CN109794276A - A kind of catalyst and preparation method thereof of hydrogenation of carbon dioxide methanol - Google Patents
A kind of catalyst and preparation method thereof of hydrogenation of carbon dioxide methanol Download PDFInfo
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- CN109794276A CN109794276A CN201910020934.4A CN201910020934A CN109794276A CN 109794276 A CN109794276 A CN 109794276A CN 201910020934 A CN201910020934 A CN 201910020934A CN 109794276 A CN109794276 A CN 109794276A
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Abstract
A kind of catalyst and preparation method thereof of hydrogenation of carbon dioxide methanol is related to a kind of catalyst and preparation method thereof, and the catalyst is using copper nitrate, copper acetate or copper chloride as copper source, using zinc nitrate, zinc acetate as zinc source.Using sodium carbonate, ammonium hydrogen carbonate, ammonium hydroxide, urea as precipitating reagent.Graphite phase carbon nitride is introduced, while introducing period of element Table VIII, IB, Group IIB transition metal chloride and nitrate as co-catalyst, using coprecipitation, staticly settles crystallisation, solvent-thermal method preparation Cu-C3N4- M-ZnO catalyst.Catalyst preparation step are as follows: be complexed active component and precipitating reagent to obtain forerunner's Cu-M-ZnO mother liquor, by the C after surface treatment3N4It is dispersed in above-mentioned mother liquor, by staticly settling crystallisation, solvent-thermal method self assembly, activated centre is along C3N4Surface growth, obtains the Cu-C with spongy porous structure3N4- M-ZnO catalyst.Cu 10-30%, co-catalyst M 0.005-5%, C3N410-30%, surplus are activity ZnO, and catalyst has good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, more particularly to a kind of urging for hydrogenation of carbon dioxide methanol
Agent and preparation method thereof.
Background technique
In recent years, due to caused by greenhouse effects global warming cause extensive concern.Global warming cause iceberg,
A series of problems, such as thawing in frozen soil and glacier, extreme weather frequency is existing, species extinction, a series of this problem has seriously threatened
To the existence of the mankind and other species.According to Intergovernmental Panel on Climate Change (IPCC) report, causing temperature
In the gaseous species of room effect, CO2Generated greenhouse effects account for about 60%.According to statistics, the CO in China at present2Discharge amount leap to
Second place of the world, China are in rapid industrial development period, and government proposes Economic Development Mode Conversion, advocate low-carbon warp energetically
Ji, while by CO2Recycle and reuse as emphasis research and develop strategy.Currently, for discharge carbon dioxide there are mainly two types of
Processing method.First is that trapping and sealing (CCS) up for safekeeping, but the method is costly, second is that by CO2Fixed conversion, is generally divided into biology
It fixes and two kinds of chemical conversion.CO2The fixed growing interest for causing people of chemistry, develop and use CO2Not only take full advantage of
Carbon resource and be conducive to environmental protection, and realize the regeneration of the energy.
Methanol is a kind of widely used chemical industry base stock and pollution-free fuel, and global annual requirement is 30,000,000
Ton or so.A series of chemical products can be produced from methanol.Methanol uses air oxidation process synthesizing formaldehyde；Methanol passes through de-
Water can make clean fuel, refrigerant, anesthetic, foaming agent etc. with dimethyl ether synthesis, dimethyl ether；Methanol can pass through carbonylation
Acetic acid is produced, generating important organic synthesis intermediate, these intermediates such as methyl formate, acetic anhydride can be used for producing drug, perfume (or spice)
Material etc.；Methanol is alternatively arranged as methylating reagent production to methylamine, methane chloride etc.；Methanol-to-olefins (MTO) are also increasingly subject to
Pay attention to, (MTO) is the important technology of coal-to-olefin, significant for energy development；Methanol or a kind of high-quality clean combustion
Material, adding part methanol in gasoline, diesel oil can be made into the novel vehicle clean fuel of low pollution, safety, and this fuel has
The advantages that reduction expense, emission reduction, safe ready.Using methanol as development of clean energy, for alleviating fossil fuel shortages, protection
Environment has great social and economic significance.
CO2Synthesizing methanol by hydrogenating has carried out this largely grinding both at home and abroad as one of the important means of low-carbon economy development
Study carefully.
Foreign overview:
The H prepared using renewable resource2Restore CO2The imagination for obtaining methanol can be used for solving what the following petroleum resources dried up
Problem, developed countries have carried out lasting in-depth study to this.In the 1920s, American industry solvent company builds up
A set of 400 ta-1Methanol generating means, with 60% CO of volume fraction2With the H of volume point 40%2(acetone-butanol factory
Fermentation gas) it is raw material, using Zn-Cr-Cu catalyst, the methanol and mass fraction 32% of output quality score 68% under 31MPa
Water.
