CN102921420A - Cu/ZrO2 catalytic agent, preparation method of Cu/ZrO2 catalytic agent and application of Cu/ZrO2 catalytic agent - Google Patents

Cu/ZrO2 catalytic agent, preparation method of Cu/ZrO2 catalytic agent and application of Cu/ZrO2 catalytic agent Download PDF

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Publication number
CN102921420A
CN102921420A CN2012104447922A CN201210444792A CN102921420A CN 102921420 A CN102921420 A CN 102921420A CN 2012104447922 A CN2012104447922 A CN 2012104447922A CN 201210444792 A CN201210444792 A CN 201210444792A CN 102921420 A CN102921420 A CN 102921420A
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zro
catalyst
zro2
preparation
catalytic agent
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郭晓明
黄夏阳
毛东森
卢冠忠
王嵩
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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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 discloses a Cu/ZrO2 catalytic agent, a preparation method of the Cu/ZrO2 catalytic agent and application of the Cu/ZrO2 catalytic agent. The Cu/ZrO2 catalytic agent is composed of reduction state copper and reduction state, and Cu:ZrO2 is 1:9 after calculating according to the molar ratio. The preparation method comprises using a sodium hydroxide aqueous solution, ZrOCl2-8H2O and Cu(NO3)2-3H2O to generate H2O, then adding reducing agent glucose, conducting a hydrothermal reaction, cooling after the hydrothermal reaction until reaction liquid is at the room temperature for filtering, using absolute ethyl alcohol and distilled water to sequentially wash and filter obtained filtering cakes, and conducting vacuum drying after no Cl- is detected in the filter liquor, namely the Cu/ZrO2 catalytic agent. The Cu/ZrO2 catalytic agent is used for a process that hydrogen is added in catalysis CO2 to prepare methane, and vapor phase reduction pre-treatment is not needed, so that production efficiency for the process that hydrogen is added in catalysis CO2 to prepare methane is relatively improved, and production energy consumption is reduced. The Cu/ZrO2 catalytic agent is safe and effective in preparation process and favorable for industrial production.

Description

A kind of Cu/ZrO 2Catalysts and its preparation method and application
Technical field
The present invention relates to a kind of Cu/ZrO 2Catalysts and its preparation method and its are at CO 2Application in the catalytic hydrogenation methyl alcohol processed.Relate in particular a kind of employing hydro-thermal method and prepare Cu/ZrO 2The method of catalyst, the method are about to copper oxide reduction in preparation process and become metallic copper, therefore, and Cu/ZrO 2Catalyst is used for CO 2During catalytic hydrogenation methyl alcohol processed, do not need the vapour phase reduction preprocessing process.
Background technology
CO 2Being a kind of main greenhouse gases, also is a kind of cheapness and abundant carbon source simultaneously.In recent years, because global warming issue is day by day serious and the petering out of fossil fuel, how to realize CO 2Effective utilization more and more receive people's concern.Pass through CO 2The catalytic hydrogenation synthesizing methanol is CO 2One of important channel of recycling.
CO 2The catalytic hydrogenation synthesizing methanol mainly carries out at copper-based catalysts.At present the copper in the copper-based catalysts is that form with cupric oxide exists, and before the use, copper-based catalysts will be in reducing atmosphere, 200-400 ℃ carries out prereduction and processes, and copper oxide reduction is become metallic copper.Reduction process length consuming time and usually be attended by strong fuel factor, this practical application to catalyst produces harmful effect.
Document (SCI, 2003,24 (7): 1296-1298) adopt precipitation-reducing process, use KBH 4Solution carries out the liquid phase chemical reduction processing to the carbonate coprecipitation of fresh preparation, directly obtains reduction-state Cu/ZnO/A1 2O 3Methanol synthesis catalyst.Yet, because KBH 4Strong reducing property, preparation process reaction is violent, has a large amount of hydrogen to emerge, and has certain unsafe factor, is unfavorable for actual production control.
This shows, exploitation is used for CO 2The copper-based catalysts simple and safe effective, that exempt from gas phase prereduction processing of catalytic hydrogenation synthesizing methanol is necessary.
