CN106076396A - A kind of preparation method and applications of the Cu support type mesoporous catalyst of Au doping - Google Patents
A kind of preparation method and applications of the Cu support type mesoporous catalyst of Au doping Download PDFInfo
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- CN106076396A CN106076396A CN201610391440.3A CN201610391440A CN106076396A CN 106076396 A CN106076396 A CN 106076396A CN 201610391440 A CN201610391440 A CN 201610391440A CN 106076396 A CN106076396 A CN 106076396A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000012265 solid product Substances 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 39
- 238000003756 stirring Methods 0.000 claims abstract description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002808 molecular sieve Substances 0.000 claims abstract description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000013019 agitation Methods 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 27
- 238000006722 reduction reaction Methods 0.000 claims abstract description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 23
- 229910002708 Au–Cu Inorganic materials 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000005574 cross-species transmission Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The present invention relates to the preparation method and applications of the Cu support type mesoporous catalyst of a kind of Au doping, belong to nano composite material technical field.By modified mesopore molecular sieve NH2SBA 15 powder is that to join concentration be 0.0025mol/LHAuCl to 30.7:1～92.1:1ml/g by liquid-solid ratio4Solution stirs, then under the conditions of ultrasonic agitation, adds reducing agent NaBH4Carry out reduction reaction, filter, wash, obtain solid product；Solid product is placed in the copper nitrate solution that concentration is 0.2mol/L stirring, then filters, washs, prepares Au Cu support type mesoporous catalyst after roasting.It is contemplated that utilize a small amount of noble metal Au to be doped in high-load Cu support type mesoporous catalyst, it is ensured that while catalysis activity, reduce catalyst particle size, increase oarse-grained dispersibility, the raising anti-sintering of catalyst and H2Dissociative ability, is finally reached and improves CO2The purpose of the catalytic performance of preparing methanol by hydrogenation.
Description
Technical field
The present invention relates to the preparation method and applications of the Cu support type mesoporous catalyst of a kind of Au doping, belong to nanometer multiple
Condensation material technical field.
Background technology
Along with developing rapidly of modern industry, CO2Discharge capacity increasing.It is known that CO2Be directly emitted on wave
Also the greenhouse effect of the earth, therefore CO is being aggravated while taking carbon resource2Exploitation be particularly important.CH3OH is as one
Plant important Organic Chemicals and there is the cleaning fuel of development prospect so that CO2Hydrogenation is for CH3OH is CO2Recycle
One of effective way, significant in environmental protection and energy field.
Obtaining effective catalyst is to realize CO2Hydrogenation CH3The key of OH process industrialization.What at present research was more is with
The copper-based catalysts Cu/ZnO/Al that coprecipitation is prepared2O3Or Cu/ZnO/ZrO2Catalyst.Wherein Cu/ZnO/ZrO2Urge
Agent can be by CO under the conditions of low-temp low-pressure2Change into methanol, be the most promising hydrogenation catalyst of one.But co-precipitation legal system
There is the defects such as specific surface area is little, dispersion is poor, active ingredient copper easy-sintering, therefore, some high-ratio surfaces in the catalyst obtained
Mesoporous material starts to receive much concern.Wherein mesoporous molecular sieve SBA-15 with the pore passage structure of its high-sequential, high-specific surface area, can
The advantages such as the aperture adjusted, big wall thickness, good hydrothermal stability are widely used in various catalytic reaction.
There are some researches show, H on copper-based catalysts2The absorption amount of dissociating inadequate so that CO2Conversion ratio relatively low.Cause
How this, improve H2Volume of activation be improve CO2One of key technology of conversion ratio.In recent years, Au nano-particle is superior with it
Catalytic performance and enjoy extensive concern.Can by high-ratio surface in Au is limited its duct by mesoporous molecular sieve SBA-15 to obtain
Secure satisfactory grades Au nano-particle scattered, undersized.Meanwhile, there are some researches show the activation H that can dissociate in Au active sites2And Au and Cu
It is respectively positioned on IB race, there is similar lattice structure and make it be easily formed alloy to improve overall anti-caking power and to reduce integral particle
Size, carries high catalytic activity.