CO is completed in rope company, Top, Denmark2 The design work of catalytic hydrogenation synthesizing methanol industrialized unit, the device need
It will be to low concentration H2 Enrichment purification, under MK101 catalyst action, with CO2 In 220~270 DEG C of reaction temperature and reaction
Synthesizing methanol is reacted under the conditions of 5.0~8.0MPa of pressure.
The CO of ISIS company, U.S. exploitation2Synthesizing methanol by hydrogenating technology, in 0.1~0.2MPa of reaction pressure, reaction temperature
It can be carried out under the temperate condition of 150 DEG C and nonpolar solvent, be not necessarily to metallic catalyst, H2In B (C6F5) 3It is constituted with pyridine
Lewis Acids and Bases pair under the action of heterolytic fission, CO2 Direct hydrogenation generates high concentration methanol product.
German Lurge and S ü d-Chemie company apply the C79-5Gl catalyst of cooperative development in synthesizing methanol device
On, with a certain proportion of CO2、H2It is unstripped gas with inert gas, operating condition is similar to traditional synthesis first in addition to reaction temperature
Alcohol technique, C79-5Gl show relatively good performance, and continuously-running 4 years.
Korean Institute of Science and Technology develops CO2Substep preparing methanol by hydrogenation technology, and complete 100 kgd-1Synthesis
Methanol pilot plant test, using Zn-Al catalyst, H2With CO2 Under the conditions of reaction pressure 0.1MPa and 600 DEG C of reaction temperature,
Inverse water gas reaction occurs and generates CO and H2O, work off one's feeling vent one's spleen dewatered CO and H2Again under Cu-Zn-Zr-Al catalyst action,
Synthesizing methanol under the conditions of 5MPa and 250 DEG C.
100 ta have been built up in the investment of Mitsui Chemical Co., Ltd.-1CO2Preparing methanol by hydrogenation industrial demonstration unit,
CO2From burning waste gas, H2From naphtha pyrolysis, using fixed bed reactors, raw material is from upper end into, methanol product from lower end
Out, influence of the bed pressure drop to production can be reduced by adjusting feed rate.Long-play demonstrate device safety and
The economy of Product transport, while realizing CO2Resource utilization, reduce the discharge of greenhouse gases, protect environment.To mention
It rises unit efficiency and reduces operating cost, Mitsui Chemicals, Inc is to CO2Purification, photocatalytic water splitting hydrogen manufacturing, catalyst
The technologies such as separate of optimization and water and methanol are researched and developed, and title technique can expand to 10,000 tons commercial plant.
Domestic survey:
By environmental protection pressure, resource is nervous and carbon emission cost is influenced, and domestic major colleges and universities, research institution and enterprise are to CO2Again
The research utilized is more and more paid close attention to, and the maximum discharges such as coal plant, power plant and petrochemical plant enterprise is to CO2Preparing methanol by hydrogenation project is more next
It is interested.Sichuan vinylon plant is rich in CO using volume fraction 12.4%~33.2%2The synthesis gas (H of high level2
It is converted from natural gas, the CO of suitable proportion2From other devices) it is unstripped gas, using ICI51-1 as catalyst, in
Methanol is produced in conventional apparatus, in 4.0~4.5MPa of reaction pressure, 210~260 DEG C of reaction temperature, CO2Volume fraction 19.6%
Under the conditions of CO volume fraction 6.1%, CO2It is respectively 10.7% and 29.0%, methanol yield 10.8%, operation with CO conversion ratio
Statistics indicate that stability and service life are constant at the process conditions for catalyst.Xiamen University's hair has a kind of carbon dioxide straight
Meet the catalyst of synthesizing methanol by hydrogenating and preparation method thereof patent (CN101690894A)；SaiDing Engineering Co., Ltd's hair has one kind
The technique patent (CN106699508A) of efficient, the environmentally friendly synthesizing methanol methanol of coke-stove gas；Southwest Chemical Research and Design Institute hair has
A kind of process patent (CN10386564) of hydrogen and carbon dioxide-synthesized methanol.
The country is to CO2Catalysis material and the reaction process research of synthesizing methanol by hydrogenating are more, and to process and reaction
Device research is less, it is believed that traditional methanol process and device can meet application, can expand examination in kiloton to the research of the technology
Grade pilot-plant, but there is no pilot-plant to build up at present.
Ammonia from coal becomes the most important production method of China's methanol production, and ammonia from coal production capacity accounts for national aggregated capacity
77.3%, followed by methanol from natural gas, the 13.2% of Zhan Quanguo aggregated capacity.According to incompletely statistics, by the end of the year 2017, national first
Totally 193 sets of the device that alcohol has been gone into operation (not including that device is discarded), amounts to 7855.5 ten thousand tons of production capacity.