Summary of the invention
One of purpose of the present invention provides a kind of Cu/ZrO 2Catalyst, this Cu/ZrO 2Copper in the catalyst exists with the metallic copper form.
Two of the object of the invention provides above-mentioned a kind of Cu/ZrO 2The preparation method of catalyst, this preparation method is at preparation Cu/ZrO 2During catalyst the raw material copper oxide reduction is become metallic copper, so that the Cu/ZrO of final gained 2Catalyst is being used for CO 2During the catalytic hydrogenation synthesizing methanol, needn't carry out again gas phase prereduction and process, and this preparation method is simple and safe effectively.
The technical solution used in the present invention
A kind of Cu/ZrO 2Catalyst is comprised of copper and the zirconia of reduction-state, calculates in molar ratio, and Cu:Zr wherein is 1:9.
Above-mentioned a kind of Cu/ZrO 2The preparation method of catalyst is namely at first with sodium hydrate aqueous solution, ZrOCl 28H 2The O aqueous solution and Cu (NO 3) 23H 2The O aqueous solution generates precipitation and adds reducing agent glucose, carries out hydro-thermal reaction;
Then the reactant liquor that is cooled to room temperature after the hydro-thermal reaction is filtered, the filter cake of gained washs, filters with absolute ethyl alcohol and distilled water successively, until inspection does not measure Cl in the filtrate -Final vacuum is dry, namely gets Cu/ZrO 2Catalyst, it specifically comprises the steps:
(1), takes by weighing a certain amount of NaOH, ZrOCl 28H 2O, Cu (NO 3) 23H 2O and glucose are prepared respectively NaOH, ZrOCl 28H 2O, Cu (NO 3) 23H 2The aqueous solution of O and glucose;
(2), with ZrOCl 28H 2The O aqueous solution and the NaOH aqueous solution mix, and rear adding Cu (NO stirs 3) 23H 2The O aqueous solution and D/W are transferred in the low-temp reaction still that polytetrafluoroethylliner liner is housed after continuing to stir 10 ~ 30min, and the control temperature is 180 ~ 220 ℃, and the time is that 2 ~ 20h carries out hydro-thermal reaction, and reaction naturally cools to room temperature after finishing;
Wherein the NaOH aqueous solution, ZrOCl 28H 2The O aqueous solution, Cu (NO 3) 23H 2The consumption of the O aqueous solution and D/W calculates in molar ratio, i.e. NaOH:ZrOCl 28H 2O:Cu (NO 3) 23H 2O: glucose is 100:9:1:1.0 ~ 4;
(3), the product that is cooled to room temperature after step (2) hydro-thermal reaction is filtered, the filter cake of gained successively with absolute ethyl alcohol and distilled water washing, filter, until inspection does not measure Cl in the filtrate -Final vacuum is dry, namely gets Cu/ZrO 2Catalyst;
Described vacuum drying control temperature is 20 ~ 80 ℃.
The Cu/ZrO of above-mentioned gained 2Catalyst is used for the reaction of catalysis hydrogenation of carbon dioxide to generate methanol.
Beneficial effect of the present invention
A kind of Cu/ZrO of the present invention 2Catalyst is owing to preparing Cu/ZrO in hydro-thermal method 2Add reducing agent glucose in the process of catalyst, in liquid phase, just copper oxide reduction has been become metallic copper, therefore, the Cu/ZrO of final gained 2Copper is to exist with the metallic copper form in the catalyst, this Cu/ZrO 2Catalyst is used for CO 2During the standby methyl alcohol of Hydrogenation, do not need to carry out the vapour phase reduction preliminary treatment.
Further, a kind of Cu/ZrO of the present invention 2Catalyst is used for catalysis CO 2During the standby methyl alcohol reaction of Hydrogenation, owing to not needing to use H 2To Cu/ZrO 2Catalyst carries out gas phase prereduction to be processed, thus relative raising CO 2The production efficiency of the standby methyl alcohol of Hydrogenation has reduced energy consumption.
A kind of Cu/ZrO of the present invention 2The employed equipment of the preparation method of catalyst is simple, and process tolerant is wide, and the reducing agent glucose performance of using is gentle, safe and effective, meets the Green Chemistry theory, is conducive to suitability for industrialized production.
