CN103263926A - Catalyst for synthesizing methanol through carbon dioxide hydrogenation as well as preparation method and application thereof - Google Patents
Catalyst for synthesizing methanol through carbon dioxide hydrogenation as well as preparation method and application thereof Download PDFInfo
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- CN103263926A CN103263926A CN2013101758089A CN201310175808A CN103263926A CN 103263926 A CN103263926 A CN 103263926A CN 2013101758089 A CN2013101758089 A CN 2013101758089A CN 201310175808 A CN201310175808 A CN 201310175808A CN 103263926 A CN103263926 A CN 103263926A
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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
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- 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 catalyst for synthesizing methanol through carbon dioxide hydrogenation, which is composed of oxides, wherein measured by metals, the mole ratio of various metals is as follows: [n(Cu)+n(Zn)+n(MA)]:[n(Al)+n(MB)]=2-15, n(Cu):n(Zn)=0.5-4, n(MA):n(Zn)=0-1, and n(MB):n(Al)=0-9, MA represents monovalent or divalent metal ions, and MB represents trivalent or tetravalent metal ions. The catalyst has the advantages of high carbon dioxide conversion ratio, good methanol selectivity and high methanol yield.
Description
Technical field
The invention belongs to a kind of catalyst and preparation method, relate to a kind of synthesizing methanol by hydrogenating carbon dioxide catalyst and preparation method and application specifically.
Background technology
In order to alleviate even to eliminate too much CO
2Discharging harm that environment is caused, and solve the carbon resource problem, need the exploitation can be with CO
2Be converted into the technology of valuable material.In view of methyl alcohol is the important source material of chemical industry and petrochemical industry, is a kind of fuel of cleaning again, CO
2The synthesizing methanol by hydrogenating process is subjected to extensive concern.Yet, CO
2Highly stable, activation is difficult to, so the catalyst development of this process is crucial.
Because the active advantages of higher of cheapness and low pressure, copper-based catalysts has become the maximum catalyst system of research, becomes important research direction by adding auxiliary agent exploitation modified copper-based catalysts.It is catalyst based that some researchers usually modify Cu by units such as adding Mg, Mn, Al, Cr, La, B, In, Ga, Gd, Ce, Y, Ti, Zr and V, as (petrochemical industries such as Huang Shupeng, 2009,38 (5), 482-485) adopt coprecipitation to prepare CuO-ZnO-A1
2O
3Catalyst has been investigated ZrO
2, Ag
2O, La
2O
3, MnO, CeO
2, Fe
2O
3The CuO-ZnO-Al of six kinds of additive modifications
2O
3Catalyst is to CO
2The catalytic performance of synthesizing methanol by hydrogenating reaction.Experimental result shows, uses ZrO
2Or AgO modification CuO-ZnO-Al
2O
3Behind the catalyst, at 240 ℃, 2.0 MPa, air speed 3600 h
-1, n (H
2): n (CO
2) under the reaction condition of mol ratio=3, CO
2Conversion ratio is 10-15 %, and methyl alcohol selectively is 25-38 %, and the methyl alcohol yield is 2.8-4.1 %.The researcher who also has studies method for preparing catalyst, as Cong Yu etc. (the catalysis journal, 2000,21 (3), 247-250) adopt sol-gal process, coprecipitation and azeotropic distillation method to prepare the different ultra-fine CuO-ZnO-ZrO of granularity respectively
2Catalyst is at 250 ℃, 3.0 MPa, air speed 8000 h
-1, n (H
2): n (CO
2) under the reaction condition of mol ratio=3, CO
2Conversion ratio is 5-13 %, and methyl alcohol selectively is 35-50 %, and the methyl alcohol yield is 0.07-0.11 g g
Cat -1h
-1Publication number is that the synthetic LaCr of conflagration method has been reported in the application for a patent for invention of CN101690894A
1-xCu
xO
3Catalyst is at 250 ℃, 2.0 MPa, air speed 9000 mL h
-1g
-1, n (H
2): n (CO
2) under the reaction condition of mol ratio=2, its CO
2Conversion ratio is at 3-12 %, and the methyl alcohol yield is at 0.06-0.38 g g
Cat -1h
-1But the problem that the copper-based catalysts of present synthesizing methanol by hydrogenating carbon dioxide mainly exists is that carbon dioxide conversion is on the low side, and methyl alcohol is selective and yield is not high.