Due to CO2Inertia and unfavorable factor thermodynamically so that carbon dioxide is difficult to activating and reducing, such as with conventional method
The catalyst of infusion process and co-precipitation preparation, more than there is conversion ratios low, by-product and the deficiencies of methanol selectivity is not high, therefore
New catalyst and method for preparing catalyst are studied, the reactivity and selectivity for improving catalyst are with Optimum utilization carbon dioxide
Resource just shows particularly significant.
Graphite phase carbon nitride is unique soft phase crystal, g-C in five kinds of crystal structures of carbonitride3N4Material, which has, partly leads
Body material properties has good chemical stability and thermal stability, and preparation method is simple, and the extensive price of raw material sources is low
It is honest and clean.Due to g-C3N4Visible light ability and high stability, be mainly used at present photoelectrocatalysis research.In recent years, g-C3N4's
Research no longer rests on photoelectrocatalysis, and also has in the oxidation of benzene, the degradation of organic-fuel and the activation of carbon dioxide
Many researchs.
Summary of the invention
The purpose of the present invention is to provide a kind of catalyst and preparation method thereof of hydrogenation of carbon dioxide methanol, the present invention
Methanol reaction is prepared for carbon dioxide recycling, a kind of novel carbon dioxide synthesizing methanol by hydrogenating catalyst is designed, utilizes
C3N4High-specific surface area, multi-pore channel structure improves catalyst to the adsorption capacity of carbon dioxide and hydrogen and improves mass-and heat-transfer
Ability and the reactivity that carbon dioxide is improved to the activation of carbon dioxide, with C3N4Copper zinc is prepared for catalyst carrier to urge
Agent, so that the selectivity of methanol is improved, the yield of titanium dioxide charcoal percent conversion and methanol.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of catalyst of hydrogenation of carbon dioxide methanol, the main active ingredient Cu and its oxides 10-30% of catalyst, is helped
Catalyst is period of element Table VIII, IB, Group IIB transition metal chloride and nitrate 0.005-5%, and carrier is to be with urea
The graphite phase carbon nitride C of presoma3N410-30% and surplus are activity ZnO；The reaction that catalyst is applicable in, hydrogenation of carbon dioxide
Reaction principal product is methanol.
A kind of catalyst of hydrogenation of carbon dioxide methanol, the catalyst coprecipitation prepare Cu, Zn forerunner
Body mother liquor, preparation step is successively are as follows:
1) mantoquita, zinc salt are dissolved in deionized water under room temperature, it is lasting to stir, form uniform blue-tinted transparent solution；
2) precipitating reagent (sodium carbonate, ammonium hydrogen carbonate, ammonium hydroxide, urea) is dissolved in deionized water under room temperature, is formed colorless and transparent
Solution；
3) under continuous agitation by surfactant (CTAB, Pluronic P123, PEO20-PPO70-PEO20,
Aldrich it) is added and is dissolved in copper zinc solution；
4) 100ml deionized water is added in the beaker of 2000ml as mother liquor, temperature is controlled at 60 DEG C, is continued under stirring condition
The copper zinc mixed liquor that step 1 obtains and the sodium carbonate liquor that step 2 obtains is slowly added dropwise, pH value keeps 7, forms uniformly blue
Cu, Zn forerunner's mother liquor.
A kind of catalyst of hydrogenation of carbon dioxide methanol, Cu, Zn forerunner mother liquor preparation method, precipitating reagent
The molar concentration of (sodium carbonate, ammonium hydrogen carbonate, ammonium hydroxide, urea) is 0.1-1.0 mol/L.
A kind of catalyst of hydrogenation of carbon dioxide methanol, the catalyst carrier are with class graphene knot
The graphite phase carbon nitride of structure, specific surface area are 100~200m2/ g, preparation step is successively are as follows:
1) melamine is placed in four crucibles, and aluminum sealing lid prevents powder metallurgy from dispersing；
2) room temperature is begun to warm up, 1-10 DEG C of heating rate/min, constant temperature 240min at 550 DEG C；
3) 20-80 DEG C of cooling rate/h, near room temperature obtain faint yellow C3N4Powder.
A kind of catalyst of the hydrogenation of carbon dioxide methanol, the co-catalyst be period of element Table VIII, IB,
Group IIB transition metal chloride and nitrate, additive amount 0.005%-5%.
A kind of catalyst of hydrogenation of carbon dioxide methanol, the catalyst copper source include copper nitrate, copper acetate
And copper chloride, load capacity is in 10%-30%.
