CN105498780B - A kind of Cu/ZnO catalyst and preparation method thereof and in CO2Application in chemical conversion - Google Patents
A kind of Cu/ZnO catalyst and preparation method thereof and in CO2Application in chemical conversion Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000126 substance Substances 0.000 title abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 56
- 239000000969 carrier Substances 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 1
- 239000008246 gaseous mixture Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000005431 greenhouse gas Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000005516 engineering process Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000011943 nanocatalyst Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- 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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Abstract
The invention discloses a kind of Cu/ZnO catalyst and preparation method thereof and in CO2Application in chemical conversion, belong to catalysis and greenhouse gases CO2Emission reduction field.The preparation method of Cu/ZnO catalyst is：Soluble zinc salt and hexamethylenetetramine are dissolved in glycol water；Under inert atmosphere, 200~300W of power reactions synthesis ZnO carriers in microwave reactor；Active metal copper is supported on the ZnO carriers of synthesis using deposition-precipitation method.The ZnO carriers of synthesis have homogeneous flower-shaped or nanometer rods pattern, and Cu loadings are 5~15wt%.The catalyst is in CO2High activity and stability is shown in the reaction of catalyzed conversion synthesis of low-carbon alcohol.The catalyst that the present invention synthesizes has the advantages that technique is simple, cost is low, catalytic performance is high, meets the development trend of green chemical industry；And in CO2Chemical conversion synthesis important chemical field has broad application prospects.
Description
Technical field
The present invention relates to a kind of Cu/ZnO catalyst and preparation method thereof and in CO2Application in chemical conversion, belongs to and urges
Chemistry and reduction of greenhouse gas discharge field.
Background technology
Greenhouse gases CO2The burning and exhausting of fossil resource is mainly derived from, with the rapid development of modern industry, in air
CO2Concentration more and more higher, cause greenhouse effects, global temperatures rise, have a strong impact on human being's production, life.Reduce CO2In air
Content turns into one of hot fields studied at present.Based on CO2It is a kind of cheap, abundant C1Resource considers, by CO2As carbon
Oxygen resource uses, and is to solve CO using chemical conversion synthesis high valuable chemicals2The important channel of effect on environment, and solution
Certainly effective measures of chemicals heavy dependence non-renewable resources fossil fuel for a long time, with traditional CO2Capture, separate,
The treatment technology such as burying and comparing has prior society and economic implications.Methanol is a kind of important Organic Chemicals, is
C1The basis of chemical industry, and a kind of good organic solvent and the liquid fuel for being expected to replacing gasoline.Utilize CO2Hydrogenation synthesis first
Alcohol can either reduce or maintain CO in air2Concentration, and can obtain important energy carrier methanol, are one and " kill two birds with one stone, become
Waste be changed into values " technology path, therefore its research receives much attention.Due to CO2Thermodynamic stability and chemical inertness, realize CO2
The key of synthesizing methanol by hydrogenating process route is to build design high activity, high stability catalyst.CO in recent years2Hydrogenation first
Alcohol catalyst system is mainly based on copper system and noble metal systems (Pt, Ru etc.).Although noble metal catalyst has greater activity
And selectivity, but turn into the shortcomings of price is high, active temperature range is narrow and restrict its wide variety of bottleneck problem.
The copper-based catalyst of transition metal, domestic and international study hotspot is turned into its high activity, low cost.But copper-based catalysts exist
In course of reaction active copper surface area easily reduce, loss of active component, catalyst easy in inactivation suppresses its extensive industrial applications.Structure
Meter efficient stable copper-based catalysts are built, suppress the loss of active Cu components in course of reaction, to CO2The exploitation of hydrogenation catalyst
With important promotion meaning, wherein the sciences problems contained are worth us to further investigate.
Recent nanometer material science research has shown that the catalytic performance of nanocatalyst is not only influenceed by dimensional effect, also with urging
The pattern of agent is closely related.The crystal face that the different nano-material surface of pattern preferentially exposes is different, the atom composition on surface, matches somebody with somebody
Significant changes can occur for bit pattern, electronic structure, thus adsorb and the ability of activated reactant can difference, cause different
Pattern effect in catalytic perfomance, i.e. nano-catalytic.Catalysis material controlledly synthesis under nanoscale and true to its
The understanding of structure-effect relation is the key issue of nano-catalytic under reaction atmosphere.Traditional hydro-thermal, solvent thermal technology can pass through choosing
Presoma is selected, using ion slow release preparation and structure directing agent etc., accurate modulation preparation parameter, obtaining pattern to a certain extent can
The solid catalyst of control.Specific morphology catalyst is synthesized compared with conventional heating techniques using microwave technology, microwave firing rate
Hurry up, homogeneous heating, efficient energy-saving, equipment it is simple, easily controllable.