The specific embodiment
Below by embodiment the present invention is described in further detail, but do not limit the present invention.
Gases used from the big wound calibrating gas in Shanghai Co., Ltd in the various embodiments of the present invention, other reagent is all available from Shanghai reagent company of traditional Chinese medicines group, and it is pure that reagent is analysis.
Catalytic reaction of the present invention is carried out in fixed bed reactors, gained Cu/ZrO 2The phase structure of catalyst adopts the X-ray diffractometer (X ' Pert) of Dutch PANalytical company to measure, and catalytic reaction products such as carbon dioxide, carbon monoxide and methyl alcohol adopt the Agilent gas chromatograph for determination.The method that detailed detection method reference literature (F. Arena, K. Barbera, G. Italiano, G. Bonura, L. Spadaro, F. Frusteri, J. Catal. 249 (2007) 185-194) provides.
Used equipment is model, the specification of analytical instrument in the various embodiments of the present invention, and the information such as manufacturer are as shown in table 1.
Table 1 the present invention is usedThe model of instrument, specification, manufacturer
Instrument, device name Model Manufacturer
The polytetrafluoroethylene (PTFE) reactor LTG-100 Upper oceanic rise is opened up Instr Ltd.
Constant temperature blender with magnetic force B85-2 Anting Scientific Instrument Factory, Shanghai
Vacuum drying oven BPZ-6033LC Shanghai Yiheng Scientific Instruments Co., Ltd
X-ray diffractometer X’Pert Holland PANalytical company
The Agilent gas chromatograph 6820 Agilent science and technology Shanghai Co., Ltd
Fixed bed reactors LW-4 Wuxi drawing instrument factory
Embodiment 1
A kind of preparation method of Cu-Zr catalyst specifically comprises the following steps:
(1), get 4.0g NaOH and join in the 20ml deionized water, forming molar concentration is the NaOH aqueous solution of 5mol/L;
Get the ZrOCl of 2.90g 28H 2O is dissolved in the 20ml deionized water, forms 0.45mol/L ZrOCl 2The aqueous solution;
Get 0.24g Cu (NO 3) 23H 2O joins in the 20ml deionized water, and forming molar concentration is the Cu (NO of 0.05mol/L 3) 2The aqueous solution;
Get 0.36g glucose and join in the 20ml deionized water, forming molar concentration is the D/W of 0.1mol/L;
(2), with the NaOH aqueous solution and the ZrOCl of step (1) gained 2Aqueous solution adds Cu (NO after continuing to stir 30min simultaneously 3) 2With the aqueous solution of glucose, and transfer to behind the continuation stirring 30min and carry out hydro-thermal reaction in the reactor that polytetrafluoroethylliner liner is housed, hydro-thermal reaction control temperature is 200 ℃, and the time is 12h, gets reactant liquor;
Wherein the NaOH aqueous solution, ZrOCl 28H 2The O aqueous solution, Cu (NO 3) 23H 2The consumption of the O aqueous solution and D/W calculates in molar ratio, i.e. NaOH:ZrOCl 28H 2O:Cu (NO 3) 23H 2O: glucose is 100:9:1:2;
(3), filter after the reactant liquor of step (2) gained is cooled to room temperature, the filter cake of gained is used AgNO with absolute ethyl alcohol and successively washing precipitation of distilled water 3Solution detects, until inspection does not measure Cl -After with filter cake in vacuum drying oven, the control temperature is 60 ℃ of lower dry 4h, namely gets Cu/ZrO 2Catalyst A.
The Cu/ZrO of above-mentioned gained 2The phase structure of catalyst A adopts the X-ray diffractometer analysis of Dutch PANalytical company, and its XRD collection of illustrative plates as shown in Figure 1.As can be seen from Figure 1, be the characteristic diffraction peak that Cu has appearred in 43.3 places at 2 θ, show that CuO has been become Cu by Reduction of Glucose.Other diffraction maximum is ZrO 2Characteristic diffraction peak.
