CN101690894A - Catalyst for synthesizing methanol by direct hydrogenation of carbon dioxide and preparation method thereof - Google Patents
Catalyst for synthesizing methanol by direct hydrogenation of carbon dioxide and preparation method thereof Download PDFInfo
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- CN101690894A CN101690894A CN200910112654A CN200910112654A CN101690894A CN 101690894 A CN101690894 A CN 101690894A CN 200910112654 A CN200910112654 A CN 200910112654A CN 200910112654 A CN200910112654 A CN 200910112654A CN 101690894 A CN101690894 A CN 101690894A
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- carbon dioxide
- catalyst
- synthesizing methanol
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- direct hydrogenation
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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 catalyst for synthesizing methanol by direct hydrogenation of carbon dioxide and a preparation method thereof and relates to the catalyst. The invention provides the catalyst for synthesizing the methanol by direct hydrogenation of the carbon dioxide and the preparation method thereof. The catalyst is LaCr1-xCuxO3, wherein x is the relative mole fraction of a main component of Cu, x is equal to 0.1-0.9, and La: Cr: Cu is equal to 1: (1-x): x. The preparation method comprises the steps of preparing copper nitrate, chromium nitrate, lanthanum nitrate and citric acid into water solution, forming a sol under the radiation of an infrared lamp, heating, decomposing nitrogen oxides and organic acids, pre-baking in an atmosphere furnace at the temperature of 350-450 DEG C for 2-4h, baking at the temperature of 700-800 DEG C, and obtaining the catalyst for synthesizing the methanol by direction hydrogenation of the carbon dioxide. The citric acid complexation-rapid combustion method is adopted for overcoming the disadvantages of lower conversion rate, poorer selectivity of the methanol and the like during the catalysis of the carbon dioxide by using the existing catalyst for synthesizing the methanol by hydrogenation of the carbon dioxide, and the prepared catalyst has stable performances.
Description
Technical field
The present invention relates to a kind of catalyst, especially relate to a kind of Catalysts and its preparation method of synthesizing methanol by direct hydrogenation of carbon dioxide.
Background technology
China's energy resource structure is based on fossil class A fuel As such as coal, oil, and the carbon dioxide greenhouse gas that combustion process produces is the main inducing that causes global warming.Be one of effective ways that reduce the greenhouse gas emission total amount at present with the carbon dioxide trans-utilization.The direct catalytic hydrogenation of carbon dioxide is converted into methyl alcohol not only makes carbon dioxide obtain utilizing, and the fuel and the industrial chemicals of oxygen containing low-carbon (LC) cleaning can be provided again, has become carbon dioxide and has transformed and the direction of utilizing.Utilize enterprise's coproduct hydrogen such as chlor-alkali to carry out that catalytic hydrogenation of carbon dioxide is produced methyl alcohol or suitably add carbon dioxide in synthesis gas to come synthesizing methanol be one of effective way of utilizing of carbon dioxide, publication number is that the application for a patent for invention of CN101386564 has reported that the copper-based catalysts that utilizes the co hydrogenation synthesizing methanol carries out the technology of carbon dioxide-synthesized methanol.But the problem that the copper-based catalysts of the present direct synthesizing methanol of hydrogenation of carbon dioxide mainly exists is that the conversion ratio of carbon dioxide is on the low side, and the selectivity of methyl alcohol is not high.Overcome these deficiencies, the development of new catalyst is vital.Publication number is that the application for a patent for invention of CN101444731 has been introduced and utilized precious metal palladium to be main active constituent, presents very high catalytic activity and methyl alcohol selectivity with the CNT for the preparing carriers composite catalyst is used for synthesizing methanol by hydrogenating carbon dioxide.Comparatively speaking, prepare efficient copper-based catalysts, can reduce the catalyst cost, be more conducive to use in the industrialization generation.Bibliographical information (Catalysis Letter, 1991,8,335-344) copper based perovskite type LaTi
1-xCu
xO
3Catalyst presents higher catalytic activity and selectivity in the carbon monoxide synthesizing methanol.But the Ca-Ti ore type copper-based catalysts is used for synthesizing methanol by hydrogenating carbon dioxide yet there are no relevant report.
Summary of the invention
The objective of the invention is at the conversion ratio of existing synthesizing methanol by hydrogenating carbon dioxide catalyst carbon dioxide lowlyer, shortcoming such as the selectivity of methyl alcohol is relatively poor provides a kind of Catalysts and its preparation method of synthesizing methanol by direct hydrogenation of carbon dioxide.
The catalyst of a kind of synthesizing methanol by direct hydrogenation of carbon dioxide of the present invention is the catalyst LaCr of brand-new copper based perovskite type synthesizing methanol by hydrogenating carbon dioxide
1-xCu
xO
3, wherein x is the relative molar fraction of major constituent Cu, x=0.1～0.9, La: Cr: Cu=1: (1-x): x, the stable performance of catalyst.
The optimum range of x is 0.25～0.75.
The Preparation of catalysts method of a kind of synthesizing methanol by direct hydrogenation of carbon dioxide of the present invention adopts citric acid complex-conflagration method, may further comprise the steps:
1) copper nitrate, chromic nitrate, lanthanum nitrate and citric acid are mixed with the aqueous solution, penetrate at infrared lamp irradiation and form colloidal sol down;
2) nitrogen oxide and organic acid are decomposed the colloidal sol heating, in 350～450 ℃ atmosphere furnace, carry out preroast 2～4h then,, get the catalyst LaCr of synthesizing methanol by direct hydrogenation of carbon dioxide at last 700～800 ℃ of following roastings
1-xCu
xO
3
In step 1), La: Cr: Cu: citric acid is preferably 1 in molar ratio: (1-x): x: (1.0～2.0), x=0.1～0.9, the optimum range of x is 0.25～0.75; The concentration of the aqueous solution is preferably 0.2～0.5M.
In step 2) in, the described time 700～800 ℃ of following roastings is preferably 4h.
Below provide the method for synthesizing methanol by hydrogenating carbon dioxide:
Synthesizing methanol by hydrogenating carbon dioxide carries out in fixed bed reactors, and catalyst is 0.4～1.0g, with CO
2: H
2: N
2=31: 64: 5 reacting gas feeds in the reactor, and at pressure 1.0～3.0MPa, 250～350 ℃ of reaction temperatures are carried out under GHSV=2000～40000ml/ (hg) reaction condition.Before the reaction, oxidation state presoma LaCr
1-xCu
xO
3Under normal pressure, use V (H
2)/V (N
2)=1: gaseous mixture reduction (gas flow 30～120ml/min) 6～8h of (5～10).
Reaction back gas enters the gas-chromatography on-line analysis after 120 ℃ of insulations, adopt thermal conductivity detector (TCD) (TCD) to detect inorganic gas and with N
2For benchmark carries out CO
2Conversion ratio and CO generate the selectivity analysis; Product content such as the organic matter alcohol that employing hydrogen flame detector (FID) detection generates, ether, hydrocarbon are analyzed by the Carbon balance normalization method.
Shortcomings such as the present invention adopts citric acid complex-conflagration method, and the conversion ratio that has overcome existing synthesizing methanol by hydrogenating carbon dioxide catalyst carbon dioxide is lower, and the selectivity of methyl alcohol is relatively poor, prepared catalyst performance stabilised.
The specific embodiment
The present invention is further illustrated by the following examples, but do not limit the scope that the present patent application is asked for protection.
Embodiment 1
With copper nitrate, chromic nitrate, lanthanum nitrate and citric acid by 0.1: 0.9: 1.0: 1.5 are made into the 0.5M mixed solution.Become colloidal sol under infrared lamp irradiation, light rapidly on electric furnace, the pressed powder that obtains is through 400 ℃ of calcining 2h, again through 800 ℃ of roasting 4h.With gained perovskite LaCr
0.9Cu
0.1O
3Presoma, compressing tablet become the 40-60 order.Get presoma 0.5g 350 ℃ of normal pressures down behind the reduction 6h (flow velocity 60ml/min) cut to reactor feed gas and react, reaction condition is: pressure 2.0MPa, 250 ℃ of temperature, V (H
2)/V (CO
2)/V (N
2)=64: 31: 5, GHSV=9000ml/ (h.g), product carries out check and analysis by TCD and fid detector, and the conversion ratio of carbon dioxide and methyl alcohol selectivity and other accessory substance selectivity see Table one.
Embodiment 2
With copper nitrate, chromic nitrate, lanthanum nitrate and citric acid by 0.3: 0.7: 1.0: 1.0 are made into the 0.4M mixed solution.Under the infrared lamp irradiation, become gel, through 350 ℃ of calcining 2h, again through 750 ℃ of roasting 4h.The perovskite LaCr that obtains
0.7Cu
0.3O
3Be the oxidation state presoma of catalyst, catalytically active assessment the results are shown in Table 1 with embodiment 1.
Embodiment 3
With copper nitrate, chromic nitrate, lanthanum nitrate and citric acid by 0.5: 0.5: 1.0: 2.0 will be made into the 0.5M mixed solution.Under the infrared lamp irradiation, become gel, through 350 ℃ of calcining 2h, again through 750 ℃ of roasting 4h.The perovskite LaCr that obtains
0.5Cu
0.5O
3Be the oxidation state presoma, the catalyst activity evaluation is with embodiment 1, and evaluation result sees Table 1.
Embodiment 4
With copper nitrate, chromic nitrate, lanthanum nitrate and citric acid by 0.7: 0.3: 1.0: 1.6 will be made into the 0.5M mixed solution.Under the infrared lamp irradiation, become gel, through 400 ℃ of calcining 2h, again through 800 ℃ of roasting 4h.The perovskite LaCr that obtains
0.3Cu
0.7O
3Be the oxidation state presoma, the catalyst activity evaluation is with embodiment 1, and evaluation result sees Table 1.
Embodiment 5
With copper nitrate, chromic nitrate, lanthanum nitrate and citric acid by 0.9: 0.1: 1.0: 1.2 will be made into the 0.3M mixed solution.Under the infrared lamp irradiation, become gel, through 400 ℃ of calcining 2h, again through 800 ℃ of roasting 4h.The perovskite LaCr that obtains
0.1Cu
0.9O
3Be the oxidation state presoma, the catalyst activity evaluation is with embodiment 1, and evaluation result sees Table 1.
Embodiment 6
With copper nitrate, chromic nitrate, lanthanum nitrate and citric acid by 0.1: 0.9: 1.0: 1.8 will be made into the 0.4M mixed solution.Under the infrared lamp irradiation, become gel, through 400 ℃ of calcining 2h, again through 800 ℃ of roasting 4h.The perovskite LaCr that obtains
0.9Cu
0.1O
3Be the oxidation state presoma, the catalyst activity evaluation, reaction temperature is 270 ℃, and all the other are with embodiment 1, and evaluation result sees Table 2.
Embodiment 7
With copper nitrate, chromic nitrate, lanthanum nitrate and citric acid by 0.3: 0.7: 1.0: 2.0 will be made into the 0.5M mixed solution.Under the infrared lamp irradiation, become gel, through 400 ℃ of calcining 2h, again through 800 ℃ of roasting 4h.The perovskite LaCr that obtains
0.7Cu
0.3O
3Be the oxidation state presoma, the catalyst activity evaluation is with embodiment 6, and evaluation result sees Table 2.
Embodiment 8
With copper nitrate, chromic nitrate, lanthanum nitrate and citric acid by 0.5: 0.5: 1.0: 2.0 will be made into the 0.5M mixed solution.Under the infrared lamp irradiation, become gel, through 400 ℃ of calcining 2h, again through 800 ℃ of roasting 4h.The perovskite LaCr that obtains
0.5Cu
0.5O
3Be the oxidation state presoma, the catalyst activity evaluation is with embodiment 1, and evaluation result sees Table 2.
Embodiment 9
With copper nitrate, chromic nitrate, lanthanum nitrate and citric acid by 0.7: 0.3: 1.0: 2.0 will be made into the 0.5M mixed solution.Under the infrared lamp irradiation, become gel, through 400 ℃ of calcining 2h, again through 800 ℃ of roasting 4h.The perovskite LaCr that obtains
0.3Cu
0.7O
3Be the oxidation state presoma, the catalyst activity evaluation is with embodiment 1, and evaluation result sees Table 2.
Embodiment 10
With copper nitrate, chromic nitrate, lanthanum nitrate and citric acid by 0.9: 0.1: 1.0: 2.0 will be made into the 0.5M mixed solution.Under the infrared lamp irradiation, become gel, through 400 ℃ of calcining 2h, again through 800 ℃ of roasting 4h.The perovskite LaC that obtains
R0.1Cu
0.9O
3Be the oxidation state presoma, the catalyst activity evaluation is with embodiment 1, and evaluation result sees Table 2.
Table 1LaCr
1-xCu
xO
3Catalysis synthesizing methanol by hydrogenating carbon dioxide catalytic activity
Reaction condition: 2MPa, 250 ℃, V (H
2)/V (CO
2)/V (N
2)=64: 31: 5, GHSV=9000ml/ (hg)
Table 2LaCr
1-xCu
xO
3Catalysis synthesizing methanol by hydrogenating carbon dioxide catalytic activity
Reaction condition: 2MPa, 270 ℃, V (H
2)/V (CO
2)/V (N
2)=64: 31: 5, GHSV=9000ml/ (hg)
Claims (7)
1. the catalyst of a synthesizing methanol by direct hydrogenation of carbon dioxide is characterized in that the catalyst LaCr for copper based perovskite type synthesizing methanol by hydrogenating carbon dioxide
1-xCu
xO
3, wherein x is the relative molar fraction of major constituent Cu, x=0.1～0.9, La: Cr: Cu=1: (1-x): x.
2. the catalyst of a kind of synthesizing methanol by direct hydrogenation of carbon dioxide as claimed in claim 1 is characterized in that described x is 0.25～0.75.
3. the Preparation of catalysts method of a kind of synthesizing methanol by direct hydrogenation of carbon dioxide as claimed in claim 1 is characterized in that may further comprise the steps:
1) copper nitrate, chromic nitrate, lanthanum nitrate and citric acid are mixed with the aqueous solution, penetrate at infrared lamp irradiation and form colloidal sol down;
2) nitrogen oxide and organic acid are decomposed the colloidal sol heating, in 350～450 ℃ atmosphere furnace, carry out preroast 2～4h then,, get the catalyst LaCr of synthesizing methanol by direct hydrogenation of carbon dioxide at last 700～800 ℃ of following roastings
1-xCu
xO
3
4. the Preparation of catalysts method of a kind of synthesizing methanol by direct hydrogenation of carbon dioxide as claimed in claim 3, it is characterized in that in step 1) La: Cr: Cu: citric acid is 1 in molar ratio: (1-x): x: (1.0～2.0), x=0.1～0.9.
5. the Preparation of catalysts method of a kind of synthesizing methanol by direct hydrogenation of carbon dioxide as claimed in claim 4 is characterized in that described x is 0.25～0.75.
6. the Preparation of catalysts method of a kind of synthesizing methanol by direct hydrogenation of carbon dioxide as claimed in claim 3 is characterized in that in step 1), and the concentration of the aqueous solution is 0.2～0.5M.
7. the Preparation of catalysts method of a kind of synthesizing methanol by direct hydrogenation of carbon dioxide as claimed in claim 3 is characterized in that in step 2) in, the described time 700～800 ℃ of following roastings is 4h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103182308A (en) * | 2011-12-29 | 2013-07-03 | 中国石油化工股份有限公司 | Perovskite/metal composite oxide catalyst and preparation method thereof |
| CN103252241A (en) * | 2013-05-14 | 2013-08-21 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesising methanol by hydrogenation of carbon dioxide as well as preparation method and application thereof |
| CN104549313A (en) * | 2015-01-12 | 2015-04-29 | 中南民族大学 | Preparation method and application of porous La1-xCexCoO3 perovskite catalyst |
| CN105709760A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Copper-chromium catalyst and its preparation method and use |
| CN106268619A (en) * | 2016-11-07 | 2017-01-04 | 西安元创化工科技股份有限公司 | A kind of preparation method of room temperature oil product desulfurizer |
| CN110227472A (en) * | 2019-06-26 | 2019-09-13 | 内蒙古科技大学 | High-performance adds hydrogen Cu base catalyst and preparation method and application |
| CN113304744A (en) * | 2021-06-10 | 2021-08-27 | 中国科学院城市环境研究所 | Catalyst, preparation method and application thereof |
-
2009
- 2009-10-13 CN CN200910112654A patent/CN101690894A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103182308A (en) * | 2011-12-29 | 2013-07-03 | 中国石油化工股份有限公司 | Perovskite/metal composite oxide catalyst and preparation method thereof |
| CN103182308B (en) * | 2011-12-29 | 2015-05-20 | 中国石油化工股份有限公司 | Perovskite/metal composite oxide catalyst and preparation method thereof |
| CN103252241A (en) * | 2013-05-14 | 2013-08-21 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesising methanol by hydrogenation of carbon dioxide as well as preparation method and application thereof |
| CN105709760A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Copper-chromium catalyst and its preparation method and use |
| CN105709760B (en) * | 2014-12-04 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of Cu-Cr catalyst and its preparation method and application |
| CN104549313A (en) * | 2015-01-12 | 2015-04-29 | 中南民族大学 | Preparation method and application of porous La1-xCexCoO3 perovskite catalyst |
| CN106268619A (en) * | 2016-11-07 | 2017-01-04 | 西安元创化工科技股份有限公司 | A kind of preparation method of room temperature oil product desulfurizer |
| CN106268619B (en) * | 2016-11-07 | 2019-01-22 | 西安元创化工科技股份有限公司 | A kind of preparation method of room temperature oil product desulfurizer |
| CN110227472A (en) * | 2019-06-26 | 2019-09-13 | 内蒙古科技大学 | High-performance adds hydrogen Cu base catalyst and preparation method and application |
| CN113304744A (en) * | 2021-06-10 | 2021-08-27 | 中国科学院城市环境研究所 | Catalyst, preparation method and application thereof |
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Application publication date: 20100407 |