Summary of the invention
The problem existed for above-mentioned prior art and deficiency, Cu support type that the present invention provides a kind of Au to adulterate is mesoporous urges
The preparation method and applications of agent.It is contemplated that utilize a small amount of noble metal Au to be doped in the high-load mesoporous catalysis of Cu support type
Agent, it is ensured that catalysis activity while, reduce catalyst particle size, increase oarse-grained dispersibility, improve the anti-sintering of catalyst and
H2Dissociative ability, is finally reached and improves CO2The purpose of the catalytic performance of preparing methanol by hydrogenation, the present invention passes through techniques below side
Case realizes.
The preparation method of the Cu support type mesoporous catalyst of a kind of Au doping, by modified mesopore molecular sieve NH2-SBA-15
Powder is that to join concentration be 0.0025mol/LHAuCl to 30.7:1～92.1:1ml/g by liquid-solid ratio4Solution stirs, then
Under the conditions of ultrasonic agitation, add reducing agent NaBH4Carry out reduction reaction, filter, wash, obtain solid product；Solid product
It is placed in the copper nitrate solution that concentration is 0.2mol/L stirring, then filters, wash, prepare Au-Cu support type after roasting
Mesoporous catalyst.
Specifically comprise the following steps that
(1) first by modified mesopore molecular sieve NH2-SBA-15 powder is that 30.7:1～92.1:1ml/g joins by liquid-solid ratio
Concentration is 0.0025mol/LHAuCl4In solution, magnetic agitation 3h at 25 DEG C；Then, under the conditions of ultrasonic agitation, add dense
Degree is the reducing agent NaBH of 0.1mol/L4Carry out reduction reaction 30min, filter, wash and (use dehydrated alcohol to carry out filtering 4～6
Secondary, washing 2～3 times), obtain solid product；
(2) solid product that step (1) obtains is placed in the copper nitrate solution that concentration is 0.2mol/L, is 50 DEG C in temperature and stirs
Mixing 3h and obtain mixed solution, obtain solid product after mixed solution filtration, washing, solid product is dried (dry at 80～110 DEG C
Dry 16～18h) after at temperature is 300～500 DEG C roasting 5h, i.e. prepare Au-Cu support type mesoporous catalyst.
Above-mentioned prepare the mass fraction=(m of Au in Au-Cu support type mesoporous catalystAu/m(CuO+NH2-SBA-15))×
100%；The mass fraction of CuO=(mCuO/m(CuO +NH2-SBA-15))×100%。
The mesopore molecular sieve NH of described modification2The preparation of-SBA-15 powder specifically comprises the following steps that
1. under 40 DEG C of stirring conditions, by P123Be dissolved in aqueous hydrochloric acid solution, be subsequently adding TEOS, agitated, crystallization, filtration,
Dry, calcination steps, prepares SBA-15；Above-mentioned P123, aqueous hydrochloric acid solution, the mol ratio of TEOS be 1:340:60；
2. SBA-15,300ml dehydrated alcohol that 1. 12mlAPTES, 4g step obtains is mixed in there-necked flask, ultrasonic agitation
30min, 120 DEG C of return stirring 16h obtain solution；
3. 2. step is obtained solution spend dehydrated alcohol carry out filtering 5 times, washing obtain solid 3 times；
4. 3. step is obtained solid at 60 DEG C, is dried 16h, i.e. prepare modified mesopore molecular sieve NH2-SBA-15 powder.
A kind of above-mentioned Au-Cu of preparing support type mesoporous catalyst can be applied at CO2Hydrogenation reaction prepares methanol process
In, concrete steps:
1.5gAu-Cu support type mesoporous catalyst is positioned over CO2In the fixed bed reactors of preparing methanol by hydrogenation.First in 5%
H2Reduction 8h at/95%Ar atmosphere 250 DEG C, then in 75%CO2/25%H2The lower 280 DEG C of reaction 7h of atmosphere, finally by Agilent
Technologies 6890 gas chromatogram (GC) carries out detection and analyzes tail gas and liquid product, calculates X by external standard methodCO2
(CO2Conversion ratio) and YCH3OH(yield of methanol).
The invention has the beneficial effects as follows:
(1) catalyst has high specific surface area, good dispersibility；
(2) Au-Cu synergism is to improve the anti-caking power of Au, Cu, and reduces integral particle size；
(3) addition of Au promotes the generation of Hydrogen spillover phenomenon, beneficially H2Dissociative；
(4) for CO2Hydrogenation CH3OH reacts, and compares the Cu support type mesoporous catalyst relatively prepared with condition, and Au-Cu loads
Type mesoporous catalyst catalytic effect significantly improves.
