CN106423175A - Method for preparing copper-based catalyst for catalyzing carbon dioxide hydrogenation reduction - Google Patents
Method for preparing copper-based catalyst for catalyzing carbon dioxide hydrogenation reduction Download PDFInfo
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- CN106423175A CN106423175A CN201610944828.1A CN201610944828A CN106423175A CN 106423175 A CN106423175 A CN 106423175A CN 201610944828 A CN201610944828 A CN 201610944828A CN 106423175 A CN106423175 A CN 106423175A
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- ball milling
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/04—Methanol
-
- 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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- 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 belongs to the technical field of copper-based catalyst preparation and particularly relates to a method for preparing a copper-based catalyst for catalyzing carbon dioxide hydrogenation reduction. High energy generated through ball milling makes metal ions of different compounds substitute for one another, and accordingly the copper-based catalyst for catalyzing carbon dioxide hydrogenation reduction is prepared. Specifically, at the air atmosphere, basic cupric carbonate, basic zinc carbonate and basic carbonate or oxides of other catalyst carriers and auxiliaries are mixed, then ball milling is conducted, the product is forged and reduced, and the catalyst is obtained. The method has the advantages of being easy to prepare, high in yield and the like. The catalyst prepared through the ball milling method is excellent in catalytic performance, can catalyze carbon dioxide hydrogenation reduction at 240 DEG C and at 3 MPa, and has good conversion efficiency.
Description
Technical field
The invention belongs to copper-based catalysts preparing technical field is and in particular to one kind prepares catalysis hydrogenation of carbon dioxide reduction
Copper-based catalysts method, the method to prepare the copper-based catalysts of high catalytic activity in particular with ball milling.
Background technology
CO in air2The continuous rising of concentration, causes global warming and the serious consequence such as Catastrophe climate takes place frequently.?
Reduce CO2While discharge, how to reclaim and utilize CO2Cause the concern of national governments and researcher.By chemical mode
By CO2Being converted into useful chemical raw material or fuel is CO2The effective way of recycling.By hydrogenation of carbon dioxide catalysis also
Former synthesizing methanol is one of focus of domestic and international research, and how to prepare the catalysis of high performance catalysis hydrogenation of carbon dioxide reduction
Agent is key technology therein.
At present, the preparation of the catalyst of catalysis hydrogenation of carbon dioxide reduction typically has coprecipitation, infusion process, collosol and gel
Multiple methods such as method, micro emulsion method, fast fuel method, wherein with sol-gal process and coprecipitation most study, using the widest.
[1-3] sol-gal process is to hydrolyze or alcoholysis organic metal salt under certain condition, then forms colloidal sol through shrink or acetal, so
Afterwards solvent removal is made the method that colloidal sol is converted into gel.[4,5] coprecipitation is each through catalyst in the presence of precipitating reagent
The salting liquid of component is co-precipitated, and is subsequently catalyzed precipitation through aging, washing, suction filtration, drying, calcining and reduction
Agent.[6] but, these methods are prepared the complex steps of catalyst, process tedious and are needed to be accurately controlled reaction condition.Cause
This, [7,8] develop a kind of simple and the copper-based catalysts of energy prepare with scale catalysis hydrogenation of carbon dioxide reduction methods, can pole
The research of the big catalyst performance promoting catalysis hydrogenation of carbon dioxide reduction, accelerates its practicalization.
Jadhav S G, Vaidya P D, Bhanage B M, et al.Chem. Engineering Research & Design, 2014, 92(11)：2557-2567.
(1)Lyle M J, Warschkow O, Delley B, et al.Surface Science, 2015, 641：97–
104.
(2)Farahani B V, Rajabi F H, Bahmani M, et al.Applied Catalysis A General, 2014, 482(28)：237–244.
(3) Zhu Yiqing, Ma Yanfeng etc.Catalysis journal.1998,19(5)：393-397.
(4) Sun Qi etc.,Institution of higher educationization is reported,1997(7),26.
