CN110102294A - Composite oxide supported Pd base catalyst and its preparation method and application - Google Patents
Composite oxide supported Pd base catalyst and its preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 152
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 106
- 238000006243 chemical reaction Methods 0.000 claims abstract description 104
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 65
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 54
- 238000001035 drying Methods 0.000 claims abstract description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 230000032683 aging Effects 0.000 claims description 27
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 23
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 230000009467 reduction Effects 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 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 claims description 13
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- YTXAYGAYACWVGD-UHFFFAOYSA-N palladium;hydrate Chemical compound O.[Pd] YTXAYGAYACWVGD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000008188 pellet Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910002676 Pd(NO3)2·2H2O Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000012495 reaction gas Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 243
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 2
- 229960004424 carbon dioxide Drugs 0.000 description 71
- 230000000694 effects Effects 0.000 description 16
- 239000010949 copper Substances 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance 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
- KRQUFUKTQHISJB-YYADALCUSA-N 2-[(E)-N-[2-(4-chlorophenoxy)propoxy]-C-propylcarbonimidoyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one Chemical compound CCC\C(=N/OCC(C)OC1=CC=C(Cl)C=C1)C1=C(O)CC(CC1=O)C1CCCSC1 KRQUFUKTQHISJB-YYADALCUSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910005224 Ga2O Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- C07C29/157—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 containing platinum group metals 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)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to loaded catalyst technical fields, disclose a kind of composite oxide supported Pd base catalyst and its preparation method and application, the catalyst is using ZnO-xAl composite oxides as carrier, and Pd is active component, and Al is as structural promoter；When preparation, active component Pd is introduced using Co deposited synthesis ZnO-xAl composite oxide carrier, then using deposition-precipitation method, drying and roasting obtains Pd/ZnO-xAl catalyst.Catalyst of the present invention is suitable for hydrogenation of carbon dioxide reaction for preparing methanol, using Pd as active component, has CO compared to unmodified Pd series catalysts2High conversion rate, the high feature of methanol yield.
Description
Technical field
The present invention relates to loaded catalyst technical fields, are to be related to one kind with ZnO-xAl composite oxides specifically
The application of precious metals pd catalyst for carrier and preparation method thereof and the catalyst in hydrogenation of carbon dioxide methanol.
Background technique
The exploitation and use of industrial fossil fuel, while pushing civilization of human society process, largely with sacrificial
Domestic animal ecological environment is cost.Since the industrial revolution, due to the burning of a large amount of fossil energies, cause the carbon dioxide concentration in air by
Year improves, and the climatic issues such as greenhouse effects caused seriously threaten the living environment of the mankind.In April, 2016, the United Nations was big
The whole world after " Paris agreement " proposes the year two thousand twenty can be passed through to cope with climate change, realize blueprint and hope that green low-carbon develops
Scape, to realize global average temperature before 2100 compared with elevation amplitude control horizontal before industrialization 2 DEG C within the scope of
Target.In addition to the discharge of carbon dioxide, the burning of fossil energy can also discharge in large quantities nitrogen oxides, oxysulfide and its
His combustion product, produces direct destruction to environment.Often there is wide range of haze in recent years in China, also to clean energy resource
Using proposing more urgent requirement.
It can't be ignored, carbon dioxide is also carbon source abundant on the earth.Atmosphere is reduced except through energy-saving and emission-reduction
In carbon dioxide, pass through to carbon dioxide carry out chemistry utilization.In July, 2016, European catalyticing research cluster (European
Cluster on Catalysis) publication " European catalytic science and Technology Roadmap ", it is indicated that carbon dioxide will become important
This trend of raw material.While reducing CO2 emission, producing some high value-added products will be more meaningful.?
Carbon dioxide use aspects research and develop artificial photosynthetic process, convert chemical products and fuel for carbon dioxide (and hydrogen), this mistake
Journey will be used as future 10-20 goal in research.Nobel Laureate's Aura once foretold that methanol will become the important energy of substitution oil gas
Source.Synthesizing methanol by hydrogenating carbon dioxide reaction, is the utilization to carbon dioxide, and is stored to the chemistry of renewable hydrogen energy.Turn
The methanol that metaplasia produces is important the raw material of industry and good liquid energy carrier.
The research and development of hydrogenation of carbon dioxide catalyst at present are referred to methanol-fueled CLC industry more, carry out to synthesising gas systeming carbinol
It is modified.Early in nineteen twenties, methanol-fueled CLC industry is begun setting up, synthesis gas (CO+H2) (item at high temperature under high pressure
Part) synthesizing methanol on Zn-Cr base catalyst.Nineteen sixties, Zn-Cr are gradually catalyzed by nontoxic efficient Cu base
Agent replaces, and uses till today.CO2Preparing methanol by hydrogenation process has industrial demonstration unit report, but conversion per pass is lower and selects
Property it is insufficient.At present in synthesizing methanol by hydrogenating carbon dioxide catalyst system, research is most widely Cu base catalyst.Due to titanium dioxide
The reaction of carbon synthesizing methanol by hydrogenating structure-sensitive, the Cu partial size for controlling smaller size are especially important.And Cu is during the reaction
It is easy agglomeration, Cu nano particle is caused to become larger, activity and methanol selectivity seriously reduce.With synthesis gas synthesizing methanol (CO+
2H2=CH3OH) different, synthesizing methanol by hydrogenating carbon dioxide reacts (CO2+3H2=CH3OH+H2It O also include vapour change against the current in)
Change side reaction (CO2+H2=H2O+CO).Compared with the system of synthesising gas systeming carbinol, had in hydrogenation of carbon dioxide system more
Water generates, and water undoubtedly can also promote the sintering of Cu.
It is active using needing to carry out to it due to carbon dioxide very inertia itself.Cu catalyst is easy to burn in addition to existing
Except the problem of knot, the ability that Cu dissociates hydrogen is also weaker, it is difficult to CO2Two C=O keys in molecule are all broken apart, therefore are produced
It is mainly carbon monoxide in object, the selectivity of methanol is lower and is practically free of methane, and activity is relatively low.Since Pd has
There is stronger dissociation Hydrogen Energy power, the extensive utilization in various hydrogenation reactions, also there are many researchs in hydrogenation of carbon dioxide.Pd tool
There is anti-caking power more better than Cu, and after oxidation and reduction process repeatedly, Pd can maintain the stability of structure.