Accompanying drawing explanation
Fig. 1 is the Au-Cu support type mesoporous catalyst HRTEM figure that the embodiment of the present invention 3 prepares；
Fig. 2 is the Cu support type mesoporous catalyst HRTEM figure that contrast test of the present invention prepares；
Fig. 3 is the Au-Cu support type mesoporous catalyst CO of the different Au content that contrast test, embodiment 1 to 4 prepare2Turn
Rate comparison diagram；
Fig. 4 is the Au-Cu support type mesoporous catalyst CH of the different Au content that contrast test, embodiment 1 to 4 prepare3OH
Selectivity comparison diagram.
Detailed description of the invention
Below in conjunction with the accompanying drawings and detailed description of the invention, the invention will be further described.
Embodiment 1
The preparation method of the Cu support type mesoporous catalyst of this Au doping, specifically comprises the following steps that
(1) first by the mesopore molecular sieve NH of 1.5g modification2-SBA-15 powder is that 30.7:1ml/g joins concentration by liquid-solid ratio
For 0.0025mol/LHAuCl4In solution, magnetic agitation 3h at 25 DEG C；Then, under the conditions of ultrasonic agitation, 5ml concentration is added
Reducing agent NaBH for 0.1mol/L4Carry out reduction reaction 30min, filter, wash and (use dehydrated alcohol to carry out filtering 4～6
Secondary, washing 2～3 times), obtain solid product；
(2) the 1.523g solid product that step (1) obtains is placed in 50ml, concentration be 0.2mol/L copper nitrate solution in,
Temperature is that 50 DEG C of stirring 3h obtain mixed solution, and mixed solution filters, obtain solid product after washing, solid product be dried (
At 110 DEG C be dried 16h) after at temperature is 350 DEG C roasting 5h, i.e. prepare Au-Cu support type mesoporous catalyst and (be designated as 1%
Au-35%Cu/SBA-15).
The mesopore molecular sieve NH of above-mentioned modification2The preparation of-SBA-15 powder specifically comprises the following steps that
1. under 40 DEG C of stirring conditions, by P123Being dissolved in concentration is in 2mol/L aqueous hydrochloric acid solution, is subsequently adding TEOS, through stirring
Mix, crystallization, filter, be dried, roasting (roasting 5h under the conditions of temperature is 550 DEG C) step, prepare SBA-15；Above-mentioned P123, hydrochloric acid
Aqueous solution, the mol ratio of TEOS are 1:340:60；
2. SBA-15,300ml dehydrated alcohol that 1. 12mlAPTES, 4g step obtains is mixed in there-necked flask, ultrasonic agitation
30min, 120 DEG C of return stirring 16h obtain solution；
3. 2. step is obtained solution spend dehydrated alcohol carry out filtering 5 times, washing obtain solid 3 times；
4. 3. step is obtained solid at 60 DEG C, is dried 16h, i.e. prepare modified mesopore molecular sieve NH2-SBA-15 powder.
Embodiment 2
The preparation method of the Cu support type mesoporous catalyst of this Au doping, specifically comprises the following steps that
(1) first by the mesopore molecular sieve NH of 1.5g modification2By liquid-solid ratio ,-SBA-15 powder is that 46.05:1ml/g joins dense
Degree is 0.0025mol/LHAuCl4In solution, magnetic agitation 3h at 25 DEG C；Then, under the conditions of ultrasonic agitation, 5ml is added dense
Degree is the reducing agent NaBH of 0.1mol/L4Carry out reduction reaction 30min, filter, wash and (use dehydrated alcohol to carry out filtering 4～6
Secondary, washing 2～3 times), obtain solid product；
(2) the 1.535g solid product that step (1) obtains is placed in 50ml, concentration be 0.2mol/L copper nitrate solution in,
Temperature is that 50 DEG C of stirring 3h obtain mixed solution, and mixed solution filters, obtain solid product after washing, solid product be dried (
At 110 DEG C be dried 16h) after at temperature is 350 DEG C roasting 5h, i.e. prepare Au-Cu support type mesoporous catalyst and (be designated as
1.5%Au-35%Cu/SBA-15).