(5) Bansode A, Urakawa A.J. of Catalysis, 2014, 309(6)：66-70.
(6)Behrens M, Zander S, Kurr P, et al..J. of the American Chem. Society,
2013, 135(16)：6061-6068.
(7)Li J L, Inui T..Applied Catalysis A General, 1996, 137(1)：105-117.
Content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, provides a kind of copper preparing catalysis hydrogenation of carbon dioxide reduction
The method of base catalyst.
The copper-based catalysts preparation method of the catalysis hydrogenation of carbon dioxide reduction that the present invention provides, concretely comprises the following steps：
（1）Ball milling：Put in ball grinder after basic copper carbonate, basic zinc carbonate and aluminum oxide are mixed, and in ball milling
Add stainless steel ball in tank, ball grinder is arranged in ball mill and carries out ball milling, the catalyst precursor obtaining；Wherein, ball milling
Time is 10 ~ 30 hours, every 2-3 hour during ball milling, stops 5-10 minute；The rotating speed of ball milling is 200-400 rpm；
（2）Calcining：Catalyst precursor is calcined, calcining heat is 300-340 DEG C, calcination time is 2-4 hour, is urged
Change the copper-based catalysts of hydrogenation of carbon dioxide reduction.
In the present invention, described ball grinder as reactor, its structure as shown in Figure 1, this ball grinder by ball milling tank body 1,
Ball milling cover 2 forms, and the top edge of ball milling tank body 1 has one layer of rubber ring, and its effect is to cover ball milling cover 2 in ball milling tank body 1
On put into ball mill after, make under the fixation of ball mill ball grinder cavity keep airtight.
In the present invention, the mol ratio of described basic copper carbonate and basic zinc carbonate is 2:1~3:1, the molar fraction of aluminum oxide
For 5 ~ 10%, stainless steel ball is 10 with the mass ratio of raw material:1-20:1, preferred mass is than for 15:1.
In the present invention, the mol ratio of preferably basic copper carbonate and basic zinc carbonate is 7:3, the molar fraction of aluminum oxide is
8.5%.
In the present invention, preferably Ball-milling Time is 20 hours, every 2 hours during ball milling, stops 6 minutes.
In the present invention, preferred calcination temperature is 320 DEG C, and calcination time is 3 hours.
In the present invention, the presoma that ball milling uses, in addition to basic copper carbonate and basic zinc carbonate, also can add according to required
The subcarbonate of other structural promoters and carrier or oxide, wherein addible structural promoter and carrier are selected from alkali formula
Aluminium carbonate, zirconium oxycarbonate, aluminum oxide, zirconium oxide, silica and titanium dioxide etc..
The present invention mainly makes the metal ion in subcarbonate occur mutually using the high-energy that milling atmosphere produces
Replace, after ball milling, the catalyst precursor of generation can uniformly mix, and have that size is little, specific surface area big and load
The advantages of uniformity is good.
In mechanical milling process, the copper zinc ion in basic copper carbonate and basic zinc carbonate is made to occur due to mechanical alloy principle
It is substituted for each other, define the basic copper carbonate zinc phase containing high temperature carbonate, and rotational speed of ball-mill is more high more is conducive to this thing phase
Generation.In the catalyst that this thing phase precursor obtains after calcining, CuO and ZnO nano particle are in the way of alternateing
Arrangement form porous skeleton structure, ZnO particle plays the effect of interval CuO, hinders activity in reduction with course of reaction and becomes
Divide sintering and the reunion of copper, make catalyst show excellent catalysis activity.Due to existing more in presoma when rotational speed of ball-mill is high
Many basic copper carbonate zinc phases, in the catalyst of preparation under therefore high rotational speed of ball-mill, the crystallite dimension of CuO is little and reduction temperature is low,
High rotating speed also makes the Interaction enhanced in catalyst between each component simultaneously, thus improve catalysis activity.