A kind of catalyst of hydrogenation of carbon dioxide methanol, the catalyst ethyl alcohol and ethylene glycol as solvent,
Dispersing agent, surfactant；Additive amount is 2-20%.
A kind of method for preparing catalyst of hydrogenation of carbon dioxide methanol, the preparation method include using to staticly settle knot
Crystallization, solvent-thermal method prepare Cu-C3N4- M-ZnO catalyst；The preparation step of two methods is respectively as follows:
1) staticly settle crystallisation: co-catalyst and graphite phase carbon nitride is added in Cu, Zn presoma mother liquor under agitation, adds
Enter 2-20% ethyl alcohol to be sufficiently stirred, seal up preservative film, stand 12h, grain growth, beaker bottom has atrament precipitation, then open
Standing for 24 hours afterwards pours out supernatant liquor；Remaining substance is put in a vacuum drying oven, the dry 4h at 120 DEG C, after drying
Catalyst put into Muffle furnace, be warming up to 3-8 hours formation crystal transfers of 500 DEG C of calcinings；Last shaping of catalyst is granulated,
Reduction；
2) solvent-thermal method: being added co-catalyst and graphite phase carbon nitride under Cu, Zn presoma mother liquor stirring condition, 2-20% is added
Ethylene glycol, 40 DEG C are sufficiently stirred 1 h, obtain light blue suspension, pour into autoclave liner, 120 DEG C of reaction 12h；60
DEG C deionized water is washed five times, and 120 DEG C of filter cake dry 5h, 500 DEG C of roasting 3-8h are obtained by filtration.Molding granulation, reduction.
A kind of method for preparing catalyst of hydrogenation of carbon dioxide methanol, the gas phase hydrogenation reaction, reaction
Temperature is 150~300 DEG C, reaction pressure 1.5-3MPa.
The advantages and effects of the present invention are:
Catalyst of the present invention carries out the reaction that carbon dioxide gas phase hydrogenation generates methanol, one way feed stock conversion with higher and
Target product selectivity, method for preparing catalyst is simple, low in cost, while having high stability.
Specific embodiment
The following describes the present invention in detail with reference to examples.
Embodiment 1
Step 1: weighing melamine 15.00g, place it in Muffle furnace, setting parameter, and 20 DEG C of room temperature, 2 DEG C of heating rate/
Min, heating-up time 265min, the constant temperature 240min at 550 DEG C, 80 DEG C/h of cooling rate.Obtain faint yellow C3N4Powder.
Step 2: 1.93 g Cu (NO are weighed3)2·3H2O, 2.38 g Zn (NO3)2·6H2O is dissolved in 300ml deionization
In water, the blue solution of clear is obtained.
Step 3: Surfactant CTAB is dispersed in Cu, Zn solution under continuous agitation.Nitric acid
Copper: zinc nitrate: CTAB=5:5:1.
Precipitating reagent sodium carbonate: being dissolved in deionized water by step 4 under room temperature, forms colourless transparent solution, mole dense
Degree is 0.40mol/L.
Step 5: mentioning 60 DEG C for the copper zinc solution temperature of step 2, continues that slowly drop sodium carbonate is added dropwise under stirring condition
Solution, pH value keep 7, form uniformly blue Cu, Zn forerunner's mother liquor.
Step 6: addition graphite phase carbon nitride 0.23g under above-mentioned presoma mother liquor stirring condition, 5% ethylene glycol of addition, 40
DEG C 60 min are sufficiently stirred.
Step 7: above-mentioned mixed solution is poured into the polytetrafluoroethylene (PTFE) autoclave liner of 160ml, liner is put into
In Constant Temp. Oven, 12h is reacted at being 120 DEG C in temperature.Step 8: product being washed and is filtered, dry at 120 DEG C
5h will have become jade-green solid powder and be put into 500 DEG C of calcining 4h in Muffle furnace after drying, obtained solid catalyst is grey black
Obtained powder catalyst is carried out tabletting, is granulated by color powder, and reduction, 20-40 mesh catalyst is fitted into reactor, is reacted
Condition: 170 DEG C of reaction temperature, reaction pressure 2.5MPa, material molar ratio CO2: H2: Ar=3:9:1.
Remember CZC-1, the results are shown in Table one.
Embodiment 2
Step 1: two the same as embodiment 1.
Step 3: Surfactant CTAB is dispersed in Cu, Zn solution under continuous agitation. Cu
(NO3)2·3H2O:Zn(NO3)2·6H2O:CTAB=10:10:1。
Step 4: five, six, seven the same as embodiment 1.
It is denoted as CZC-2, the results are shown in Table one.
