temperature is changed into 140 DEG C, and oxidative pressure is changed into 0.4MPa, and mixing speed is changed into 150r/min, and oxidization time is changed into 2h；High temperature
During N doping, the quality of melamine is changed into 6g, obtains high temperature N doping multi-walled carbon nanotube, and nitrogen-doped carbon nanometer pipe compares surface
Product is 117m2/ g, pore volume 0.6ml/g, average pore size 14.1nm, elementary analysis atomic percent are that carbon element content is
89.8%, oxygen element content is 3.4%, nitrogen element content 6.8%.
Prepare nitrogen-doped carbon nanometer pipe confinement copper catalyst
1., weigh 0.340g Cu (NO3)2·3H2O, 3mL deionized waters are measured, added in beaker, magnetic agitation 10min,
Into 0.469mol/L copper nitrate aqueous solution；
2., weigh N doping multi-walled carbon nanotube 1g, be added in above-mentioned solution, be placed in ultrasound reactor and stir
60min, ultrasonic frequency 50KHz；
3., the mixture after supersound process stood into 16h at room temperature,
4., stand after by beaker place baking oven in dry, 30 DEG C of drying temperature, drying time 10h；Into N doping after drying
CNT confinement copper catalyst precursor body；
5., dried presoma in tube furnace lead to 20ml/min nitrogen, 350 DEG C of perseverances are risen to 10 DEG C/min speed
Temperature roasting 240min, naturally cools to room temperature taking-up, Cu/NCNT catalyst is obtained, consisting of Cu-9wt%, NCNT-
91wt%.
The specific reactions steps that catalyst is evaluated in Oxidative Carbonylation Synthesis of DMC reactivity are such as
Under：
1., by 0.6g catalyst and 3g quartz sands it is well mixed after be fitted into stainless steel tubular reactor；
2., set heating schedule, when the reaction bed temperature in reactor is heated into 135 DEG C, open CO and O2, first
Alcohol is squeezed into by the type micro-sampling pumps of Series III, preheating gasification furnace gasified and with CO and O2Tow channel gas are sufficiently mixed, and are adopted
With online gas chromatographic analysis, methanol feed rate 0.04ml/min, CO and O2Charging rate be respectively 36ml/min and
4.0ml/min, volume space velocity 6240h-1, reaction pressure 0.8MPa.The nitrogen-doped carbon nanometer pipe confinement copper catalyst is catalyzed
Methanol oxidative carbonylation synthesizes DMC space-time yield STYDMC416.8mgg is reached-1·h-1, methanol conversion is
15.2%, DMC are selectively 92.0%, and start active slowly decline in 45h.
Embodiment 5
Operation and step with embodiment 1 is identical, but the concentration of hydrothermal oxidization aqueous solution of nitric acid is changed into 1.0mol/L,
Oxidizing temperature is changed into 160 DEG C, and oxidative pressure is changed into 0.8MPa, and mixing speed is changed into 250r/min, and oxidization time is changed into 4h；High temperature
During N doping, the quality of melamine is changed into 1.5g, obtains the more wall CNTs of high temperature N doping, nitrogen-doped carbon nanometer pipe ratio
Surface area is 169m2/ g, pore volume 0.7ml/g, average pore size 15.2nm, elementary analysis atomic percent are carbon element content
For 88.6%, oxygen element content is 5.6%, nitrogen element content 5.8%.
Prepare nitrogen-doped carbon nanometer pipe confinement copper catalyst
1., weigh 0.378g Cu (NO3)2·3H2O, 3mL deionized waters are measured, added in beaker, magnetic agitation 10min,
Into 0.520mol/L copper nitrate aqueous solution；
2., weigh N doping multi-walled carbon nanotube 1g, be added in above-mentioned solution, be placed in ultrasound reactor and stir
60min, ultrasonic frequency 60KHz；
3., the mixture after supersound process stood into 18h at room temperature,
4., stand after by beaker place baking oven in dry, 35 DEG C of drying temperature, drying time 12h；Into N doping after drying
CNT confinement copper catalyst precursor body；
5., dried presoma lead to 35ml/min 350 DEG C of nitrogen constant temperature calcining 240min in tube furnace, it is naturally cold
But taken out to room temperature, Cu/NCNT agents are obtained, consisting of Cu-10wt%, NCNT-90wt%.
