CN108745363A - It is a kind of for the copper-based catalysts and preparation method of hydrogen from methyl alcohol and application - Google Patents
It is a kind of for the copper-based catalysts and preparation method of hydrogen from methyl alcohol and application Download PDFInfo
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- CN108745363A CN108745363A CN201810454927.0A CN201810454927A CN108745363A CN 108745363 A CN108745363 A CN 108745363A CN 201810454927 A CN201810454927 A CN 201810454927A CN 108745363 A CN108745363 A CN 108745363A
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- copper
- hydrogen
- methyl alcohol
- based catalysts
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000001257 hydrogen Substances 0.000 title claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 48
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000011109 contamination Methods 0.000 abstract description 2
- 238000002441 X-ray diffraction Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 238000010009 beating Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000446 fuel Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 229910018572 CuAlO2 Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- -1 9.8g nickel acetates Chemical class 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 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
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004817 gas chromatography Methods 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
- 239000003676 hair preparation Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/83—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 rare earths or actinides
-
- 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
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
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- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A kind of copper-based catalysts for hydrogen from methyl alcohol are by CuO, Al2O3It is formed with auxiliary agent, each component is with mass fraction：CuO 12.0%-65.0%,Al2O334.0%-85.0%, auxiliary agent 0%-5.0%, and the CuAlO with delafossite structure in catalyst2.The present invention has catalytic activity high, and stability is good, free of contamination advantage.
Description
Technical field
The present invention relates to a kind of catalyst for hydrogen from methyl alcohol, and in particular to a kind of cupper-based catalyst for hydrogen from methyl alcohol
Agent and preparation method and application.
Technical background
The energy and environment are the two big major issues that human society faces, and currently have become and restrict various countries' sustained economic development
An important factor for, it therefore, taps a new source of energy, reduces environmental pollution and cause more and more extensive attention.
Auto industry is to be only second to the second largest industry of petrochemical industry, and the pollution that tail gas is brought accounts for about entire atmosphere pollution
42%, therefore develop cleaning alternative fuel, realize energy-saving and emission-reduction, have great importance.In recent decades, for automobile work
Industry, various countries have carried out the exploitation of a variety of new-energy automobiles in succession, and wherein fuel cell car is quickly grown at present, by each international politics
The great attention at mansion.The development of fuel cell car, one of important auxiliary facility needed, i.e. hydrogenation stations.Chinese relevant policies
It explicitly points out, the year two thousand twenty builds up 100 hydrogenation stations, builds up within 2025 300 hydrogenation stations, and the year two thousand thirty builds up 1000 hydrogenation stations.
However for investment and security standpoint, the hydrogen source of hydrogenation stations is little by the possibility of pipeline transportation centralizedly supply, this
It is necessarily required to the matching of hydrogen producing technology.It is best side by hydrogen from methyl alcohol by the technology of comprehensive analysis current industrial hydrogen manufacturing
Formula has the characteristics that at low cost, mild condition, corrosion-free and product component are few easily separated, and scalable.
Catalyst is the core place of Technology for Production Hydrogen from Methanol, has developed a variety of catalyst system and catalyzings for many years, includes mainly your gold
Belong to and two big catalyst system and catalyzing of base metal.The active high and good feature [chemistry of fuel of stability of noble metal systems catalyst
Journal, 2005,33 (4), 391-395; Appl. Catal. B:Environ., 2011,101,409-416.], but due to
It is expensive, greatly limits its development.Base metal System Catalyst includes mainly nickel system and copper system, and nickel catalyst is steady
Qualitative good but active at low temperature low, selectivity is poor.And Cu-series catalyst is most study, application in hydrogen from methyl alcohol reaction
Most wide catalyst system and catalyzing [Appl. Catal. B:Environ., 2010,99,43-57.], as industrial most widely used
CuZnAl catalyst.Existing copper-based catalysts mostly use infusion process [Appl. Catal. A, 2006,297,151-158], are total to
The precipitation method [J. Catal., 2003,219,389-403； J. Power Sources, 2006,159, 1296-1299;] etc.
Prepared by method, the presoma of active ingredient copper is mainly copper nitrate in these preparation methods, and preparation process brings the row of nitride
It puts, co-precipitation hair preparation process is cumbersome in addition, and brings a large amount of discharge of wastewater, it is difficult to meet the needs of current environmental protection.
For copper-based catalysts, there is a problem of one it is important, i.e., catalytic stability is poor, this is primarily due to
Copper easily occurs sintering and grows up [Topics in Catal., 22 (3-4), 191-203], so as to cause the inactivation of catalyst, and
The catalyst of inactivation is difficult to regenerate reuse.As Yin Yongquan et al. study industrial methanol synthetic catalyst inactivation with again
Raw, as a result display is only dissolved by nitric acid, prepares catalyst again, catalytic activity can just be restored to the state of fresh catalyst
[gas chemical industry, 2000 (25), 34-36].
