CN107715877A - A kind of hollow mesoporous carbosphere shell confinement copper catalyst and preparation method and application - Google Patents

A kind of hollow mesoporous carbosphere shell confinement copper catalyst and preparation method and application Download PDF

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CN107715877A
CN107715877A CN201710958424.2A CN201710958424A CN107715877A CN 107715877 A CN107715877 A CN 107715877A CN 201710958424 A CN201710958424 A CN 201710958424A CN 107715877 A CN107715877 A CN 107715877A
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temperature
carbon
copper
catalyst
deionized water
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CN107715877B (en
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李忠
张国强
贾东森
闫俊芬
王佳君
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Taiyuan University of Technology
Shanxi Luan Mining Group Co Ltd
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/398—Egg yolk like
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    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
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    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/618—Surface area more than 1000 m2/g
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
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Abstract

A kind of hollow mesoporous carbosphere shell confinement copper catalyst, it is characterised in that catalyst is made up of the hollow mesoporous lamella carbon ball of carrier and active ingredient copper, in terms of metal, 7.0~11.5wt% of copper, 88.5~93.0wt% of carbon；Specific surface area is 480~1240 m2/ g, pore volume are 1.7~2.3 cm3/ g, shell most probable pore size are 3.5~8.5nm；Carbon ball average cavity size is 160~200nm, and shell average thickness is 60~180nm, and average grain diameter is 280~560nm.The advantages of active and stability of the present invention is high.

Description

A kind of hollow mesoporous carbosphere shell confinement copper catalyst and preparation method and application
Technical field
The present invention relates to a kind of hollow mesoporous carbosphere shell confinement copper catalyst and preparation method and application.
Background technology
Dimethyl carbonate (DMC), it is a kind of industrial chemicals nontoxic, environmental-protecting performance is excellent, widely used.Its molecular structure In containing the functional group such as carbonyl, methyl and methoxyl group, there are a variety of reactivity worth, be a kind of important organic synthesis intermediate； The electrolyte of lithium ion battery is also used as, reduces gasoline additive of pollutant emission etc., therefore with hair well Exhibition prospect and market potential.
DMC production method has phosgenation, ester-interchange method, oxidative carbonylation of methanol method, methanol direct method and urea at present Alcoholysis method.Oxidative carbonylation of methanol method is because its selectivity is high, and atom utilization is high, and production cost is low, and activity is good, green The advantages that there is good application prospect.
Research shows, Cu in the copper species loaded in molecular sieve or carbon material carrierⅠIt is main active specy.Density is general Letter theoretical calculation shows, Cu2O (111) crystal face is advantageous to Methanol Decomposition generation methoxyl group, and its oxygen defect site is advantageous to O2Suction Dissociation is echoed, promotes DMC generation.
Patent CN102600843A, CN102872879A report activated carbon supported nanometer copper catalyst in methanol vapor phase oxygen Changing in carbonylation Synthesis of dimethyl carbonate has higher catalytic activity.It is but a large amount of living because activated carbon is mainly microcellular structure Property Nanometer Copper species be mainly scattered in carrier surface, surface energy is higher, during the course of the reaction easily occur reunion grow up, cause to urge Changing activity reduces, and catalyst stability declines.
Patent CN103599781A, CN104324757A are reported nanometer copper particle dropping place in hollow carbon balls cavity structure In, coreshell type structure is constructed, prepares core-shell-type carbon-coated nano-copper catalyst, to improve the catalytic activity of catalyst and stably Property.But because the copper species in catalyst are mainly Cu0, rather than CuⅠ, cause its catalytic activity relatively low；And carbon ball cavity volume is too Greatly, Nanometer Copper species can still reunite during the course of the reaction, cause catalyst stability to decline.
The content of the invention
It is an object of the invention to provide a kind of activity and the high hollow mesoporous carbosphere shell confinement copper catalyst of stability And preparation method and the application in Synthesis of dimethyl carbonate.
The present invention is in view of activated carbon supported nanometer copper catalyst and core-shell-type carbon-coated nano-copper catalyst have copper and received The shortcomings that rice corpuscles is easily reunited, using tetraethyl orthosilicate, resorcinol, formaldehyde as primary raw material, formulated solution, Hydrothermal Synthesiss, Carbonization etching, shell is prepared rich in a large amount of mesoporous hollow carbon balls, the carrier of catalyst is used as, recycles ultrasonic wave auxiliary Help equi-volume impregnating by copper species load to shell it is mesoporous in and prepare hollow mesoporous carbosphere shell confinement copper catalyst, Reaction for Oxidative Carbonylation Synthesis of DMC.In this way obtained catalyst have carbon ball particle diameter and The characteristics of shell mesoporous pore size is adjustable, active specy nano copper particle be evenly dispersed in shell it is mesoporous in, particle diameter is small and anti-group Cumulative power is strong, and catalytic activity is high and stability is good.
The catalyst of the present invention is made up of the hollow mesoporous lamella carbon ball of carrier and active ingredient copper, in terms of metal, copper 7.0 ~11.5wt%, 88.5~93.0wt% of carbon；Specific surface area is 480~1240m2/ g, pore volume are 1.7~2.3cm3/ g, shell is most Can several apertures be 3.5~8.5nm；Carbon ball average cavity size is 160~200nm, and shell average thickness is 60~180nm, is put down Equal particle diameter is 280~560nm.
The preparation method of catalyst of the present invention is as follows：
(1) absolute ethyl alcohol, deionized water, the ammoniacal liquor that concentration is 25wt% are stirred into 5~10min at 25~30 DEG C, then Tetraethyl orthosilicate is added, continues 6~8h of stirring, forms solid sol-gel agent；Wherein absolute ethyl alcohol：Deionized water：Ammoniacal liquor：Just The volume ratio of silester is 80~100：16~20：2.1~2.3：3~4；
(2) it is 2~4: 1 addition deionized water by deionized water and CTAC mass ratioes, stirring is prepared the CTAC aqueous solution, pressed Deionized water is 4~6: 1 with absolute ethyl alcohol volume ratio, and deionized water and absolute ethyl alcohol are added in solid silicon ball colloidal sol, stirring Mixed solution is obtained, then the CTAC aqueous solution is added in mixed solution dropwise under the state that is stirred vigorously, adds resorcinol, Formaldehyde, tetraethyl orthosilicate are eventually adding, 10~12h is stirred at 25~30 DEG C, obtains carbon silicon polymer mixed solution, wherein CTAC：Absolute ethyl alcohol：Solid silicon ball colloidal sol：Resorcinol：Formaldehyde：Tetraethyl orthosilicate mol ratio=3.5~10.5: 110~120 : 2~2.5: 1~3: 4~12: 2~6.
(3) by carbon silicon polymer mixed solution at 100~200 DEG C 18~30h of hydro-thermal, formed carbon silicon polymer microballoon before Body is driven, is then centrifuged for separating, by sediment deionized water centrifuge washing 2~5 times, 18~24h is dried at 40~60 DEG C, is obtained Carbon silicon polymer microballoon precursor powder；
(4) precursor powder is placed in tube type high-temperature furnace, input 20~30mL/ of nitrogen (gcatMin), heating rate 4 ~6 DEG C/min, 700~800 DEG C of heating-up temperature, constant temperature keeps 3~5h, then naturally cools to room temperature, completes carbonisation, raw Into carbon silicon polymer microballoon, carbon silicon polymer microsphere powder is added in 5~10wt% hydrofluoric acid aqueous solution, standing 18~ 24h, to remove silica, with deionized water by sediment centrifuge washing 2~5 times, then put the precipitate at 70~90 DEG C 10~14h is dried, hollow mesoporous lamella carbon ball is produced after drying；
(5) Cu (NO, are weighed3)2·3H2O, add deionized water, stir concentration be 0.176~0.310mol/L nitre Sour copper solution, is formed by catalyst, is weighed hollow mesoporous lamella carbon ball, is added in above-mentioned solution, is placed in after stirring super 50~70min of ultrasound in sound wave reactor, ultrasonic frequency are 80~100KHz.By the mixture after supersound process 30~50 18~24h is dried at DEG C, catalyst precursor is produced after drying；
(6) catalyst precursor is placed in tube type high-temperature furnace, input 20~30mL/ of nitrogen (gcatMin), heating speed 2~4 DEG C/min of rate, 300~400 DEG C of heating-up temperature, constant temperature keep 3~5h, make the copper species in presoma in high temperature, nitrogen gas Reacted under atmosphere with carbon carrier, by CuⅡIt is reduced to CuⅠ, product naturally cools to room temperature, produces hollow mesoporous carbosphere shell Confinement copper catalyst.
The present invention catalyst be used for Oxidative Carbonylation Synthesis of DMC reaction, its reactions steps and Process conditions are as follows：
(1) quartz sand is weighed for 1: 5~10 by catalyst and quartz sand mass ratio, loads after both are well mixed and fix In bed tubular reactor, in a nitrogen atmosphere, the reaction bed temperature in reactor is heated to 120~140 DEG C.
(2) raw material is CH according to mol ratio3OH∶CO∶O2=2~6: 6~18: 1~3 composition enters preheating furnace, preheated For stove heat to reactor is entered after 110~130 DEG C, charging gaseous phase volume air speed is 5840~17520h-1, reaction temperature 120 ~140 DEG C, pressure is reacted under conditions of being normal pressure~1.0MPa.
Product storage
The catalyst of the present invention should be stored in the storage of closed lucifuge, waterproof, sun-proof, anti-acid-alkali salt to corrode, storage temperature 15~25 DEG C, relative humidity≤10%.
Test, analysis and characterization
Pattern, chemical physical property and the catalytic activity of the hollow mesoporous carbosphere shell confinement copper catalyst of preparation are entered Row test, analysis and characterization.Formed with the element of Atomic Absorption Spectrometer AAS analysis of catalyst；Detected and be catalyzed with physical adsorption appearance The texture property and pore passage structure of agent；With the pattern of transmission electron microscope tem observation catalyst and the decentralization of active specy.
The present invention has the following advantages that compared with prior art：
The present invention be directed to the drawbacks of the preparation of dimethyl carbonate synthesis Carbon Materials copper-loading catalyst, be rich in using shell big Carrier of the mesoporous hollow carbon balls as catalyst is measured, copper species are loaded into shell using ultrasonic assistant equi-volume impregnating Confinement type copper-based catalysts are prepared in mesoporous.This preparation method is simple to operate, and technique is advanced, has carbon ball particle diameter and shell The characteristics of mesoporous pore size is adjustable, the confinement effect of carbon ball mesoporous lamella cause active specy nano copper particle to be evenly dispersed in shell During layer is mesoporous, particle diameter is small and anti-agglomeration ability is strong, is received with traditional activated carbon supported nanometer copper catalyst and hud typed carbon coating Rice copper catalyst compares the reunion that can be effectively prevented from copper species, so as to significantly improve catalytic activity and stability.Methanol turns Rate is that the space-time yield that 12%~20%, DMC selectivity is 85%~93%, DMC reaches 350~600mgg-1·h-1, Catalytic activity, which can be stablized, maintains 80h~120h.
Brief description of the drawings
Fig. 1 is that the nitrogen suction of hollow mesoporous carbosphere shell confinement copper catalyst prepared by the embodiment of the present invention 2,4,5 is de- Attached isollaothermic chart.
Fig. 2 is the pore-size distribution of hollow mesoporous carbosphere shell confinement copper catalyst prepared by the embodiment of the present invention 2,4,5 Figure.
Embodiment
The present invention is further illustrated with below by specific embodiment, but does not limit the present invention.
Comparative example 1
The specific step of the catalysis methanol oxidative carbonylation Synthesis of dimethyl carbonate of core-shell-type carbon-coated nano-copper catalyst I reaction Suddenly：
(1) oleic acid copper complex is prepared
Copper nitrate 2.42g, enuatrol 6.09g are weighed, absolute ethyl alcohol 20mL, deionized water 15mL, hexane 35mL is measured, adds Enter in three-necked flask, three-necked flask is heated to 70 DEG C, and stir 2h, into complex liquid.Complex liquid is added in separatory funnel, entered Row separation, stands 10min, upper organic layer is retained after liquid separation；Organic layer is added in beaker, deionized water 100mL is added, stirs Washing 10min is mixed, cleaning solution is added in separatory funnel, then is separated, 10min is stood, upper organic layer is retained after liquid separation. Organic be placed in baking oven is dried, 50 DEG C, drying time 5h of drying temperature, into oleic acid copper complex (C after drying18H33O2)2Cu。
(2) copper oleate emulsion is prepared
Oleic acid copper complex 0.12g is weighed, measures deionized water 5mL, is added in beaker, stirs 5min, into copper oleate breast Liquid.
(3) D/W is prepared
Glucose 0.9g is weighed, measures deionized water 100mL, is added in beaker, 5min is stirred, into 0.05mol/L Portugal Grape sugar aqueous solution.
(4) mixed solution is prepared
The D/W prepared, copper oleate emulsion are placed in beaker, is subsequently placed in water-bath and heats, is heated 30 DEG C of temperature, 40min is stirred with 150r/min rotating speed, into mixed emulsion.
(6) Hydrothermal Synthesiss
Mixed emulsion is transferred in polytetrafluoroethylcontainer container, is placed in reactor, it is closed, then reactor is placed in Heated in baking oven, 180 DEG C, heat time 4h of heating-up temperature, carry out Hydrothermal Synthesiss, form carbon coating copper presoma.Hydrothermal Synthesiss Afterwards, stop heating, reactor is cooled to room temperature with the furnace.
(7) centrifuge
Kettle is driven, the suspension in polytetrafluoroethylcontainer container is moved into centrifuge tube, is centrifuged, separates revolution 8000r/min, disengaging time 10min, sediment is retained after separation, discards upper liquid.
(8) wash, filter
Put the precipitate in beaker, add deionized water 100mL, agitator treating 5min, it is then qualitative with three layers of middling speed Filter paper is filtered, and obtains product cake；Product cake is placed in beaker, adds absolute ethyl alcohol 100mL, agitator treating 5min, Filtered again with three layers of middling speed qualitative filter paper, obtain product cake.
(9) dry
Product cake is placed in baking oven and dried, 50 DEG C, drying time 6h of drying temperature, before producing carbon coating copper after drying Drive body powder.
(10) carbonizing reduction
Carbon coating copper precursor powder is placed in quartz boat, is subsequently placed in the quartz heating-pipe of tube type high-temperature furnace, and Nitrogen is inputted, nitrogen input speed 20mL/min, the heating heating of tube type high-temperature furnace is opened, 10 DEG C/min of heating rate, heats 500 DEG C of temperature, constant temperature keep 2h, make product carbonizing reduction.Carbon coating copper precursor powder is carbonized under high temperature, nitrogen atmosphere, Cu inside carbon ballⅡIt is reduced into Cu0, oleic acid complex compound decomposes at high temperature, hollow structure is formed, into carbon ball coated.Treat After the completion of reaction, stop heating, naturally cool to room temperature with stove under nitrogen protection, produce hud typed carbon-coated nano copper catalysis Agent I.Catalyst composition is copper 14.3wt%, carbon 85.7wt%.
(11) catalysis methanol oxidative carbonylation Synthesis of dimethyl carbonate reacts
1. weighing catalyst 0.3g, quartz sand 2.1g, it is fitted into after both are well mixed in fixed-bed tube reactor, and It is passed through N2, N2Flow is 20mL/min.The heating heating of preheating furnace and reacting furnace is opened, preheating furnace is heated to 130 DEG C, reaction Reaction bed temperature in device is heated to 140 DEG C.
2. close N2, it is passed through CO, O2And methanol.CO and O2Inputted by mass flowmenter, CO flows are 40mL/min, O2Stream Measure as 5mL/min；Methanol is inputted by the type micro-sampling pumps of Series III, methanol flow 0.05mL/min, is gasified in preheating furnace And with CO and O2It is sufficiently mixed, subsequently into reactor.It is 29200h to feed gaseous phase volume air speed-1。
3. reacting and being 140 DEG C in temperature and pressure is to carry out under conditions of normal pressure, the product come out from reactor is condensed Reclaimed after device condensation.
Comparative example 2
The catalysis methanol oxidative carbonylation Synthesis of dimethyl carbonate of core-shell-type carbon-coated nano-copper catalyst II reacts specific Step：
(1) solution is prepared
Copper acetate 8g is weighed, measures absolute ethyl alcohol 40mL, formaldehyde 3mL, is added in rustless steel container, on magnetic stirring apparatus 4h is stirred, into mixed solution.
(2) solvent-thermal process
The rustless steel container for filling mixed solution is placed in reactor, it is closed, reactor is then placed in resistance heating In stove, 10 DEG C/min of heating rate, 400 DEG C, heat time 8h of heating-up temperature, solvent-thermal process is carried out.When temperature rises to 100 DEG C When, copper acetate dehydration；When temperature rises to 300 DEG C, under absolute ethyl alcohol subsidiary conditions, copper acetate thermal decomposition, Cu is generated2O；When When temperature rises to 300~400 DEG C, Cu2O under formaldehyde effect in-situ reducing into Cu；Organic precursor carbonization generation carbon, is deposited on Copper nano-particle surface, form hud typed carbon-coated nano copper.After solvent-thermal process, stop heating, make reactor furnace cooling To room temperature.
(3) centrifuge
Kettle is driven, the mixed solution in rustless steel container is moved into centrifuge tube, is centrifuged, separation revolution 8000r/ Min, disengaging time 10min, sediment, abandoning supernatant are retained after separation.
(4) wash, centrifuge
Put the precipitate in beaker, add deionized water 100mL, agitator treating 5min, then by cleaning solution move into from In heart pipe, it is centrifuged, separates revolution 8000r/min, disengaging time 10min, sediment, supernatant discarding are retained after separation Liquid.Washing, centrifugation repeat 3 times.
(5) aqueous hydrochloric acid solution is prepared
Hydrochloric acid 25mL, deionized water 50mL are measured, is added in beaker, 5min is stirred, into 6mol/L aqueous hydrochloric acid solution.
(6) salt acid etch
Sediment after washing, centrifuging is added in aqueous hydrochloric acid solution, stirs 5min, into mixed solution, then will Mixed solution is placed in ultrasonic 3min in ultrasound reactor, supersonic frequency 40kHz.During ultrasonic disperse, salt acid etch carbon The copper in nanometer copper particle is coated, obtains the hud typed carbon-coated nano copper particle mixed liquor of cavity structure.
(7) centrifuge
Hud typed carbon-coated nano copper particle mixed liquor is moved into centrifuge tube, is centrifuged, separates revolution 8000r/min, disengaging time 10min, sediment, abandoning supernatant are retained after separation.
(8) wash, centrifuge
Put the precipitate in beaker, add deionized water 100mL, agitator treating 5min, then by cleaning solution move into from In heart pipe, it is centrifuged, separates revolution 8000r/min, disengaging time 10min, sediment, supernatant discarding are retained after separation Liquid.Washing, centrifugation repeat 3 times.
(9) dry
Sediment after washing, centrifuging is placed in baking oven and dried, 60 DEG C, drying time 6h of drying temperature, is dried After produce core-shell-type carbon-coated nano-copper catalyst II.Catalyst composition is copper 17.7wt%, carbon 82.3wt%
(10) catalysis methanol oxidative carbonylation Synthesis of dimethyl carbonate reacts
1. weighing catalyst 0.3g, quartz sand 2.1g, it is fitted into after both are well mixed in fixed-bed tube reactor, and It is passed through N2, N2Flow is 20mL/min.The heating heating of preheating furnace and reacting furnace is opened, preheating furnace is heated to 130 DEG C, reaction Reaction bed temperature in device is heated to 140 DEG C.
2. close N2, it is passed through CO, O2And methanol.CO and O2Inputted by mass flowmenter, CO flows are 40mL/min, O2Stream Measure as 5mL/min；Methanol is inputted by the type micro-sampling pumps of Series III, methanol flow 0.05mL/min, is gasified in preheating furnace And with CO and O2It is sufficiently mixed, subsequently into reactor.It is 29200h to feed gaseous phase volume air speed-1。
3. reacting and being 140 DEG C in temperature and pressure is to carry out under conditions of normal pressure, the product come out from reactor is condensed Reclaimed after device condensation.
Embodiment 1
(1) solid sol-gel agent is prepared
1. measuring absolute ethyl alcohol 80mL, deionized water 16mL, ammoniacal liquor 2.15mL (25wt%), add in beaker, then put In the water-bath with magnetic agitation, 5min is stirred at 25 DEG C.
2. measuring tetraethyl orthosilicate 3.1mL, add in above-mentioned beaker, continue to stir 6h at 25 DEG C, form colloidal sol, be Solid sol-gel agent.
(2) hollow mesoporous lamella carbon ball is prepared
1. prepare the CTAC aqueous solution：Weigh CTAC2.319g to add in beaker, add deionized water 4.638g, stir 10min, into the CTAC aqueous solution.
2. measuring absolute ethyl alcohol 52mL, deionized water 208mL, add in solid silicon ball colloidal sol, stirred at 25 DEG C 10min, into mixed solution.
3. making mixed solution keep being stirred vigorously state, the CTAC aqueous solution is then added dropwise, after addition, at 25 DEG C Lower stirring 30min.
4. weighing resorcinol 0.93g adds mixed solution, continue to stir 30min at 25 DEG C.
5. measuring formaldehyde 1.26mL (37wt%), tetraethyl orthosilicate 3.75mL, while mixed solution is added, stirred at 25 DEG C Mix 10h.
6. mixed solution is transferred in polytetrafluoroethylcontainer container, it is placed in reactor, it is closed, then reactor is put Heated in baking oven, 100 DEG C, heat time 18h of heating-up temperature, carry out Hydrothermal Synthesiss, form carbon silicon polymer microballoon presoma. After Hydrothermal Synthesiss, baking oven is closed, reactor is taken out, reactor is naturally cooled to room temperature in atmosphere.
7. driving kettle, the suspension in polytetrafluoroethylcontainer container is moved into centrifuge tube, is centrifuged, separate rotating speed 8000r/min, disengaging time 2min, sediment, abandoning supernatant are retained after separation.
8. putting the precipitate in beaker, deionized water 200mL is added, agitator treating 5min, is then moved into cleaning solution In centrifuge tube, it is centrifuged, separates rotating speed 8000r/min, disengaging time 2min, retain sediment after separation, discard Clear liquid.Washing, centrifugation repeat 2 times.
Dried 9. putting the precipitate in baking oven, 40 DEG C, drying time 24h of drying temperature, before obtaining carbon silicon polymer microballoon Drive body powder.
10. precursor powder is placed in quartz boat, it is subsequently placed in the quartz heating-pipe of tube type high-temperature furnace, and inputs nitrogen Gas, nitrogen input speed 20mL/ (gcat·min).Open the heating heating of tube type high-temperature furnace, 4 DEG C/min of heating rate, heating 700 DEG C of temperature, constant temperature keep 3h, presoma is carbonized under high temperature, nitrogen atmosphere, generate carbon silicon polymer microballoon.Question response After the completion of, stop heating, product is naturally cooled to room temperature with stove under nitrogen protection.
Configure hydrofluoric acid aqueous solution：Measure deionized water 150mL to add in plastic beaker, then measure hydrofluoric acid 22.4mL (40wt%) is added thereto, and then side adds deionization waterside to stir, and is settled to 200mL, the hydrofluoric acid into 5wt% is water-soluble Liquid.
Carbon silicon polymer microsphere powder is added in above-mentioned hydrofluoric acid aqueous solution, 24h is stood, to remove titanium dioxide Silicon.
The supernatant in beaker is outwelled, deionized water 200mL is added, agitator treating 5min, then moves into cleaning solution In centrifuge tube, it is centrifuged, separates rotating speed 8000r/min, disengaging time 2min, retain sediment after separation, discard Clear liquid.Washing, centrifugation repeat 2 times.
Sediment after washing, centrifuging is placed in baking oven and dried, 70 DEG C, drying time 14h of drying temperature, Hollow mesoporous lamella carbon ball is produced after drying.
(3) hollow mesoporous carbosphere shell confinement copper catalyst is prepared
1. weigh Cu (NO3)2·3H2O 0.085g, deionized water 2mL is measured, added in beaker, into nitre after stirring 5min Sour copper liquor.
2. weighing hollow mesoporous lamella carbon ball 0.3g, it is added in above-mentioned solution, stirs 10 minutes, be subsequently placed in ultrasonic wave Ultrasonic 50min in reactor, ultrasonic frequency 80KHz.
Dried 3. the mixture after supersound process is placed in baking oven, 30 DEG C, drying time 24h of drying temperature, after drying Produce hollow mesoporous carbosphere shell confinement copper catalyst precursor body.
4. dried precursor powder is placed in quartz boat, it is subsequently placed in the quartz heating-pipe of tube type high-temperature furnace, And nitrogen is inputted, nitrogen input speed 20mL/ (gcat·min).The heating for opening tube type high-temperature furnace is heated, and 2 DEG C of heating rate/ Min, 300 DEG C of heating-up temperature, constant temperature keep 3h, the copper species in presoma is occurred under high temperature, nitrogen atmosphere with carbon carrier Reaction, by CuⅡIt is reduced to CuⅠ.After the completion of question response, stop heating, product is naturally cooled to room with stove under nitrogen protection Temperature, produce hollow mesoporous carbosphere shell confinement copper catalyst.Catalyst composition is copper 7.0wt%, carbon 93.0wt%；Compare surface Product is 720m2/ g, pore volume 2.1cm3/ g, shell most probable pore size are 3.5nm；Carbon ball average cavity size is 160nm, shell Average thickness is 60nm, average grain diameter 280nm.
(4) catalysis methanol oxidative carbonylation Synthesis of dimethyl carbonate reacts
1. weighing catalyst 0.15g, quartz sand 0.75g, it is fitted into after both are well mixed in fixed-bed tube reactor, And it is passed through N2, N2Flow is 20mL/min.The heating heating of preheating furnace and reacting furnace is opened, preheating furnace is heated to 110 DEG C, instead The reaction bed temperature in device is answered to be heated to 120 DEG C.
2. close N2, it is passed through CO, O2And methanol.CO and O2Inputted by mass flowmenter, CO flows are 6mL/min, O2Flow For 1mL/min；Methanol is inputted by the type micro-sampling pumps of Series III, methanol flow 0.01mL/min, in preheating furnace gasification simultaneously With CO and O2It is sufficiently mixed, subsequently into reactor.It is 5840h to feed gaseous phase volume air speed-1。
3. reacting and being 120 DEG C in temperature and pressure is to carry out under conditions of normal pressure, the product come out from reactor is condensed Reclaimed after device condensation.
Embodiment 2
(1) solid sol-gel agent is prepared
1. measuring absolute ethyl alcohol 90mL, deionized water 18mL, ammoniacal liquor 2.22mL (25wt%), add in beaker, then put In the water-bath with magnetic agitation, 10min is stirred at 25 DEG C.
2. measuring tetraethyl orthosilicate 3.6mL, add in above-mentioned beaker, continue to stir 7h at 25 DEG C, form colloidal sol, be Solid sol-gel agent.
(2) hollow mesoporous lamella carbon ball is prepared
1. prepare the CTAC aqueous solution：Weigh CTAC4.638g to add in beaker, add deionized water 13.914g, stir 15min, into the CTAC aqueous solution.
2. measuring absolute ethyl alcohol 55mL, deionized water 275mL, add in solid silicon ball colloidal sol, stirred at 25 DEG C 15min, into mixed solution.
3. making mixed solution keep being stirred vigorously state, the CTAC aqueous solution is then added dropwise, after addition, at 25 DEG C Lower stirring 30min.
4. weighing resorcinol 1.86g adds mixed solution, continue to stir 30min at 25 DEG C.
5. measuring formaldehyde 2.52mL (37wt%), tetraethyl orthosilicate 7.50mL, while mixed solution is added, stirred at 28 DEG C Mix 11h.
6. mixed solution is transferred in polytetrafluoroethylcontainer container, it is placed in reactor, it is closed, then reactor is put Heated in baking oven, 100 DEG C, heat time 24h of heating-up temperature, carry out Hydrothermal Synthesiss, form carbon silicon polymer microballoon presoma. After Hydrothermal Synthesiss, baking oven is closed, reactor is taken out, reactor is naturally cooled to room temperature in atmosphere.
7. driving kettle, the suspension in polytetrafluoroethylcontainer container is moved into centrifuge tube, is centrifuged, separate rotating speed 8000r/min, disengaging time 2min, sediment, abandoning supernatant are retained after separation.
8. putting the precipitate in beaker, deionized water 200mL is added, agitator treating 5min, is then moved into cleaning solution In centrifuge tube, it is centrifuged, separates rotating speed 8000r/min, disengaging time 2min, retain sediment after separation, discard Clear liquid.Washing, centrifugation repeat 3 times.
Dried 9. putting the precipitate in baking oven, 50 DEG C, drying time 20h of drying temperature, before obtaining carbon silicon polymer microballoon Drive body powder.
10. precursor powder is placed in quartz boat, it is subsequently placed in the quartz heating-pipe of tube type high-temperature furnace, and inputs nitrogen Gas, nitrogen input speed 25mL/ (gcat·min).Open the heating heating of tube type high-temperature furnace, 5 DEG C/min of heating rate, heating 750 DEG C of temperature, constant temperature keep 4h, presoma is carbonized under high temperature, nitrogen atmosphere, generate carbon silicon polymer microballoon.Question response After the completion of, stop heating, product is naturally cooled to room temperature with stove under nitrogen protection.
Configure hydrofluoric acid aqueous solution：Measure deionized water 150mL to add in plastic beaker, then measure hydrofluoric acid 35.8mL (40wt%) is added thereto, and then side adds deionization waterside to stir, and is settled to 200mL, the hydrofluoric acid into 8wt% is water-soluble Liquid.
Carbon silicon polymer microsphere powder is added in above-mentioned hydrofluoric acid aqueous solution, 20h is stood, to remove titanium dioxide Silicon.
The supernatant in beaker is outwelled, deionized water 200mL is added, agitator treating 5min, then moves into cleaning solution In centrifuge tube, it is centrifuged, separates rotating speed 8000r/min, disengaging time 2min, retain sediment after separation, discard Clear liquid.Washing, centrifugation repeat 3 times.
Sediment after washing, centrifuging is placed in baking oven and dried, 80 DEG C, drying time 12h of drying temperature, Hollow mesoporous lamella carbon ball is produced after drying.
(3) hollow mesoporous carbosphere shell confinement copper catalyst is prepared
1. weigh Cu (NO3)2·3H2O 0.118g, deionized water 2mL is measured, added in beaker, into nitre after stirring 5min Sour copper liquor.
2. weighing hollow mesoporous lamella carbon ball 0.3g, it is added in above-mentioned solution, stirs 10 minutes, be subsequently placed in ultrasonic wave Ultrasonic 60min in reactor, ultrasonic frequency 90KHz.
Dried 3. the mixture after supersound process is placed in baking oven, 40 DEG C, drying time 20h of drying temperature, after drying Produce hollow mesoporous carbosphere shell confinement copper catalyst precursor body.
4. dried precursor powder is placed in quartz boat, it is subsequently placed in the quartz heating-pipe of tube type high-temperature furnace, And nitrogen is inputted, nitrogen input speed 25mL/ (gcat·min).The heating for opening tube type high-temperature furnace is heated, and 3 DEG C of heating rate/ Min, 350 DEG C of heating-up temperature, constant temperature keep 4h, the copper species in presoma is occurred under high temperature, nitrogen atmosphere with carbon carrier Reaction, by CuⅡIt is reduced to CuⅠ.After the completion of question response, stop heating, product is naturally cooled to room with stove under nitrogen protection Temperature, produce hollow mesoporous carbosphere shell confinement copper catalyst.Catalyst composition is copper 9.7wt%, carbon 90.3wt%；Compare surface Product is 980m2/ g, pore volume 2.2cm3/ g, shell most probable pore size are 3.5nm；Carbon ball average cavity size is 180nm, shell Average thickness is 120nm, average grain diameter 420nm.
(4) catalysis methanol oxidative carbonylation Synthesis of dimethyl carbonate reacts
1. weighing catalyst 0.22g, quartz sand 1.76g, it is fitted into after both are well mixed in fixed-bed tube reactor, And it is passed through N2, N2Flow is 20mL/min.The heating heating of preheating furnace and reacting furnace is opened, preheating furnace is heated to 120 DEG C, instead The reaction bed temperature in device is answered to be heated to 130 DEG C.
2. close N2, it is passed through CO, O2And methanol.CO and O2Inputted by mass flowmenter, CO flows are 12mL/min, O2Stream Measure as 2mL/min；Methanol is inputted by the type micro-sampling pumps of Series III, methanol flow 0.02mL/min, is gasified in preheating furnace And with CO and O2It is sufficiently mixed, subsequently into reactor.It is 11680h to feed gaseous phase volume air speed-1。
Carried out 3. reacting under conditions of temperature is 130 DEG C and pressure is 1.0MPa, the product come out from reactor is through cold Reclaimed after condenser condensation.
Embodiment 3
(1) solid sol-gel agent is prepared
1. measuring absolute ethyl alcohol 100mL, deionized water 20mL, ammoniacal liquor 2.30mL (25wt%), add in beaker, then put In the water-bath with magnetic agitation, 5min is stirred at 25 DEG C.
2. measuring tetraethyl orthosilicate 4.0mL, add in above-mentioned beaker, continue to stir 8h at 25 DEG C, form colloidal sol, be Solid sol-gel agent.
(2) hollow mesoporous lamella carbon ball is prepared
1. prepare the CTAC aqueous solution：Weigh CTAC6.957g to add in beaker, add deionized water 27.828g, stir 20min, into the CTAC aqueous solution.
2. measuring absolute ethyl alcohol 58mL, deionized water 348mL, add in solid silicon ball colloidal sol, stirred at 25 DEG C 20min, into mixed solution.
3. making mixed solution keep being stirred vigorously state, the CTAC aqueous solution is then added dropwise, after addition, at 25 DEG C Lower stirring 30min.
4. weighing resorcinol 2.79g adds mixed solution, continue to stir 30min at 25 DEG C.
5. measuring formaldehyde 3.78mL (37wt%), tetraethyl orthosilicate 11.25mL, while mixed solution is added, at 30 DEG C Stir 12h.
6. mixed solution is transferred in polytetrafluoroethylcontainer container, it is placed in reactor, it is closed, then reactor is put Heated in baking oven, 100 DEG C, heat time 30h of heating-up temperature, carry out Hydrothermal Synthesiss, form carbon silicon polymer microballoon presoma. After Hydrothermal Synthesiss, baking oven is closed, reactor is taken out, reactor is naturally cooled to room temperature in atmosphere.
7. driving kettle, the suspension in polytetrafluoroethylcontainer container is moved into centrifuge tube, is centrifuged, separate rotating speed 8000r/min, disengaging time 2min, sediment, abandoning supernatant are retained after separation.
8. putting the precipitate in beaker, deionized water 200mL is added, agitator treating 5min, is then moved into cleaning solution In centrifuge tube, it is centrifuged, separates rotating speed 8000r/min, disengaging time 2min, retain sediment after separation, discard Clear liquid.Washing, centrifugation repeat 4 times.
Dried 9. putting the precipitate in baking oven, 60 DEG C, drying time 18h of drying temperature, before obtaining carbon silicon polymer microballoon Drive body powder.
10. precursor powder is placed in quartz boat, it is subsequently placed in the quartz heating-pipe of tube type high-temperature furnace, and inputs nitrogen Gas, nitrogen input speed 30mL/ (gcat·min).Open the heating heating of tube type high-temperature furnace, 6 DEG C/min of heating rate, heating 800 DEG C of temperature, constant temperature keep 5h, presoma is carbonized under high temperature, nitrogen atmosphere, generate carbon silicon polymer microballoon.Question response After the completion of, stop heating, product is naturally cooled to room temperature with stove under nitrogen protection.
Configure hydrofluoric acid aqueous solution：Measure deionized water 150mL to add in plastic beaker, then measure hydrofluoric acid 44.7mL (40wt%) is added thereto, and then side adds deionization waterside to stir, and 200mL is settled to, into 10wt% hydrofluoric acid water Solution.
Carbon silicon polymer microsphere powder is added in above-mentioned hydrofluoric acid aqueous solution, 18h is stood, to remove titanium dioxide Silicon.
The supernatant in beaker is outwelled, deionized water 200mL is added, agitator treating 5min, then moves into cleaning solution In centrifuge tube, it is centrifuged, separates rotating speed 8000r/min, disengaging time 2min, retain sediment after separation, discard Clear liquid.Washing, centrifugation repeat 4 times.
Sediment after washing, centrifuging is placed in baking oven and dried, 90 DEG C, drying time 10h of drying temperature, Hollow mesoporous lamella carbon ball is produced after drying.
(3) hollow mesoporous carbosphere shell confinement copper catalyst is prepared
1. weigh Cu (NO3)2·3H2O 0.150g, deionized water 2mL is measured, added in beaker, into nitre after stirring 5min Sour copper liquor.
2. weighing hollow mesoporous lamella carbon ball 0.3g, it is added in above-mentioned solution, stirs 10 minutes, be subsequently placed in ultrasonic wave Ultrasonic 70min in reactor, ultrasonic frequency 100KHz.
Dried 3. the mixture after supersound process is placed in baking oven, 50 DEG C, drying time 18h of drying temperature, after drying Produce hollow mesoporous carbosphere shell confinement copper catalyst precursor body.
4. dried precursor powder is placed in quartz boat, it is subsequently placed in the quartz heating-pipe of tube type high-temperature furnace, And nitrogen is inputted, nitrogen input speed 30mL/ (gcat·min).The heating for opening tube type high-temperature furnace is heated, and 4 DEG C of heating rate/ Min, 400 DEG C of heating-up temperature, constant temperature keep 5h, the copper species in presoma is occurred under high temperature, nitrogen atmosphere with carbon carrier Reaction, by CuⅡIt is reduced to CuⅠ.After the completion of question response, stop heating, product is naturally cooled to room with stove under nitrogen protection Temperature, produce hollow mesoporous carbosphere shell confinement copper catalyst.Catalyst composition is copper 11.5wt%, carbon 88.5wt%；Compare table Area is 1240m2/ g, pore volume 2.3cm3/ g, shell most probable pore size are 3.5nm；Carbon ball average cavity size is 200nm, shell Layer average thickness is 180nm, average grain diameter 560nm.
(4) catalysis methanol oxidative carbonylation Synthesis of dimethyl carbonate reacts
1. weighing catalyst 0.30g, quartz sand 3.00g, it is fitted into after both are well mixed in fixed-bed tube reactor, And it is passed through N2, N2Flow is 20mL/min.The heating heating of preheating furnace and reacting furnace is opened, preheating furnace is heated to 130 DEG C, instead The reaction bed temperature in device is answered to be heated to 140 DEG C.
2. close N2, it is passed through CO, O2And methanol.CO and O2Inputted by mass flowmenter, CO flows are 18mL/min, O2Stream Measure as 3mL/min；Methanol is inputted by the type micro-sampling pumps of Series III, methanol flow 0.03mL/min, is gasified in preheating furnace And with CO and O2It is sufficiently mixed, subsequently into reactor.It is 17520h to feed gaseous phase volume air speed-1。
Carried out 3. reacting under conditions of temperature is 140 DEG C and pressure is 0.5MPa, the product come out from reactor is through cold Reclaimed after condenser condensation.
Embodiment 4
(1) solid sol-gel agent is prepared
1. measuring absolute ethyl alcohol 85mL, deionized water 17mL, ammoniacal liquor 2.18mL (25wt%), add in beaker, then put In the water-bath with magnetic agitation, 8min is stirred at 25 DEG C.
2. measuring tetraethyl orthosilicate 3.3mL, add in above-mentioned beaker, continue to stir 6h at 25 DEG C, form colloidal sol, be Solid sol-gel agent.
(2) hollow mesoporous lamella carbon ball is prepared
1. prepare the CTAC aqueous solution：Weigh CTAC3.478g to add in beaker, add deionized water 8.695g, stir 10min, into the CTAC aqueous solution.
2. measuring absolute ethyl alcohol 53mL, deionized water 238mL, add in solid silicon ball colloidal sol, stirred at 25 DEG C 10min, into mixed solution.
3. making mixed solution keep being stirred vigorously state, the CTAC aqueous solution is then added dropwise, after addition, at 25 DEG C Lower stirring 30min.
4. weighing resorcinol 1.39g adds mixed solution, continue to stir 30min at 25 DEG C.
5. measuring formaldehyde 1.89mL (37wt%), tetraethyl orthosilicate 5.62mL, while mixed solution is added, stirred at 26 DEG C Mix 10h.
6. mixed solution is transferred in polytetrafluoroethylcontainer container, it is placed in reactor, it is closed, then reactor is put Heated in baking oven, 150 DEG C, heat time 21h of heating-up temperature, carry out Hydrothermal Synthesiss, form carbon silicon polymer microballoon presoma. After Hydrothermal Synthesiss, baking oven is closed, reactor is taken out, reactor is naturally cooled to room temperature in atmosphere.
7. driving kettle, the suspension in polytetrafluoroethylcontainer container is moved into centrifuge tube, is centrifuged, separate rotating speed 8000r/min, disengaging time 2min, sediment, abandoning supernatant are retained after separation.
8. putting the precipitate in beaker, deionized water 200mL is added, agitator treating 5min, is then moved into cleaning solution In centrifuge tube, it is centrifuged, separates rotating speed 8000r/min, disengaging time 2min, retain sediment after separation, discard Clear liquid.Washing, centrifugation repeat 5 times.
Dried 9. putting the precipitate in baking oven, 45 DEG C, drying time 22h of drying temperature, before obtaining carbon silicon polymer microballoon Drive body powder.
10. precursor powder is placed in quartz boat, it is subsequently placed in the quartz heating-pipe of tube type high-temperature furnace, and inputs nitrogen Gas, nitrogen input speed 22mL/ (gcat·min).Open the heating heating of tube type high-temperature furnace, 4 DEG C/min of heating rate, heating 720 DEG C of temperature, constant temperature keep 3.5h, presoma is carbonized under high temperature, nitrogen atmosphere, generate carbon silicon polymer microballoon.Treat anti- After the completion of answering, stop heating, product is naturally cooled to room temperature with stove under nitrogen protection.
Configure hydrofluoric acid aqueous solution：Measure deionized water 150mL to add in plastic beaker, then measure hydrofluoric acid 26.9mL (40wt%) is added thereto, and then side adds deionization waterside to stir, and is settled to 200mL, the hydrofluoric acid into 6wt% is water-soluble Liquid.
Carbon silicon polymer microsphere powder is added in above-mentioned hydrofluoric acid aqueous solution, 22h is stood, to remove titanium dioxide Silicon.
The supernatant in beaker is outwelled, deionized water 200mL is added, agitator treating 5min, then moves into cleaning solution In centrifuge tube, it is centrifuged, separates rotating speed 8000r/min, disengaging time 2min, retain sediment after separation, discard Clear liquid.Washing, centrifugation repeat 5 times.
Sediment after washing, centrifuging is placed in baking oven and dried, 75 DEG C, drying time 13h of drying temperature, Hollow mesoporous lamella carbon ball is produced after drying.
(3) hollow mesoporous carbosphere shell confinement copper catalyst is prepared
1. weigh Cu (NO3)2·3H2O 0.102g, deionized water 2mL is measured, added in beaker, into nitre after stirring 5min Sour copper liquor.
2. weighing hollow mesoporous lamella carbon ball 0.3g, it is added in above-mentioned solution, stirs 10 minutes, be subsequently placed in ultrasonic wave Ultrasonic 55min in reactor, ultrasonic frequency 85KHz.
Dried 3. the mixture after supersound process is placed in baking oven, 35 DEG C, drying time 22h of drying temperature, after drying Produce hollow mesoporous carbosphere shell confinement copper catalyst precursor body.
4. dried precursor powder is placed in quartz boat, it is subsequently placed in the quartz heating-pipe of tube type high-temperature furnace, And nitrogen is inputted, nitrogen input speed 22mL/ (gcat·min).The heating for opening tube type high-temperature furnace is heated, and 2 DEG C of heating rate/ Min, 320 DEG C of heating-up temperature, constant temperature keep 3.5h, the copper species in presoma is sent out under high temperature, nitrogen atmosphere with carbon carrier Raw reaction, by CuⅡIt is reduced to CuⅠ.After the completion of question response, stop heating, product is naturally cooled under nitrogen protection with stove Room temperature, produce hollow mesoporous carbosphere shell confinement copper catalyst.Catalyst composition is copper 8.3wt%, carbon 91.7wt%；Compare table Area is 660m2/ g, pore volume 1.9cm3/ g, shell most probable pore size are 5.9nm；Carbon ball average cavity size is 170nm, shell Layer average thickness is 90nm, average grain diameter 350nm.
(4) catalysis methanol oxidative carbonylation Synthesis of dimethyl carbonate reacts
1. weighing catalyst 0.18g, quartz sand 1.08g, it is fitted into after both are well mixed in fixed-bed tube reactor, And it is passed through N2, N2Flow is 20mL/min.The heating heating of preheating furnace and reacting furnace is opened, preheating furnace is heated to 115 DEG C, instead The reaction bed temperature in device is answered to be heated to 125 DEG C.
2. close N2, it is passed through CO, O2And methanol.CO and O2Inputted by mass flowmenter, CO flows are 9mL/min, O2Flow For 1.5mL/min；Methanol is inputted by the type micro-sampling pumps of Series III, methanol flow 0.02mL/min, is gasified in preheating furnace And with CO and O2It is sufficiently mixed, subsequently into reactor.It is 8760h to feed gaseous phase volume air speed-1。
Carried out 3. reacting under conditions of temperature is 125 DEG C and pressure is 0.7MPa, the product come out from reactor is through cold Reclaimed after condenser condensation.
Embodiment 5
(1) solid sol-gel agent is prepared
1. measuring absolute ethyl alcohol 95mL, deionized water 19mL, ammoniacal liquor 2.26mL (25wt%), add in beaker, then put In the water-bath with magnetic agitation, 5min is stirred at 25 DEG C.
2. measuring tetraethyl orthosilicate 3.8mL, add in above-mentioned beaker, continue to stir 7.5h at 25 DEG C, form colloidal sol, i.e., For solid sol-gel agent.
(2) hollow mesoporous lamella carbon ball is prepared
1. prepare the CTAC aqueous solution：Weigh CTAC5.797g to add in beaker, add deionized water 20.289g, stir 15min, into the CTAC aqueous solution.
2. measuring absolute ethyl alcohol 56mL, deionized water 308mL, add in solid silicon ball colloidal sol, stirred at 25 DEG C 10min, into mixed solution.
3. making mixed solution keep being stirred vigorously state, the CTAC aqueous solution is then added dropwise, after addition, at 25 DEG C Lower stirring 30min.
4. weighing resorcinol 2.32g adds mixed solution, continue to stir 30min at 25 DEG C.
5. measuring formaldehyde 3.15mL (37wt%), tetraethyl orthosilicate 9.37mL, while mixed solution is added, stirred at 29 DEG C Mix 12h.
6. mixed solution is transferred in polytetrafluoroethylcontainer container, it is placed in reactor, it is closed, then reactor is put Heated in baking oven, 200 DEG C, heat time 27h of heating-up temperature, carry out Hydrothermal Synthesiss, form carbon silicon polymer microballoon presoma. After Hydrothermal Synthesiss, baking oven is closed, reactor is taken out, reactor is naturally cooled to room temperature in atmosphere.
7. driving kettle, the suspension in polytetrafluoroethylcontainer container is moved into centrifuge tube, is centrifuged, separate rotating speed 8000r/min, disengaging time 2min, sediment, abandoning supernatant are retained after separation.
8. putting the precipitate in beaker, deionized water 200mL is added, agitator treating 5min, is then moved into cleaning solution In centrifuge tube, it is centrifuged, separates rotating speed 8000r/min, disengaging time 2min, retain sediment after separation, discard Clear liquid.Washing, centrifugation repeat 3 times.
Dried 9. putting the precipitate in baking oven, 55 DEG C, drying time 19h of drying temperature, before obtaining carbon silicon polymer microballoon Drive body powder.
10. precursor powder is placed in quartz boat, it is subsequently placed in the quartz heating-pipe of tube type high-temperature furnace, and inputs nitrogen Gas, nitrogen input speed 28mL/ (gcat·min).Open the heating heating of tube type high-temperature furnace, 6 DEG C/min of heating rate, heating 780 DEG C of temperature, constant temperature keep 4.5h, presoma is carbonized under high temperature, nitrogen atmosphere, generate carbon silicon polymer microballoon.Treat anti- After the completion of answering, stop heating, product is naturally cooled to room temperature with stove under nitrogen protection.
Configure hydrofluoric acid aqueous solution：Measure deionized water 150mL to add in plastic beaker, then measure hydrofluoric acid 40.2mL (40wt%) is added thereto, and then side adds deionization waterside to stir, and is settled to 200mL, the hydrofluoric acid into 9wt% is water-soluble Liquid.
Carbon silicon polymer microsphere powder is added in above-mentioned hydrofluoric acid aqueous solution, 19h is stood, to remove titanium dioxide Silicon.
The supernatant in beaker is outwelled, deionized water 200mL is added, agitator treating 5min, then moves into cleaning solution In centrifuge tube, it is centrifuged, separates rotating speed 8000r/min, disengaging time 2min, retain sediment after separation, discard Clear liquid.Washing, centrifugation repeat 3 times.
Sediment after washing, centrifuging is placed in baking oven and dried, 85 DEG C, drying time 11h of drying temperature, Hollow mesoporous lamella carbon ball is produced after drying.
(3) hollow mesoporous carbosphere shell confinement copper catalyst is prepared
1. weigh Cu (NO3)2·3H2O 0.134g, deionized water 2mL is measured, added in beaker, into nitre after stirring 5min Sour copper liquor.
2. weighing hollow mesoporous lamella carbon ball 0.3g, it is added in above-mentioned solution, stirs 10 minutes, be subsequently placed in ultrasonic wave Ultrasonic 65min in reactor, ultrasonic frequency 95KHz.
Dried 3. the mixture after supersound process is placed in baking oven, 45 DEG C, drying time 19h of drying temperature, after drying Produce hollow mesoporous carbosphere shell confinement copper catalyst precursor body.
4. dried precursor powder is placed in quartz boat, it is subsequently placed in the quartz heating-pipe of tube type high-temperature furnace, And nitrogen is inputted, nitrogen input speed 28mL/ (gcat·min).The heating for opening tube type high-temperature furnace is heated, and 4 DEG C of heating rate/ Min, 380 DEG C of heating-up temperature, constant temperature keep 4.5h, the copper species in presoma is sent out under high temperature, nitrogen atmosphere with carbon carrier Raw reaction, by CuⅡIt is reduced to CuⅠ.After the completion of question response, stop heating, product is naturally cooled under nitrogen protection with stove Room temperature, produce hollow mesoporous carbosphere shell confinement copper catalyst.Catalyst composition is copper 10.6wt%, carbon 89.4wt%；Than Surface area is 480m2/ g, pore volume 1.7cm3/ g, shell most probable pore size are 8.5nm；Carbon ball average cavity size is 190nm, Shell average thickness is 150nm, average grain diameter 490nm.
(4) catalysis methanol oxidative carbonylation Synthesis of dimethyl carbonate reacts
1. weighing catalyst 0.26g, quartz sand 2.34g, it is fitted into after both are well mixed in fixed-bed tube reactor, And it is passed through N2, N2Flow is 20mL/min.The heating heating of preheating furnace and reacting furnace is opened, preheating furnace is heated to 125 DEG C, instead The reaction bed temperature in device is answered to be heated to 135 DEG C.
2. close N2, it is passed through CO, O2And methanol.CO and O2Inputted by mass flowmenter, CO flows are 15mL/min, O2Stream Measure as 2.5mL/min；Methanol is inputted by the type micro-sampling pumps of Series III, methanol flow 0.02mL/min, in preheating furnace gas Change and with CO and O2It is sufficiently mixed, subsequently into reactor.It is 14600h to feed gaseous phase volume air speed-1。
Carried out 3. reacting under conditions of temperature is 135 DEG C and pressure is 0.3MPa, the product come out from reactor is through cold Reclaimed after condenser condensation.
Using methanol conversion, methanol to DMC selectivity and DMC space-time yields as index, the gained reactivity worth such as institute of table 1 Show：
Table 1
The invention is not restricted to embodiment of above, present patent application personnel can be variously modified and become according to the present invention Shape, without departing from the spirit of the present invention, the scope of the present invention all should be belonged to.

Claims (3)

1. a kind of hollow mesoporous carbosphere shell confinement copper catalyst, it is characterised in that catalyst is by the hollow mesoporous lamella of carrier Carbon ball and active ingredient copper composition, in terms of metal, 7.0~11.5wt% of copper, 88.5~93.0wt% of carbon；Specific surface area be 480~ 1240 m2/ g, pore volume are 1.7~2.3 cm3/ g, shell most probable pore size are 3.5~8.5nm；Carbon ball average cavity size is 160~200nm, shell average thickness are 60~180nm, and average grain diameter is 280~560nm.
2. a kind of preparation method of hollow mesoporous carbosphere shell confinement copper catalyst as claimed in claim 1, its feature exist In comprising the following steps：
（1）Absolute ethyl alcohol, deionized water, the ammoniacal liquor that concentration is 25wt% are stirred into 5~10min at 25~30 DEG C, added just Silester, continue 6~8h of stirring, form solid sol-gel agent；Wherein absolute ethyl alcohol：Deionized water：Ammoniacal liquor：Positive silicic acid second The volume ratio of ester is 80~100：16~20：2.1~2.3：3~4；
（2）Be to add deionized water at 2~4: 1 by deionized water and CTAC mass ratioes, the CTAC aqueous solution is prepared in stirring, by go from Sub- water is 4~6: 1 with absolute ethyl alcohol volume ratio, deionized water and absolute ethyl alcohol is added in solid silicon ball colloidal sol, stirring to mix Solution is closed, then the CTAC aqueous solution is added in mixed solution dropwise under the state that is stirred vigorously, adds resorcinol, finally Formaldehyde, tetraethyl orthosilicate are added, 10~12h is stirred at 25~30 DEG C, obtains carbon silicon polymer mixed solution, wherein CTAC： Absolute ethyl alcohol：Solid silicon ball colloidal sol：Resorcinol：Formaldehyde：Tetraethyl orthosilicate mol ratio=3.5~10.5: 110~120: 2~ 2.5: 1~3: 4~12: 2~6；
（3）By carbon silicon polymer mixed solution at 100~200 DEG C 18~30h of hydro-thermal, formed carbon silicon polymer microballoon forerunner Body, it is then centrifuged for separating, by sediment deionized water centrifuge washing 2~5 times, 18~24h is dried at 40~60 DEG C, obtains carbon Silicon polymer microballoon precursor powder；
（4）Precursor powder is placed in tube type high-temperature furnace, 20~30mL/ of input nitrogen（gcat·min）, heating rate 4~6 DEG C/min, 700~800 DEG C of heating-up temperature, constant temperature 3~5h of holding, room temperature is then naturally cooled to, generation carbon silicon polymer is micro- Ball, carbon silicon polymer microsphere powder is added in 5~10wt% hydrofluoric acid aqueous solution, stands 18~24h, use deionized water By sediment centrifuge washing 2~5 times, then put the precipitate in and 10~14h is dried at 70~90 DEG C, produced after drying hollow mesoporous Shell carbon ball；
（5）Weigh Cu (NO3)2·3H2O, add deionized water, stir concentration be 0.176~0.310 mol/L copper nitrate Solution, formed by catalyst, weigh hollow mesoporous lamella carbon ball, be added in above-mentioned solution, ultrasonic wave is placed in after stirring 50~70min of ultrasound in reactor, ultrasonic frequency are 80~100KHz；By the mixture after supersound process at 30~50 DEG C 18~24h is dried, catalyst precursor is produced after drying；
（6）Catalyst precursor is placed in tube type high-temperature furnace, 20~30mL/ of input nitrogen（gcat·min）, heating rate 2~4 DEG C/min, 300~400 DEG C of heating-up temperature, constant temperature keeps 3~5h, and product naturally cools to room temperature, produce hollow mesoporous carbosphere Shell confinement copper catalyst.
3. a kind of application of hollow mesoporous carbosphere shell confinement copper catalyst as claimed in claim 1, it is characterised in that urge Agent is used for the reaction of Oxidative Carbonylation Synthesis of DMC, and its reactions steps and process conditions are as follows：
（1）Quartz sand is weighed for 1: 5~10 by catalyst and quartz sand mass ratio, loads fixed bed pipe after both are well mixed In formula reactor, in a nitrogen atmosphere, the reaction bed temperature in reactor is heated to 120~140 DEG C；
（2）Raw material is CH according to mol ratio3OH∶CO∶O2=2~6: 6~18: 1~3 composition enters preheating furnace, and preheated stove adds Enter reactor after hot to 110~130 DEG C, charging gaseous phase volume air speed is 5840~17520h-1, reaction temperature is 120~140 DEG C, pressure is reacted under conditions of being normal pressure~1.0MPa.
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