CO2The oxidisability having can during the reaction gradually aoxidize Cu, this is also an influence factor of Cu base catalyst inactivation.
In addition to this, in terms of the influence for resisting the poisonous substances such as sulphur, chlorine, Pd base catalyst also has apparent advantage compared to copper, therefore
Pd base catalyst is given more sustained attention in recent years.The study found that Pd base catalyst is used for carbon dioxide hydrogenation reaction, carrier, grain
The electronic state of diameter and Pd have a significant impact to selectivity of product.In reducibility carrier such as ZnO, CeO2On tend to give birth to
At methanol and carbon monoxide, and in inert carrier such as Al2O3、SiO2On tend to generate methane.Larger metal Pd particle updip
To in generating methane, and be conducive to the generation of carbon monoxide on smaller Pd particle.In Pd base catalyst, ZnO, Ga2O are used3
And In2O3With very high methanol activity, think that there are strong metal-support interaction (SMSI) Pd and its in these systems
The alloy that the metallic element of carrier is formed is its active site, and the partial size of smaller PdZn alloy is more advantageous to the selection of methanol
Property.Some researchs also found that Pd has the advantage under low pressure relative to Cu.However Pd, as a kind of noble metal, reserves are rare, must
Its utilization efficiency must be improved.
Summary of the invention
The present invention is to solve the technical problem that existing Pd base catalyst carbon dioxide conversion is low, methanol yield is low,
A kind of composite oxide supported Pd base catalyst and preparation method thereof is provided, the application in hydrogenation of carbon dioxide promotes
CO in reaction process2Activation, to improve methanol yield, while also improving the utilization efficiency of Pd.
In order to solve the above-mentioned technical problem, the present invention is achieved by technical solution below:
A kind of composite oxide supported Pd base catalyst, using ZnO-xAl composite oxides as carrier, Pd is the catalyst
Active component, Al are obtained as structural promoter, and by following preparation method:
(1) the nine water aluminum nitrate and the zinc nitrate hexahydrate is soluble in water, it is formed by precursor solution total concentration
For 0.1-2M, the molar ratio of the nine water aluminum nitrate and the zinc nitrate hexahydrate is 0.01-0.5；Natrium carbonicum calcinatum is dissolved in
In water, being formed by sodium carbonate liquor concentration is 0.1-2M；
(2) under 40-80 DEG C of water-bath and stirring condition, the obtained presoma of a dropping step (1) simultaneously in water
Solution is with the sodium carbonate liquor until pH value is 5-10；Aging 0.5-5h after precipitating is filtered, and washing solid sediment is more
It is secondary；Solid is deposited at 60-120 DEG C dry 6-24h, then 1-6h is roasted at 250-550 DEG C, it is compound to obtain ZnO-xAl
Oxide carrier.
(3) ZnO-xAl composite oxide carrier is ground uniformly, uniform ultrasonic disperse Yu Shuizhong, obtaining concentration is 1-6g/
The ZnO-xAl composite oxide dispersion of L；By Na2CO3Soluble in water with NaOH, concentration is respectively 0.5-2M and 0.5-2M, is obtained
To precipitant solution；By two water palladium nitrate (Pd (NO3)2·2H2O it) is dissolved in water, concentration 0.0001M-0.01M is added drop-wise to above-mentioned
In composite oxide dispersion, wherein metal Pd load capacity on ZnO-xAl composite oxides is 0.1-5wt.%；In 40-80
Under DEG C water-bath and stirring condition, the precipitant solution is added dropwise into the ZnO-xAl composite oxide dispersion until pH
Value is 5-10；Aging 0.5-5h after precipitating is filtered, and washing solid sediment is multiple；Solid is deposited at 60-120 DEG C
Dry 6-24h, then roasts 1-6h at 250-550 DEG C, obtains the Pd/ZnO-xAl catalyst of support type.
Further, precursor solution total concentration described in step (1) is 0.5M；The nine water aluminum nitrate and six water
The molar ratio of zinc nitrate is 0.087；The concentration of the sodium carbonate liquor is 1.5M.
Further, the bath temperature in step (2) is 65 DEG C；PH value is 7；Ageing time is 3h；Drying temperature is 90
DEG C, drying time 12h；Maturing temperature is 350 DEG C, calcining time 3h.
Further, the concentration of ZnO-xAl composite oxide dispersion described in step (3) is 3g/L, the Na2CO3It is molten
The concentration of liquid is 0.8M, and the concentration of the NaOH solution is 1.2M, and the concentration of the two water palladium nitrate solution is 0.0028M；Its
Middle metal Pd load capacity on ZnO-xAl composite oxides is 2.5wt.%；
Bath temperature in step (3) is 60 DEG C；PH value is 10；Ageing time is 3h；Drying temperature is 90 DEG C, when dry
Between be 12h；Maturing temperature is 400 DEG C, calcining time 4h.
A kind of preparation method of above-mentioned composite oxide supported Pd base catalyst, this method follow the steps below:
(1) zinc nitrate hexahydrate and nine water aluminum nitrates is soluble in water, being formed by precursor solution total concentration is 0.1-2M,
The molar ratio of the nine water aluminum nitrate and the zinc nitrate hexahydrate is 0.01-0.5；Natrium carbonicum calcinatum is soluble in water, institute's shape
At sodium carbonate liquor concentration be 0.1-2M；
(2) under 40-80 DEG C of water-bath and stirring condition, the obtained presoma of a dropping step (1) simultaneously in water
Solution is with the sodium carbonate liquor until pH value is 5-10；Aging 0.5-5h after precipitating is filtered, and washing solid sediment is more
It is secondary；Solid is deposited at 60-120 DEG C dry 6-24h, then 1-6h is roasted at 250-550 DEG C, it is compound to obtain ZnO-xAl
Oxide carrier.