Embodiment 3
Step 1: 1.93 g Cu (NO are weighed3)2·3H2O, 2.38 g Zn (NO3)2·6H2O is dissolved in 300ml deionized water,
Obtain the blue solution of clear.
Precipitating reagent sodium carbonate: being dissolved in deionized water by step 2 under room temperature, forms colourless transparent solution, mole dense
Degree is 0.40mol/L.
Step 3: being added 100ml deionized water as mother liquor in the beaker of 2000ml, and temperature is controlled at 60 DEG C, is continued
Slowly drop sodium carbonate liquor and copper zinc mixed liquor are added dropwise under stirring condition, pH value keeps 7, forms uniformly blue Cu, Zn precipitating.
Step 4: after titration, 1h is persistently stirred.12h is staticly settled, is washed with 60 DEG C of warm water, and carry out vacuum pumping
Product after washing is placed in evaporating dish by filter after operating 3-4 times repeatedly, and dry 12h, the solid after drying are placed at 120 DEG C
It is calcined in Muffle furnace, calcines 4h at 400 DEG C, obtained powder catalyst is subjected to tabletting, is granulated, reduction, 20-40 mesh
Catalyst is fitted into reactor, reaction condition: 170 DEG C of reaction temperature, reaction pressure 2.5MPa, material molar ratio CO2: H2: Ar
=3:9:1。
It is denoted as CZ.It the results are shown in Table one.
Embodiment 4
Step 1: 1.93 g Cu (NO are weighed3)2·3H2O, 2.38 g Zn (NO3)2·6H2O, 1.29 g Al (NO3)3·9H2O
It is dissolved in 300ml deionized water, obtains the solution of clear.
Step 2 is the same as embodiment 3.
Step 3: being added 100ml deionized water as mother liquor in the beaker of 2000ml, and temperature is controlled at 60 DEG C, is continued
Slowly drop sodium carbonate liquor and cu zn/aluminium mixed liquor are added dropwise under stirring condition, pH value keeps 7, forms uniformly blue Cu, Zn, Al
Precipitating.
Step 4: after titration, 1h is persistently stirred.12h is staticly settled, is washed with 60 DEG C of warm water, and carry out vacuum pumping
Product after washing is placed in evaporating dish by filter after operating 3-4 times repeatedly, and dry 12h, the solid after drying are placed at 120 DEG C
It is calcined in Muffle furnace, calcines 4h at 400 DEG C, obtained powder catalyst is subjected to tabletting, is granulated, reduction, 20-40 mesh
Catalyst is fitted into reactor, reaction condition: 170 DEG C of reaction temperature, reaction pressure 2.5MPa, material molar ratio CO2: H2: Ar
=3:9:1。
It is denoted as CZA.It the results are shown in Table one.
Embodiment 5
Step 1: 1.93 g Cu (NO are weighed3)2·3H2O, 2.38 g Zn (NO3)2·6H2O, 1.29 g Al (NO3)3·
9H2O, 4.24g Zr (NO3)3·5H2O is dissolved in 300ml deionized water, obtains the solution of clear.
Step 2 is the same as embodiment 3.
Step 3: being added 100ml deionized water as mother liquor in the beaker of 2000ml, and temperature is controlled at 60 DEG C, is continued
The slow drop sodium carbonate liquor of dropwise addition and cu zn/aluminium mixed liquor under stirring condition, pH value holding 7, the uniform blue Cu, Zn of formation,
Al, Zr precipitating.
Step 4: after titration, 1h is persistently stirred.12h is staticly settled, is washed with 60 DEG C of warm water, and carry out vacuum pumping
Product after washing is placed in evaporating dish by filter after operating 3-4 times repeatedly, and dry 12h, the solid after drying are placed at 120 DEG C
It is calcined in Muffle furnace, calcines 4h at 400 DEG C, obtained powder catalyst is subjected to tabletting, is granulated, reduction, 20-40 mesh
Catalyst is fitted into reactor, reaction condition: 170 DEG C of reaction temperature, reaction pressure 2.5MPa, material molar ratio CO2: H2: Ar
=3:9:1。
It is denoted as CZAZ.It the results are shown in Table one.
Embodiment 6
Preparation catalyst
Step 1: with embodiment 1.
Step 2: the C of 0.1g is weighed3N4It is placed in the crucible of 30ml, the deionized water of 5ml is measured with 10ml graduated cylinder, it is standby
With.Ultrasonic cleaner is opened, with rubber head dropper to C3N4Deionized water is added dropwise to being saturated, estimates C roughly3N4Kong Rong.
Step 3: copper nitrate solution is prepared.The copper nitrate of 6.01 g is weighed, the deionized water of 12.63 ml is added, uses glass
Glass stick stirs evenly, and obtains blue-tinted transparent solution.