Invention content
To insufficient existing for existing copper-based catalysts, the object of the present invention is to provide a kind of catalytic activity height, and stability is good,
Free of contamination copper-based catalysts and preparation method and application for hydrogen from methyl alcohol.
In order to reach object above, catalyst of the invention is by CuO, Al2O3It is formed with auxiliary agent, each component quality point
Number is：CuO 12.0%-65.0%,Al2O334.0%-85.0%, auxiliary agent 0%-5.0%, and there is delafossite structure in catalyst
CuAlO2。
Auxiliary agent as described above is NiO, La2O3One or two.
The preparation method of catalyst of the present invention, includes the following steps：
After the predecessor of copper predecessor, aluminium predecessor and auxiliary agent is sufficiently mixed uniformly by the composition of catalyst, ball milling 1-10h,
1-10h is roasted under protective atmosphere, beats sheetmolding to get catalyst.
The predecessor of copper is that Kocide SD or copper oxide are one or two kinds of in the present invention；The predecessor of aluminium be aluminium hydroxide,
Boehmite or aluminium oxide are one or more of；The predecessor of auxiliary agent nickel is that nickel acetate or nickel oxide are one or more of；Auxiliary agent lanthanum
Predecessor be lanthanum sesquioxide.
The application of catalyst of the present invention, includes the following steps：
Catalyst of the present invention is applied to hydrogen from methyl alcohol, and H is being not necessarily to using preceding2Pre-reduction treatment, use condition are：Reaction temperature
250 DEG C -400 DEG C, 0.1 h of mass space velocity-1-3.0h-1, reaction pressure normal pressure -3.0MPa, H2O：CH3The molar ratio of OH is 1.0-
3.0。
Catalyst after use of the present invention can regenerate reuse completely.The hydrogen production process can be used to fixed hydrogen manufacturing
System, it can also be used to mobile hydrogen generating system.Gained hydrogen can be directly used for hydrogen fuel cell after pressure-variable adsorption or UF membrane
Or it is used directly as fuel, industrial chemicals.
Catalyst of the present invention has the following advantages：
1. the preparation method of catalyst is simply controllable, three-waste free discharge, process is environmentally protective；
2. H can be not necessarily to before catalyst use2Pre-reduction treatment enormously simplifies engineering startup procedure；
3. catalyst has preferable catalytic activity and stability, continuous experiment 300 hours, methanol conversion first increases to be kept afterwards
Stablize, and conversion ratio is more than 80%；
4. catalyst has preferable regenerability, reusable.
Description of the drawings
Fig. 1 is the XRD diffraction spectrograms of fresh catalyst and regenerated catalyst
Fig. 2 be in embodiment 1, embodiment 8 and comparative example 1 on catalyst methanol conversion with the reaction time variation diagram.
Specific implementation mode
Following examples will further illustrate the present invention." the fresh catalyst occurred in embodiment
(fresh) " refer to that catalyst uses for the first time, after " regenerated catalyst (regeneration) " refers to catalyst use,
Catalyst after handling under certain conditions.
The test method of catalyst of the present invention is：Carry out catalyst performance test using fixed bed reactors, to gas phase and
Liquid product is analyzed, and is carried out using two gas-chromatographies for being respectively provided with Porapak T columns, TDX-01 columns and thermal conductivity cell detector
Analysis obtains conversion ratio and selectivity.
Embodiment 1
30.0g Kocide SDs, 22.3g boehmites (Al are weighed successively2O3Mass fraction be 70%), after being sufficiently mixed,
It is placed in ball mill（QM2*2, Nantong Machinery Co., Ltd. of friendly nation）In, ball milling 1h, in a nitrogen atmosphere, 1100 DEG C roast gained powder
4h is burnt, through beating sheetmolding after, obtains catalyst, group becomes (mass fraction)：CuO=63.0%,Al2O3=37.0%。
Catalyst is characterized using X-ray diffraction (XRD) technology, the results are shown in Figure 1.As seen from the figure, diffraction maximum
All it is attributed to CuAlO2Diffraction maximum, show in catalyst with delafossite structure CuAlO2。
Catalyst is crushed, after taking 8-16 mesh 2.5g to be packed into reactor, (30ml/min) rises in a nitrogen atmosphere
300 DEG C, after temperature arrives, stop nitrogen, starts charging reaction, evaluation condition and the results are shown in Table 1.
Catalyst carries out prolonged life experiment, as a result such as Fig. 2.As seen from the figure, in 520h, methanol conversion first increases
After reach stable, close to 100%.Then increase mass space velocity to 2.16h-1, methanol conversion is declined slightly, but prolonged anti-
It should remain to that higher catalytic activity, methanol conversion is kept to be more than 90%.From reaction is started to end, 1047h, 1047h are run altogether
Methanol conversion is 91.5%.
