CN110327933A - Hydrogenation of carbon dioxide prepares catalyst of methanol and its preparation method and application - Google Patents
Hydrogenation of carbon dioxide prepares catalyst of methanol and its preparation method and application Download PDFInfo
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- CN110327933A CN110327933A CN201910675995.4A CN201910675995A CN110327933A CN 110327933 A CN110327933 A CN 110327933A CN 201910675995 A CN201910675995 A CN 201910675995A CN 110327933 A CN110327933 A CN 110327933A
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- Prior art keywords
- catalyst
- carbon dioxide
- methanol
- hydrogenation
- roasting
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 138
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 76
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 68
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 58
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 29
- 230000032683 aging Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000000465 moulding Methods 0.000 claims abstract description 8
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 7
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 7
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 229960004424 carbon dioxide Drugs 0.000 description 48
- 239000012065 filter cake Substances 0.000 description 19
- 230000001376 precipitating effect Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 8
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 8
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910003178 Mo2C Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910004369 ThO2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910007470 ZnO—Al2O3 Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
Abstract
The present invention relates to a kind of catalyst for preparing methanol, and in particular to a kind of hydrogenation of carbon dioxide prepares catalyst of methanol and its preparation method and application.The mixed salt solution of mantoquita, zinc salt and aluminium salt and sodium carbonate liquor mixing are precipitated, aging is carried out again, filtering, it is then placed into filtration cakes torrefaction in container, is filled with carbon dioxide gas roasting, in roasting process, pressure is set to be maintained at 2-4MPa, decrease temperature and pressure obtains catalyst precursor after roasting, obtains catalyst after molding.Catalyst of the present invention has high activity and High selectivity of methanol, and under lower reaction temperature (200 DEG C of conditions), carbon dioxide conversion reaches 25% or more, and the selectivity of methanol reaches 85% or more.Preparation method provided by the invention makes catalyst crystal form to absorption and activation carbon dioxide conversion is easier to, so that its catalytic performance be greatly improved.
Description
Technical field
The present invention relates to a kind of catalyst for preparing methanol, and in particular to a kind of hydrogenation of carbon dioxide prepares the catalysis of methanol
Agent and its preparation method and application.
Background technique
A large amount of use of fossil fuel brings the rapid development of human economy since the industrial revolution, however mistake at the same time
More CO2Discharge also brings a series of global environment such as greenhouse effects, climate warming, Melting Glacierss, unusual weather conditions and asks
Topic, reasonable utilization CO2As carbon source, can regenerate to form recycling for carbon resource by chemical means, this
The dependence to traditional fossil energy will not only be mitigated, simultaneously for improvement environment, it is ensured that the sustainable development of the mankind has weight
The realistic meaning wanted, wherein CO2The utilization of synthesizing methanol by hydrogenating is in modern society to CO2The important way recycled it
One, but about CO2Prepare methanol industrialization there is a problem of one it is important be exactly catalyst selectivity is relatively low, conversion
Rate is poor.
CO2Most of preparing methanol by hydrogenation catalyst is researched and developed on the basis of CO preparing methanol by hydrogenation catalyst, mesh
The preceding catalysts for preparing methanol about carbon dioxide can be substantially divided into three categories, the first is the catalysis of copper-based type
Agent, main catalyst for example have Cu/ZnO/Al2O3、Cu/ZnO/ZrO2、Cu/ZnO/SiO2、Cu/NiO2/TiO2Etc., wherein
Cu is as main active component, ZnO, NiO2Very big facilitation is played to reaction Deng as auxiliary agent, Al2O3、
SiO2、TiO2Deng then playing the role of skeleton as carrier, at the same also can dispersed catalyst active component, improve CO2Absorption
And conversion ratio.The emphasis that copper-based System Catalyst is always studied both at home and abroad especially adds into copper-based catalysts, adulterates other
Metal is always CO2The main flow direction of synthesizing methanol by hydrogenating catalyst developmental research, as in CuO/ZnO/Al2O3Add in catalyst
Enter Ni and Fe auxiliary agent to be modified catalyst, catalyst activity can be improved, when Ni content is lower and Fe content is higher, urges
Agent activity is preferably.And in Cu/ZnO/Al2O3B is added in catalyst2O3, then will increase the dispersibility and catalyst stabilization of Cu
Property, to improve catalyst activity, further for the proportion of each component in catalyst, the dispersion degree of copper, method for preparing catalyst,
The factors such as catalyst surface pattern can also generate important influence to the performance of copper-based catalysts, be prepared using special coprecipitation
Nanometer Cu/Zn/Al/Zr fiber catalyst out has large specific surface area, partial size small, and the characteristics of good heat stability, is being catalyzed
After Zr auxiliary agent is added in agent, the activity of catalyst is improved, but its activity and selectivity is still unable to satisfy requirement.