The specific reactions steps that catalyst is evaluated in Oxidative Carbonylation Synthesis of DMC reactivity are such as
Under：
1., by 0.8g catalyst and 2.5g quartz sands it is well mixed after be fitted into stainless steel tubular reactor；
2., set heating schedule, when the reaction bed temperature in reactor is heated into 140 DEG C, open CO and O2, first
Alcohol is squeezed into by the type micro-sampling pumps of Series III, preheating gasification furnace gasified and with CO and O2Tow channel gas are sufficiently mixed, and are adopted
With online gas chromatographic analysis, methanol feed rate 0.06ml/min, CO and O2Charging rate be respectively 60ml/min and
6.0ml/min, volume space velocity 7470h-1, reaction pressure 1.5MPa.The nitrogen-doped carbon nanometer pipe confinement copper catalyst is catalyzed
Methanol oxidative carbonylation synthesizes DMC space-time yield STYDMC345.2mgg is reached-1·h-1, methanol conversion is
12.6%, DMC are selectively 93.4%, and start active slowly decline in 40h.
Claims (9)
1. a kind of preparation method of efficiently nitrogen-doped carbon nanometer pipe, it is characterised in that comprise the following steps：
（1）Hydrothermal oxidization CNT
By multi-walled carbon nanotube：Salpeter solution is 1-2g：50-100mL, it is 0.05- by multi-walled carbon nanotube addition concentration
In 0.5mol/L salpeter solution, said mixture is transferred to the height equipped with temperature controller and propeller system
Press in kettle, autoclave is closed, and the oxygen dissolved three times to drain in solution is put with nitrogen punching, and system is further forced into 0.4-
1.0MPa, stirred with 100-300r/min speed, be then heated to 120-200 DEG C and keep 1-4h, last autoclave cooling
Pressure release after to room temperature, with ion water washing to neutrality, filter, be placed in baking oven in 80-100 DEG C of dry 8-12h；
（2）Step（1）CNT after hydrothermal oxidization is with melamine solid using mass ratio as 1:1-4 is mixed and ground with mortar
Even, 600 DEG C of -900 DEG C of high-temperature roasting 2h-4h, are dried after being washed to neutrality with distillation after the completion of roasting in nitrogen, are obtained nitrogen and are mixed
Miscellaneous CNT.
A kind of 2. preparation method of efficiently nitrogen-doped carbon nanometer pipe as claimed in claim 1, it is characterised in that step（1）It is described
CNT be multi-walled carbon nanotube, specific surface area is 180-260 m2/ g, pore volume 0.70-0.98 ml/g, average pore size are
7.6-12.8nm。
A kind of 3. preparation method of efficiently nitrogen-doped carbon nanometer pipe as claimed in claim 1 or 2, it is characterised in that nitrogen-doped carbon
The nitrogen content of nanotube is 4.6wt%-10.3wt%, and specific surface area is 134-180 m2/ g, pore volume are 0.60-0.80 ml/g, are put down
Equal aperture is 12.6-15.2nm.
4. the catalyst prepared using claim 3 nitrogen-doped carbon nanometer pipe, it is characterised in that catalyst is by active ingredient copper
Formed with nitrogen-doped carbon nanometer pipe, wherein Cu3.0-10.0wt%, nitrogen-doped carbon nanometer pipe 90-97wt%.
5. the preparation method of catalyst as claimed in claim 4, it is characterised in that comprise the following steps：
(1) formed by catalyst, concentration is added dropwise into nitrogen for 0.156-0.52mol/L soluble non-chlorine copper salt solutions mixes
In miscellaneous CNT, 30-60 min are stirred in ultrasound reactor, 8-15h is then dried at 30-50 DEG C, obtains drying
Presoma；
(2) dry presoma under an inert atmosphere, rise to 300-450 DEG C with 2-10 DEG C/min speed, constant temperature calcining 180-
240min, room temperature taking-up is naturally cooled to, that is, obtains nitrogen-doped carbon nanometer pipe copper-loading catalyst,.
6. the preparation method of catalyst as claimed in claim 5, it is characterised in that described soluble non-chlorine mantoquita is copper nitrate
Or copper acetate.
7. the preparation method of catalyst as claimed in claim 5, it is characterised in that described inert atmosphere is nitrogen or argon gas.
8. the application of catalyst as claimed in claim 4, it is characterised in that comprise the following steps：
Catalyst is used for the reaction of Oxidative Carbonylation Synthesis of DMC, by catalyst and the mixture of quartz sand
It is fitted into fixed bed reactors, in a nitrogen atmosphere, the reaction bed temperature in reactor is heated to 120-140 DEG C；Instead
It is CO to answer volumetric flow of gas ratio composition：O2：First=8:1:0.01-11:1:The 0.01 preheated device of raw material is heated to 110-
130℃；The material that preheater comes out enters tubular reactor from the upper end of reactor, and material gaseous phase volume air speed is 4980-
16600 h-1, reacted under conditions of temperature is 120-140 DEG C and pressure is normal pressure -2.0MPa, the material come out from reactor
Reaction product is obtained after condensed device condensation.