Embodiment 2
20.0g copper oxide, 114.8g aluminium oxide, 7.5g nickel oxide are weighed, after being sufficiently mixed, ball milling 10h, gained powder is in argon gas
Under atmosphere, 900 DEG C of roasting 10h obtain catalyst, group becomes (mass fraction) through beating sheetmolding after：CuO=14.6%,Al2O3=
84.0%,NiO=1.4%.Determination contains CuAlO after XRD characterization2.Evaluating catalyst mode with embodiment 1, reaction condition with it is anti-
1 should be the results are shown in Table.Initial methanol conversion is 90.0%, 300h continuous experiments the results show that methanol conversion presentation first increases
After reach stable, 300h methanol conversions be 91.3%.
Embodiment 3
Weigh 12.5g copper oxide, 15.3g Kocide SDs, 48.8g aluminium hydroxides [Al (OH)3], 3.8g lanthanum sesquioxides
[La2O3], after being sufficiently mixed, ball milling 5h, under helium atmosphere, 1000 DEG C of roasting 5h are obtained gained powder through beating sheetmolding after
Catalyst, group become (mass fraction)：CuO=32.2%,Al2O3=62.9%、La2O3=4.9%.Determination contains after XRD characterization
CuAlO2.Evaluating catalyst mode is shown in Table 1 with embodiment 1, reaction condition with reaction result.Initial methanol conversion is 93.2%,
300h continuous experiments the results show that methanol conversion presentation first increases and reaches stable afterwards, 300h methanol conversions are 98.5%.
Embodiment 4
Accurately weigh 19.5g Kocide SDs, 8.6g copper oxide, 44.6g boehmites (Al2O3Mass fraction be 70%),
46.8g aluminium oxide, 9.8g nickel acetates [Ni (CH3COO)2•4H2O], 9.6g nickel oxide, after being sufficiently mixed, ball milling 6h, gained powder
Under nitrogen and helium mix atmosphere, 1200 DEG C of roasting 1h obtain catalyst, group becomes (mass fraction) through beating sheetmolding after：
CuO=23.4%、Al2O3=74.5%,NiO=2.1%.Determination contains CuAlO after XRD characterization2.Evaluating catalyst mode is the same as implementation
Example 1, reaction condition are shown in Table 1 with reaction result.Initial methanol conversion is 81.6%, 300h continuous experiments the results show that methanol
Conversion ratio presentation first increases reaches stable afterwards, and 300h methanol conversions are 85.8%.
Embodiment 5
40.0g Kocide SDs, 6.5g aluminium oxide, 29.8g aluminium hydroxides, 1.0g nickel oxide, 1.5g lanthanum sesquioxides are weighed, fully
After mixing, ball milling 3h, gained powder is under nitrogen, argon gas, helium mix atmosphere, 950 DEG C of roasting 8h, through beating sheetmolding after,
Catalyst is obtained, group becomes (mass fraction)：CuO=53.4%,Al2O3=42.5%、NiO=1.6%、La2O3=2.5%.Through XRD characterization
Determination contains CuAlO afterwards2.Evaluating catalyst mode is shown in Table 1 with embodiment 1, reaction condition with reaction result.Initial methanol conversion
Rate is 80.1%, 300h continuous experiments the results show that methanol conversion presentation first increases and reaches stable afterwards, and 300h methanol converts
Rate is 90.0%.
Embodiment 6
Weigh 30.0g Kocide SDs, 10.2g aluminium oxide, 26.0g aluminium hydroxides, 9.7g boehmites (Al2O3Quality point
Number for 70%), 0.9g nickel oxide, after being sufficiently mixed, ball milling 8h, gained powder is under nitrogen and argon gas mixed atmosphere, 1050 DEG C of roastings
3h is burnt, through beating sheetmolding after, obtains catalyst, group becomes (mass fraction)：CuO=41.2%,Al2O3=57.2%、NiO=1.5%。
Determination contains CuAlO after XRD characterization2.Evaluating catalyst mode is shown in Table 1 with embodiment 1, reaction condition with reaction result.Just
Beginning methanol conversion is 84.8%, 300h continuous experiments the results show that methanol conversion presentation first increases and reaches stable afterwards,
300h methanol conversions are 90.1%.
Embodiment 7
Weigh 45.0g Kocide SDs, 16.6g aluminium hydroxides, 28.8g boehmites (Al2O3Mass fraction be 70%),
2.5g lanthanum sesquioxides, after being sufficiently mixed, ball milling 5h, gained powder is under argon gas and helium mix atmosphere, 1150 DEG C of roasting 3h,
Through beating sheetmolding after, catalyst is obtained, group becomes (mass fraction)：CuO=57.3%,Al2O3=39.5%、La2O3=3.2%.Through
Determination contains CuAlO after XRD characterization2.Evaluating catalyst mode is shown in Table 1 with embodiment 1, reaction condition with reaction result.Initially
Methanol conversion is 86.0%, 300h continuous experiments the results show that methanol conversion presentation first increases reaches stable, 300h afterwards
Methanol conversion is 89.2%.
