CN109621956A - A kind of copper-based spinel catalyst and preparation method thereof for hydrogenation of carbon dioxide methanol - Google Patents
A kind of copper-based spinel catalyst and preparation method thereof for hydrogenation of carbon dioxide methanol Download PDFInfo
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- CN109621956A CN109621956A CN201811459080.1A CN201811459080A CN109621956A CN 109621956 A CN109621956 A CN 109621956A CN 201811459080 A CN201811459080 A CN 201811459080A CN 109621956 A CN109621956 A CN 109621956A
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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
- B01J23/005—Spinels
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
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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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- 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
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- 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
- C07C29/156—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 iron group metals, platinum group metals or compounds thereof
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- 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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- 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
- Y02P20/584—Recycling of catalysts
Abstract
A kind of copper aluminate catalyst composition for hydrogenation of carbon dioxide methanol are as follows: copper aluminate content is 40.0-99.9wt%, and oxidation copper content is 0.04-10.0wt%, and alumina content 0.06-50%, other oxide contents are 0-20.0%.Preparation method of the invention is simple, low in cost, environmental-friendly, has that catalytic activity is high, stability is good and the significant advantages such as renewable.
Description
Fields
The present invention relates to the copper-based spinel catalysts and its preparation method and application for hydrogenation of carbon dioxide.
Background technique
The fossil energies such as petroleum, coal, natural gas are still that the current mankind depend on for existence one of the main energy sources of development.So
And the energy consumption of sustainable growth brings the row of many negative effects, especially GHG carbon dioxide to ecological environment
Global warming phenomenon caused by putting widely is paid close attention to by all circles.How effectively to store and utilize carbon dioxide to become us must
The problem that must be faced.Methanol is a kind of common Organic Ingredients, using hydrogenation of carbon dioxide methanol can make carbon dioxide as
A kind of carbon resource is efficiently utilized.
The core of hydrogenation of carbon dioxide methanol technology is the research and development of catalyst.Currently, common catalyst is copper-based urges
Agent, majority are developed on the basis of synthesising gas systeming carbinol.Pass through the side such as coprecipitation, infusion process, sol-gal process
Method prepares CuO type catalyst, and is catalyzed carbon dioxide methanol by hydrogen reducing before the reaction to obtain active metal copper
Reaction.Since the Tamman's temperature of metallic copper is relatively low, the phenomenon that copper-based catalysts generally existing sintering deactivation.Researcher passes through
The second metal, preferred vector is added, improves the sintering that the methods of copper dispersion degree improves the activity of copper and alleviates copper.However, being directed to
Hydrogenation of carbon dioxide methanol process, it still needs further improvement with stability for the activity of catalyst.
Summary of the invention
The object of the present invention is to provide a kind of copper-based spinel catalysts of the hydrogenation of carbon dioxide methanol of efficient stable
And its preparation method and application.
Specifically, problem to be solved by this invention first is that developing a kind of hydrogenation of carbon dioxide first of efficient stable
The copper-based catalysts of alcohol.Problem to be solved by this invention second is that the preparation method of this efficient stable catalyst.The present invention
Problem to be solved third is that this effective catalyst be applied to hydrogenation of carbon dioxide methanol process method.
For one of technical problem, The technical solution adopted by the invention is as follows: hydrogenation of carbon dioxide catalyst for methanol
Composition are as follows: copper aluminate content is 40.0-99.9wt%, and oxidation copper content is 0.04-10.0wt%, and alumina content is
0.06-50.0%, other oxide contents are 0-20.0%.Other oxides can be Fe2O3、Cr2O3、Mn2O3、MgO、CaO、
BaO、ZrO2, one of components such as ZnO or a variety of, help to improve copper aluminate dispersion degree and its catalytic performance.
For the two of technical problem, catalyst of the present invention can be prepared by the following method:
Copper source, silicon source, promoter metal source, complexing agent and solvent are configured to uniform collosol and gel by sol-gal process
Liquid steams solvent, obtains dry spinelle precursor.Alternatively, it is also possible to by solid phase method that copper source, silicon source and auxiliary agent is golden
After the direct physical mixed in category source is uniform, spinelle precursor is obtained.By spinelle precursor at 600-1200 DEG C, air or oxygen
0.5-10h is roasted in gas atmosphere, obtains copper aluminate catalyst.
Copper source, silicon source and other source metals can be nitrate, chloride, sulfate, phosphate, acetate, citric acid
The mixture of one or more of salt, hydroxide, carbonate, subcarbonate, oxide etc..Complexing agent can be lemon
Acid, maleic acid, one of oxalic acid etc. or a variety of.The molar ratio of complexing agent and copper source is 0.5-5.0:1.Solvent can be water or
Alcohols solvent it is one or more.