Other than copper-based series catalysts, second of catalyst about carbon dioxide methanol is with transition element metal
Or noble metal (Pt, Pd, Au, Rh etc.) is the loaded catalyst of main active component, due to the stronger H of precious metal surface2
Dissociation and activation capacity, this metalloid may be used as the catalyst of hydrogenation of carbon dioxide methanol, as Pd/SiO2、Pd/Al2O3、
Pd/ThO2Etc., Pd is supported on SiO by Solymosi etc.2、MgO、Al2O3Loaded catalyst application is prepared on equal oxides
In carbon dioxide hydrogenation reaction, wherein the dispersion degree of Pd influences particularly evident, the higher Shi Fanying of dispersion degree to the selectivity of product
Principal product be methane, otherwise when low polydispersity has methanol generation, for these catalyst of these a large amount of metal/oxides
The Chen Jingguang of system, Brookhaven National Laboratory has carried out an inducing classification to it, carries out to its selectivity and yield
The summary of one system, the Liu Yinfeng of Shanghai University provide a kind of reference noble metal in the patent that it is delivered and receive to modify
The method of rice ZnS/ polyaniline composite photocatalyst, in addition there are other some type of catalyst can also be used for carbon dioxide
The reaction for preparing methanol, as metal carbides are due to its stable chemical property, often as catalyst carrier.Vidal etc. will
Au and Cu particulate load is in Mo2C、Fe3C, on TaC and TiC, catalyst series are prepared for.BASF research and development be with chromium and zinc
The ZnO-CrO of main component3Or ZnO-Cr2O3Catalyst.But these catalyst carbon dioxide conversions are still unable to reach business
The requirement of change.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide the catalysis that a kind of hydrogenation of carbon dioxide prepares methanol
Agent has high activity and High selectivity of methanol, has good catalytic activity under lower reaction temperature low temperature；The present invention is also
Preparation method and application are provided.
Hydrogenation of carbon dioxide of the present invention prepares the catalyst of methanol, by the mixed metal of mantoquita, zinc salt and aluminium salt
Salting liquid is precipitated with sodium carbonate liquor mixing, then carries out aging, is filtered, by filtration cakes torrefaction, is then placed into container
In, it is filled with carbon dioxide gas and roasts, in roasting process, so that pressure is maintained at 2-4MPa, decrease temperature and pressure obtains after roasting
Catalyst precursor obtains catalyst after molding.
The rate of addition for controlling sodium carbonate liquor, makes the pH of precipitation system in 8-9；The temperature precipitated is controlled in 70-
80℃。
The molar ratio of Cu, Zn, Al are 1:0.5~1:2.5~3 in mixed salt solution.
Aging is carried out again are as follows: stirring progress aging in 2~2.5 hours.
By the condition of filtration cakes torrefaction are as follows: 0.8~1 hour dry at 100~105 DEG C in an oven.
Calcining time is 10-12 hours, and maturing temperature is 600~700 DEG C.
Hydrogenation of carbon dioxide of the present invention prepares the preparation method of the catalyst of methanol: being prepared using coprecipitation
CuO-ZnO-Al2O3Metal composite oxide mixes the mixed salt solution of mantoquita, zinc salt and aluminium salt with sodium carbonate liquor
Stirring is precipitated, then carries out aging, filters, filtration cakes torrefaction is then placed into container, is filled with carbon dioxide gas roasting
It burns, in roasting process, pressure is made to be maintained at 2-4MPa, decrease temperature and pressure obtains catalyst precursor after roasting, after molding
To catalyst.