Embodiment 2
A kind of Cu/ZrO 2The preparation method of catalyst, the quality that just takes by weighing glucose in the step (1) is 0.54g, the NaOH aqueous solution, ZrOCl in the step (2) 28H 2The O aqueous solution, Cu (NO 3) 23H 2The consumption of the O aqueous solution and D/W calculates in molar ratio, i.e. NaOH:ZrOCl 28H 2O:Cu (NO 3) 23H 2O: glucose is 100:9:1:3, and the other the same as in Example 1 finally obtains Cu/ZrO 2Catalyst B.
Embodiment 3
A kind of Cu/ZrO 2The preparation method of catalyst, the quality that just takes by weighing glucose in the step (1) is 0.72g, the NaOH aqueous solution, ZrOCl in the step (2) 28H 2The O aqueous solution, Cu (NO 3) 23H 2The consumption of the O aqueous solution and D/W calculates in molar ratio, i.e. NaOH:ZrOCl 28H 2O:Cu (NO 3) 23H 2O: glucose is 100:9:1:4, and other finally obtain Cu/ZrO with embodiment 1 2Catalyst C.
Embodiment 4
A kind of Cu/ZrO 2The preparation method of catalyst, the quality that just takes by weighing glucose in the step (1) is 0.27g, the NaOH aqueous solution, ZrOCl in the step (2) 28H 2The O aqueous solution, Cu (NO 3) 23H 2The consumption of the O aqueous solution and D/W calculates in molar ratio, i.e. NaOH:ZrOCl 28H 2O:Cu (NO 3) 23H 2O: glucose is 100:9:1:1.5, and other finally obtain Cu/ZrO with embodiment 1 2Catalyst D.
Embodiment 5
A kind of Cu/ZrO 2The preparation method of catalyst, the quality that just takes by weighing glucose in the step (1) is 0.18g, the NaOH aqueous solution, ZrOCl in the step (2) 28H 2The O aqueous solution, Cu (NO 3) 23H 2The consumption of the O aqueous solution and D/W calculates in molar ratio, i.e. NaOH:ZrOCl 28H 2O:Cu (NO 3) 23H 2O: glucose is 100:9:1:1, and other finally obtain Cu/ZrO with embodiment 1 2Catalyst E.
Application Example 1
The Cu/ZrO that embodiment 1,2,3,4,5 is obtained 2Catalyst A, B, C, D, E are used for catalysis CO 2The standby methyl alcohol of Hydrogenation
Get the Cu/ZrO that embodiment 1,2,3,4,5 obtains 2Catalyst A, B, C, each 0.5g of D, E are seated in respectively in the stainless steel reaction pipe, pass into respectively unstripped gas CO 2, H 2, unstripped gas CO 2, H 2Flow velocity is respectively 20mL/min, and regulating respectively counterbalance valve to Pressure gauge is 3.0MPa, respectively the stainless steel reaction pipe is heated to 240 ℃ simultaneously, and question response carries out distinguishing sampling and measuring CO behind the 4h 2Conversion ratio, CH 3OH is selective, and test result is as shown in table 2 (to contain CO in the above-mentioned reacted product gas 2, CO, CH 4And CH 3OH, each content of material adopt the Agilent chromatograph to measure):
Table 2, test result
Catalyst CO 2Conversion ratio CH 3OH is selective
Cu/ZrO 2Catalyst A 2.7 52.2
Cu/ZrO 2Catalyst B 2.7 51.6
Cu/ZrO 2Catalyst C 2.6 50.5
Cu/ZrO 2Catalyst D 2.9 53.6
Cu/ZrO 2Catalyst E 2.1 54.7
As can be seen from Table 2, the CuO/ZrO of gained in the various embodiments of the present invention 2Catalyst is used for CO 2The preparing methanol by hydrogenation reaction in the pretreated situation without hydrogen reducing, has obtained higher CO 2Conversion ratio and CH 3OH is selective, has shown thus the CuO/ZrO that the present invention makes 2Catalyst has higher catalytic activity for the hydrogenation of carbon dioxide to generate methanol reaction.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.

Claims (9)

1. Cu/ZrO 2Catalyst is characterized in that described Cu/ZrO 2Catalyst forms in molar ratio calculating, i.e. Cu:ZrO by copper and the zirconia of reduction-state 2Be 1:9.