Summary of the invention
At the shortcoming of prior art, the purpose of this invention is to provide a kind of carbon dioxide conversion height, methyl alcohol is selectively good, synthesizing methanol by hydrogenating carbon dioxide Catalysts and its preparation method and application that the methyl alcohol yield is high.
Catalyst of the present invention is to obtain by the compound thermal decomposition that contains hydrotalcite-like compound, and the chemical composition of houghite compound has following general formula: [M
2+ 1 xM
3+ x(OH)
2]
X+(A
n)
X/nMH
2O, wherein M
2+And M
3+Be respectively divalence and trivalent metal cation, be positioned on the main body laminate; A
N-Be interlayer anion; X is M
3+/ (M
2++ M
3+) molar ratio; M is the number of intermediary water molecule.In addition, there are bibliographical information monovalence or tetravalent metal cation such as Li, Zr, Ti etc. also can be incorporated into hydrotalcite-like compound and form houghite compound (China YouSe Acta Metallurgica Sinica, 2007,17 (7), 1213-1218; Journal of Catalysis (catalysis journal), 2013,298,51-60).With the houghite material be that the composite metal oxide of presoma preparation has that the easy modulation of zwitterion, specific surface height, heat endurance height, alkalescence are strong, advantages such as the even distribution that can realize metallic element and interaction modulation, and show excellent catalytic activity.
Catalyst of the present invention is made up of oxide, and in metal, the mol ratio of various metals is: [n (Cu)+n (Zn)+n (M
A)]: [n (Al)+n (M
B)]=2-15, n (Cu): n (Zn)=0.5-4, n (M
A): n (Zn)=0-1, n (M
B): n (Al)=0-9;
M wherein
ARepresent monovalence or bivalent metal ion, comprise Li
+, K
+, Ag
+, Mg
2+, Mn
2+, Co
2+, Fe
2+, Pd
2+, Pt
2+Deng; M
BRepresent trivalent or quadrivalent metallic ion, comprise V
3+, Cr
3+, Mn
3+, Fe
3+, Co
3+, Ga
3+, Ru
3+, Rh
3+, Y
3+, Ce
3+, Sm
3+, Gd
3+, La
3+, Ir
3+, Dy
3+, Ti
4+, Zr
4+, Sn
4+Deng.
Preparation of catalysts method of the present invention comprises the steps:
Method one: catalyst adopts the coprecipitation preparation, Zr is with the form of zirconyl nitrate or zirconium nitrate, all the other elements all are dissolved in the deionized water with the form of nitrate, be made into mixed aqueous solution according to the above ratio, in addition, NaOH and sodium carbonate example in molar ratio are made into the mixed precipitation agent solution for 2-10:1, under 10-60 ℃, two mixed liquors carry out co-precipitation, and precipitation process needs fully to stir, and keeps pH=6-13, post precipitation needs aging 1-36 h under 40-100 ℃ of stirring condition, precipitation through deionized water washing till do not have sodium ion and detect, then 60-160 ℃ dry down, 400-700 ℃ of roasting 2-8 h.
Method two: catalyst adopts the coprecipitation preparation, copper nitrate is made into the aqueous solution (solution A) separately, Zr is with the form of zirconyl nitrate or zirconium nitrate, all the other elements all form mixed solution (solution B) according to the above ratio with the form of nitrate, in addition, NaOH and sodium carbonate in molar ratio example be made into the mixed precipitation agent solution for 2-8:1.Under 10-60 ℃, solution B and precipitant solution are carried out co-precipitation earlier, after treating that B solution precipitation fully, carry out the co-precipitation of solution A and precipitating reagent again, precipitation process needs fully to stir, and keeps pH=8-13, post precipitation needs aging 8-36 h under 40-100 ℃ of stirring condition, precipitation through deionized water washing till do not have sodium ion and detect, then 60-160 ℃ dry down, 400-600 ℃ of roasting 2-8 h.
