CN103191747B - A kind of method of hydrogenation of carbon dioxide formate low-carbon alcohol catalyst - Google Patents
A kind of method of hydrogenation of carbon dioxide formate low-carbon alcohol catalyst Download PDFInfo
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- CN103191747B CN103191747B CN201310117025.5A CN201310117025A CN103191747B CN 103191747 B CN103191747 B CN 103191747B CN 201310117025 A CN201310117025 A CN 201310117025A CN 103191747 B CN103191747 B CN 103191747B
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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 present invention relates to a kind of method of hydrogenation of carbon dioxide formate low-carbon alcohol catalyst, belong to new material technology field.Configuration Cu (NO
3)
2, Zn (NO
3)
2with Zr (NO
3)
4mixed solution, keep reaction temperature be under the condition of 50 ~ 90 DEG C, by the mixed solution of step (1) gained and Na
2cO
3solution drip are surely and constantly stir and obtain suspension, the process of titration keeps the pH value of suspension to be 7 ~ 10, then under the condition stirred, continue reaction 1 ~ 2 hour, stop stirring aging 2 ~ 4 hours, filter rear deionized water washing sediment until cleaning solution pH value is 7; Carry out roasting by after drying precipitate, then the sediment after roasting being put into concentration is carry out drying again after the nitrate solution dipping 24 ~ 48h of 1 ~ 10wt%, obtains the low C catalyst of 20 ~ 40 object after finally again carrying out roasting, granulation.The hydrogenation of carbon dioxide formate low-carbon alcohol catalyst prepared has that carbon dioxide conversion cheap, easy and simple to handle is high, alcohol is selective also higher in product.
Description
Technical field
The present invention relates to a kind of method of hydrogenation of carbon dioxide formate low-carbon alcohol catalyst, belong to new material technology field.
Background technology
Due to a large amount of discharges of carbon dioxide, consequent greenhouse effects receive the common concern of people.Therefore, carbon dioxide utilizes and is fixedly one and has the problem of great strategic significance to the mankind.And catalytic hydrogenation of carbon dioxide synthesis of low-carbon alcohol is the important channel effectively utilizing carbon dioxide.The current whole world generally adopts MTBE as gasoline additive, but recent research finds, MTBE exists serious problem as gasoline additive, as stored, transport and being easy to leakage and polluted drinking water etc. in use procedure, threatens human health.And low-carbon alcohols is positioned in gasoline additive with its good performance indications always, a common recognition since this becomes the oil crisis seventies.Low-carbon alcohols is fuel as an alternative, and neither containing aromatic series, also not sulfur-bearing and octane number is high, has important environmental protection potentiality and economic worth.Simultaneously low-carbon alcohols also has immense value as chemical products and large Chemical Manufacture raw material, and the Application in Chemical Engineering prospect of low-carbon alcohols is progressively had an optimistic view of in recent years, low-carbon alcohols through be separated can obtain second, third, fourth, alcohols that the economic worth such as amylalcohol is higher.
Chinese patent CN96112685.X relates to a kind of employing step impregnation, step-by-step reduction prepares M/Rh-M-Fe/SiO
2formate low-carbon alcohol catalyst, M=Li, Na, Rh load capacity is 2%(wt%), M/Rh, Mn/Rh, Fe/Rh atomic ratio is respectively 3.8 ~ 21.8,0.5 ~ 1.5,0.2 ~ 0.4, and the unstripped gas used is the CO gas containing higher value.Employ precious metal material in this catalyst, add the preparation cost of catalyst, and employing distribution is flooded, distribution is reduced to prepare and both wasted the plenty of time, consumes mass energy again.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of method of hydrogenation of carbon dioxide formate low-carbon alcohol catalyst, the hydrogenation of carbon dioxide formate low-carbon alcohol catalyst prepared have that carbon dioxide conversion cheap, easy and simple to handle is high, alcohol is selective also higher in product feature.
Technical scheme of the present invention is: adopt infusion process to prepare hydrogenation of carbon dioxide formate low-carbon alcohol catalyst, concrete steps comprise as follows:
(1) Cu (NO is configured
3)
2, Zn (NO
3)
2with Zr (NO
3)
4mixed solution, the mol ratio of Cu, Zn and Zr in mixed solution is 0.3 ~ 0.5:0.3 ~ 0.5:0 ~ 0.4, the concentration of copper ion is 3.5mol/L ~ 4.2mol/L;
(2) reaction temperature is kept to be under the condition of 50 ~ 90 DEG C, by the mixed solution of step (1) gained and Na
2cO
3
Solution drip are surely and constantly stir and obtain suspension, the process of titration keeps the pH value of suspension to be 7 ~ 10, then under the condition stirred, continue reaction 1 ~ 2 hour, stop stirring aging 2 ~ 4 hours, filter rear deionized water washing sediment until cleaning solution pH value is 7;
(3) roasting is carried out after the drying precipitate after step (2) being washed, then the sediment after roasting being put into concentration is carry out drying again after the nitrate solution dipping 24 ~ 48h of 1 ~ 10wt%, obtains the low C catalyst of 20 ~ 40 object after finally again carrying out roasting, granulation.
Described Na
2cO
3the concentration of solution is 0.5 ~ 1.0mol/L.