The mesopore molecular sieve NH of above-mentioned modification2The preparation of-SBA-15 powder specifically comprises the following steps that
1. under 40 DEG C of stirring conditions, by P123Being dissolved in concentration is in 2mol/L aqueous hydrochloric acid solution, is subsequently adding TEOS, through stirring
Mix, crystallization, filter, be dried, roasting (roasting 5h under the conditions of temperature is 550 DEG C) step, prepare SBA-15；Above-mentioned P123, hydrochloric acid
Aqueous solution, the mol ratio of TEOS are 1:340:60；
2. SBA-15,300ml dehydrated alcohol that 1. 12mlAPTES, 4g step obtains is mixed in there-necked flask, ultrasonic agitation
30min, 120 DEG C of return stirring 16h obtain solution；
3. 2. step is obtained solution spend dehydrated alcohol carry out filtering 5 times, washing obtain solid 3 times；
4. 3. step is obtained solid at 60 DEG C, is dried 16h, i.e. prepare modified mesopore molecular sieve NH2-SBA-15 powder.
Embodiment 3
The preparation method of the Cu support type mesoporous catalyst of this Au doping, specifically comprises the following steps that
(1) first by the mesopore molecular sieve NH of 1.5g modification2-SBA-15 powder is that 61.4:1ml/g joins concentration by liquid-solid ratio
For 0.0025mol/LHAuCl4In solution, magnetic agitation 3h at 25 DEG C；Then, under the conditions of ultrasonic agitation, 10ml is added dense
Degree is the reducing agent NaBH of 0.1mol/L4Carry out reduction reaction 30min, filter, wash and (use dehydrated alcohol to carry out filtering 4～6
Secondary, washing 2～3 times), obtain solid product；
(2) the 1.546g solid product that step (1) obtains is placed in 50ml, concentration be 0.2mol/L copper nitrate solution in,
Temperature is that 50 DEG C of stirring 3h obtain mixed solution, and mixed solution filters, obtain solid product after washing, solid product be dried (
At 110 DEG C be dried 16h) after at temperature is 350 DEG C roasting 5h, i.e. prepare Au-Cu support type mesoporous catalyst and (be designated as 2%
Au-35%Cu/SBA-15), the Au-Cu support type mesoporous catalyst HRTEM prepared schemes as shown in Figure 1.
The mesopore molecular sieve NH of above-mentioned modification2The preparation of-SBA-15 powder specifically comprises the following steps that
1. under 40 DEG C of stirring conditions, by P123Being dissolved in concentration is in 2mol/L aqueous hydrochloric acid solution, is subsequently adding TEOS, through stirring
Mix, crystallization, filter, be dried, roasting (roasting 5h under the conditions of temperature is 550 DEG C) step, prepare SBA-15；Above-mentioned P123, hydrochloric acid
Aqueous solution, the mol ratio of TEOS are 1:340:60；
2. SBA-15,300ml dehydrated alcohol that 1. 12mlAPTES, 4g step obtains is mixed in there-necked flask, ultrasonic agitation
30min, 120 DEG C of return stirring 16h obtain solution；
3. 2. step is obtained solution spend dehydrated alcohol carry out filtering 5 times, washing obtain solid 3 times；
4. 3. step is obtained solid at 60 DEG C, is dried 16h, i.e. prepare modified mesopore molecular sieve NH2-SBA-15 powder.
Embodiment 4
The preparation method of the Cu support type mesoporous catalyst of this Au doping, specifically comprises the following steps that
(1) first by the mesopore molecular sieve NH of 1.5g modification2-SBA-15 powder is that 92.1:1ml/g joins concentration by liquid-solid ratio
For 0.0025mol/LHAuCl4In solution, magnetic agitation 3h at 25 DEG C；Then, under the conditions of ultrasonic agitation, 15ml is added dense
Degree is the reducing agent NaBH of 0.1mol/L4Carry out reduction reaction 30min, filter, wash and (use dehydrated alcohol to carry out filtering 4～6
Secondary, washing 2～3 times), obtain solid product；
(2) the 1.569 g solid products that step (1) obtains are placed in 50 ml, concentration be 0.2mol/L copper nitrate solution in,
Being that 50 DEG C of stirring 3h obtain mixed solution in temperature, obtain solid product after mixed solution filtration, washing, solid product is dried
After (at 110 DEG C be dried 16h) at temperature is 350 DEG C roasting 5h, i.e. prepare Au-Cu support type mesoporous catalyst (note
For 3%Au-35%Cu/SBA-15).