As a kind of perferred technical scheme, hydrogenation of carbon dioxide of the present invention prepares the preparation of the catalyst of methanol
Method: CuO-ZnO-Al is prepared using coprecipitation2O3Metal composite oxide, weigh the copper nitrate of different quality, zinc nitrate and
Aluminum nitrate is dissolved in deionized water, is stirred evenly, and is prepared certain density sodium carbonate liquor and is kept it slightly excessive true
Protecting metal ion can precipitate completely.By the mixed salt solution of mantoquita, zinc salt and aluminium salt and sodium carbonate liquor be mixed into
Row precipitating, controls the rate of addition of sodium carbonate, makes the pH of precipitation system in 8-9, and the temperature for controlling precipitation system is controlled in 70-80
DEG C, it is then stirred for progress aging in 2-2.5 hours, filters, filtration cakes torrefaction is then placed into container, is filled with carbon dioxide
Gas roast roasts at 600-700 DEG C, in roasting process, pressure is made to be maintained at 2-4MPa, roasting carries out 10-12 hours, roasting
Decrease temperature and pressure obtains catalyst precursor after burning, obtains catalyst after molding.
Preferably, mixed salt solution and sodium carbonate liquor are added drop-wise in round-bottomed flask simultaneously, are sufficiently stirred, controlled
70-80 DEG C of the temperature of system, pH continue to stir progress aging in 2-2.5 hours after precipitating is complete, then filter, filter cake is used in 8-9
Deionized water is sufficiently washed repeatedly, is eliminated as much as remaining in nitrate ion and sodium ion in filter cake, filter cake is in an oven
0.8-1 hours dry at 105 DEG C, products therefrom is placed in pressure resistant vessel, carbon dioxide gas is filled with, at 600-700 DEG C
It roasts, in roasting process, pressure in pressure resistant vessel is adjusted by pressure-regulating valve, pressure is made to be maintained at 2-4MPa, roasting carries out
10-12 hours, the presoma of hydrogenation of carbon dioxide catalyst for methanol was obtained after decrease temperature and pressure, obtains catalyst after molding.
The main bugbear of carbon dioxide hydrogenation reaction is the absorption and activation of carbon dioxide, is different from carbon monoxide, dioxy
Change carbon structure to stablize, it is not easy to and carrier occurs chemisorption and is activated, therefore, the catalytic activity of Yao Tigao catalyst, just
So that the microstructure of catalyst is easier that chemisorption occurs with carbon dioxide, and is activated into and is easy to happen hydrogenation reaction
Intermediate adsorbent state.This depends on how to construct the microcosmic of carrier, auxiliary agent and the activated centre for having high absorption capacity to carbon dioxide
Structure.The present invention is prepared for CuO-ZnO-Al using coprecipitation2O3Metal composite oxide, by presoma roasting process
Middle introducing high-pressure carbon dioxide atmosphere makes prepared metal oxide have the crystal form of close carbon dioxide, to improve it to two
The chemical adsorption capacity of carbonoxide realizes the raising of carbon dioxide conversion.
Hydrogenation of carbon dioxide of the present invention prepares the application of the catalyst of methanol: carrying out carbon dioxide hydrogenation reaction
Before, the catalyst is passed through atmospheric hydrogen in reactor, in-situ reducing at 280~320 DEG C then passes to 3-3.5:1
Carbon dioxide and hydrogen mixed gas, carbon dioxide hydrogenation reaction is carried out under 180-200 DEG C, 1.8-2.2MPa.
Preferably, before carrying out carbon dioxide hydrogenation reaction, the catalyst is passed through atmospheric hydrogen in reactor,
In-situ reducing 3 hours at 300 DEG C then pass to the carbon dioxide and hydrogen mixed gas of 3:1, two are carried out under 200 DEG C, 2.0MPa
Carbonoxide hydrogenation reaction.
Compared with prior art, the invention has the following advantages that
(1) hydrogenation of carbon dioxide of the present invention prepares the catalyst of methanol, has high activity and High selectivity of methanol,
It is 2000-3000h in volume space velocity-1, there is good catalytic activity under lower reaction temperature low temperature, it is warm in lower reaction
It spends under (200 DEG C of conditions), carbon dioxide conversion reaches 25% or more, and the selectivity of methanol reaches 85% or more.