After adding structural promoter, the CuO/ZnO in catalyst is attached to structural promoter surface, improves the ratio table of catalyst
Area, the effect serving dispersion cupric oxide is so that catalyst shows more excellent catalytic performance.
Brief description
Fig. 1 is structure of reactor schematic diagram.
Fig. 2 is that according to copper zinc ion, basic copper carbonate and basic zinc carbonate are compared Cu2+:Zn2+=7:After 3 mixing and ball milling, urge
The XRD spectrum of agent presoma.
Fig. 3 be embodiment 1 catalyst in 240 DEG C of temperature, carry out CO under pressure 3 MPa2Hydrogenating reduction test result.
Fig. 4 be embodiment 2 catalyst in 240 DEG C of temperature, carry out CO under pressure 3 MPa2Hydrogenating reduction test result.
Fig. 5 be embodiment 3 catalyst in 240 DEG C of temperature, carry out CO under pressure 3 MPa2Hydrogenating reduction test result.
Fig. 6 be embodiment 4 catalyst in 240 DEG C of temperature, carry out CO under pressure 3 MPa2Hydrogenating reduction test result.
In figure label：1 is ball milling tank body, and 2 is ball milling cover, 3 stainless steel balls.
Specific embodiment
Further illustrate the present invention below by embodiment.
Embodiment 1：
（1）The preparation of CuO/ZnO catalyst
Basic copper carbonate and basic zinc carbonate are compared Cu according to copper zinc ion2+:Zn2+=7:3 weigh after be added to ball milling tank body 1
In, it is 15 according to ball material mass ratio:1 addition stainless steel ball.Then proper amount of acetone is added so that powder sample is become in ball grinder
Pasty state, ball grinder is loaded on ball mill, with rotating speed for 200 rpm（Rpm）, 300 rpm and 400 rpm ball respectively
Grind 20 h（Hour）, wherein stop once, stop 6 min every time every 2 h（Minute）.After ball milling terminates, treat that acetone volatilization finishes, will
Steel ball is separated with sample and collection catalyst presoma.The catalyst precursor obtaining is calcined 3 h at 320 DEG C, terminates it
Obtain the CuO/ZnO catalyst of black afterwards.The XRD of the CuO/ZnO catalyst precursor of synthesis under different drum'ss speed of rotation
Spectrum is as shown in Figure 2.
（2）The performance characterization of CuO/ZnO catalyst
CuO/ZnO catalyst is reduced 3 h in hydrogen, reduction temperature is 280 DEG C, after reduction, gas is switched to reaction gas
CO2/H2, wherein gas volume fraction is than for CO2:H2= 1:3, reacting gas flow velocity is 80 mL/min（Milliliter is per minute）；?
240 DEG C of temperature（Degree Celsius）, pressure 3 MPa（MPa）Under carry out CO2Hydrogenating reduction is tested.Test result is as shown in Figure 3.
Embodiment 2：
（1）The preparation of CuO/ZnO catalyst
By basic copper carbonate, basic zinc carbonate and zirconium oxide according to Cu2+:Zn2+:Zr4+=2：1 weigh after be added to ball milling tank body 1
In, it is 20 according to ball material mass ratio:1 addition stainless steel ball.Then proper amount of acetone is added so that powder sample is become in ball grinder
Pasty state, ball grinder is loaded on ball mill, with rotating speed be 200 rpm, 300 rpm and 400 rpm ball milling 30 h respectively, wherein
Stop once, stop 10 min every time every 2 h.After ball milling terminates, treat that acetone volatilization finishes, steel ball is separated with sample and collects and urges
Agent presoma.The catalyst precursor obtaining is calcined at 310 DEG C 3 h, after terminating, obtain the CuO/ZnO catalysis of black
Agent.
（2）The performance characterization of CuO/ZnO catalyst
CuO/ZnO catalyst is reduced 3 h in hydrogen, reduction temperature is 280 DEG C, after reduction, gas is switched to reaction gas
CO2/H2, wherein gas volume fraction is than for CO2:H2= 1:3, reacting gas flow velocity is 80 mL/min；In 240 DEG C of temperature, pressure
Carry out CO under strong 3 MPa2Hydrogenating reduction is tested.Test result is as shown in Figure 4.
Embodiment 3：
（1）CuO/ZnO/Al2O3The preparation of catalyst
By basic copper carbonate, basic zinc carbonate and aluminum oxide according to Cu2+:Zn2+:Al3+=58:25:17 weigh after be added to ball milling
In tank body 1, it is 20 according to ball material mass ratio:1 addition stainless steel ball.Then proper amount of acetone is added to make powder sample in ball grinder
Become pasty state, ball grinder be loaded on ball mill, with rotating speed be 200 rpm, 300 rpm and 400 rpm ball milling 20 h respectively,
Wherein stop once, stop 12 min every time every 2 h.After ball milling terminates, treat that acetone volatilization finishes, steel ball is separated with sample and receives
Collection catalyst precursor.The catalyst precursor obtaining is calcined at 320 DEG C 3 h, after terminating, obtain the CuO/ of black
ZnO/Al2O3Catalyst.
（2）CuO/ZnO/Al2O3The performance characterization of catalyst
By CuO/ZnO/Al2O3Catalyst reduces 3 h in hydrogen, and reduction temperature is 280 DEG C, after reduction switches to anti-gas
Should gas CO2/H2, wherein gas volume fraction is than for CO2:H2= 1:3, reacting gas flow velocity is 80 mL/min；In temperature 240
DEG C, carry out CO under pressure 3 MPa2Hydrogenating reduction is tested.Test result is as shown in Figure 5.
Embodiment 4：
（1）CuO/ZnO/Al2O3The preparation of catalyst
By basic copper carbonate, basic zinc carbonate and aluminum oxide according to Cu2+:Zn2+:Al3+=60:20:20 weigh after be added to ball milling
In tank body 1, it is 10 according to ball material mass ratio:1 addition stainless steel ball.Then proper amount of acetone is added to make powder sample in ball grinder
Become pasty state, ball grinder be loaded on ball mill, with rotating speed be 200 rpm, 300 rpm and 400 rpm ball milling 10 h respectively,
Wherein stop once, stop 6 min every time every 3 h.After ball milling terminates, treat that acetone volatilization finishes, steel ball is separated with sample and receives
Collection catalyst precursor.The catalyst precursor obtaining is calcined at 330 DEG C 4 h, after terminating, obtain the CuO/ of black
ZnO/Al2O3Catalyst.
（2）CuO/ZnO/Al2O3The performance characterization of catalyst
By CuO/ZnO/Al2O3Catalyst reductase 12 h in hydrogen, reduction temperature is 280 DEG C, after reduction switches to anti-gas
Should gas CO2/H2, wherein gas volume fraction is than for CO2:H2= 1:3, reacting gas flow velocity is 80 mL/min；In temperature 240
DEG C, carry out CO under pressure 3 MPa2Hydrogenating reduction is tested.Test result is as shown in Figure 6.
Claims (4)
1. a kind of method of the copper-based catalysts preparing catalysis hydrogenation of carbon dioxide reduction is it is characterised in that concretely comprise the following steps：
（1）Ball milling：Put in ball grinder after basic copper carbonate, basic zinc carbonate and aluminum oxide are mixed, and in ball milling
Add stainless steel ball in tank, ball grinder is arranged in ball mill and carries out ball milling, obtain catalyst precursor；Wherein, during ball milling
Between be 10 ~ 30 hours, every 2-3 hour during ball milling, stop 5-10 minute；The rotating speed of ball milling is 200-400 rpm；
（2）Calcining：Catalyst precursor is calcined, calcining heat is 300-340 DEG C, calcination time is 2-4 hour, is urged
Change the copper-based catalysts of hydrogenation of carbon dioxide reduction.
2. the method for the copper-based catalysts of preparation catalysis hydrogenation of carbon dioxide reduction according to claim 1, its feature exists
In the mol ratio of described basic copper carbonate and basic zinc carbonate is 2:1~3:1, the molar fraction of aluminum oxide is 5 ~ 10%, stainless steel
Ball is 10 with the mass ratio of raw material:1-20:1.
3. the method for the copper-based catalysts of preparation catalysis hydrogenation of carbon dioxide reduction according to claim 1 and 2, its feature
It is, during ball milling, according to the required subcarbonate that also can add other structural promoters and carrier or oxide, described structure
Auxiliary agent and carrier are selected from aluminum carbonate basic, zirconium oxycarbonate, aluminum oxide, zirconium oxide, silica and titanium dioxide.
4. the method for the copper-based catalysts of preparation catalysis hydrogenation of carbon dioxide reduction according to claim 1 and 2, its feature
It is, as reactor, its structure is made up of described ball grinder ball milling tank body, ball milling cover, and the top edge of ball milling tank body has one
As sealing ring, after so that ball milling cover is covered and put into ball mill on ball milling tank body, ball grinder cavity keeps airtight to layer rubber ring.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108483394A (en) * | 2018-04-28 | 2018-09-04 | 洛阳师范学院 | A method of carbon dioxide is carried out with hydrogen storage material to add hydrogen |
| CN108671933A (en) * | 2018-04-26 | 2018-10-19 | 东南大学 | The preparation and method application of a kind of heterojunction photocatalyst |
| CN109078605A (en) * | 2017-06-13 | 2018-12-25 | 阿克森斯公司 | Prepare the method for solid and the purposes of these solids |
| CN109794250A (en) * | 2018-12-29 | 2019-05-24 | 广东富海新能源科技有限公司 | A kind of hydrogen synthetic catalyst and preparation method thereof |
| CN112246247A (en) * | 2020-10-15 | 2021-01-22 | 中国科学院过程工程研究所 | Organic silicon monomer synthesis reaction catalyst and preparation method and application thereof |
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| CN103263924A (en) * | 2013-06-07 | 2013-08-28 | 李溪 | Compound catalyst for preparing ethanol from biomass synthesis gases by using one-step method and solid phase preparation method of compound catalyst |
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2016
- 2016-11-02 CN CN201610944828.1A patent/CN106423175A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103263924A (en) * | 2013-06-07 | 2013-08-28 | 李溪 | Compound catalyst for preparing ethanol from biomass synthesis gases by using one-step method and solid phase preparation method of compound catalyst |
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| CN109078605A (en) * | 2017-06-13 | 2018-12-25 | 阿克森斯公司 | Prepare the method for solid and the purposes of these solids |
| CN109078605B (en) * | 2017-06-13 | 2023-08-22 | 阿克森斯公司 | Method for producing solids and use of these solids |
| CN108671933A (en) * | 2018-04-26 | 2018-10-19 | 东南大学 | The preparation and method application of a kind of heterojunction photocatalyst |
| CN108483394A (en) * | 2018-04-28 | 2018-09-04 | 洛阳师范学院 | A method of carbon dioxide is carried out with hydrogen storage material to add hydrogen |
| CN108483394B (en) * | 2018-04-28 | 2021-09-14 | 洛阳师范学院 | Method for hydrogenating carbon dioxide by using hydrogen storage material |
| CN109794250A (en) * | 2018-12-29 | 2019-05-24 | 广东富海新能源科技有限公司 | A kind of hydrogen synthetic catalyst and preparation method thereof |
| CN112246247A (en) * | 2020-10-15 | 2021-01-22 | 中国科学院过程工程研究所 | Organic silicon monomer synthesis reaction catalyst and preparation method and application thereof |
| CN116037132A (en) * | 2022-12-28 | 2023-05-02 | 鄂尔多斯市瀚博科技有限公司 | For CO 2 Catalyst for preparing methanol by hydrogenation, preparation method and application thereof |
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Application publication date: 20170222 |