Sol-gal process, which prepares catalyst, has maturing temperature low, the high feature of prepared active component dispersion degree.Solid phase
When the catalyst of method preparation will reach specified spinelle content, required maturing temperature is higher than sol-gal process maturing temperature, but
It is that it has the characteristics that preparation process is simpler, solvent-free, inexpensive.Therefore, two methods are each advantageous, can be according to reality
Situation selection.
For the three of technical problem, technical scheme is as follows: before the reaction, catalyst does not need to carry out prereduction
Processing, can directly lead to unstripped gas and start to react.Using carbon dioxide and hydrogen as Material synthesis methanol, reaction temperature 230~340
℃；1.5~10.0MPa of reaction pressure；The volume ratio of hydrogen and carbon dioxide is 2.5~4.0；Feed space velocity be 2000~
15000mL/(h·g).Catalyst regeneration is can be achieved by roasting again in catalyst after reaction, prepared by regeneration condition and original
The roasting condition of catalyst requires identical.Copper aluminate catalyst after regeneration still has preferable catalytic performance.
The invention has the following advantages over the prior art:
The invention discloses the synthesis of the copper aluminate catalyst and its hydrogenation of carbon dioxide of a kind of high activity and high stability
The application of methanol.The method for preparing catalyst is simple, low in cost, environmental-friendly, has that catalytic activity is high, stability is good and can
The significant advantages such as regeneration.
Detailed description of the invention
Fig. 1 is to apply the copper aluminate type that catalyst precursor is prepared after 1000 DEG C and 500 DEG C roastings respectively in example 1
With the XRD spectra of non-spinelle copper oxide catalyst.
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1:
18.8g copper nitrate, nine water aluminum nitrate of 75.0g, 23.2g maleic acid are uniformly mixed with 150ml water, it is solidifying to form colloidal sol
Glue obtains dry spinelle precursor after steaming water.1000 DEG C of roasting 4h in air atmosphere obtain copper aluminate
Type catalyst.In the catalyst, copper aluminate content is 99.9wt%, aoxidizes copper content 0.04% and alumina component
0.06%.Catalyst is without pre-reduction treatment, in 260 DEG C, 6MPa, H2/CO2Molar ratio=3.0, air speed 6000mL/
(hg) under the conditions of, after continuous operation 100h, methanol generating rate are as follows: copper generates 0.77 mole of methanol per hour per mol.
Comparative example: with embodiment 1, when maturing temperature being only changed to 500 DEG C, synthesized catalyst is the catalysis of copper oxide type
Agent is free of copper-based spinel components, and main component is copper oxide (content 35.0wt%) and aluminium oxide (content 65.0wt%), connects
After reforwarding row 100h, methanol generating rate are as follows: it is only 0.21 mole that copper, which generates quantity of methyl alcohol, per hour per mol.Two kinds of catalyst
XRD characterization is shown in Fig. 1.
Embodiment 2:
18.8g copper nitrate, nine water aluminum nitrate of 204.1g, 4.8g magnesium chloride, 4.5g oxalic acid are uniformly mixed with 350ml water,
Sol gel solution is formed, dry spinelle precursor is obtained after water is steamed.1200 DEG C of roasting 0.5h in air atmosphere,
Obtain copper aluminate type catalyst.In the catalyst, copper aluminate content is 40.0wt%, aoxidizes copper content 4.6%,
The content of aluminium oxide and magnesia is respectively 50.0% and 5.4%.In 260 DEG C, 8MPa, H2/CO2Molar ratio=4.0, air speed are
Under the conditions of 2000mL/ (hg), after continuous operation 100h, methanol generating rate are as follows: copper generates methanol 0.63 per hour per mol
Mole.
Embodiment 3
By 20.0g copper acetate, nine water aluminum nitrate of 93.8g, 2.4g ironic citrate, 1.6g calcium acetate, 96.1g citric acid with
100ml ethyl alcohol and 100ml water are uniformly mixed, and form sol gel solution, dry spinelle precursor is obtained after solvent is steamed.
1000 DEG C of roasting 1h in air atmosphere obtain copper aluminate type catalyst.In the catalyst, copper aluminate content is
68.7wt% aoxidizes copper content 1.1%, alumina content 24.0%, iron oxide content 3.6%, calcium oxide content 2.6%.?
230℃、1.5MPa、H2/CO2Molar ratio=4.0, air speed is under the conditions of 3000mL/ (hg), after continuous operation 100h, methanol is raw
At rate are as follows: copper generates 0.54 mole of methanol per hour per mol.