(3) ZnO-xAl composite oxide carrier is ground uniformly, uniform ultrasonic disperse Yu Shuizhong, obtaining concentration is 1-6g/
The ZnO-xAl composite oxide dispersion of L；By Na2CO3Soluble in water with NaOH, concentration is respectively 0.5-2M and 0.5-2M, is obtained
To precipitant solution；By two water palladium nitrate (Pd (NO3)2·2H2O it) is dissolved in water, concentration 0.0001M-0.01M is added drop-wise to above-mentioned
In composite oxide dispersion, wherein metal Pd load capacity on ZnO-xAl composite oxides is 0.1-5wt.%；In 40-80
Under DEG C water-bath and stirring condition, the precipitant solution is added dropwise into the ZnO-xAl composite oxide dispersion until pH
Value is 5-10；Aging 0.5-5h after precipitating is filtered, and washing solid sediment is multiple；Solid is deposited at 60-120 DEG C
Dry 6-24h, then roasts 1-6h at 250-550 DEG C, obtains the Pd/ZnO-xAl catalyst of support type.
A kind of application of above-mentioned composite oxide supported Pd base catalyst, prepares ethyl alcohol for hydrogenation of carbon dioxide, tool
Body follows the steps below:
(a) catalyst of above-mentioned preparation is subjected to tabletting and screening process, to obtain pellet type catalyst；
(b) above-mentioned pellet type catalyst is packed into fixed bed reactors, carries out reduction treatment；
(c) it is passed through nitrogen to pressurize and be warming up to reaction temperature, is passed through reaction gas and is reacted.
Further, catalyst is subjected to compressing tablet process in step (a), sieved to obtain the particulate catalytic of 20-40 mesh
Agent carry out using.
Further, the reduction treatment in step (b) uses nitrogen and hydrogen mixture, and hydrogen volume ratio is in nitrogen and hydrogen mixture
50%, reduction temperature is 300-500 DEG C, recovery time 0.5-4h.
Further, reduction temperature is 400 DEG C, recovery time 2h.
Further, the reaction velocity in step (c) is 3000-9000mL/h/gcat。
The beneficial effects of the present invention are:
(1) catalyst of the invention is using PdZn as dissociation hydrogen activity center, with ZnO-xAl composite oxide carrier work
It is prepared using a small amount of Al as structural promoter for the activated centre of adsorption activation carbon dioxide and stable phase Central Shanxi Plain mesosome
Carrier has high-specific surface area, introduces Pd in conjunction with deposition-precipitation method, is on the one hand conducive to active component and is uniformly distributed and keeps
The lesser particle size of noble metal；On the other hand, ZnO lattice is entered by the Al doping of proper content, carries out effect of acidity and basicity
The regulation and optimization of matter promote the activation of carbon dioxide in reaction process, can preferably promote catalytic activity.Due to ZnO-
XAl composite oxides prepare simple and easy, have very big promotion as pure ZnO carrier catalysis performance is compared after carrier, and opposite
It can be realized high methanol yield under lower Pd load capacity, therefore there is certain industrial significance.
(2) catalyst of the invention is suitable under condition of high voltage, has good effect to hydrogenation of carbon dioxide methanol
Fruit, carbon dioxide conversion are higher than 10%, and methanol selectivity can reach 50%.
Detailed description of the invention
Fig. 1 is the activity of 2.5wt.%Pd/ZnO-xAl catalyst hydrogenation of carbon dioxide prepared by embodiment 1 and institute
Product distribution (250 DEG C, 30bar, air speed=6000mL/h/gcat, H2/CO2/N2=69/23/8)；
Fig. 2 is the transmission electron microscope figure of 2.5wt.%Pd/ZnO-xAl catalyst prepared by embodiment 1.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail, and following embodiment can make this profession
The present invention, but do not limit the invention in any way is more completely understood in technical staff.
Embodiment 1
(1) zinc nitrate hexahydrate and nine water aluminum nitrates is soluble in water, being formed by precursor solution total concentration is 0.5M, institute
The molar ratio for stating nine water aluminum nitrates and the zinc nitrate hexahydrate is 0.087；Natrium carbonicum calcinatum is soluble in water, it is formed by carbon
Acid sodium solution concentration is 1.5M；
(2) under 65 DEG C of water-baths and stirring condition, while precursor solution and sodium carbonate liquor in (1) is added dropwise, and tie up
Holding pH value is 7.Aging 3h after precipitating, filtering and washing；
(3) solid in (2) is deposited at 90 DEG C dry 12h, then roasts 3h at 350 DEG C, obtains for load
Composite oxide carrier；
(4) by the uniform simultaneously ultrasonic disperse Yu Shuizhong of composite oxide carrier grinding in (3), obtaining concentration is the compound of 3g/L
Oxidate dispersion solution；
(5) by Na2CO3Soluble in water with NaOH, concentration is respectively 0.8M and 1.2M, obtains precipitant solution.By two water nitre
Sour palladium (Pd (NO3)2·2H2O) it is dissolved in water, concentration 0.0028M.Two water palladium nitrate solutions are added dropwise in dispersion liquid, wherein gold
Category Pd load capacity is 2.5wt.%；
(6) under 60 DEG C of water bath conditions and stirring condition, it is straight in dispersion liquid in (5) that precipitant solution in (5) is added dropwise
It is 10 to pH value.Aging 3h after precipitating, filtering and washing.
(7) solid is deposited at 90 DEG C dry 12h, then roasts 4h at 400 DEG C, obtains the Pd/ZnO- of support type
XAl catalyst；
It (8) is the pellet type catalyst of 20-40 mesh by 2.5wt.%Pd/ZnO-xAl fine catalyst tabletting；
(9) the 2.5wt.%Pd/ZnO-xAl catalyst after tabletting is packed into fixed bed reactors, is passed through nitrogen and hydrogen mixture,
Reductase 12 h is carried out to the catalyst at a temperature of 400 DEG C, hydrogen volume ratio is 50% in nitrogen and hydrogen mixture；It is passed through N2, pressurization
Reaction gas is switched to when reaching 250 DEG C of reaction temperature to 30bar, wherein carbon dioxide and hydrogen molar ratio are 3:1, Balance Air
For nitrogen, air speed=6000mL/h/gcat, H2/CO2/N2=69/23/8；
Catalyst activity is indicated with conversion ratio and produced methanol and carbon monoxide selective, selectivity of product following formula
It is calculated:
Conversion ratio:
Selectivity:
Yield:
Yield(CH3OH%)=Conversion (CH3OH%) × Selectivity (CH3OH%) × 100%
Yield (CO%)=Conversion (CO%) × Selectivity (CO%) × 100%
Yield(CH4%)=Conversion (CH4%) × Selectivity (CH4%) × 100%
Wherein, X(in)Representing the volume flow rate of X at reactor inlet, (X represents CO2,CO,CH3OH,N2And CH4)
corresponds to the X concentrations at the inlet,and X(out)Represent reactor exit volume
Flow velocity.Reaction product uses gas chromatograph on-line analysis.