The mesopore molecular sieve NH of above-mentioned modification2The preparation of-SBA-15 powder specifically comprises the following steps that
1. under 40 DEG C of stirring conditions, by P123Being dissolved in concentration is in 2mol/L aqueous hydrochloric acid solution, is subsequently adding TEOS, through stirring
Mix, crystallization, filter, be dried, roasting (roasting 5h under the conditions of temperature is 550 DEG C) step, prepare SBA-15；Above-mentioned P123, hydrochloric acid
Aqueous solution, the mol ratio of TEOS are 1:340:60；
2. SBA-15,300ml dehydrated alcohol that 1. 12mlAPTES, 4g step obtains is mixed in there-necked flask, ultrasonic agitation
30min, 120 DEG C of return stirring 16h obtain solution；
3. 2. step is obtained solution spend dehydrated alcohol carry out filtering 5 times, washing obtain solid 3 times；
4. 3. step is obtained solid at 60 DEG C, is dried 16h, i.e. prepare modified mesopore molecular sieve NH2-SBA-15 powder.
Contrast test
The process preparing Cu support type mesoporous catalyst is:
First by the mesopore molecular sieve NH of 1.5g modification2-SBA-15 powder (mesopore molecular sieve NH2-SBA-15 powder preparing processes
As shown in embodiment 1 to 4) be placed in 50ml, concentration be 0.2mol/L copper nitrate solution in, temperature be 50 DEG C stirring 3h obtain
Mixed solution, mixed solution filters, obtain solid product after washing, and solid product is dried after (at 110 DEG C be dried 16h) in temperature
Degree is roasting 5h at 350 DEG C, i.e. prepares Cu support type mesoporous catalyst (being designated as 35%Cu/SBA-15), prepares Cu support type
Mesoporous catalyst HRTEM schemes as shown in Figure 2.
The Au-Cu support type mesoporous catalyst of Au content different in embodiment 1 to 4 and contrast test is applied at CO2
Hydrogenation reaction is prepared in methanol process, concrete steps:
1.5gAu-Cu support type mesoporous catalyst is positioned over CO2In the fixed bed reactors of preparing methanol by hydrogenation.First in 5%
H2Reduction 8h at/95%Ar atmosphere 250 DEG C, then in 75%CO2/25%H2The lower 280 DEG C of reaction 7h of atmosphere, finally by Agilent
Technologies 6890 gas chromatogram (GC) carries out detection and analyzes tail gas and liquid product, calculates X by external standard methodCO2With
SCH3OH。
The Au-Cu support type mesoporous catalyst CO of different Au content2Conversion ratio comparison diagram is as it is shown on figure 3, permissible from Fig. 3
Find out the increase X along with Au contentCO2First raise and reduce afterwards and Au load capacity is to be up to 24.9% during 2wt.%, in institute's test sample product
The highest XCO2；The Au-Cu support type mesoporous catalyst CH of different Au content3OH selectivity comparison diagram as shown in Figure 4, from Fig. 4
Can be seen that the increase CH along with Au content3OH selectivity first increases and then decreases, when Au content is 2wt.%, CH3OH selectivity
Reach optimum level.
Embodiment 5
The preparation method of the Cu support type mesoporous catalyst of this Au doping, specifically comprises the following steps that
(1) first by the mesopore molecular sieve NH of 1.5g modification2-SBA-15 powder is that 92.1:1ml/g joins concentration by liquid-solid ratio
For 0.0025mol/LHAuCl4In solution, magnetic agitation 3h at 25 DEG C；Then, under the conditions of ultrasonic agitation, 20ml is added dense
Degree is the reducing agent NaBH of 0.1mol/L4Carry out reduction reaction 30min, filter, wash and (use dehydrated alcohol to carry out filtering 4～6
Secondary, washing 2～3 times), obtain solid product；
(2) the 1.569g solid product that step (1) obtains is placed in 50ml, concentration be 0.2mol/L copper nitrate solution in,
Temperature is that 50 DEG C of stirring 3h obtain mixed solution, and mixed solution filters, obtain solid product after washing, solid product be dried (
At 80 DEG C be dried 18h) after at temperature is 300 DEG C roasting 5h, i.e. prepare Au-Cu support type mesoporous catalyst and (be designated as 3%
Au-35%Cu/SBA-15).