Being reflected in the fixed bed reactors of synthesizing methanol by hydrogenating carbon dioxide carried out, the reducing condition of catalyst of the present invention is: with pure hydrogen at 250-350 ℃ of reduction 4-15 h, the condition of synthesizing methanol by hydrogenating carbon dioxide is: reaction pressure is 2.0-11.0 MPa, reaction temperature is 200-350 ℃, and volume space velocity is 2000-10000 h
-1, n (H
2): n (CO
2) mol ratio=2-4.
The present invention compared with prior art has following advantage:
Shortcomings such as it is lower 1) to have overcome the conversion ratio of existing synthesizing methanol by hydrogenating carbon dioxide catalyst carbon dioxide, and the selective relatively poor and methyl alcohol yield of methyl alcohol is low, prepared catalyst performance stabilised.
2) specific area of catalyst is big, the decentralization height of Cu, and the strong basicity bit quantity is many, is conducive to H
2Dissociate absorption and CO
2Stable absorption.
3) this method for preparing catalyst is simple, operation easily, and catalyst performance repeatability is relatively good, is easy to realize the industry amplification.
4) but catalyst straight forming before dry does not need adding additives.And catalyst is after roasting, and mechanical strength is relatively good.
The specific embodiment:
Embodiment 1. forms mixed solution in the middle of all being dissolved in deionized water with the form of nitrate by each element of following metallic atom mol ratio preparation mixed solution: Cu2Zn1Al0.9La0.1(), in addition, NaOH and sodium carbonate in molar ratio example be made into the mixed precipitation agent solution for 10:1.Under 60 ℃, two mixed liquors carry out co-precipitation, and precipitation process needs fully to stir, keep pH=13, aging 36 h under 40 ℃ of stirring conditions, precipitation through the deionized water washing till do not have sodium ion and detect, dry under 160 ℃, 700 ℃ of roasting 2 h obtain CuO/ZnO/Al
2O
3/ La
2O
3Metal oxide catalyst, the metallic atom mol ratio of this catalyst is: n (Cu): n (Zn): n (Al): n (La)=2:1:0.9:0.1 is crushed to the 40-60 order with it.Being reflected in the fixed bed reactors of synthesizing methanol by hydrogenating carbon dioxide carried out, and is down to room temperature with pure hydrogen behind 250 ℃ of reduction 15 h, switches to reaction gas and reacts, and reaction condition is as follows: P=2.0 MPa, T=350 ℃, GHSV=10000 h
-1, n (H
2): n (CO
2) mol ratio=3, collect liquid product with ice-water bath, the gas chromatographic analysis product is formed.The gained result is as follows:
Embodiment 2. forms mixed solution in the middle of all being dissolved in deionized water with the form of nitrate by each element of following metallic atom mol ratio preparation mixed solution: Cu1Zn1Al0.9Ga0.1(), in addition, NaOH and sodium carbonate in molar ratio example be made into the mixed precipitation agent solution for 2:1.Under 10 ℃, two mixed liquors carry out co-precipitation, and precipitation process needs fully to stir, keep pH=13, aging 1 h under 100 ℃ of stirring conditions, precipitation through the deionized water washing till do not have sodium ion and detect, dry under 60 ℃, 400 ℃ of roasting 8 h obtain CuO/ZnO/Al
2O
3/ Ga
2O
3Metal oxide catalyst, the metallic atom mol ratio of this catalyst is: n (Cu): n (Zn): n (Al): n (Ga)=1:1:0.9:0.1 is crushed to the 40-60 order with it.Being reflected in the fixed bed reactors of synthesizing methanol by hydrogenating carbon dioxide carried out, and is down to room temperature with pure hydrogen behind 350 ℃ of reduction 4 h, and reaction condition is: P=11.0 MPa, T=200 ℃, GHSV=3500 h
-1, n (H
2): n (CO
2) mol ratio=2, collect liquid product with ice-water bath, the gas chromatographic analysis product is formed.The gained result is:
Embodiment 3. removes Zr with the form of zirconyl nitrate by following metallic atom mol ratio preparation mixed solution: Cu2Zn1Al0.8Y0.1Zr0.1(, all the other elements form mixed solution in the middle of all being dissolved in deionized water with the form of nitrate), in addition, NaOH and sodium carbonate in molar ratio example be made into the mixed precipitation agent solution for 5:1.Under 25 ℃, two mixed liquors carry out co-precipitation, and precipitation process needs fully to stir, keep pH=10, aging 15 h under 60 ℃ of stirring conditions, precipitation through the deionized water washing till do not have sodium ion and detect, dry under 80 ℃, 500 ℃ of roasting 4 h obtain CuO/ZnO/Al
2O
3/ Y
2O
3/ ZrO
2Metal oxide catalyst, the metallic atom mol ratio of this catalyst is: n (Cu): n (Zn): n (Al): n (Y): n (Zr)=2:1:0.8:0.1:0.1 is crushed to the 40-60 order with it.Being reflected in the fixed bed reactors of synthesizing methanol by hydrogenating carbon dioxide carried out, and is down to room temperature with pure hydrogen behind 300 ℃ of reduction 8 h, and reaction condition is: P=7.0 MPa, T=230 ℃, GHSV=3000 h
-1, n (H
2): n (CO
2) mol ratio=4, collect liquid product with ice-water bath, the gas chromatographic analysis product is formed.The gained result is:
Embodiment 4. preparations are equal to example 3, CuO/ZnO/Al with evaluation method
2O
3/ Y
2O
3The metallic atom mol ratio of catalyst is: n (Cu): n (Zn): n (Al): n (Y)=2:1:0.95:0.05, behind 280 ℃ of reduction 10 h, be down to room temperature with pure hydrogen, and reaction condition is: P=5.0 MPa, T=270 ℃, GHSV=3000 h
-1, n (H
2): n (CO
2) mol ratio=3, the gained result is:
Embodiment 5. preparations are equal to example 3, CuO/ZnO/Al with evaluation method
2O
3/ ZrO
2The metallic atom mol ratio of catalyst is: n (Cu): n (Zn): n (Al): n (Zr)=2:1:0.1:0.9, behind 300 ℃ of reduction 8 h, be down to room temperature with pure hydrogen, and reaction condition is: P=5.0 MPa, T=270 ℃, GHSV=4000 h
-1, n (H
2): n (CO
2) mol ratio=3, the gained result is:
Embodiment 6. preparations and evaluation method are equal to example 3, CuO/ZnO/MgO/Al
2O
3/ ZrO
2The metallic atom mol ratio of catalyst is: n (Cu): n (Zn): n (Mg): n (Al): n (Zr)=2:0.5:0.5:0.9:0.1, behind 300 ℃ of reduction 8 h, be down to room temperature with pure hydrogen, and reaction condition is: P=5.0 MPa, T=270 ℃, GHSV=4000 h
-1, n (H
2): n (CO
2) mol ratio=3, the gained result is:
Embodiment 7. preparations and evaluation method are equal to example 3, CuO/ZnO/MnO/Al
2O
3The metallic atom mol ratio of catalyst is: n (Cu): n (Zn): n (Mn): n (Al)=2:0.9:0.1:1, behind 290 ℃ of reduction 10 h, be down to room temperature with pure hydrogen, and reaction condition is: P=5.0 MPa, T=290 ℃, GHSV=4000 h
-1, n (H
2): n (CO
2) mol ratio=3, the gained result is:
Embodiment 8. removes Zr with the form of zirconyl nitrate by following metallic atom mol ratio preparation salting liquid: Cu1.5Zn3Al0.7Zr0.3(, all the other elements form mixed solution in the middle of all being dissolved in deionized water with the form of nitrate), copper nitrate is made into the aqueous solution separately, other metallic elements are made into mixing salt solution, in addition, NaOH and sodium carbonate in molar ratio example be made into the mixed precipitation agent solution for 2:1.At first, under 60 ℃, mixing salt solution and precipitant solution are carried out co-precipitation, precipitation process needs fully to stir, keep pH=8, treat that various precipitation by metallic ion fully after, add copper nitrate solution again and above-mentioned precipitating reagent carries out co-precipitation, continue to keep pH=8, aging 36 h under 40 ℃ of stirring conditions, precipitation through the deionized water washing till do not have sodium ion and detect, dry down at 160 ℃, 600 ℃ of roasting 2 h obtain CuO/ZnO/Al
2O
3/ ZrO
2Metal oxide catalyst, the metallic atom mol ratio of this catalyst is: n (Cu): n (Zn): n (Al): n (Zr)=1.5:3:0.7:0.3 is crushed to the 40-60 order with it.Being reflected in the fixed bed reactors of synthesizing methanol by hydrogenating carbon dioxide carried out, the reaction before with pure hydrogen 350 ℃ the reduction 4 h, switch to reaction gas and react, reaction condition is as follows: P=5.0 MPa, T=250 ℃, GHSV=4000 h