Embodiment 2:
It is reacted using 1 method of embodiment, difference is only that zinc nitrate hexahydrate and the nine water aluminum nitrate institutes of step (1)
The precursor solution total concentration of formation is 0.1M
Embodiment 3:
It is reacted using 1 method of embodiment, difference is only that zinc nitrate hexahydrate and the nine water aluminum nitrate institutes of step (1)
The precursor solution total concentration of formation is 1M
Embodiment 4:
It is reacted using 1 method of embodiment, difference is only that zinc nitrate hexahydrate and the nine water aluminum nitrate institutes of step (1)
The precursor solution total concentration of formation is 2M
Embodiment 5:
It is reacted using 1 method of embodiment, difference is only that nine water aluminum nitrates of step (1) rub with zinc nitrate hexahydrate
You are than being 0.
Embodiment 6:
It is reacted using 1 method of embodiment, difference is only that nine water aluminum nitrates of step (1) rub with zinc nitrate hexahydrate
You are than being 0.010.
Embodiment 7:
It is reacted using 1 method of embodiment, difference is only that nine water aluminum nitrates of step (1) rub with zinc nitrate hexahydrate
You are than being 0.031.
Embodiment 8:
It is reacted using 1 method of embodiment, difference is only that nine water aluminum nitrates of step (1) rub with zinc nitrate hexahydrate
You are than being 0.307.
Embodiment 9:
It is reacted using 1 method of embodiment, difference is only that nine water aluminum nitrates of step (1) rub with zinc nitrate hexahydrate
You are than being 0.507.
Embodiment 10:
It is reacted using 1 method of embodiment, difference is only that in step (1) that sodium carbonate liquor concentration is 0.1M.
Embodiment 11:
It is reacted using 1 method of embodiment, difference is only that in step (1) that sodium carbonate liquor concentration is 2M.
Embodiment 12:
It is reacted using 1 method of embodiment, difference is only that the bath temperature of step (2) is 40 DEG C.
Embodiment 13:
It is reacted using 1 method of embodiment, difference is only that the bath temperature of step (2) is 80 DEG C.
Embodiment 14:
It is reacted using 1 method of embodiment, difference is only that the pH value of step (2) is 5.
Embodiment 15:
It is reacted using 1 method of embodiment, difference is only that the pH value of step (2) is 10.
Embodiment 16:
It is reacted using 1 method of embodiment, difference is only that the ageing time of step (2) is 0.5h.
Embodiment 17:
It is reacted using 1 method of embodiment, difference is only that the ageing time of step (2) is 5h.
Embodiment 18:
It is reacted using 1 method of embodiment, difference is only that the drying temperature of step (3) is 60 DEG C.
Embodiment 19:
It is reacted using 1 method of embodiment, difference is only that the drying temperature of step (3) is 120 DEG C.
Embodiment 20:
It is reacted using 1 method of embodiment, difference is only that the drying time of step (3) is 6h.
Embodiment 21:
It is reacted using 1 method of embodiment, difference is only that the drying time of step (3) is for 24 hours.
Embodiment 22:
It is reacted using 1 method of embodiment, difference is only that the maturing temperature of step (3) is 250 DEG C.
Embodiment 23:
It is reacted using 1 method of embodiment, difference is only that the maturing temperature of step (3) is 550 DEG C.
Embodiment 24:
It is reacted using 1 method of embodiment, difference is only that the calcining time of step (3) is 1h.
Embodiment 25:
It is reacted using 1 method of embodiment, difference is only that the calcining time of step (3) is 6h.
Embodiment 26:
It is reacted using 1 method of embodiment, difference is only that the composite oxide dispersion concentration of step (4) is
1g/L。
Embodiment 27:
It is reacted using 1 method of embodiment, difference is only that the composite oxide dispersion concentration of step (4) is
6g/L。
Embodiment 28:
It is reacted using 1 method of embodiment, difference is only that the Na of step (5)2CO3Concentration is 0.5M.
Embodiment 29:
It is reacted using 1 method of embodiment, difference is only that the Na of step (5)2CO3Concentration is 2M.
Embodiment 30:
It is reacted using 1 method of embodiment, difference is only that the NaOH concentration of step (5) is 0.5M.
Embodiment 31:
It is reacted using 1 method of embodiment, difference is only that the NaOH concentration of step (5) is 2M.
Embodiment 32:
It is reacted using 1 method of embodiment, difference is only that the Pd (NO of step (5)3)2·2H2O concentration is
0.0001M。
Embodiment 33:
It is reacted using 1 method of embodiment, difference is only that the Pd (NO of step (5)3)2·2H2O concentration is
0.01M。
Embodiment 34:
It is reacted using 1 method of embodiment, difference is only that the metal Pd load capacity of step (5) is 0.1wt.%.
Embodiment 35:
It is reacted using 1 method of embodiment, difference is only that the metal Pd load capacity of step (5) is 5wt.%.
Embodiment 36:
It is reacted using 1 method of embodiment, difference is only that the bath temperature of step (6) is 40 DEG C.
Embodiment 37:
It is reacted using 1 method of embodiment, difference is only that the bath temperature of step (6) is 80 DEG C.
Embodiment 38:
It is reacted using 1 method of embodiment, difference is only that the pH value of step (6) is 8.
Embodiment 39:
It is reacted using 1 method of embodiment, difference is only that the pH value of step (6) is 12.
Embodiment 40:
It is reacted using 1 method of embodiment, difference is only that the ageing time of step (6) is 0.5h.
Embodiment 41:
It is reacted using 1 method of embodiment, difference is only that the ageing time of step (6) is 5h.
Embodiment 42:
It is reacted using 1 method of embodiment, difference is only that the drying temperature of step (7) is 60 DEG C.
Embodiment 43:
It is reacted using 1 method of embodiment, difference is only that the drying temperature of step (7) is 120 DEG C.
Embodiment 44:
It is reacted using 1 method of embodiment, difference is only that the drying time of step (7) is 6h.
Embodiment 45:
It is reacted using 1 method of embodiment, difference is only that the drying time of step (7) is for 24 hours.