Step 4: under ultrasound condition, copper nitrate solution is added drop-wise to C3N4, carry out incipient impregnation, the load capacity of Cu
For 20 wt%.
Step 5: by impregnated Cu-C3N4Presoma is placed in drying box, 120 DEG C of dry 12h.Powder after drying is put
It is calcined in Muffle furnace, 4h is calcined at 500 DEG C, calcined catalyst is in blackyellow.By obtained fine catalyst into
Row tabletting is granulated, and reduction, 20-40 mesh catalyst is fitted into reactor, reaction condition: 170 DEG C of reaction temperature, reaction pressure
2.5MPa, material molar ratio CO2: H2: Ar=3:9:1.
It is denoted as CC.It the results are shown in Table one.
Embodiment 7
It staticly settles crystallisation and prepares catalyst.
Step 1: according to copper acetate: zinc acetate: ethanol amine: urea=1:1:1:1 molar ratio weighs reagent, will weigh
Copper acetate and zinc acetate are placed in 250ml beaker, are poured into beaker measuring suitable ethanol amine with graduated cylinder, are added later
The dissolution of 150ml dehydrated alcohol, solution is in navy blue transparence after glass bar stirring.
Step 2: load weighted urea is placed in another beaker, is dissolved with 150ml dehydrated alcohol.By two beakers
All prevent ethyl alcohol from volatilizing with preservative film sealing.
Step 3: three-necked flask is placed in water-bath, and heating water bath opens mechanical stirring to 55 DEG C.By two beakers
In solution be poured slowly into three-necked flask simultaneously, it is lasting to stir, start timing when all pouring into solution in flask after, stir and
Heated at constant temperature 6h.
Step 4: the solution after stirring is poured into 500ml beaker, seals up preservative film, and after standing 12h, beaker bottom has
Atrament is precipitated, then open stand for 24 hours afterwards pours out supernatant liquor.Remaining substance is put in a vacuum drying oven, 120
Dry 4h at DEG C.
Step 5: the catalyst after drying is put into Muffle furnace, is calcined with 500 DEG C.By obtained fine catalyst into
Row tabletting is granulated, and reduction, 20-40 mesh catalyst is fitted into reactor, reaction condition: 170 DEG C of reaction temperature, reaction pressure
2.5MPa, material molar ratio CO2: H2: Ar=3:9:1.
It is denoted as CZN-1.It the results are shown in Table one.
Embodiment 8
Step 1: according to copper acetate: zinc acetate: ethanol amine: urea=1:1:1:5 molar ratio weighs reagent, will weigh acetic acid
Copper and zinc acetate are placed in 250ml beaker, are poured into beaker measuring suitable ethanol amine with graduated cylinder, are added 150ml later
Dehydrated alcohol dissolution, solution is in navy blue transparence after glass bar stirring.
Step 2: three, four, five the same as embodiment 7
It is denoted as CZN-2.It the results are shown in Table one.
。
Claims (9)
1. a kind of catalyst of hydrogenation of carbon dioxide methanol, which is characterized in that the main active ingredient copper of the catalyst and its oxygen
Compound 10-30%, co-catalyst be period of element Table VIII, IB, Group IIB transition metal chloride and nitrate 0.005-5%,
Carrier is using urea as the graphite phase carbon nitride C of presoma3N410-30% and surplus are activity ZnO；Catalyst is applicable in anti-
It answers, carbon dioxide hydrogenation reaction principal product is methanol.
2. a kind of catalyst of hydrogenation of carbon dioxide methanol according to claim 1, which is characterized in that the catalyst
Coprecipitation prepares Cu, Zn presoma mother liquor, and preparation step is successively are as follows:
1) mantoquita, zinc salt are dissolved in deionized water under room temperature, it is lasting to stir, form uniform blue-tinted transparent solution；
2) precipitating reagent (sodium carbonate, ammonium hydrogen carbonate, ammonium hydroxide, urea) is dissolved in deionized water under room temperature, is formed colorless and transparent
Solution；
3) under continuous agitation by surfactant (CTAB, Pluronic P123, PEO20-PPO70-PEO20,
Aldrich it) is added and is dissolved in copper zinc solution；
4) 100ml deionized water is added in the beaker of 2000ml as mother liquor, temperature is controlled at 60 DEG C, is continued under stirring condition
The copper zinc mixed liquor that step 1 obtains and the sodium carbonate liquor that step 2 obtains is slowly added dropwise, pH value keeps 7, forms uniformly blue
Cu, Zn forerunner's mother liquor.