(2) preparation method provided by the invention has used high-pressure carbon dioxide modified catalyst in roasting process, makes to urge
Agent crystal form is to absorption and activation carbon dioxide conversion is easier to, so that its catalytic performance be greatly improved.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
Embodiment 1
241.6 grams of nitrate trihydrate copper are weighed, 148.7 grams of zinc nitrate hexahydrate, 1775.5 grams of ANN aluminium nitrate nonahydrate, is dissolved
In 10000 grams of deionized waters, the molar ratio of three kinds of metals is 1:0.5:2.5, stirs evenly, prepares 5% sodium carbonate liquor
It can precipitate completely.Mixed salt solution and sodium carbonate liquor are added drop-wise in round-bottomed flask simultaneously, are sufficiently stirred, control system
Temperature 70 C, pH 8, precipitating completely after continue to stir progress aging in 2 hours, then filter, filter cake is washed with deionized
It is 7 to water outlet pH, filter cake is 1 hour dry at 105 DEG C in an oven, and products therefrom is placed in pressure resistant vessel, is filled with titanium dioxide
Carbon gas roasts at 600 DEG C, in roasting process, adjusts pressure in pressure resistant vessel by pressure-regulating valve, is maintained at pressure
2MPa, roasting carry out 10 hours, and the presoma of hydrogenation of carbon dioxide catalyst for methanol is obtained after decrease temperature and pressure.It is shaped to diameter
The cylindrical particle of 2.5mm, length 3mm obtain catalyst.
Embodiment 2
241.6 grams of nitrate trihydrate copper are weighed, 148.7 grams of zinc nitrate hexahydrate, 1775.5 grams of ANN aluminium nitrate nonahydrate, is dissolved
In 10000 grams of deionized waters, the molar ratio of three kinds of metals is 1:0.5:2.5, stirs evenly, prepares 5% sodium carbonate liquor
It can precipitate completely.Mixed salt solution and sodium carbonate liquor are added drop-wise in round-bottomed flask simultaneously, are sufficiently stirred, control system
80 DEG C of temperature, pH 9, precipitating completely after continue to stir progress aging in 2 hours, then filter, filter cake is washed with deionized
It is 7 to water outlet pH, filter cake is 1 hour dry at 105 DEG C in an oven, and products therefrom is placed in pressure resistant vessel, is filled with titanium dioxide
Carbon gas roasts at 700 DEG C, in roasting process, adjusts pressure in pressure resistant vessel by pressure-regulating valve, is maintained at pressure
4MPa, roasting carry out 12 hours, and the presoma of hydrogenation of carbon dioxide catalyst for methanol is obtained after decrease temperature and pressure.It is shaped to diameter
The cylindrical particle of 2.5mm, length 3mm obtain catalyst.
Embodiment 3
241.6 grams of nitrate trihydrate copper are weighed, 297.4 grams of zinc nitrate hexahydrate, 2130.6 grams of ANN aluminium nitrate nonahydrate, is dissolved
In 10000 grams of deionized waters, the molar ratio of three kinds of metals is 1:1:3, is stirred evenly, the sodium carbonate liquor for preparing 5% can be complete
Full precipitating.Mixed salt solution and sodium carbonate liquor are added drop-wise in round-bottomed flask simultaneously, are sufficiently stirred, the temperature of control system
80 DEG C of degree, pH continue to stir progress aging in 2 hours after precipitating is complete, then filter, filter cake is washed with deionized to out 8
Water pH is 7, and filter cake is 1 hour dry at 105 DEG C in an oven, and products therefrom is placed in pressure resistant vessel, is filled with carbon dioxide gas
Body roasts at 600 DEG C, in roasting process, adjusts pressure in pressure resistant vessel by pressure-regulating valve, is maintained at pressure
2MPa, roasting carry out 12 hours, and the presoma of hydrogenation of carbon dioxide catalyst for methanol is obtained after decrease temperature and pressure.It is shaped to diameter
The cylindrical particle of 2.5mm, length 3mm obtain catalyst.