Embodiment 46:
It is reacted using 1 method of embodiment, difference is only that the maturing temperature of step (7) is 250 DEG C.
Embodiment 47:
It is reacted using 1 method of embodiment, difference is only that the maturing temperature of step (7) is 550 DEG C.
Embodiment 48:
It is reacted using 1 method of embodiment, difference is only that the calcining time of step (7) is 1h.
Embodiment 49:
It is reacted using 1 method of embodiment, difference is only that the calcining time of step (7) is 6h.
Embodiment 50:
It is reacted using 1 method of embodiment, difference is only that the reduction temperature of step (9) is 300 DEG C.
Embodiment 51:
It is reacted using 1 method of embodiment, difference is only that the reduction temperature of step (9) is 500 DEG C.
Embodiment 52:
It is reacted using 1 method of embodiment, difference is only that the recovery time of step (9) is 0.5h.
Embodiment 53:
It is reacted using 1 method of embodiment, difference is only that the reduction temperature of step (9) is 4h.
Embodiment 54:
It is reacted using 1 method of embodiment, difference is only that the air speed of step (9) is 3000mL/h/gcat。
Embodiment 55:
It is reacted using 1 method of embodiment, difference is only that the air speed of step (9) is 9000mL/h/gcat。
About above-described embodiment result and data, activity data when being all made of reaction 4h is compared, to investigate different systems
Standby influence of the parameter to catalyst reaction performance.
(1) step (1) zinc nitrate hexahydrate and the total concentration of nine water aluminum nitrate precursor solutions are active to catalyst reaction
It influences, referring to table 1.Reaction condition is the same as embodiment 1,2,3,4.
The total concentration of table 1, step (1) zinc nitrate hexahydrate and nine water aluminum nitrate precursor solutions is to hydrogenation of carbon dioxide activity
Influence
| Concentration (M) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 0.1 | 12.8 | 58.1 | 7.3 |
| 0.5 | 12.3 | 57.0 | 7.0 |
| 1 | 11.7 | 56.8 | 6.6 |
| 2 | 11.4 | 55.9 | 6.4 |
As can be seen from the table, in step (1) total concentration of zinc nitrate hexahydrate and nine water aluminum nitrate precursor solutions to two
The influence of carbonoxide hydrogenation activity is not significant.
(2) nine water aluminum nitrates and zinc nitrate hexahydrate molar ratio are on the active influence of catalyst reaction, ginseng in step (1)
It is shown in Table 2.Reaction condition is the same as embodiment 1,5,6,7,8,9.
Table 2, step (1) composite oxide carrier difference Al content are on the active influence of hydrogenation of carbon dioxide
As can be seen from the table, with the increase of Al content in step (1), carbon dioxide conversion and methanol yield first increase
Reduce after adding, wherein when Al content is 8%, CO2Conversion ratio reaches 14.2%, and methanol yield reaches 7.3%, and methanol selects
Property is maintained at 50% or more.
(3) sodium carbonate liquor concentration is on the active influence of catalyst reaction in step (1), referring to table 3.Reaction condition is same
Embodiment 1,10,11.
Sodium carbonate liquor concentration is on the active influence of hydrogenation of carbon dioxide in table 3, step (1)
| Concentration (M) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 0.1 | 14.4 | 51.3 | 7.4 |
| 1.5 | 14.2 | 51.6 | 7.3 |
| 2 | 13.9 | 52.2 | 7.3 |
As can be seen from the table, the influence active on hydrogenation of carbon dioxide of sodium carbonate liquor concentration is not shown in step (1)
It writes.
(4) bath temperature is on the active influence of catalyst reaction in step (2), referring to table 4.The same embodiment of reaction condition
1、12、13。
Bath temperature is on the active influence of hydrogenation of carbon dioxide in table 4, step (2)
| Bath temperature (DEG C) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 40 | 12.3 | 52.2 | 6.4 |
| 65 | 14.2 | 51.6 | 7.3 |
| 80 | 13.6 | 52.4 | 7.1 |
As can be seen from the table, bath temperature influence active on hydrogenation of carbon dioxide is not significant in step (2).
(5) pH value of step (2) is on the active influence of catalyst reaction, referring to table 5.Reaction condition with embodiment 1,14,
15。
PH value is on the active influence of hydrogenation of carbon dioxide in table 5, step (2)
| pH | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 5 | 13.8 | 45.7 | 5.3 |
| 7 | 14.2 | 51.6 | 7.3 |
| 9 | 10.4 | 57.1 | 6.0 |
As can be seen from the table, pH value increases in step (2), CO2The reduced trend of conversion ratio presentation, and methanol selectivity
Increased trend is presented, highest methanol yield can be obtained when wherein pH value is 7.
(6) ageing time of step (2) is on the active influence of catalyst reaction, referring to table 6.The same embodiment of reaction condition
1、15、16。
Ageing time is on the active influence of hydrogenation of carbon dioxide in table 6, step (2)
| Ageing time (h) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 0.5 | 12.2 | 48.9 | 6.0 |
| 3 | 14.2 | 51.6 | 7.3 |
| 5 | 13.9 | 50.8 | 7.1 |
As can be seen from the table, when ageing time is 0.5h in step (2), catalytic activity is lower.Ageing time extends
To 3h, activity is improved.Continue to extend to 5h, there is no significant changes.
(7) drying temperature of step (3) is on the active influence of catalyst reaction, referring to table 7.The same embodiment of reaction condition
2、18、19。
Drying temperature is on the active influence of hydrogenation of carbon dioxide in table 7, step (3)
| Drying temperature (DEG C) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 60 | 14.6 | 51.4 | 7.5 |
| 90 | 14.2 | 51.6 | 7.3 |
| 120 | 14.3 | 51.3 | 7.3 |
As can be seen from the table, drying temperature influence active on hydrogenation of carbon dioxide is not significant in step (3).
(8) drying time of step (3) is on the active influence of catalyst reaction, referring to table 8.The same embodiment of reaction condition
1、20、21。
Drying time is on the active influence of hydrogenation of carbon dioxide in table 8, step (3)
| Drying time (h) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 6 | 13.9 | 51.7 | 7.2 |
| 12 | 14.2 | 51.6 | 7.3 |
| 24 | 14.1 | 52.0 | 7.3 |
As can be seen from the table, drying time influence active on hydrogenation of carbon dioxide is not significant in step (3).