3. a kind of catalyst of hydrogenation of carbon dioxide methanol according to claim 2, which is characterized in that described Cu, Zn
Forerunner's mother liquor preparation method, the molar concentration of precipitating reagent (sodium carbonate, ammonium hydrogen carbonate, ammonium hydroxide, urea) are 0.1-1.0 mol/L.
4. a kind of catalyst of hydrogenation of carbon dioxide methanol according to claim 1, which is characterized in that the catalysis
Agent carrier is the graphite phase carbon nitride with class graphene-structured, and specific surface area is 100~200m2/ g, preparation step is successively
Are as follows:
1) melamine is placed in four crucibles, and aluminum sealing lid prevents powder metallurgy from dispersing；
2) room temperature is begun to warm up, 1-10 DEG C of heating rate/min, constant temperature 240min at 550 DEG C；
3) 20-80 DEG C of cooling rate/h, near room temperature obtain faint yellow C3N4Powder.
5. a kind of catalyst of hydrogenation of carbon dioxide methanol according to claim 1, which is characterized in that the co-catalysis
Agent is period of element Table VIII, IB, Group IIB transition metal chloride and nitrate, additive amount 0.005%-5%.
6. a kind of catalyst of hydrogenation of carbon dioxide methanol according to claim 1, which is characterized in that the catalyst
Copper source includes copper nitrate, copper acetate and copper chloride, and load capacity is in 10%-30%.
7. a kind of catalyst of hydrogenation of carbon dioxide methanol according to claim 1, which is characterized in that the catalyst
Ethyl alcohol and ethylene glycol are as solvent, dispersing agent, surfactant；Additive amount is 2-20%.
8. a kind of method for preparing catalyst of hydrogenation of carbon dioxide methanol, which is characterized in that the preparation method includes using
Staticly settle crystallisation, solvent-thermal method preparation Cu-C3N4- M-ZnO catalyst；The preparation step of two methods is respectively as follows:
1) staticly settle crystallisation: co-catalyst and graphite phase carbon nitride is added in Cu, Zn presoma mother liquor under agitation, adds
Enter 2-20% ethyl alcohol to be sufficiently stirred, seal up preservative film, stand 12h, grain growth, beaker bottom has atrament precipitation, then open
Standing for 24 hours afterwards pours out supernatant liquor；Remaining substance is put in a vacuum drying oven, the dry 4h at 120 DEG C, after drying
Catalyst put into Muffle furnace, be warming up to 3-8 hours formation crystal transfers of 500 DEG C of calcinings；Last shaping of catalyst is granulated,
Reduction；
2) solvent-thermal method: being added co-catalyst and graphite phase carbon nitride under Cu, Zn presoma mother liquor stirring condition, 2-20% is added
Ethylene glycol, 40 DEG C are sufficiently stirred 1 h, obtain light blue suspension, pour into autoclave liner, 120 DEG C of reaction 12h；60
DEG C deionized water is washed five times, and 120 DEG C of filter cake dry 5h, 500 DEG C of roasting 3-8h are obtained by filtration；Molding granulation, reduction.
9. a kind of method for preparing catalyst of hydrogenation of carbon dioxide methanol according to claim 8, which is characterized in that institute
Gas phase hydrogenation reaction is stated, reaction temperature is 150~300 DEG C, reaction pressure 1.5-3MPa.