-1, n (H
2): n (CO
2) mol ratio=3, collect liquid product with ice-water bath, the gas chromatographic analysis product is formed.The gained result is as follows:
Embodiment 9. removes Zr with the form of zirconyl nitrate by following metallic atom mol ratio preparation mixed solution: Cu12Zn3Al0.7Zr0.3(, all the other elements form mixed solution in the middle of all being dissolved in deionized water with the form of nitrate), copper nitrate is made into the aqueous solution separately, other metallic elements are made into mixing salt solution, in addition, NaOH and sodium carbonate in molar ratio example be made into the mixed precipitation agent solution for 8:1.At first, under 10 ℃, mixing salt solution and precipitant solution are carried out co-precipitation, precipitation process needs fully to stir, keep pH=13, treat that various precipitation by metallic ion fully after, add copper nitrate solution again and above-mentioned precipitating reagent carries out co-precipitation, continue to keep pH=13, aging 8 h under 100 ℃ of stirring conditions, precipitation through the deionized water washing till do not have sodium ion and detect, dry down at 60 ℃, 400 ℃ of roasting 8 h obtain CuO/ZnO/Al
2O
3/ ZrO
2Metal oxide catalyst, the metallic atom mol ratio of this catalyst is: n (Cu): n (Zn): n (Al): n (Zr)=12:3:0.7:0.3 is crushed to the 40-60 order with it.Being reflected in the fixed bed reactors of synthesizing methanol by hydrogenating carbon dioxide carried out, and is down to room temperature with pure hydrogen behind 350 ℃ of reduction 8 h, and reaction condition is: P=5.0 MPa, T=250 ℃, GHSV=4000 h
-1, n (H
2): n (CO
2) mol ratio=3, collect liquid product with ice-water bath, the gas chromatographic analysis product is formed.The gained result is:
Embodiment 10. forms mixed solution in the middle of all being dissolved in deionized water with the form of nitrate by each element of following metallic atom mol ratio preparation salting liquid: Cu6Zn3Al1(), copper nitrate is made into the aqueous solution separately, other metallic elements are made into mixing salt solution, in addition, NaOH and sodium carbonate in molar ratio example be made into the mixed precipitation agent solution for 4:1.At first, under 30 ℃, mixing salt solution and precipitant solution are carried out co-precipitation, precipitation process needs fully to stir, keep pH=11, treat that various precipitation by metallic ion fully after, add copper nitrate solution again and above-mentioned precipitating reagent carries out co-precipitation, continue to keep pH=11, aging 15 h under 80 ℃ of stirring conditions, precipitation through the deionized water washing till do not have sodium ion and detect, dry down at 120 ℃, 450 ℃ of roasting 4 h obtain CuO/ZnO/Al
2O
3Metal oxide catalyst, the metallic atom mol ratio of this catalyst is: n (Cu): n (Zn): n (Al)=6:3:1 is crushed to the 40-60 order with it.Being reflected in the fixed bed reactors of synthesizing methanol by hydrogenating carbon dioxide carried out, the reaction before with pure hydrogen 350 ℃ the reduction 8 h, switch to reaction gas and react, reaction condition is as follows: P=5.0 MPa, T=290 ℃, GHSV=4000 h
-1, n (H
2): n (CO
2) mol ratio=3, collect liquid product with ice-water bath, the gas chromatographic analysis product is formed.The gained result is as follows:
。
Claims (6)
1. synthesizing methanol by hydrogenating carbon dioxide catalyst is characterized in that catalyst is made up of oxide, and in metal, the mol ratio of various metals is: [n (Cu)+n (Zn)+n (M
A)]: [n (Al)+n (M
B)]=2-15, n (Cu): n (Zn)=0.5-4, n (M
A): n (Zn)=0-1, n (M
B): n (Al)=0-9;
M wherein
ARepresent monovalence or bivalent metal ion, M
BRepresent trivalent or quadrivalent metallic ion.
2. a kind of synthesizing methanol by hydrogenating carbon dioxide catalyst as claimed in claim 1 is characterized in that described M
ABe Li
+, K
+, Ag
+, Mg
2+, Mn
2+, Co
2+, Fe
2+, Pd
2+Or Pt
2+
3. a kind of synthesizing methanol by hydrogenating carbon dioxide catalyst as claimed in claim 1 is characterized in that described M
BBe V
3+, Cr
3+, Mn
3+, Fe
3+, Co
3+, Ga
3+, Ru
3+, Rh
3+, Y
3+, Ce
3+, Sm
3+, Gd
3+, La
3+, Ir
3+, Dy
3+, Ti
4+, Zr
4+Or Sn
4+
4. as each described a kind of synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method of claim 1-3, it is characterized in that comprising the steps:
Zr is with the form of zirconyl nitrate or zirconium nitrate, all the other elements all are dissolved in the deionized water with the form of nitrate, be made into mixed aqueous solution according to the above ratio, in addition, NaOH and sodium carbonate example in molar ratio are made into the mixed precipitation agent solution for 2-10:1, under 10-60 ℃, two mixed liquors carry out co-precipitation, precipitation process needs fully to stir, keep pH=6-13, post precipitation needs aging 1-36 h under 40-100 ℃ of stirring condition, precipitation through the deionized water washing till do not have sodium ion and detect, dry under 60-160 ℃ then, 400-700 ℃ of roasting 2-8 h.
5. as each described a kind of synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method of claim 1-3, it is characterized in that comprising the steps:
Copper nitrate is made into water solution A separately, and Zr is with the form of zirconyl nitrate or zirconium nitrate, and all the other elements all form mixed solution B according to the above ratio with the form of nitrate, and in addition, NaOH and sodium carbonate example in molar ratio are made into the mixed precipitation agent solution for 2-8:1;
Under 10-60 ℃, solution B and precipitant solution are carried out co-precipitation earlier, after treating that B solution precipitation fully, carry out the co-precipitation of solution A and precipitating reagent again, precipitation process needs fully to stir, and keeps pH=8-13, post precipitation needs aging 8-36 h under 40-100 ℃ of stirring condition, precipitation through deionized water washing till do not have sodium ion and detect, then 60-160 ℃ dry down, 400-600 ℃ of roasting 2-8 h.
6. as each described a kind of synthesizing methanol by hydrogenating carbon dioxide Application of Catalyst of claim 1-3, it is characterized in that comprising the steps: that being reflected in the fixed bed reactors of synthesizing methanol by hydrogenating carbon dioxide carry out, the reducing condition of catalyst is: with pure hydrogen at 250-350 ℃ of reduction 4-15 h, the condition of synthesizing methanol by hydrogenating carbon dioxide is: reaction pressure is 2.0-11.0 MPa, reaction temperature is 200-350 ℃, and volume space velocity is 2000-10000 h
-1, n (H
2): n (CO
2) mol ratio=2-4.
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| CN104549299A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of copper based hydrogenation catalyst |
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| CN107008332A (en) * | 2016-01-27 | 2017-08-04 | 中国科学院大连化学物理研究所 | A kind of catalyst of synthesizing methanol by hydrogenating carbon dioxide and its preparation and application |
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| CN115672341A (en) * | 2022-11-18 | 2023-02-03 | 中国科学院山西煤炭化学研究所 | Bifunctional composite metal oxide catalyst and preparation method and application thereof |
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