(9) maturing temperature of step (3) is on the active influence of catalyst reaction, referring to table 9.The same embodiment of reaction condition
1、22、23。
Maturing temperature is on the active influence of hydrogenation of carbon dioxide in table 9, step (3)
As can be seen from the table, maturing temperature influence active on hydrogenation of carbon dioxide is more significant in step (3), wherein
Catalytic activity when maturing temperature is 350 DEG C is better than catalytic activity when maturing temperature is 250 DEG C and 550 DEG C.
(10) calcining time of step (3) is on the active influence of catalyst reaction, referring to table 10.The same embodiment of reaction condition
1、24、25。
Calcining time is on the active influence of hydrogenation of carbon dioxide in table 10, step (3)
| Calcining time (h) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 1 | 9.5 | 56.6 | 5.3 |
| 3 | 14.2 | 51.6 | 7.3 |
| 6 | 13.9 | 51.2 | 7.1 |
As can be seen from the table, when calcining time is 1 in step (3), catalytic activity is lower.Calcining time extends to 3h,
Activity improves.Continue to extend to 5h, there is no significant changes.
Composite oxide dispersion concentration is on the active influence of catalyst reaction in (11) step (4), referring to table 11.Instead
Answer condition with embodiment 1,26,27.
Composite oxide dispersion concentration is on the active influence of hydrogenation of carbon dioxide in table 11, step (4)
| Concentration (g/L) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 1 | 15.1 | 53.4 | 8.0 |
| 3 | 14.2 | 51.6 | 7.3 |
| 6 | 12.8 | 49.7 | 6.4 |
As can be seen from the table, composite oxide dispersion concentration is lower in step (4), hydrogenation of carbon dioxide active
It is higher.
Na in (12) step (5)2CO3Concentration is on the active influence of catalyst reaction, referring to table 12.Reaction condition is the same as real
Apply example 1,28,29.
Na in table 12, step (5)2CO3Concentration is on the active influence of hydrogenation of carbon dioxide
As can be seen from the table, Na in step (5)2CO3Concentration influence active on hydrogenation of carbon dioxide is not significant.
NaOH concentration is on the active influence of catalyst reaction in (13) step (5), referring to table 13.Reaction condition is the same as implementation
Example 1,30,31.
NaOH concentration is on the active influence of hydrogenation of carbon dioxide in table 13, step (5)
| Concentration (M) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 0.5 | 14.4 | 51.3 | 7.4 |
| 1.5 | 14.2 | 51.6 | 7.3 |
| 2 | 13.9 | 52.1 | 7.2 |
As can be seen from the table, NaOH concentration influence active on hydrogenation of carbon dioxide is not significant in step (5).
Pd (NO in (14) step (5)3)2·2H2O concentration is on the active influence of catalyst reaction, referring to table 14.Reaction
Condition is the same as embodiment 1,32,33.
Pd (NO in table 14, step (5)3)2·2H2O concentration is on the active influence of hydrogenation of carbon dioxide
| Concentration (M) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 0.0001 | 15.7 | 54.4 | 8.5 |
| 0.0028 | 14.2 | 51.6 | 7.3 |
| 0.01 | 12.8 | 49.3 | 6.3 |
As can be seen from the table, Pd (NO in step (5)3)2·2H2O concentration is lower, and hydrogenation of carbon dioxide is active higher.
Metal Pd load capacity is on the active influence of catalyst reaction in (15) step (5), referring to table 15.Reaction condition is same
Embodiment 1,34,35.
Metal Pd load capacity is on the active influence of hydrogenation of carbon dioxide in table 15, step (5)
| Load capacity (%) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 0.1 | 2.7 | 67.3 | 1.8 |
| 2.5 | 14.2 | 51.6 | 7.3 |
| 5 | 16.7 | 50.5 | 8.4 |
As can be seen from the table, metal Pd load capacity is higher in step (5), and hydrogenation of carbon dioxide is active higher.
Bath temperature is on the active influence of catalyst reaction in (16) step (6), referring to table 16.Reaction condition is the same as implementation
Example 1,36,37.
Bath temperature is on the active influence of hydrogenation of carbon dioxide in table 16, step (6)
| Bath temperature (DEG C) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 40 | 13.9 | 52.0 | 7.2 |
| 60 | 14.2 | 51.6 | 7.3 |
| 80 | 13.7 | 52.1 | 7.1 |
As can be seen from the table, bath temperature influence active on hydrogenation of carbon dioxide is not significant in step (6).
PH value is on the active influence of catalyst reaction in (17) step (6), referring to table 17.Reaction condition with embodiment 1,
38、39。
PH value is on the active influence of hydrogenation of carbon dioxide in table 17, step (6)
| pH | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 8 | 13.7 | 52.3 | 7.2 |
| 10 | 14.2 | 51.6 | 7.3 |
| 12 | 14.3 | 51.0 | 7.2 |
As can be seen from the table, pH value influence active on hydrogenation of carbon dioxide is not significant in step (6).
Ageing time is on the active influence of catalyst reaction in (18) step (6), referring to table 18.Reaction condition is the same as implementation
Example 1,40,41.
Ageing time is on the active influence of hydrogenation of carbon dioxide in table 18, step (6)
| Ageing time (h) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 0.5 | 14.6 | 53.3 | 7.8 |
| 3 | 14.2 | 51.6 | 7.3 |
| 5 | 13.8 | 49.6 | 6.8 |
As can be seen from the table, ageing time is shorter in step (6), and hydrogenation of carbon dioxide activity is higher.
Drying temperature is on the active influence of catalyst reaction in (19) step (7), referring to table 19.Reaction condition is the same as implementation
Example 1,42,43.
Drying temperature is on the active influence of hydrogenation of carbon dioxide in table 19, step (7)
| Drying temperature (DEG C) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 60 | 14.4 | 52.3 | 7.5 |
| 90 | 14.2 | 51.6 | 7.3 |
| 120 | 13.9 | 51.9 | 7.2 |
As can be seen from the table, drying temperature influence active on catalyst reaction is not significant in step (7).
In (20) step (7) drying time on the active influence of catalyst reaction, referring to table 20.Reaction condition is the same as implementation
Example 1,44,45.