Embodiment 4
By 18.7g copper nitrate, nine water aluminum nitrate of 75.0g, 17.9g manganese nitrate, 2.4g barium sulfate, 38.4g citric acid with
200ml water is uniformly mixed, and forms sol gel solution, dry spinelle precursor is obtained after solvent is steamed.In air atmosphere
In 600 DEG C of roasting 10h, obtain copper aluminate type catalyst.In the catalyst, copper aluminate content is 75.2wt%, oxygen
Change copper content 2.1%, alumina content 2.7%, oxidation manganese content 14.3%, barium monoxide content 5.7%.260 DEG C,
6.0MPa、H2/CO2Molar ratio=3.0, air speed is under the conditions of 7000 mL/ (hg), after continuous operation 100h, methanol generates speed
Rate are as follows: copper generates 0.63 mole of methanol per hour per mol.
Embodiment 5
By 18.7g copper nitrate, nine water aluminum nitrate of 105.0g, 3.0g basic zirconium phosphate, 4.5g oxalic acid, 42.3g citric acid and 150ml
Water and 150ml methanol are uniformly mixed, and form sol gel solution, dry spinelle precursor is obtained after solvent is steamed.In oxygen
800 DEG C of roasting 8h in gas atmosphere obtain copper aluminate type catalyst.In the catalyst, copper aluminate content is
58.0wt% aoxidizes copper content 10.0%, alumina content 29.8%, zirconia content 2.2%.In 270 DEG C, 8.0MPa, H2/
CO2Molar ratio=3.0, under the conditions of air speed is 5000mL/ (hg), after continuous operation 100h, methanol generating rate are as follows: per small
When every mole of copper generate 0.59 mole of methanol.
Embodiment 6
18.7g copper nitrate, nine water aluminum nitrate of 75.0g, 9.4g manganese nitrate, 42.3g citric acid are mixed with 200ml water
It is even, sol gel solution is formed, dry spinelle precursor is obtained after solvent is steamed.600 DEG C of roastings in oxygen atmosphere
10h obtains copper aluminate type catalyst.In the catalyst, copper aluminate content is 80.3wt%, aoxidizes copper content
7.3%, alumina content 9.4%, oxidation manganese content 3.0%.In 250 DEG C, 8.0MPa, H2/CO2Molar ratio=3.0, air speed are
Under the conditions of 6000mL/ (hg), after continuous operation 100h, methanol generating rate are as follows: copper generates methanol 0.52 per hour per mol
Mole.
Embodiment 7
9.7g Kocide SD, 21.9g boehmite and 1.9 grams of chromium carbonates are subjected to physical mixed, in oxygen atmosphere
900 DEG C of roasting 4h obtain copper aluminate type catalyst.In the catalyst, copper aluminate content is 69.7wt%, copper oxide
Content 2.9%, alumina content 24.2%, chromic oxide content 3.2%.In 340 DEG C, 10.0MPa, H2/CO2Molar ratio=3.0,
Air speed be 15000mL/ (hg) under the conditions of, after continuous operation 100h, methanol generating rate are as follows: per hour per mol copper generate first
0.59 mole of alcohol.
Embodiment 8
22.1g basic copper carbonate, 72.7g boehmite and 3.3 grams of acetic acid zirconiums are subjected to physical mixed, in air gas gas
950 DEG C of roasting 6h in atmosphere obtain copper aluminate type catalyst.In the catalyst, copper aluminate content is 73.1wt%, oxygen
Change copper content 1.6%, alumina content 22.9%, zirconia content 2.4%.In 240 DEG C, 6.0MPa, H2/CO2Molar ratio=
4.0, under the conditions of air speed is 7000mL/ (hg), after continuous operation 100h, methanol generating rate are as follows: copper is raw per hour per mol
At 0.75 mole of methanol.
After reaction stops, catalyst in air gas atmosphere, is being warming up to 950 DEG C of roasting 6h again, after being regenerated
Copper-based spinel catalyst.In 240 DEG C, 6.0MPa, H2/CO2Molar ratio=4.0, air speed are 7000 mL/ (hg) condition
Under, after continuous operation 100h, methanol generating rate are as follows: copper generates 0.73 mole of methanol per hour per mol.