Priority Applications (1)
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327958A (en) * | 2019-06-21 | 2019-10-15 | 齐利华(武汉)资源环境科技有限公司 | A kind of CO2Catalyst of synthesizing methanol by hydrogenating and preparation method thereof, application |
| CN111437862A (en) * | 2020-04-03 | 2020-07-24 | 宁夏大学 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4257920A (en) * | 1978-11-17 | 1981-03-24 | Societe Francaise Des Produits Pour Catalyse | Catalyst containing a noble metal of the VIIIth group, copper oxide, zinc oxide and a rare earth metal, its manufacture and use in the conversion of carbon monoxide |
| JPH0892139A (en) * | 1994-09-22 | 1996-04-09 | Sumitomo Metal Ind Ltd | Decomposition of metanitrobenzoic acid and 2,6-dimethylnaphthalene complex |
| CN102441394A (en) * | 2010-10-10 | 2012-05-09 | 申世伟 | Hydrothermal production method of nano ternary copper catalyst used in process of producing methanol by hydrogenating titanium dioxide |
| CN103316683A (en) * | 2013-07-05 | 2013-09-25 | 昆明理工大学 | Preparation method of carbon nanotube loaded copper-based catalyst applied to methanol synthesis |
| CN104646045A (en) * | 2015-02-15 | 2015-05-27 | 南京工程学院 | CuO/mpg-C3N4 composite material as well as preparation method and application thereof |
| CN105535972A (en) * | 2015-12-23 | 2016-05-04 | 中国科学院长春应用化学研究所 | C3N4 nanocomposite, preparation method and application of C3N4 nanocomposite |
| CN105642332A (en) * | 2016-03-15 | 2016-06-08 | 辽宁大学 | g-C3N4/TiO2 composite photochemical catalyst and preparation method thereof |
| CN106824243A (en) * | 2017-01-25 | 2017-06-13 | 东南大学 | Z-type BiVO4‑Au/g‑C3N4The preparation of catalysis material and its photo catalytic reduction CO2Application |
| CN109092312A (en) * | 2018-09-19 | 2018-12-28 | 昆明理工大学 | A kind of hydro-thermal method prepares the method and application of copper-based catalysts |
-
2019
- 2019-01-09 CN CN201910020934.4A patent/CN109794276B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4257920A (en) * | 1978-11-17 | 1981-03-24 | Societe Francaise Des Produits Pour Catalyse | Catalyst containing a noble metal of the VIIIth group, copper oxide, zinc oxide and a rare earth metal, its manufacture and use in the conversion of carbon monoxide |
| JPH0892139A (en) * | 1994-09-22 | 1996-04-09 | Sumitomo Metal Ind Ltd | Decomposition of metanitrobenzoic acid and 2,6-dimethylnaphthalene complex |
| CN102441394A (en) * | 2010-10-10 | 2012-05-09 | 申世伟 | Hydrothermal production method of nano ternary copper catalyst used in process of producing methanol by hydrogenating titanium dioxide |
| CN103316683A (en) * | 2013-07-05 | 2013-09-25 | 昆明理工大学 | Preparation method of carbon nanotube loaded copper-based catalyst applied to methanol synthesis |
| CN104646045A (en) * | 2015-02-15 | 2015-05-27 | 南京工程学院 | CuO/mpg-C3N4 composite material as well as preparation method and application thereof |
| CN105535972A (en) * | 2015-12-23 | 2016-05-04 | 中国科学院长春应用化学研究所 | C3N4 nanocomposite, preparation method and application of C3N4 nanocomposite |
| CN105642332A (en) * | 2016-03-15 | 2016-06-08 | 辽宁大学 | g-C3N4/TiO2 composite photochemical catalyst and preparation method thereof |
| CN106824243A (en) * | 2017-01-25 | 2017-06-13 | 东南大学 | Z-type BiVO4‑Au/g‑C3N4The preparation of catalysis material and its photo catalytic reduction CO2Application |
| CN109092312A (en) * | 2018-09-19 | 2018-12-28 | 昆明理工大学 | A kind of hydro-thermal method prepares the method and application of copper-based catalysts |
Non-Patent Citations (2)
| Title |
|---|
| KAIXI DENG ET AL.: ""Cu/g-C3N4 modified ZnO/Al2O3 catalyst: methanol yield improvement of CO2 hydrogenation"", 《CATALYSIS COMMUNICATIONS》 * |
| TAHIR, BEENISH ET AL.: ""Photo-induced CO2 reduction by CH4/H2O to fuels over Cu-modified g-C3N4 nanorods under simulated solar energy"", 《APPLIED SURFACE SCIENCE 》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327958A (en) * | 2019-06-21 | 2019-10-15 | 齐利华(武汉)资源环境科技有限公司 | A kind of CO2Catalyst of synthesizing methanol by hydrogenating and preparation method thereof, application |
| EP3769837A1 (en) * | 2019-07-22 | 2021-01-27 | Fundació Institut Català d'Investigació Química (ICIQ) | Co-precipitation method and catalyst thereof |
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| CN113877622A (en) * | 2021-11-04 | 2022-01-04 | 中国船舶重工集团公司第七一九研究所 | For CO2ZnO/g-C for preparing methanol by catalytic hydrogenation3N4Process for preparing catalyst |
| CN115155602A (en) * | 2022-08-02 | 2022-10-11 | 西部金属材料股份有限公司 | Metal oxide-copper composite catalyst, and preparation method and application thereof |
| CN115569660A (en) * | 2022-10-25 | 2023-01-06 | 安徽大学 | High-dispersion carbon dioxide hydrogenation catalyst taking CuFeO2@ GO as precursor and preparation method and application thereof |
| CN115569660B (en) * | 2022-10-25 | 2024-02-06 | 安徽大学 | High-dispersion carbon dioxide hydrogenation catalyst taking CuFeO2@GO as precursor and preparation method and application thereof |
| CN116139874A (en) * | 2023-04-20 | 2023-05-23 | 潍坊学院 | Catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide and preparation method thereof |
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