Embodiment 8
Regeneration treatment is carried out to the catalyst after the operation to 1047h of embodiment 1, the lower 500 DEG C of roastings 2h of Air atmosphere then exists
N21100 DEG C of roasting 4h are warming up under atmosphere.Gained regenerated catalyst carries out XRD characterization, (figure as a result consistent with fresh catalyst
1).Activity rating is carried out to regenerated catalyst, as a result sees Fig. 2, the catalytic activity and variation tendency of regenerated catalyst with it is fresh
Catalyst is almost the same.In conjunction with XRD characterization with evaluation result it is found that catalyst can pass through regeneration after long-time is reacted
Processing is restored to the state of fresh catalyst, shows that catalyst can regenerate reuse.
Comparative example 1
Using the CuZnAl of commercial Application as catalyst, it is catalyzed under processing mode and reaction condition same as Example 1
Performance is evaluated, and as a result sees Fig. 2.As seen from the figure, the initial activity of CuZnAl catalyst is higher, reaches 91%, however as anti-
The progress answered, active rapid decrease, 103h methanol conversions are reduced to 44.5%.Regeneration treatment is carried out to post catalyst reaction,
Catalyst initial activity after evaluation result display regeneration only has 55%, is difficult to regenerate after showing the catalyst inactivation.
Since reaction temperature is higher (300 DEG C), active copper is easy to be sintered, and declines so as to cause activity, passes through work
Industry CuZnAl catalyst in 300 DEG C of catalytic performance it is found that its active ingredient copper is sintered at this temperature than more serious, to table
Reveal the feature of active rapid decrease.In contrast, catalyst of the present invention has preferable anti-sintering property, excellent to show
Different catalytic activity and stability, and reuse can be regenerated after catalyst use completely.
The above embodiment of the present invention is not to this hair just for the sake of clearly demonstrating examples made by the present invention
The restriction of bright embodiment.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.It is exhaustive there is no need and unable to be carried out to all embodiments.It is every in the present invention
Spirit and principle within made by all any modification, equivalent and improvement etc., should be included in the guarantor of the claims in the present invention
Within the scope of shield.
The reaction condition and result of 1 embodiment 1-7 of table
。
Claims (8)
1. a kind of copper-based catalysts for hydrogen from methyl alcohol, it is characterised in that catalyst is by CuO, Al2O3It is formed with auxiliary agent, respectively
Component is with mass fraction：CuO 12.0%-65.0%,Al2O334.0%-85.0%, auxiliary agent 0%-5.0%, and have in catalyst
The CuAlO of delafossite structure2。
2. a kind of copper-based catalysts for hydrogen from methyl alcohol as described in claim 1, it is characterised in that the auxiliary agent is
NiO、La2O3One or two.
3. a kind of preparation method of copper-based catalysts for hydrogen from methyl alcohol as claimed in claim 1 or 2, it is characterised in that packet
Include following steps：
After the predecessor of copper predecessor, aluminium predecessor and auxiliary agent is sufficiently mixed uniformly by the composition of catalyst, ball milling 1-10h,
1-10h is roasted under protective atmosphere, beats sheetmolding to get catalyst.
4. a kind of preparation method of copper-based catalysts for hydrogen from methyl alcohol as claimed in claim 3, it is characterised in that copper
Predecessor is that Kocide SD or copper oxide are one or two kinds of.
5. a kind of preparation method of copper-based catalysts for hydrogen from methyl alcohol as claimed in claim 3, it is characterised in that aluminium
Predecessor is that aluminium hydroxide, boehmite or aluminium oxide are one or more of.
6. a kind of preparation method of copper-based catalysts for hydrogen from methyl alcohol as claimed in claim 3, it is characterised in that auxiliary agent
The predecessor of nickel is that nickel acetate or nickel oxide are one or more of.
7. a kind of preparation method of copper-based catalysts for hydrogen from methyl alcohol as claimed in claim 3, it is characterised in that auxiliary agent
The predecessor of lanthanum is lanthanum sesquioxide.
8. a kind of application of copper-based catalysts for hydrogen from methyl alcohol as claimed in claim 1 or 2, it is characterised in that including as follows
Step：
Catalyst of the present invention is applied to hydrogen from methyl alcohol, and H is being not necessarily to using preceding2Pre-reduction treatment, use condition are：Reaction temperature 250
DEG C -400 DEG C, 0.1 h of mass space velocity-1-3.0h-1, reaction pressure normal pressure -3.0MPa, H2O：CH3The molar ratio of OH is 1.0-3.0.
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