Embodiment 4
241.6 grams of nitrate trihydrate copper are weighed, 297.4 grams of zinc nitrate hexahydrate, 2130.6 grams of ANN aluminium nitrate nonahydrate, is dissolved
In 10000 grams of deionized waters, the molar ratio of three kinds of metals is 1:1:3, is stirred evenly, the sodium carbonate liquor for preparing 5% can be complete
Full precipitating.Mixed salt solution and sodium carbonate liquor are added drop-wise in round-bottomed flask simultaneously, are sufficiently stirred, the temperature of control system
80 DEG C of degree, pH continue to stir progress aging in 2 hours after precipitating is complete, then filter, filter cake is washed with deionized to out 9
Water pH is 7, and filter cake is 1 hour dry at 105 DEG C in an oven, and products therefrom is placed in pressure resistant vessel, is filled with carbon dioxide gas
Body roasts at 700 DEG C, in roasting process, adjusts pressure in pressure resistant vessel by pressure-regulating valve, is maintained at pressure
4MPa, roasting carry out 10 hours, and the presoma of hydrogenation of carbon dioxide catalyst for methanol is obtained after decrease temperature and pressure.It is shaped to diameter
The cylindrical particle of 2.5mm, length 3mm obtain catalyst.
Comparative example 1
241.6 grams of nitrate trihydrate copper are weighed, 148.7 grams of zinc nitrate hexahydrate, 1775.5 grams of ANN aluminium nitrate nonahydrate, is dissolved
In 10000 grams of deionized waters, the molar ratio of three kinds of metals is 1:0.5:2.5, stirs evenly, prepares 5% sodium carbonate liquor
It can precipitate completely.Mixed salt solution and sodium carbonate liquor are added drop-wise in round-bottomed flask simultaneously, are sufficiently stirred, control system
Temperature 70 C, pH 8, precipitating completely after continue to stir progress aging in 2 hours, then filter, filter cake is washed with deionized
It is 7 to water outlet pH, filter cake is 1 hour dry at 105 DEG C in an oven, and products therefrom is placed in pressure resistant vessel, is filled with titanium dioxide
Carbon gas roasts at 600 DEG C, and roasting carries out under atmospheric air atmosphere, and roasting carries out 10 hours, and titanium dioxide is obtained after cooling
The presoma of carbon preparing methanol by hydrogenation catalyst.It is shaped to diameter 2.5mm, the cylindrical particle of length 3mm obtains catalyst.
Comparative example 2
241.6 grams of nitrate trihydrate copper are weighed, 148.7 grams of zinc nitrate hexahydrate, 1775.5 grams of ANN aluminium nitrate nonahydrate, is dissolved
In 10000 grams of deionized waters, the molar ratio of three kinds of metals is 1:0.5:2.5, stirs evenly, prepares 5% sodium carbonate liquor
It can precipitate completely.Mixed salt solution and sodium carbonate liquor are added drop-wise in round-bottomed flask simultaneously, are sufficiently stirred, control system
80 DEG C of temperature, pH 9, precipitating completely after continue to stir progress aging in 2 hours, then filter, filter cake is washed with deionized
It is 7 to water outlet pH, filter cake is 1 hour dry at 105 DEG C in an oven, and products therefrom is placed in pressure resistant vessel, is filled with titanium dioxide
Carbon gas roasts at 700 DEG C, and roasting carries out under atmospheric air atmosphere, and roasting carries out 12 hours, and titanium dioxide is obtained after cooling
The presoma of carbon preparing methanol by hydrogenation catalyst.It is shaped to diameter 2.5mm, the cylindrical particle of length 3mm obtains catalyst.