Both at home and abroad for specific morphology CO2The research of hydrogenation catalyst rarely has document report, and specific morphology is loaded
Copper-based catalysts are applied to CO2Chemical conversion field has no patent report.
The content of the invention
The present invention is preferentially exposed using the microwave thermal solution synthesis homogeneous ZnO nano material of pattern by changing carrier pattern
High activity crystal face, and then the superficial density in activated centre is improved, structure designs loaded copper-based catalysts based on this, utilizes
The appearance and size of modulation ZnO carriers and active metal Cu particles, enhancing activation of catalyst CO2Ability and metal -- between carrier
Degree of interaction, improve the stability of active Cu components.The catalyst is applied to CO2Preparing methanol by hydrogenation reaction system, performance
Go out high activity, high stability.
The present invention is achieved through the following technical solutions：The present invention provides a kind of Cu/ZnO catalyst, using Cu as activearm
Point, ZnO oxides are carrier；Active component content is 10~15wt% in catalyst；ZnO carriers have homogeneous in catalyst
Nano flower-like and/or nanometer rods pattern, Cu average particle sizes are 10~25nm.
The present invention provides a kind of preparation method of above-mentioned Cu/ZnO catalyst, comprises the following steps：
(1) under room temperature condition by soluble zinc salt and hexamethylenetetramine according to mol ratio 1:0.5~3 it is dissolved in 10~
In 20wt% glycol water；Under inert gas atmosphere, 200~300W of power reacts 10~15 points in microwave reactor
Clock；Room temperature is down to, precipitation suction filtration, dries 12h under being washed with hot deionized water to neutrality, 90 °；Synthesize ZnO carriers；
(2) the ZnO carriers for preparing soluble copper salt and above-mentioned steps (1) under room temperature condition are according to mass ratio 1~4:2~
11 add in 100-300mL deionized waters；60~80 DEG C are heated with stirring to, 0.1~0.3mol/L Na are slowly added dropwise2CO3Or
K2CO3Solution is 9~10 to pH, further stirs 1~3h of aging, and precipitation is filtered, washed with hot deionized water to neutrality, 90 °
12h is dried, in 4~8h of Muffle kiln roasting at 400~600 DEG C；Synthesize support type Cu/ZnO catalyst.
Further, in the above-mentioned technical solutions, in step (1), soluble zinc salt and hexamethylenetetramine mol ratio are
1:0.5~1.5；It is preferred that 1:1；ZnO carriers have homogeneous nanometer rods pattern in obtained catalyst；Length be 2000~
3000nm；10~30nm of diameter.
Further, in the above-mentioned technical solutions, in step (1), soluble zinc salt and hexamethylenetetramine mol ratio are
1:2~3；It is preferred that 1:3；ZnO carriers have homogeneous nano flower-like pattern in obtained catalyst；Petal is bar-shaped, petal length
Spend for 300~600nm；20~40nm of diameter.
Further, in the above-mentioned technical solutions, soluble zinc salt described in step (1) is selected from Zn (NO3)2.6H2O,
ZnCl2Deng.
Further, in the above-mentioned technical solutions, the inert gas is nitrogen, helium, argon gas etc..
Further, in the above-mentioned technical solutions, soluble copper salt described in step (2) is selected from Cu (NO3)2, CuSO4,
CuCl2Deng.
The present invention provides above-mentioned catalyst in CO2Application in the reaction of catalyzed conversion synthesis of low-carbon alcohol.
Further, in above-mentioned application, using conventional fixed bed reactor, 0.1~0.5g (40~60 mesh) is catalyzed
Agent is added in stainless steel reaction pipe (300mm grows, diameter 9mm, 316 type stainless steels), and addition quartz sand to beds 0.5~
2.0cm；250~270 DEG C, 30~45bar of reaction pressure, reaction gas (CO of reaction temperature2/H2=1/3, mol ratio) flow velocity is 66
~133mL/min, reaction velocity are 2000~4000h-1。
Invention beneficial effect
(1) energy consumption is low：Microwave technology belongs to body heating, there is reaction system to be heated evenly compared with conventional heating methods,
Promote the collision probability between reaction molecular, shorten reaction time, the advantages that reaction temperature low consumption energy is less.
(2) reactivity and stability are high, should not inactivate：Strong interaction between Ni metal and carrier ZnO is advantageous to
Suppressing active Cu components specific surface area in course of reaction reduces, and strengthens catalyst stability.
Brief description of the drawings
Fig. 1 is the ZnO carriers that embodiment 1 is prepared；
Fig. 2 is the ZnO carriers that embodiment 2 is prepared.
Embodiment
Embodiment 1
(1) under room temperature condition by 5g mol ratios be 1/3 Zn (NO3)2.6H2O and hexamethylenetetramine are dissolved in 100mL
In 15wt% glycol water.Under nitrogen atmosphere, power 300W reacts 10min in microwave reactor.Room temperature is down to, is sunk
Shallow lake suction filtration, dry 12h at being washed with hot deionized water to neutrality, 90 DEG C.Synthesize ZnO-1 carriers.As shown in figure 1, what is obtained urges
ZnO carriers have homogeneous nano flower-like pattern in agent；Petal is bar-shaped, and petal length is 300~600nm；Diameter 20~
40nm。
(2) by 2.84g Cu (NO under room temperature condition3)2, the ZnO carriers obtained in 5.1g (1) add 150mL deionized waters
In.Magnetic agitation is heated to 75 DEG C under 600r/min, and 0.1mol/L Na are slowly added dropwise2CO3Solution to pH be 9~10, further
Aging 2h is stirred, precipitation suction filtration, 12h is dried at being washed with hot deionized water to neutrality, 90 DEG C, at 400 DEG C in Muffle furnace
It is calcined 4h.Synthesize Cu/ZnO-1 catalyst.Catalyst outward appearance is brown powder, and XRD test results show Cu average particle sizes
It is 10-25nm.
Embodiment 2
Zn(NO3)2.6H2The mol ratio of O and hexamethylenetetramine is 1/1, and remaining is same as Example 1.Synthesize Cu/ZnO
Catalyst, it is named as Cu/ZnO-2.As shown in Fig. 2 obtained carrier has homogeneous nanometer rods pattern；Length be 2000~
3000nm；10~30nm of diameter.Catalyst outward appearance is brown powder, and XRD test results show that Cu average particle sizes equally exist
Between 10-25nm.
Embodiment 3
Zn(NO3)2.6H2The mol ratio of O and hexamethylenetetramine is 1/0.5, and remaining is same as Example 1.Synthesize Cu/
ZnO catalyst, it is named as Cu/ZnO-3.
Comparative example 1
Purchase business ZnO carriers simultaneously support Cu with the same procedure of embodiment 1, and obtained catalyst is named as Cu/ZnO-4.
Wherein ZnO carriers are purchased from Aladdin reagent (Shanghai) Co., Ltd., lot number：Z111841, purity：99.99%.Thoroughly
Radio mirror (TEM) result shows that this business ZnO carriers are unbodied particles, and particle diameter is in 20-50nm.
Application examples 1
Weigh 0.15g Cu/ZnO-1 nanocatalysts to be added in stainless steel reaction pipe, CO2/H2=1/3 (mol ratio),
GHSV:3000h-1, reaction pressure 30bar.
Table 1
Application examples 2
Weigh 0.15g 15wt%Cu/ZnO-2 nanocatalysts to be added in stainless steel reaction pipe, CO2/H2=1/3 (rubs
That ratio), GHSV:3000h-1, reaction pressure 30bar.
Table 2
Application examples 3
Weigh 0.15g 15wt%Cu/ZnO-3 nanocatalysts to be added in stainless steel reaction pipe, CO2/H2=1/3 (rubs
That ratio), GHSV:3000h-1, reaction pressure 30bar.
Table 3
Comparison study example 4
Weigh 0.15g 15wt%Cu/ZnO-4 commercial catalysts to be added in stainless steel reaction pipe, CO2/H2=1/3 (rubs
That ratio), GHSV:3000h-1, reaction pressure 30bar.
Table 4
Application examples 5
Weigh 0.15g 15wt%Cu/ZnO-2 catalyst to be added in stainless steel reaction pipe, CO2/H2=1/3 (mole
Than), GHSV:3000h-1, reaction pressure 45bar.
Table 5
Application examples 6
Weigh 0.15g 15wt%Cu/ZnO-2 catalyst to be added in stainless steel reaction pipe, CO2/H2=1/3 (mole
Than), GHSV:1500h-1, reaction pressure 45bar.
Table 6
Application examples 7
Weigh 0.15g 15wt%Cu/ZnO-2 catalyst to be added in stainless steel reaction pipe, CO2/H2=1/1 (mole
Than), GHSV:3000h-1, reaction pressure 45bar.
Table 7
Reactivity and stability contrast
Referring to table 2 and table 4, at 270 DEG C, 30bar, CO2/H2=1/3, GHSV:3000h-1It is loaded under reaction condition
CO on Cu/ZnO-2 nanocatalysts2Conversion ratio 10.3%, methanol selectivity 38% or so；And on business Cu/ZnO-4 catalyst
Under the conditions of equivalent responses, CO2Conversion ratio only has 5.1%, and methanol selectivity also only has 8.9%.
Referring to table 2 and table 4, the loaded Cu/ZnO-2 catalyst of microwave thermal solution synthesis, after reacting 60h, CO2Conversion
Rate and methanol selectivity are without significantly reducing.And after business Cu/ZnO-4 catalyst reactions 60h, CO2Conversion ratio and methanol selectivity
More than 50% is reduced, catalyst inactivation is serious.
Claims (8)
- A kind of 1. Cu/ZnO catalyst, it is characterised in that：Using copper as active component, ZnO is carrier；Active component contains in catalyst Measure as 10~15wt%；ZnO carriers have homogeneous nano flower-like and/or nanometer rods pattern, the average grain of copper particle in catalyst Footpath is 10~25nm；Nanometer rods pattern ZnO carriers；Length is 2000~3000nm；10~30nm of diameter；Nano flower-like pattern ZnO carriers；Petal is bar-shaped, and petal length is 300~600nm；20~40nm of diameter；The preparation method of the Cu/ZnO catalyst, it is characterised in that comprise the following steps：(1) prepared by ZnO carriers：By soluble zinc salt and hexamethylenetetramine according to mol ratio 1 under room temperature condition:0.5~3 is dissolved in In 10~20wt% glycol water；Under inert gas atmosphere, in microwave reactor 200~300W of power reaction 10~ 15min；Room temperature is down to, precipitation is filtered, washs, dried；Synthesize ZnO carriers；(2) supported active metals copper：Active metal copper is supported on the ZnO carriers of synthesis using deposition-precipitation method, wherein can ZnO carrier qualities ratio prepared by dissolubility mantoquita and above-mentioned steps (1) is 1~4:2~11；In step (2), the ZnO carriers for preparing soluble copper salt and above-mentioned steps (1) under room temperature condition are soluble in water；Stirring adds For heat to 60~80 DEG C, it is 9~10 that 0.1~0.3mol/L precipitant solutions, which are slowly added dropwise, to pH, further stirs 1~3h of aging, Precipitation is filtered, washs, dried, in 4~8h of Muffle kiln roasting at 400~600 DEG C；Synthesize support type Cu/ZnO catalyst.
- 2. Cu/ZnO catalyst according to claim 1, it is characterised in that：Soluble zinc salt is selected from Zn described in step (1) (NO3)2·6H2O, ZnCl2。
- 3. Cu/ZnO catalyst according to claim 1, it is characterised in that：The inert gas atmosphere is nitrogen, helium, argon Gas.
- 4. Cu/ZnO catalyst according to claim 1, it is characterised in that：Soluble copper salt is selected from Cu described in step (2) (NO3)2, CuSO4, CuCl2。
- 5. Cu/ZnO catalyst according to claim 1, it is characterised in that:Precipitating reagent is selected from Na described in step (2)2CO3, K2CO3。
- 6. catalyst is in CO according to claim 12Application in the reaction of catalyzed conversion synthesis of low-carbon alcohol.
- 7. apply according to claim 6, it is characterised in that：Using conventional fixed bed reactor, catalyst is added stainless In steel reaction tube, quartz sand is added；250~270 DEG C of reaction temperature, 30~45bar of reaction pressure.
- 8. apply according to claim 7, it is characterised in that：0.1~0.5g catalyst is added in stainless steel reaction pipe, added Add quartz sand to 0.5~2.0cm of beds；Reaction gas is the CO that mol ratio is 1/32/H2Gaseous mixture, reaction gas flow velocity are 66~133mL/min, reaction velocity are 2000~4000h-1。
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| CN114130398B (en) * | 2021-12-15 | 2022-11-18 | 大连理工大学 | Zn-based coordination polymer derived CO 2 Preparation method and application of catalyst for preparing methanol by hydrogenation |
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