Embodiment 9
7.9g copper oxide, 60.5g boehmite and 1.8 grams of zinc acetates are subjected to physical mixed, in oxygen gas atmosphere
850 DEG C of roasting 5h obtain copper aluminate type catalyst.In the catalyst, copper aluminate content is 73.4wt%, copper oxide
Content 5.2%, alumina content 18.4%, zirconia content 3.0%.In 260 DEG C, 6.0MPa, H2/CO2Molar ratio=3.0,
Air speed be 6000mL/ (hg) under the conditions of, after continuous operation 100h, methanol generating rate are as follows: per hour per mol copper generate first
0.73 mole of alcohol.
Embodiment 10
9.8g Kocide SD, 60.5g boehmite, 0.6g calcium oxide and 1.6g zirconium hydroxide are subjected to physical mixed,
950 DEG C of roasting 3h in oxygen gas atmosphere obtain copper aluminate type catalyst.In the catalyst, copper aluminate content is
77.2wt% aoxidizes copper content 2.5%, alumina content 12.7%, calcium oxide content 2.0% and zirconia content 5.6%.
In 260 DEG C, 6.0MPa, H2/CO2Molar ratio=3.0, air speed be 6000 mL/ (hg) under the conditions of, after continuous operation 100h, first
Alcohol generating rate are as follows: copper generates 0.75 mole of methanol per hour per mol.
Claims (8)
1. a kind of copper aluminate catalyst for hydrogenation of carbon dioxide methanol, it is characterised in that hydrogenation of carbon dioxide first
The composition of alcohol catalyst are as follows: copper aluminate content is 40.0-99.9wt%, and oxidation copper content is 0.04-10.0wt%, aluminium oxide
Content is 0.06-50%, and other oxide contents are 0-20.0%.
2. a kind of copper aluminate catalyst for hydrogenation of carbon dioxide methanol as described in claim 1, feature exist
In other oxides can be Fe2O3、Cr2O3、Mn2O3、MgO、CaO、BaO、ZrO2, one of ZnO component or a variety of.
3. a kind of preparation of the copper aluminate catalyst for hydrogenation of carbon dioxide methanol as claimed in claim 1 or 2
Method, it is characterised in that include the following steps:
Copper source, silicon source, promoter metal source, complexing agent and solvent are configured to uniform sol gel solution by sol-gal process,
Solvent is steamed, dry spinelle precursor is obtained；Alternatively, it is also possible to pass through solid phase method for copper source, silicon source and promoter metal
After the direct physical mixed in source is uniform, spinelle precursor is obtained, by spinelle precursor in 600-1200oUnder C, air or oxygen
0.5-10h is roasted in atmosphere, obtains copper aluminate catalyst.
4. a kind of preparation side of the copper aluminate catalyst for hydrogenation of carbon dioxide methanol as claimed in claim 3
Method, it is characterised in that copper source, silicon source and other source metals are nitrate, chloride, sulfate, phosphate, acetate, citric acid
The mixture of one or more of salt, hydroxide, carbonate, subcarbonate, oxide.
5. a kind of preparation side of the copper aluminate catalyst for hydrogenation of carbon dioxide methanol as claimed in claim 3
Method, it is characterised in that complexing agent is citric acid, maleic acid, one of oxalic acid or a variety of, and the molar ratio of complexing agent and copper source is
0.5-5.0:1。
6. a kind of preparation side of the copper aluminate catalyst for hydrogenation of carbon dioxide methanol as claimed in claim 3
Method, it is characterised in that solvent can be the one or more of water or alcohols solvent.
7. a kind of application of the copper aluminate catalyst for hydrogenation of carbon dioxide methanol as claimed in claim 1 or 2,
It is characterized by comprising following steps:
Using carbon dioxide and hydrogen as Material synthesis methanol, 230~340 DEG C of reaction temperature；1.5~10.0MPa of reaction pressure；Hydrogen
The volume ratio of gas and carbon dioxide is 2.5~4.0；Feed space velocity is 2000~15000 mL/hg.
8. a kind of application of the copper aluminate catalyst for hydrogenation of carbon dioxide methanol as claimed in claim 7,
It is characterized in that the catalyst after reacting realizes catalyst regeneration by roasting again, regeneration condition is that spinelle precursor exists
600-1200oUnder C, 0.5-10h is roasted in air or oxygen atmosphere, obtains reclaimed copper aluminate catalyst.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110743495A (en) * | 2019-09-30 | 2020-02-04 | 北京航空航天大学 | Nano manganese oxide modified biomass charcoal, preparation method thereof and method for removing copper citrate |
| CN112479703A (en) * | 2020-11-20 | 2021-03-12 | 辽宁石油化工大学 | Spinel solid solution material and preparation method and application thereof |
| CN113663678A (en) * | 2021-08-11 | 2021-11-19 | 清华大学 | Cu-based spinel catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof |
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