Comparative example 3
241.6 grams of nitrate trihydrate copper are weighed, 297.4 grams of zinc nitrate hexahydrate, 2130.6 grams of ANN aluminium nitrate nonahydrate, is dissolved
In 10000 grams of deionized waters, the molar ratio of three kinds of metals is 1:1:3, is stirred evenly, the sodium carbonate liquor for preparing 5% can be complete
Full precipitating.Mixed salt solution and sodium carbonate liquor are added drop-wise in round-bottomed flask simultaneously, are sufficiently stirred, the temperature of control system
80 DEG C of degree, pH continue to stir progress aging in 2 hours after precipitating is complete, then filter, filter cake is washed with deionized to out 8
Water pH is 7, and filter cake is 1 hour dry at 105 DEG C in an oven, and products therefrom is placed in pressure resistant vessel, is filled with carbon dioxide gas
Body roasts at 600 DEG C, and roasting carries out under atmospheric air atmosphere, and roasting carries out 12 hours, and carbon dioxide is obtained after cooling and is added
The presoma of hydrogen catalyst for methanol.It is shaped to diameter 2.5mm, the cylindrical particle of length 3mm obtains catalyst.
Comparative example 4
241.6 grams of nitrate trihydrate copper are weighed, 297.4 grams of zinc nitrate hexahydrate, 2130.6 grams of ANN aluminium nitrate nonahydrate, is dissolved
In 10000 grams of deionized waters, the molar ratio of three kinds of metals is 1:1:3, is stirred evenly, the sodium carbonate liquor for preparing 5% can be complete
Full precipitating.Mixed salt solution and sodium carbonate liquor are added drop-wise in round-bottomed flask simultaneously, are sufficiently stirred, the temperature of control system
80 DEG C of degree, pH continue to stir progress aging in 2 hours after precipitating is complete, then filter, filter cake is washed with deionized to out 9
Water pH is 7, and filter cake is 1 hour dry at 105 DEG C in an oven, and products therefrom is placed in pressure resistant vessel, is filled with carbon dioxide gas
Body roasts at 700 DEG C, and roasting carries out under atmospheric air atmosphere, and roasting carries out 10 hours, and carbon dioxide is obtained after cooling and is added
The presoma of hydrogen catalyst for methanol.It is shaped to diameter 2.5mm, the cylindrical particle of length 3mm obtains catalyst.
Comparative example 5
The preparation method of comparative example 5 is same as Example 1, only difference is that: the pressure of carbon dioxide gas when roasting
Power is 10MPa.
Comparative example 6
The preparation method of comparative example 6 is same as Example 1, only difference is that: the pressure of carbon dioxide gas when roasting
Power is 0.5MPa.
Performance test:
Embodiment 1-4 and comparative example the 1-6 catalyst being prepared are respectively charged into fixed bed reactors, in reactor
It is passed through atmospheric hydrogen, in-situ reducing 3 hours at 300 DEG C then pass to the carbon dioxide and hydrogen mixed gas that volume is 3:1, body
Product air speed is 3000h-1Carbon dioxide hydrogenation reaction is carried out under 200 DEG C, 2.0MPa.It collects product to be decomposed, the results are shown in Table
1。
1 methanol steam reforming experimental evaluation result of table
As can be seen from the table, resulting catalyst, catalytic activity are roasted using carbon dioxide atmosphere of the present invention
It is all apparently higher than with selectivity and roasts obtained catalyst using commonsense method.And excessively high and too low roasting carbon dioxide
Atmosphere pressures, it is also unfavorable to catalyst performance.
Claims (10)
1. the catalyst that a kind of hydrogenation of carbon dioxide prepares methanol, it is characterised in that: by the mixed metal of mantoquita, zinc salt and aluminium salt
Salting liquid is precipitated with sodium carbonate liquor mixing, then carries out aging, is filtered, by filtration cakes torrefaction, is then placed into container
In, it is filled with carbon dioxide gas and roasts, in roasting process, so that pressure is maintained at 2-4 MPa, decrease temperature and pressure obtains after roasting
Catalyst precursor obtains catalyst after molding.
2. the catalyst that hydrogenation of carbon dioxide according to claim 1 prepares methanol, it is characterised in that: control sodium carbonate is molten
The rate of addition of liquid makes the pH of precipitation system in 8-9.
3. the catalyst that hydrogenation of carbon dioxide according to claim 2 prepares methanol, it is characterised in that: the temperature precipitated
Degree control is at 70-80 DEG C.