2. a kind of Cu/ZrO as claimed in claim 1 2The preparation method of catalyst is characterized in that at first with sodium hydrate aqueous solution, ZrOCl 28H 2The O aqueous solution and Cu (NO 3) 23H 2The O aqueous solution generates precipitation and adds reducing agent glucose, carries out hydro-thermal reaction;
Then the reactant liquor that is cooled to room temperature after the hydro-thermal reaction is filtered, the filter cake of gained washs, filters with absolute ethyl alcohol and distilled water successively, until inspection does not measure Cl in the filtrate -Final vacuum is dry, namely gets Cu/ZrO 2Catalyst.
3. a kind of Cu/ZrO as claimed in claim 2 2The preparation method of catalyst, the addition that it is characterized in that reducing agent glucose by it with respect to Cu (NO 3) 23H 2The mol ratio of O is calculated, and is glucose: Cu (NO 3) 23H 2O is 1.0 ~ 4:1.
4. a kind of Cu/ZrO as claimed in claim 2 or claim 3 2The preparation method of catalyst is characterized in that it is 180 ~ 220 ℃ that described hydro-thermal reaction is namely controlled temperature, and the time is 2 ~ 20h.
5. a kind of Cu/ZrO as claimed in claim 4 2The preparation method of catalyst is characterized in that it is 200 ℃ that described hydro-thermal reaction is namely controlled temperature, and the time is 12h.
6. a kind of Cu/ZrO as claimed in claim 5 2The preparation method of catalyst is characterized in that described hydro-thermal reaction carries out in the low-temp reaction still of polytetrafluoroethylliner liner is housed.
7. a kind of Cu/ZrO as claimed in claim 6 2The preparation method of catalyst is characterized in that described vacuum drying control temperature is 20 ~ 80 ℃.
8. a kind of Cu/ZrO as claimed in claim 7 2The preparation method of catalyst is characterized in that described vacuum drying control temperature is 60 ℃.
9. a kind of Cu/ZrO as claimed in claim 1 2Catalyst is used for the reaction of catalysis hydrogenation of carbon dioxide to generate methanol.
CN2012104447922A 2012-11-09 2012-11-09 Cu/ZrO2 catalytic agent, preparation method of Cu/ZrO2 catalytic agent and application of Cu/ZrO2 catalytic agent Pending CN102921420A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018102676A1 (en) * 2016-12-02 2018-06-07 Basf Corporation Copper catalysts for the preparation of ethylene glycol
CN108671933A (en) * 2018-04-26 2018-10-19 东南大学 The preparation and method application of a kind of heterojunction photocatalyst
CN109999833A (en) * 2019-05-07 2019-07-12 盐城工学院 A kind of catalyst and preparation method thereof for synthesizing methanol by hydrogenating carbon dioxide
CN111790392A (en) * 2020-07-29 2020-10-20 宁夏大学 Catalyst for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof
CN114029095A (en) * 2021-12-16 2022-02-11 常州大学 Cu/SiO for preparing cyclohexanone by efficiently catalyzing anaerobic dehydrogenation of cyclohexanol2Preparation method and application of catalyst

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018102676A1 (en) * 2016-12-02 2018-06-07 Basf Corporation Copper catalysts for the preparation of ethylene glycol
CN108671933A (en) * 2018-04-26 2018-10-19 东南大学 The preparation and method application of a kind of heterojunction photocatalyst
CN109999833A (en) * 2019-05-07 2019-07-12 盐城工学院 A kind of catalyst and preparation method thereof for synthesizing methanol by hydrogenating carbon dioxide
CN111790392A (en) * 2020-07-29 2020-10-20 宁夏大学 Catalyst for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof
CN111790392B (en) * 2020-07-29 2023-03-24 宁夏大学 Catalyst for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof
CN114029095A (en) * 2021-12-16 2022-02-11 常州大学 Cu/SiO for preparing cyclohexanone by efficiently catalyzing anaerobic dehydrogenation of cyclohexanol2Preparation method and application of catalyst
CN114029095B (en) * 2021-12-16 2023-08-22 常州大学 Cu/SiO for preparing cyclohexanone by efficiently catalyzing cyclohexanol to perform anaerobic dehydrogenation 2 Preparation method and application of catalyst

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Application publication date: 20130213