9. the application of catalyst as claimed in claim 8, it is characterised in that the addition between described catalyst and quartz sand
It is catalyst for catalyst and quartz sand mass ratio：Quartz sand=1:2-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710799634.1A CN107686105B (en) | 2017-09-07 | 2017-09-07 | Preparation method of high-efficiency nitrogen-doped carbon nano tube and application of nitrogen-doped carbon nano tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710799634.1A CN107686105B (en) | 2017-09-07 | 2017-09-07 | Preparation method of high-efficiency nitrogen-doped carbon nano tube and application of nitrogen-doped carbon nano tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107686105A true CN107686105A (en) | 2018-02-13 |
| CN107686105B CN107686105B (en) | 2020-03-27 |
Family
ID=61156024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710799634.1A Active CN107686105B (en) | 2017-09-07 | 2017-09-07 | Preparation method of high-efficiency nitrogen-doped carbon nano tube and application of nitrogen-doped carbon nano tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107686105B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109019744A (en) * | 2018-08-07 | 2018-12-18 | 华南理工大学 | A kind of method of the molding carbon material Adsorption heavy metal ions in wastewater of nitrating |
| CN111036264A (en) * | 2019-12-11 | 2020-04-21 | 太原理工大学 | Preparation method of coal-based carbon nanotube catalyst for efficiently catalyzing and oxidizing toluene |
| CN111517356A (en) * | 2020-04-30 | 2020-08-11 | 浙江理工大学 | Cu2O nanotube and method for producing the same |
| CN113013405A (en) * | 2019-12-21 | 2021-06-22 | 天津大学 | Boron-sulfur co-doped carbon nanotube and preparation method and application thereof |
| CN113244942A (en) * | 2021-04-27 | 2021-08-13 | 辽宁师范大学 | Non-metal nitrogen-doped porous carbon catalyst and method for preparing methyl carboxylate compound |
| CN115518653A (en) * | 2022-09-28 | 2022-12-27 | 北京化工大学 | Catalyst for efficiently catalyzing ethanol oxidative carbonylation to prepare diethyl carbonate and preparation method thereof |
| CN115555042A (en) * | 2022-12-05 | 2023-01-03 | 河北工业职业技术学院 | Preparation method of carbon nanotube catalyst, carbon nanotube catalyst and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102861579A (en) * | 2012-09-22 | 2013-01-09 | 台州学院 | Copper-based nano denitration catalyst and preparation method thereof |
| CN102872879A (en) * | 2012-09-26 | 2013-01-16 | 太原理工大学 | Chlorine-free bimetallic catalyst for gas phase synthesis of dimethyl carbonate and preparation and application |
| CN105837391A (en) * | 2016-04-01 | 2016-08-10 | 湘潭大学 | Application of metal-free hydrogenation catalyst to catalysis of benzene hydrogenation |
| CN106219515A (en) * | 2016-07-27 | 2016-12-14 | 河南师范大学 | There is the synthetic method of the empty spherical nitrogen-doped carbon material of special crosslinking |
| CN106698410A (en) * | 2016-12-05 | 2017-05-24 | 四川大学 | Method for preparing nitrogen-atom doped carbon nanomaterial |
-
2017
- 2017-09-07 CN CN201710799634.1A patent/CN107686105B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102861579A (en) * | 2012-09-22 | 2013-01-09 | 台州学院 | Copper-based nano denitration catalyst and preparation method thereof |
| CN102872879A (en) * | 2012-09-26 | 2013-01-16 | 太原理工大学 | Chlorine-free bimetallic catalyst for gas phase synthesis of dimethyl carbonate and preparation and application |
| CN105837391A (en) * | 2016-04-01 | 2016-08-10 | 湘潭大学 | Application of metal-free hydrogenation catalyst to catalysis of benzene hydrogenation |
| CN106219515A (en) * | 2016-07-27 | 2016-12-14 | 河南师范大学 | There is the synthetic method of the empty spherical nitrogen-doped carbon material of special crosslinking |
| CN106698410A (en) * | 2016-12-05 | 2017-05-24 | 四川大学 | Method for preparing nitrogen-atom doped carbon nanomaterial |
Non-Patent Citations (1)
| Title |
|---|
| R.R.N. MARQUES ET AL.: "Controlled generation of oxygen functionalities on the surface of Single-Walled Carbon Nanotubes by HNO3 hydrothermal oxidation", 《CARBON》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109019744A (en) * | 2018-08-07 | 2018-12-18 | 华南理工大学 | A kind of method of the molding carbon material Adsorption heavy metal ions in wastewater of nitrating |
| CN111036264A (en) * | 2019-12-11 | 2020-04-21 | 太原理工大学 | Preparation method of coal-based carbon nanotube catalyst for efficiently catalyzing and oxidizing toluene |
| CN111036264B (en) * | 2019-12-11 | 2022-06-28 | 太原理工大学 | Preparation method of coal-based carbon nanotube catalyst for efficiently catalyzing and oxidizing toluene |