4. the catalyst that hydrogenation of carbon dioxide according to claim 1 prepares methanol, it is characterised in that: mixed metal salt is molten
The molar ratio of Cu, Zn, Al are 1:0.5-1:2.5-3 in liquid.
5. the catalyst that hydrogenation of carbon dioxide according to claim 1 prepares methanol, it is characterised in that: carry out aging again
Are as follows: stirring progress aging in 2-2.5 hours.
6. the catalyst that hydrogenation of carbon dioxide according to claim 1 prepares methanol, it is characterised in that: by filtration cakes torrefaction
Condition are as follows: 0.8-1 hours dry at 100-105 DEG C in an oven.
7. the catalyst that hydrogenation of carbon dioxide according to claim 1 prepares methanol, it is characterised in that: calcining time is
10-12 hours, maturing temperature was 600-700 DEG C.
8. a kind of hydrogenation of carbon dioxide as claimed in claim 1 to 7 prepares the preparation method of the catalyst of methanol, feature
It is: the mixed salt solution of mantoquita, zinc salt and aluminium salt and sodium carbonate liquor mixing is precipitated, then carries out old
Change, filtering is then placed into filtration cakes torrefaction in container, is filled with carbon dioxide gas and roasts, in roasting process, protects pressure
It holds the decrease temperature and pressure after 2-4 MPa, roasting and obtains catalyst precursor, obtain catalyst after molding.
9. the preparation method that hydrogenation of carbon dioxide according to claim 8 prepares the catalyst of methanol, it is characterised in that: will
Mantoquita, the mixed salt solution of zinc salt and aluminium salt and sodium carbonate liquor mixing are precipitated, and the dropwise addition of sodium carbonate is controlled
Speed, makes the pH of precipitation system in 8-9, and the temperature for controlling precipitation system is controlled at 70-80 DEG C, is then stirred for 2-2.5 hours
Aging is carried out, filtering is then placed into filtration cakes torrefaction in container, carbon dioxide gas roasting is filled with, at 600~700 DEG C
It roasts, in roasting process, pressure is made to be maintained at 2-4 MPa, roasting carries out 10-12 hours, and decrease temperature and pressure obtains after roasting
Catalyst precursor obtains catalyst after molding.
10. a kind of hydrogenation of carbon dioxide as claimed in claim 1 to 7 prepares the application of the catalyst of methanol, feature exists
In: before carrying out carbon dioxide hydrogenation reaction, the catalyst is passed through atmospheric hydrogen in reactor, at 280~320 DEG C
In-situ reducing then passes to the carbon dioxide and hydrogen mixed gas of 3-3.5:1, carries out under 180-200 DEG C, 1.8-2.2 MPa
Carbon dioxide hydrogenation reaction.
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| CN113856688A (en) * | 2021-11-16 | 2021-12-31 | 扬州大学 | For CO2Preparation method of Cu-based catalyst for preparing methanol by hydrogenation |
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| CN111167459A (en) * | 2020-02-12 | 2020-05-19 | 中国科学院上海高等研究院 | Catalyst for preparing methanol from mixed gas and preparation method and application thereof |
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| CN113842920A (en) * | 2021-09-24 | 2021-12-28 | 中国科学院上海高等研究院 | Catalyst for preparing methanol by carbon dioxide hydrogenation and forming method and application thereof |
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| CN113856688A (en) * | 2021-11-16 | 2021-12-31 | 扬州大学 | For CO2Preparation method of Cu-based catalyst for preparing methanol by hydrogenation |
| CN113856688B (en) * | 2021-11-16 | 2023-11-10 | 扬州大学 | For CO 2 Preparation method of Cu-based catalyst for preparing methanol by hydrogenation |
| CN114920623A (en) * | 2022-05-11 | 2022-08-19 | 太原工业学院 | CO (carbon monoxide) 2 Method for preparing methanol by hydrogenation |
| CN114920623B (en) * | 2022-05-11 | 2023-09-01 | 太原工业学院 | CO (carbon monoxide) 2 Method for preparing methanol by hydrogenation |
| CN114849718A (en) * | 2022-05-17 | 2022-08-05 | 山东亮剑环保新材料有限公司 | Rare earth doped CO 2 Preparation method of hydrogenation composite catalyst |
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