Drying time is on the active influence of hydrogenation of carbon dioxide in table 20, step (7)
| Drying time (h) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 6 | 13.8 | 53.1 | 7.3 |
| 12 | 14.2 | 51.6 | 7.3 |
| 24 | 14.3 | 52.1 | 7.5 |
As can be seen from the table, drying time influence active on catalyst reaction is not significant in step (7).
Maturing temperature is on the active influence of catalyst reaction in (21) step (7), referring to table 21.Reaction condition is the same as real
Apply example 1,46,47.
Maturing temperature is on the active influence of hydrogenation of carbon dioxide in table 21, step (7)
| Maturing temperature (DEG C) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 250 | 14.5 | 53.8 | 7.8 |
| 400 | 14.2 | 51.6 | 7.3 |
| 550 | 12.1 | 48.7 | 5.9 |
As can be seen from the table, maturing temperature is lower in step (7), and hydrogenation of carbon dioxide activity is higher.
Calcining time is on the active influence of catalyst reaction in (22) step (7), referring to table 22.Reaction condition is the same as real
Apply example 1,48,49.
Calcining time is on the active influence of hydrogenation of carbon dioxide in table 22, step (7)
As can be seen from the table, calcining time influence active on hydrogenation of carbon dioxide is not significant in step (7).
Reduction temperature is on the active influence of catalyst reaction in (23) step (9), referring to table 23.Reaction condition is the same as real
Apply example 1,50,51.
Reduction temperature is on the active influence of hydrogenation of carbon dioxide in table 23, step (9)
| Reduction temperature (DEG C) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 300 | 14.8 | 42.6 | 6.3 |
| 400 | 14.2 | 51.6 | 7.3 |
| 500 | 13.1 | 49.2 | 6.4 |
As can be seen from the table, in step (3), as reduction temperature increases, CO2Conversion ratio reduces, and methanol selectivity
Reach highest at 400 DEG C with methanol yield.
In (24) step (9) recovery time on the active influence of catalyst reaction, referring to table 24.Reaction condition is the same as real
Apply example 1,52,53.
Reduction temperature is on the active influence of hydrogenation of carbon dioxide in table 24, step (3)
| Recovery time (h) | CO2Conversion ratio (%) | Methanol selectivity (%) | Methanol yield (%) |
| 0.5 | 15.1 | 46.3 | 7.0 |
| 2 | 14.2 | 51.6 | 7.3 |
| 4 | 13.5 | 49.2 | 6.7 |
As can be seen from the table, in step (3), as the recovery time extends, CO2Conversion ratio reduces, and methanol selectivity
Reach highest in 2h with methanol yield.
Air speed is on the active influence of catalyst reaction in (25) step (9), referring to table 25.The same embodiment of reaction condition
1、54、55。
Air speed is on the active influence of hydrogenation of carbon dioxide in table 25, step (9)
As can be seen from the table, in step (3), as air speed improves, methanol selectivity is improved, and CO2Conversion ratio reduces
Decline with methanol yield.
In summary, it is seen then that Pd/ZnO-Al catalyst involved in the present invention draws on the basis of introducing Pd/ZnO
After entering Al, catalytic activity is significantly improved, and has good carbon dioxide conversion and methanol yield.When Al's and ZnO
Molar ratio is lower than 0.087, and carbon dioxide conversion and methanol yield increase with the molar ratio of Al and ZnO and increased.When
The molar ratio of Al and ZnO is higher than 0.087, and carbon dioxide conversion and methanol yield increase with the molar ratio of Al and ZnO
And it reduces.When the molar ratio of Al and ZnO is optimal 0.087, carbon dioxide conversion reaches 14.2%, and methanol yield reaches
To 7.3%.Wherein methanol space-time yield reaches 6.28gMethanol·h-1·gPd -1, shown preferably compared to previous Pd base catalyst
The catalytic efficiency of unit mass Pd.
Although the preferred embodiment of the present invention is described above in conjunction with attached drawing, the invention is not limited to upper
The specific embodiment stated, the above mentioned embodiment is only schematical, be not it is restrictive, this field it is common
Technical staff under the inspiration of the present invention, without breaking away from the scope protected by the purposes and claims of the present invention, may be used also
By make it is many in the form of specific transformation, within these are all belonged to the scope of protection of the present invention.
Claims (10)
1. a kind of composite oxide supported Pd base catalyst, which is characterized in that the catalyst is with ZnO-Al composite oxides
Carrier, Pd are active component, and Al is obtained as structural promoter, and by following preparation method:
(1) the nine water aluminum nitrate and the zinc nitrate hexahydrate is soluble in water, being formed by precursor solution total concentration is
The molar ratio of 0.1-2M, the nine water aluminum nitrate and the zinc nitrate hexahydrate is 0.01-0.5；Natrium carbonicum calcinatum is dissolved in water
In, being formed by sodium carbonate liquor concentration is 0.1-2M；
(2) under 40-80 DEG C of water-bath and stirring condition, the obtained precursor solution of a dropping step (1) simultaneously in water
With the sodium carbonate liquor until pH value is 5-10；Aging 0.5-5h after precipitating is filtered, and washing solid sediment is multiple；
Solid is deposited at 60-120 DEG C dry 6-24h, then 1-6h is roasted at 250-550 DEG C, obtains ZnO-xAl combined oxidation
Object carrier.
(3) ZnO-xAl composite oxide carrier is ground uniformly, uniform ultrasonic disperse Yu Shuizhong, obtaining concentration is 1-6g/L's
ZnO-xAl composite oxide dispersion；By Na2CO3Soluble in water with NaOH, concentration is respectively 0.5-2M and 0.5-2M, is sunk
Shallow lake agent solution；By two water palladium nitrate (Pd (NO3)2·2H2O it) is dissolved in water, concentration 0.0001M-0.01M is added drop-wise to above-mentioned compound
In oxidate dispersion solution, wherein metal Pd load capacity on ZnO-xAl composite oxides is 0.1-5wt.%；In 40-80 DEG C of water
Under bath and stirring condition, the precipitant solution is added dropwise into the ZnO-xAl composite oxide dispersion until pH value is
5-10；Aging 0.5-5h after precipitating is filtered, and washing solid sediment is multiple；Solid is deposited at 60-120 DEG C dry
Then 6-24h roasts 1-6h at 250-550 DEG C, obtain the Pd/ZnO-xAl catalyst of support type.
2. the composite oxide supported Pd base catalyst of one kind according to claim 1, which is characterized in that in step (1)
The precursor solution total concentration is 0.5M；The molar ratio of the nine water aluminum nitrate and the zinc nitrate hexahydrate is 0.087；Institute
The concentration for stating sodium carbonate liquor is 1.5M.
3. the composite oxide supported Pd base catalyst of one kind according to claim 1, which is characterized in that in step (2)
Bath temperature be 65 DEG C；PH value is 7；Ageing time is 3h；Drying temperature is 90 DEG C, drying time 12h；Maturing temperature is
350 DEG C, calcining time 3h.
4. the composite oxide supported Pd base catalyst of one kind according to claim 1, which is characterized in that in step (3)
The concentration of the ZnO-xAl composite oxide dispersion is 3g/L, the Na2CO3The concentration of solution is 0.8M, and the NaOH is molten
The concentration of liquid is 1.2M, and the concentration of the two water palladium nitrate solution is 0.0028M；Wherein metal Pd is in ZnO-xAl combined oxidation
Load capacity is 2.5wt.% on object；
Bath temperature in step (3) is 60 DEG C；PH value is 10；Ageing time is 3h；Drying temperature is 90 DEG C, and drying time is
12h；Maturing temperature is 400 DEG C, calcining time 4h.
5. a kind of preparation method of composite oxide supported Pd base catalyst as described in any one of claim 1-4, special
Sign is that this method follows the steps below:
(1) zinc nitrate hexahydrate and nine water aluminum nitrates is soluble in water, being formed by precursor solution total concentration is 0.1-2M, described
The molar ratio of nine water aluminum nitrates and the zinc nitrate hexahydrate is 0.01-0.5；Natrium carbonicum calcinatum is soluble in water, it is formed by
Sodium carbonate liquor concentration is 0.1-2M；
(2) under 40-80 DEG C of water-bath and stirring condition, the obtained precursor solution of a dropping step (1) simultaneously in water
With the sodium carbonate liquor until pH value is 5-10；Aging 0.5-5h after precipitating is filtered, and washing solid sediment is multiple；
Solid is deposited at 60-120 DEG C dry 6-24h, then 1-6h is roasted at 250-550 DEG C, obtains ZnO-xAl combined oxidation
Object carrier.
(3) ZnO-xAl composite oxide carrier is ground uniformly, uniform ultrasonic disperse Yu Shuizhong, obtaining concentration is 1-6g/L's
ZnO-xAl composite oxide dispersion；By Na2CO3Soluble in water with NaOH, concentration is respectively 0.5-2M and 0.5-2M, is sunk
Shallow lake agent solution；By two water palladium nitrate (Pd (NO3)2·2H2O it) is dissolved in water, concentration 0.0001M-0.01M is added drop-wise to above-mentioned compound
In oxidate dispersion solution, wherein metal Pd load capacity on ZnO-xAl composite oxides is 0.1-5wt.%；In 40-80 DEG C of water
Under bath and stirring condition, the precipitant solution is added dropwise into the ZnO-xAl composite oxide dispersion until pH value is
5-10；Aging 0.5-5h after precipitating is filtered, and washing solid sediment is multiple；Solid is deposited at 60-120 DEG C dry
Then 6-24h roasts 1-6h at 250-550 DEG C, obtain the Pd/ZnO-xAl catalyst of support type.
6. a kind of application of composite oxide supported Pd base catalyst as described in any one of claim 1-4, feature exist
In preparing ethyl alcohol for hydrogenation of carbon dioxide, specifically follow the steps below:
(a) catalyst of above-mentioned preparation is subjected to tabletting and screening process, to obtain pellet type catalyst；
(b) above-mentioned pellet type catalyst is packed into fixed bed reactors, carries out reduction treatment；
(c) it is passed through nitrogen to pressurize and be warming up to reaction temperature, is passed through reaction gas and is reacted.
7. a kind of application of composite oxide supported Pd base catalyst as claimed in claim 6, which is characterized in that step (a)
It is middle that catalyst is subjected to compressing tablet process, screening with obtain the pellet type catalyst of 20-40 mesh carry out using.
8. a kind of application of composite oxide supported Pd base catalyst as claimed in claim 6, which is characterized in that step (b)
In reduction treatment use nitrogen and hydrogen mixture, hydrogen volume ratio is 50% in nitrogen and hydrogen mixture, and reduction temperature is 300-500 DEG C,
Recovery time is 0.5-4h.
9. a kind of application of composite oxide supported Pd base catalyst as claimed in claim 8, which is characterized in that reduction temperature
It is 400 DEG C, recovery time 2h.
10. a kind of application of composite oxide supported Pd base catalyst as claimed in claim 6, which is characterized in that step (c)
In reaction velocity be 3000-9000mL/h/gcat。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110586064A (en) * | 2019-09-27 | 2019-12-20 | 天津大学 | Lithium-doped zirconium oxide loaded indium oxide catalyst and preparation method and application thereof |
| CN113145113A (en) * | 2021-05-07 | 2021-07-23 | 中国科学院上海高等研究院 | Carbon dioxide hydrogenation catalyst, preparation method and application thereof |
| CN113842906A (en) * | 2020-06-25 | 2021-12-28 | 现代自动车株式会社 | Catalyst for converting carbon dioxide into methanol by hydrogenation and method for preparing same |
| CN114367285A (en) * | 2022-01-17 | 2022-04-19 | 上海工程技术大学 | Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation and application thereof |
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| CN104971717A (en) * | 2015-06-25 | 2015-10-14 | 天津大学 | Pt-modified ZnO/Al2O3 catalyst and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110586064A (en) * | 2019-09-27 | 2019-12-20 | 天津大学 | Lithium-doped zirconium oxide loaded indium oxide catalyst and preparation method and application thereof |
| CN113842906A (en) * | 2020-06-25 | 2021-12-28 | 现代自动车株式会社 | Catalyst for converting carbon dioxide into methanol by hydrogenation and method for preparing same |
| CN113145113A (en) * | 2021-05-07 | 2021-07-23 | 中国科学院上海高等研究院 | Carbon dioxide hydrogenation catalyst, preparation method and application thereof |
| CN114367285A (en) * | 2022-01-17 | 2022-04-19 | 上海工程技术大学 | Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation and application thereof |
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