| CN113013405A (en) * | 2019-12-21 | 2021-06-22 | 天津大学 | Boron-sulfur co-doped carbon nanotube and preparation method and application thereof |
| CN111517356A (en) * | 2020-04-30 | 2020-08-11 | 浙江理工大学 | Cu2O nanotube and method for producing the same |
| CN111517356B (en) * | 2020-04-30 | 2022-03-29 | 浙江理工大学 | Cu2O nanotube and method for producing the same |
| CN113244942A (en) * | 2021-04-27 | 2021-08-13 | 辽宁师范大学 | Non-metal nitrogen-doped porous carbon catalyst and method for preparing methyl carboxylate compound |
| CN113244942B (en) * | 2021-04-27 | 2023-09-19 | 辽宁师范大学 | Nonmetallic nitrogen-doped porous carbon catalyst and method for preparing carboxylic acid methyl ester compound |
| CN115518653A (en) * | 2022-09-28 | 2022-12-27 | 北京化工大学 | Catalyst for efficiently catalyzing ethanol oxidative carbonylation to prepare diethyl carbonate and preparation method thereof |
| CN115518653B (en) * | 2022-09-28 | 2024-03-26 | 北京化工大学 | Catalyst for preparing diethyl carbonate by efficiently catalyzing ethanol to oxidize and carbonylate and preparation method thereof |
| CN115555042A (en) * | 2022-12-05 | 2023-01-03 | 河北工业职业技术学院 | Preparation method of carbon nanotube catalyst, carbon nanotube catalyst and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107686105B (en) | 2020-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107686105A (en) | A kind of efficiently preparation method of nitrogen-doped carbon nanometer pipe and its application of nitrogen-doped carbon nanometer pipe | |
| Domínguez-Domínguez et al. | Semihydrogenation of phenylacetylene catalyzed by palladium nanoparticles supported on carbon materials | |
| Yin et al. | Catalytic conversion of glycerol to lactic acid over graphite-supported nickel nanoparticles and reaction kinetics | |
| CN107952437B (en) | Cu/titanium dioxide nanosheet catalyst for synthesizing methanol through carbon dioxide hydrogenation and preparation method thereof | |
| CN107597109A (en) | Load type gold catalyst of nano-metal-oxide doping and preparation method and application | |
| CN102527377A (en) | High-efficiency nano Pd catalyst used in the process of preparing oxalate through CO carbonylation and prepared by dipping-controllable reduction method | |
| Xie et al. | Carbon supported copper catalyst prepared in situ by one-pot pyrolysis of Bougainvillea glabra: An efficient and stable catalyst for selective oxidation of cyclohexane | |
| CN106732559A (en) | A kind of palladium catalyst of cherry stone carbon load and preparation method and application | |
| Fernández-Catalá et al. | Photocatalytically-driven H2 production over Cu/TiO2 catalysts decorated with multi-walled carbon nanotubes | |
| Qi et al. | Solvent-free aerobic oxidation of alcohols over palladium supported on MCM-41 | |
| CN107511150A (en) | A kind of preparation method of the heterogeneous catalyst of formic acid decomposing hydrogen-production | |
| CN109529821A (en) | A kind of palladium-based catalyst for thermocatalytic Degradation Formaldehyde | |
| CN109364917A (en) | A kind of N doping charcoal metal supported catalyst and its preparation method and application | |
| CN107694563A (en) | Palladium carbon catalyst and its preparation method and application | |
| CN113477220A (en) | Noble metal ion adsorption material based on magnetic metal organic framework and preparation method thereof | |
| CN109453762A (en) | A kind of preparation method and application of modified clay mine loaded palladium catalyst | |
| CN111905755A (en) | Catalyst for hydrogenation of 2,2,4, 4-tetramethyl-1, 3-cyclobutanedione and preparation method and application thereof | |
| Zamani et al. | Selective, Efficient and Gram‐Scale Oxidation of Alcohols Using Household Bleach in the Presence of Fe3O4@ Boehmite‐NH2‐CoII Nanoparticles | |
| Kusumawati et al. | Size-controllable gold nanoparticles prepared from immobilized gold-containing ionic liquids on SBA-15 | |
| CN105727942A (en) | A palladium/carbon nanotube catalyst, a preparing method thereof and applications of the catalyst | |
| CN110339844A (en) | Fe nanometer rods and Pt@Fe Nanorods Catalyst and synthesis and application | |
| CN111389398B (en) | Preparation method of hierarchical hollow silica confinement cuprous oxide visible-light-driven photocatalyst | |
| CN114349973B (en) | Lanthanum-manganese bimetal quasi-organic framework material and preparation method and application thereof | |
| CN107185525B (en) | Octahedral Pt nanoparticle loaded gamma-Al2O3Process for preparing form catalyst | |
| CN112774690A (en) | Supported monatomic noble metal catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |