CN105498780A - Cu/ZnO catalyst, preparation method thereof and application thereof to CO2 chemical conversion - Google Patents

Cu/ZnO catalyst, preparation method thereof and application thereof to CO2 chemical conversion Download PDF

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CN105498780A
CN105498780A CN201510990534.8A CN201510990534A CN105498780A CN 105498780 A CN105498780 A CN 105498780A CN 201510990534 A CN201510990534 A CN 201510990534A CN 105498780 A CN105498780 A CN 105498780A
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zno
catalyst
preparation
carrier
reaction
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CN105498780B (en
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蔡伟杰
张绍印
崔励
张江华
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Sichuan Longmen Zhichuang Environmental Protection New Material Technology Co ltd
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Dalian Polytechnic University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—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
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a Cu/ZnO catalyst, a preparation method thereof and application thereof to CO2 chemical conversion and belongs to the fields of catalysis and greenhouse gas CO2 emission reduction. The preparation method of the Cu/ZnO catalyst includes the steps that soluble zinc salt and hexamethylene tetramine are dissolved in an ethylene glycol aqueous solution; under the inert atmosphere, a ZnO carrier is synthesized through reaction in a microwave reactor at the power of 200-300 W; by means of a deposition precipitation method, active metal copper is supported on the synthesized ZnO carrier. The synthesized ZnO carrier has uniform flowerlike or nanorod morphology, and the Cu loading is 5-15 wt%. The catalyst represents high activity and stability in the reaction of synthesizing low-carbon alcohol through CO2 catalytic conversion. The synthesized catalyst has the advantages of being simple in technology, low in cost, high in catalytic performance and the like, and accords with the development trend of green chemical engineering. Besides, the catalyst has wide application prospects in the field of synthesizing important chemicals through CO2 chemical conversion.

Description

A kind of Cu/ZnO Catalysts and its preparation method and at CO 2application in chemical conversion
Technical field
The present invention relates to a kind of Cu/ZnO Catalysts and its preparation method and at CO 2application in chemical conversion, belongs to catalytic chemistry and reduction of greenhouse gas discharge field.
Background technology
Greenhouse gases CO 2be mainly derived from the burning and exhausting of fossil resource, along with developing rapidly of modern industry, CO in air 2concentration is more and more higher, causes greenhouse effects, global temperatures to raise, has a strong impact on human being's production, life.Reduce CO 2in air, content becomes one of hot fields of research at present.Based on CO 2a kind of cheapness, abundant C 1resource is considered, by CO 2use as carbon oxygen resource, utilizing chemical conversion to synthesize high valuable chemicals is solve CO 2to the important channel of ambient influnence, be also the effective measures solving chemicals heavy dependence non-renewable resources fossil fuel for a long time, with traditional CO 2treatment technologies such as catching, be separated, bury is compared has prior society and economic implications.Methyl alcohol is a kind of important Organic Chemicals, is C 1the basis of chemical industry is also a kind of good organic solvent and the liquid fuel being expected to replacing gasoline.Utilize CO 2synthesizing methanol by hydrogenating can either reduce or maintain CO in air 2concentration, can obtain again important energy carrier methyl alcohol, is the technology path of " kill two birds with one stone, turn waste into wealth ", and therefore its research receives much attention.Due to CO 2thermodynamic stability and chemical inertness, realize CO 2the key of synthesizing methanol by hydrogenating process route is to build design high activity, high stability catalyst.CO in recent years 2preparing methanol by hydrogenation catalyst system is mainly main with copper system and noble metal systems (Pt, Ru etc.).Although noble metal catalyst has greater activity and selective, the shortcomings such as price is high, active temperature range is narrow become the bottleneck problem of its extensive use of restriction.
Transition metal copper-based catalysts, becomes domestic and international study hotspot with its high activity, low cost.But copper-based catalysts active copper surface area in course of reaction easily reduces, loss of active component, and catalyst easy in inactivation suppresses its extensive industrial applications.Build design efficient stable copper-based catalysts, suppress the loss of active Cu component in course of reaction, to CO 2the exploitation of hydrogenation catalyst has important promotion meaning, and the sciences problems wherein contained is worth us to further investigate.
Recent nanometer material science research proves that the catalytic performance of nanocatalyst not only affects by dimensional effect, and the pattern also with catalyst is closely related.The crystal face that the different nano-material surface of pattern preferentially exposes is different, can marked change be there is in the atom composition on surface, coordination mode, electronic structure, therefore the ability of absorption and activated reactant can difference to some extent, causes different catalytic perfomances, the pattern effect namely in nano-catalytic.Catalysis material controlledly synthesis under nanoscale and be the key issue of nano-catalytic to the understanding of structure-effect relationship under its actual response atmosphere.Traditional hydro-thermal, solvent heat technology can by selecting presoma, and utilize ion slow release preparation and structure directing agent etc., accurate modulation preparation parameter, obtains the solid catalyst of morphology controllable to a certain extent.Utilize microwave technology to synthesize specific morphology catalyst compared with conventional heating techniques, heating using microwave speed is fast, homogeneous heating, efficient energy-saving, equipment are simple, be easy to control.
Both at home and abroad for specific morphology CO 2the research of hydrogenation catalyst rarely has bibliographical information, and specific morphology supported copper is catalyst based is applied to CO 2chemical conversion field has no patent report.
Summary of the invention
The present invention adopts microwave thermal solution to synthesize the homogeneous ZnO nano material of pattern, high activity crystal face is preferentially exposed by changing carrier pattern, and then improve the superficial density in activated centre, build design supported copper based on this catalyst based, utilize the appearance and size of modulation ZnO carrier and active metal Cu particle, strengthen catalyst activation CO 2ability and metal--the Degree of interaction between carrier, improves the stability of active Cu component.This catalyst application is in CO 2preparing methanol by hydrogenation reaction system, shows high activity, high stability.
The present invention is achieved through the following technical solutions: the invention provides a kind of Cu/ZnO catalyst, take Cu as active component, and ZnO oxide is carrier; In catalyst, active component content is 10 ~ 15wt%; In catalyst, ZnO carrier has homogeneous nano flower-like and/or nanometer rods pattern, and Cu average particle size is 10 ~ 25nm.
The invention provides a kind of preparation method of above-mentioned Cu/ZnO catalyst, comprise the following steps:
(1) under room temperature condition, soluble zinc salt and hexamethylenetetramine are dissolved in the glycol water of 10 ~ 20wt% according to mol ratio 1:0.5 ~ 3; Under inert gas atmosphere, in microwave reactor, power 200 ~ 300W reacts 10 ~ 15 minutes; Be down to room temperature, precipitation suction filtration, with hot deionized water washing to neutral, dry 12h under 90 °; Synthesis ZnO carrier;
(2) under room temperature condition, ZnO carrier prepared by soluble copper salt and above-mentioned steps (1) is added in 100-300mL deionized water according to mass ratio 1 ~ 4:2 ~ 11; Be heated with stirring to 60 ~ 80 DEG C, slowly drip 0.1 ~ 0.3mol/LNa 2cO 3or K 2cO 3solution is 9 ~ 10 to pH, further stirs aging 1 ~ 3h, precipitation suction filtration, with hot deionized water washing to neutral, dry 12h under 90 °, at 400 ~ 600 DEG C in Muffle furnace roasting 4 ~ 8h; Synthesis support type Cu/ZnO catalyst.
Further, in technique scheme, in step (1), soluble zinc salt and hexamethylenetetramine mol ratio are 1:0.5 ~ 1.5; Preferred 1:1; In the catalyst obtained, ZnO carrier has homogeneous nanometer rods pattern; Length is 2000 ~ 3000nm; Diameter 10 ~ 30nm.
Further, in technique scheme, in step (1), soluble zinc salt and hexamethylenetetramine mol ratio are 1:2 ~ 3; Preferred 1:3; In the catalyst obtained, ZnO carrier has homogeneous nano flower-like pattern; Petal is bar-shaped, and petal length is 300 ~ 600nm; Diameter 20 ~ 40nm.
Further, in technique scheme, described in step (1), soluble zinc salt is selected from Zn (NO 3) 2.6H 2o, ZnCl 2deng.
Further, in technique scheme, described inert gas is nitrogen, helium, argon gas etc.
Further, in technique scheme, described in step (2), soluble copper salt is selected from Cu (NO 3) 2, CuSO 4, CuCl 2deng.
The invention provides above-mentioned catalyst at CO 2application in the reaction of catalyzed conversion synthesis of low-carbon alcohol.
Further, in above-mentioned application, conventional fixed bed reactor is utilized, (300mm is long 0.1 ~ 0.5g (40 ~ 60 order) catalyst to be added stainless steel reaction pipe, diameter 9mm, 316 type stainless steels) in, add quartz sand to beds 0.5 ~ 2.0cm; Reaction temperature 250 ~ 270 DEG C, reaction pressure 30 ~ 45bar, reaction gas (CO 2/ H 2=1/3, mol ratio) flow velocity is 66 ~ 133mL/min, reaction velocity is 2000 ~ 4000h -1.