The mesopore molecular sieve NH of above-mentioned modification2The preparation of-SBA-15 powder specifically comprises the following steps that
1. under 40 DEG C of stirring conditions, by P123Being dissolved in concentration is in 2mol/L aqueous hydrochloric acid solution, is subsequently adding TEOS, through stirring
Mix, crystallization, filter, be dried, roasting (roasting 5h under the conditions of temperature is 550 DEG C) step, prepare SBA-15；Above-mentioned P123, hydrochloric acid
Aqueous solution, the mol ratio of TEOS are 1:340:60；
2. SBA-15,300ml dehydrated alcohol that 1. 12mlAPTES, 4g step obtains is mixed in there-necked flask, ultrasonic agitation
30min, 120 DEG C of return stirring 16h obtain solution；
3. 2. step is obtained solution spend dehydrated alcohol carry out filtering 5 times, washing obtain solid 3 times；
4. 3. step is obtained solid at 60 DEG C, is dried 16h, i.e. prepare modified mesopore molecular sieve NH2-SBA-15 powder.
Embodiment 6
The preparation method of the Cu support type mesoporous catalyst of this Au doping, specifically comprises the following steps that
(1) first by the mesopore molecular sieve NH of 1.5g modification2-SBA-15 powder is that 92.1:1ml/g joins concentration by liquid-solid ratio
For 0.0025mol/LHAuCl4In solution, magnetic agitation 3h at 25 DEG C；Then, under the conditions of ultrasonic agitation, 20ml is added dense
Degree is the reducing agent NaBH of 0.1mol/L4Carry out reduction reaction 30min, filter, wash and (use dehydrated alcohol to carry out filtering 4～6
Secondary, washing 2～3 times), obtain solid product；
(2) the 1.569g solid product that step (1) obtains is placed in 50ml, concentration be 0.2mol/L copper nitrate solution in,
Temperature is that 50 DEG C of stirring 3h obtain mixed solution, and mixed solution filters, obtain solid product after washing, solid product be dried (
At 80 DEG C be dried 18h) after at temperature is 500 DEG C roasting 5h, i.e. prepare Au-Cu support type mesoporous catalyst and (be designated as 3%
Au-35%Cu/SBA-15).
The mesopore molecular sieve NH of above-mentioned modification2The preparation of-SBA-15 powder specifically comprises the following steps that
1. under 40 DEG C of stirring conditions, by P123Being dissolved in concentration is in 2mol/L aqueous hydrochloric acid solution, is subsequently adding TEOS, through stirring
Mix, crystallization, filter, be dried, roasting (roasting 5h under the conditions of temperature is 550 DEG C) step, prepare SBA-15；Above-mentioned P123, hydrochloric acid
Aqueous solution, the mol ratio of TEOS are 1:340:60；
2. SBA-15,300ml dehydrated alcohol that 1. 12mlAPTES, 4g step obtains is mixed in there-necked flask, ultrasonic agitation
30min, 120 DEG C of return stirring 16h obtain solution；
3. 2. step is obtained solution spend dehydrated alcohol carry out filtering 5 times, washing obtain solid 3 times；
4. 3. step is obtained solid at 60 DEG C, is dried 16h, i.e. prepare modified mesopore molecular sieve NH2-SBA-15 powder.
Above in association with accompanying drawing, the detailed description of the invention of the present invention is explained in detail, but the present invention is not limited to above-mentioned
Embodiment, in the ken that those of ordinary skill in the art are possessed, it is also possible to before without departing from present inventive concept
Put that various changes can be made.
Claims (4)
1. the preparation method of the Cu support type mesoporous catalyst of an Au doping, it is characterised in that: by modified mesopore molecular sieve
NH2-SBA-15 powder is that to join concentration be 0.0025mol/LHAuCl to 30.7:1～92.1:1ml/g by liquid-solid ratio4In solution
Stirring, then under the conditions of ultrasonic agitation, adds reducing agent NaBH4Carry out reduction reaction, filter, wash, obtain solid product；
Solid product is placed in the copper nitrate solution that concentration is 0.2mol/L stirring, then filters, washs, prepares Au-after roasting
Cu support type mesoporous catalyst.
The preparation method of the Cu support type mesoporous catalyst of Au the most according to claim 1 doping, it is characterised in that concrete
Step is as follows:
(1) first by modified mesopore molecular sieve NH2-SBA-15 powder is that 30.7:1～92.1:1ml/g joins by liquid-solid ratio
Concentration is 0.0025mol/LHAuCl4In solution, magnetic agitation 3h at 25 DEG C；Then, under the conditions of ultrasonic agitation, add dense
Degree is the reducing agent NaBH of 0.1mol/L4Carry out reduction reaction 30min, filter, wash, obtain solid product；
(2) solid product that step (1) obtains is placed in the copper nitrate solution that concentration is 0.2mol/L, is 50 DEG C in temperature and stirs
Mixing 3h and obtain mixed solution, mixed solution filters, obtain solid product after washing, solid product after drying temperature be 300～
Roasting 5h at 500 DEG C, i.e. prepares Au-Cu support type mesoporous catalyst.
The preparation method of the Cu support type mesoporous catalyst of Au the most according to claim 1 and 2 doping, it is characterised in that:
The mesopore molecular sieve NH of described modification2The preparation of-SBA-15 powder specifically comprises the following steps that
1. under 40 DEG C of stirring conditions, by P123Be dissolved in aqueous hydrochloric acid solution, be subsequently adding TEOS, agitated, crystallization, filtration,
Dry, calcination steps, prepares SBA-15；
2. the SBA-15, the dehydrated alcohol that APTES, step are 1. obtained are mixed in there-necked flask, ultrasonic agitation 30min, 120 DEG C
Return stirring 16h obtains solution；
3. 2. step is obtained solution spend dehydrated alcohol carry out filtering 5 times, washing obtain solid 3 times；
4. 3. step is obtained solid at 60 DEG C, is dried 16h, i.e. prepare modified mesopore molecular sieve NH2-SBA-15 powder.
4. one kind according to claim 1 to 2 arbitrarily described in prepare Au-Cu support type mesoporous catalyst and can apply at CO2Hydrogenation
In reaction preparation methanol process.
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Cited By (3)
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| CN106881143A (en) * | 2017-04-10 | 2017-06-23 | 中国科学院过程工程研究所 | A kind of CuAu bimetallic catalysts and its preparation method and application |
| IT201800004130A1 (en) * | 2018-03-30 | 2019-09-30 | Sotacarbo – Soc Tecnologie Avanzate Low Carbon S P A | Efficient catalyst for the conversion of CO2 to methanol |
| WO2021215408A1 (en) | 2020-04-24 | 2021-10-28 | 東京都公立大学法人 | Carbon dioxide reduction catalyst and carbon dioxide reduction method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106881143A (en) * | 2017-04-10 | 2017-06-23 | 中国科学院过程工程研究所 | A kind of CuAu bimetallic catalysts and its preparation method and application |
| IT201800004130A1 (en) * | 2018-03-30 | 2019-09-30 | Sotacarbo – Soc Tecnologie Avanzate Low Carbon S P A | Efficient catalyst for the conversion of CO2 to methanol |
| WO2019185223A1 (en) | 2018-03-30 | 2019-10-03 | Sotacarbo - Società Tecnologie Avanzate Low Carbon S.P.A. | Efficient catalyst for the conversion of co2 to methanol |
| US11446641B2 (en) | 2018-03-30 | 2022-09-20 | Sotacarbo—Societa Technologie Avanzate Low Carbon S.P.A. | Efficient catalyst for the conversion of CO2 to methanol |
| WO2021215408A1 (en) | 2020-04-24 | 2021-10-28 | 東京都公立大学法人 | Carbon dioxide reduction catalyst and carbon dioxide reduction method |
| JPWO2021215408A1 (en) * | 2020-04-24 | 2021-10-28 | ||
| JP7193037B2 (en) | 2020-04-24 | 2022-12-20 | 中国電力株式会社 | Carbon dioxide reduction catalyst and carbon dioxide reduction method |
| CN115551636A (en) * | 2020-04-24 | 2022-12-30 | 中国电力株式会社 | Carbon dioxide reduction catalyst and carbon dioxide reduction method |
| CN115551636B (en) * | 2020-04-24 | 2024-04-02 | 中国电力株式会社 | Carbon dioxide reduction catalyst and carbon dioxide reduction method |
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