Invention beneficial effect
(1) energy consumption is low: microwave technology belongs to body heating, has that reaction system is heated evenly, the advantage such as promote the collision probability between reaction molecular, Reaction time shorten, reaction temperature low consumption energy less compared with conventional heating methods.
(2) reactivity and stability high, should not inactivation: the strong interaction between Ni metal and carrier ZnO is conducive to suppressing active Cu ratio of component surface area in course of reaction to reduce, strengthen catalyst stability.
Accompanying drawing explanation
Fig. 1 is the ZnO carrier that embodiment 1 prepares;
Fig. 2 is the ZnO carrier that embodiment 2 prepares.
Detailed description of the invention
Embodiment 1
(1) under room temperature condition by 5g mol ratio be 1/3 Zn (NO 3) 2.6H 2o and hexamethylenetetramine are dissolved in the glycol water of 100mL15wt%.Under nitrogen atmosphere, in microwave reactor, power 300W reacts 10min.Be down to room temperature, precipitation suction filtration, with hot deionized water washing to neutral, dry 12h at 90 DEG C.Synthesis ZnO-1 carrier.As shown in Figure 1, in the catalyst obtained, ZnO carrier has homogeneous nano flower-like pattern; Petal is bar-shaped, and petal length is 300 ~ 600nm; Diameter 20 ~ 40nm.
(2) under room temperature condition by 2.84gCu (NO 3) 2, the ZnO carrier obtained in 5.1g (1) adds in 150mL deionized water.600r/min lower magnetic force is heated with stirring to 75 DEG C, slowly drips 0.1mol/LNa 2cO 3solution is 9 ~ 10 to pH, further stirs aging 2h, precipitation suction filtration, with hot deionized water washing to neutral, dry 12h at 90 DEG C, at 400 DEG C in Muffle furnace roasting 4h.Synthesis Cu/ZnO-1 catalyst.Catalyst outward appearance is brown powder, and XRD test result shows that Cu average particle size is 10-25nm.
Embodiment 2
Zn (NO 3) 2.6H 2the mol ratio of O and hexamethylenetetramine is 1/1, and all the other are identical with embodiment 1.Synthesis Cu/ZnO catalyst, called after Cu/ZnO-2.As shown in Figure 2, the carrier obtained has homogeneous nanometer rods pattern; Length is 2000 ~ 3000nm; Diameter 10 ~ 30nm.Catalyst outward appearance is brown powder, and XRD test result shows that Cu average particle size is equally between 10-25nm.
Embodiment 3
Zn (NO 3) 2.6H 2the mol ratio of O and hexamethylenetetramine is 1/0.5, and all the other are identical with embodiment 1.Synthesis Cu/ZnO catalyst, called after Cu/ZnO-3.
Comparative example 1
Buy business ZnO carrier and support Cu by embodiment 1 same procedure, the catalyst called after Cu/ZnO-4 obtained.
Wherein ZnO carrier is purchased from Aladdin reagent (Shanghai) Co., Ltd., lot number: Z111841, purity: 99.99%.Transmission electron microscope (TEM) result shows that this business ZnO carrier is unbodied particle, and particle diameter is at 20-50nm.
Application examples 1
Taking 0.15gCu/ZnO-1 nanocatalyst joins in stainless steel reaction pipe, CO 2/ H 2=1/3 (mol ratio), GHSV:3000h -1, reaction pressure 30bar.
Table 1
Application examples 2
Taking 0.15g15wt%Cu/ZnO-2 nanocatalyst joins in stainless steel reaction pipe, CO 2/ H 2=1/3 (mol ratio), GHSV:3000h -1, reaction pressure 30bar.
Table 2
Application examples 3
Taking 0.15g15wt%Cu/ZnO-3 nanocatalyst joins in stainless steel reaction pipe, CO 2/ H 2=1/3 (mol ratio), GHSV:3000h -1, reaction pressure 30bar.
Table 3
Comparison study example 4
Taking 0.15g15wt%Cu/ZnO-4 commercial catalysts joins in stainless steel reaction pipe, CO 2/ H 2=1/3 (mol ratio), GHSV:3000h -1, reaction pressure 30bar.
Table 4
Application examples 5
Taking 0.15g15wt%Cu/ZnO-2 catalyst joins in stainless steel reaction pipe, CO 2/ H 2=1/3 (mol ratio), GHSV:3000h -1, reaction pressure 45bar.
Table 5
Application examples 6
Taking 0.15g15wt%Cu/ZnO-2 catalyst joins in stainless steel reaction pipe, CO 2/ H 2=1/3 (mol ratio), GHSV:1500h -1, reaction pressure 45bar.
Table 6
Application examples 7
Taking 0.15g15wt%Cu/ZnO-2 catalyst joins in stainless steel reaction pipe, CO 2/ H 2=1/1 (mol ratio), GHSV:3000h -1, reaction pressure 45bar.
Table 7
Reactivity and stability contrast
See table 2 and table 4, at 270 DEG C, 30bar, CO 2/ H 2=1/3, GHSV:3000h -1under reaction condition, CO on loaded Cu/ZnO-2 nanocatalyst 2conversion ratio 10.3%, methyl alcohol selective about 38%; And on business Cu/ZnO-4 catalyst under equivalent responses condition, CO 2conversion ratio only has 5.1%, and methyl alcohol is selective also only has 8.9%.
See table 2 and table 4, the loaded Cu/ZnO-2 catalyst of microwave thermal solution synthesis, after reaction 60h, CO 2conversion ratio and the selective nothing of methyl alcohol significantly reduce.And after business Cu/ZnO-4 catalyst reaction 60h, CO 2conversion ratio and the selective all reductions by more than 50% of methyl alcohol, catalysqt deactivation is serious.

Claims (10)

1. a Cu/ZnO catalyst, is characterized in that: take copper as active component, and ZnO is carrier; In catalyst, active component content is 10 ~ 15wt%; In catalyst, ZnO carrier has homogeneous nano flower-like and/or nanometer rods pattern, and copper particle average grain diameter is 10 ~ 25nm.
2. the preparation method of Cu/ZnO catalyst as claimed in claim 1, is characterized in that comprising the following steps:
(1) ZnO carrier preparation: under room temperature condition, soluble zinc salt and hexamethylenetetramine are dissolved in the glycol water of 10 ~ 20wt% according to mol ratio 1:0.5 ~ 3; Under inert gas atmosphere, in microwave reactor, power 200 ~ 300W reacts 10 ~ 15min; Be down to room temperature, precipitation suction filtration, washing, drying; Synthesis ZnO carrier;
(2) supported active metals copper: utilize deposition-precipitation method to be supported on the ZnO carrier of synthesis by active metal copper, the ZnO carrier quality ratio that wherein prepared by soluble copper salt and above-mentioned steps (1) is 1 ~ 4:2 ~ 11.
3. the preparation method of Cu/ZnO catalyst according to claim 2, it is characterized in that: in step (2), ZnO carrier soluble copper salt and above-mentioned steps (1) prepared under room temperature condition is soluble in water; Be heated with stirring to 60 ~ 80 DEG C, slowly dripping 0.1 ~ 0.3mol/L precipitant solution to pH is 9 ~ 10, further stirs aging 1 ~ 3h, precipitation suction filtration, washing, drying, at 400 ~ 600 DEG C in Muffle furnace roasting 4 ~ 8h; Synthesis support type Cu/ZnO catalyst.
4. the preparation method of Cu/ZnO catalyst according to claim 2, is characterized in that: described in step (1), soluble zinc salt is selected from Zn (NO 3) 2.6H 2o, ZnCl 2.
5. the preparation method of Cu/ZnO catalyst according to claim 2, is characterized in that: described inert gas is nitrogen, helium, argon gas.
6. the preparation method of Cu/ZnO catalyst according to claim 2, is characterized in that: described in step (2), soluble copper salt is selected from Cu (NO 3) 2, CuSO 4, CuCl 2.
7. the preparation method of Cu/ZnO catalyst according to claim 2, is characterized in that: described in step (2), precipitating reagent is selected from Na 2cO 3, K 2cO 3.
8. according to claim 1 catalyst at CO 2application in the reaction of catalyzed conversion synthesis of low-carbon alcohol.
9. apply according to claim 8, it is characterized in that: utilize conventional fixed bed reactor, catalyst is added in stainless steel reaction pipe, add quartz sand; Reaction temperature 250 ~ 270 DEG C, reaction pressure 30 ~ 45bar.
10. apply according to claim 9, it is characterized in that: 0.1 ~ 0.5g catalyst is added in stainless steel reaction pipe, add quartz sand to beds 0.5 ~ 2.0cm; Reaction gas to be mol ratio be 1/3 CO 2/ H 2gaseous mixture, reaction gas flow velocity is 66 ~ 133mL/min, and reaction velocity is 2000 ~ 4000h -1.
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