In described step (3), twice drying is all dry 10 ~ 15h at 110 ~ 120 DEG C of temperature.
In described step (3), first time roasting is roasting 5.0 ~ 6.0h under the condition of 480 ~ 550 DEG C.
Nitrate in described step (3) refers to any one or a few the arbitrary proportion mixture of Fe, Co, Ni, Li, Na, K, Cs, Al or Ce.
In described step (3), second time roasting is roasting 2.0 ~ 2.5h under the condition of 200 ~ 300 DEG C.
Described low C catalyst refers to the catalyst of mix products preparing methyl alcohol, ethanol, propyl alcohol, butanols, and the ratio of mix products is different according to different experiment condition results.
The invention has the beneficial effects as follows: because global carbon dioxide gas purging amount increases year by year, various countries more and more pay close attention to CO
2recycling, make CO
2be fully utilized.This catalyst is not because using noble metal, and thus production cost is lower, and easy and simple to handle.Utilize this catalyst can comprehensive utilization of C O under certain condition
2reach emission reduction effect, and the MAS generated can obtain methyl alcohol, ethanol, propyl alcohol and butanols etc. after separated simultaneously, these alcohols are all Elementary Chemical Industry raw materials, can create more economic worth after separation.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described.
Embodiment one: the method for the present embodiment hydrogenation of carbon dioxide formate low-carbon alcohol catalyst is:
(1) Cu (NO is configured
3)
2, Zn (NO
3)
2with Zr (NO
3)
4mixed solution, the mol ratio of Cu, Zn and Zr in mixed solution is 0.3:0.5:0.2, the concentration of copper ion is 3.5mol/L;
(2) keeping reaction temperature to be under the condition of 70 DEG C, is 0.5mol/L by the mixed solution of step (1) gained and concentration
Na
2cO
3surely and constantly stir and obtain suspension, the process of titration keeps the pH value of suspension to be 8, then under the condition stirred, continues reaction 1 hour, stops stirring aging 2 hours, filters rear deionized water washing sediment until cleaning solution pH value is 7 for solution drip;
(3) by step (2) wash after drying precipitate after under the condition of 500 DEG C roasting 5.0h, then the sediment after roasting being put into concentration is carry out drying again after the iron nitrate solution of 2wt% floods 48h, finally again under the condition of 200 DEG C, obtains 20 ~ 40 object low C catalyst Cat1 sample after roasting 2.0h, granulation.Twice drying is all dry 15h at 110 DEG C of temperature.
Embodiment two: the method for the present embodiment hydrogenation of carbon dioxide formate low-carbon alcohol catalyst is:
(1) Cu (NO is configured
3)
2, Zn (NO
3)
2with Zr (NO
3)
4mixed solution, the mol ratio of Cu, Zn and Zr in mixed solution is 0.3:0.3:0.4, the concentration of copper ion is 4mol/L;
(2) keeping reaction temperature to be under the condition of 50 DEG C, is 0.8mol/L by the mixed solution of step (1) gained and concentration
Na
2cO
3surely and constantly stir and obtain suspension, the process of titration keeps the pH value of suspension to be 9, then under the condition stirred, continues reaction 2 hours, stops stirring aging 3 hours, filters rear deionized water washing sediment until cleaning solution pH value is 7 for solution drip;
(3) by step (2) wash after drying precipitate after under the condition of 480 DEG C roasting 6.0h, then the sediment after roasting being put into concentration is carry out drying again after the lithium nitrate solution of 10wt% floods 24h, finally again under the condition of 300 DEG C, obtains 20 ~ 40 object low C catalyst Cat2 sample after roasting 2.2h, granulation.Twice drying is all dry 12h at 120 DEG C of temperature.
Embodiment three: the method for the present embodiment hydrogenation of carbon dioxide formate low-carbon alcohol catalyst is:
(1) Cu (NO is configured
3)
2, Zn (NO
3)
2with Zr (NO
3)
4mixed solution, the mol ratio of Cu, Zn and Zr in mixed solution is 4.5:4.5:1, the concentration of copper ion is 4.2mol/L;
(2) keeping reaction temperature to be under the condition of 90 DEG C, is 1.0mol/L by the mixed solution of step (1) gained and concentration
Na
2cO
3solution drip are surely and constantly stir and obtain suspension, the process of titration keeps the pH value of suspension to be 10, then under the condition stirred, continue reaction 1.5 hours, stop stirring aging 4 hours, filter rear deionized water washing sediment until cleaning solution pH value is 7;
(3) by step (2) wash after drying precipitate after under the condition of 550 DEG C roasting 5.5h, then the sediment after roasting being put into concentration is carry out drying again after the nickel nitrate solution of 4wt% floods 40h, finally again under the condition of 280 DEG C, obtains 20 ~ 40 object low C catalyst Cat3 sample after roasting 2.5h, granulation.Twice drying is all dry 11h at 115 DEG C of temperature.
Embodiment four: the method for the present embodiment hydrogenation of carbon dioxide formate low-carbon alcohol catalyst is:
(1) Cu (NO is configured
3)
2, Zn (NO
3)
2with Zr (NO
3)
4mixed solution, the mol ratio of Cu, Zn and Zr in mixed solution is 0.3:0.5:0.2, the concentration of copper ion is 3.8mol/L;
(2) keeping reaction temperature to be under the condition of 80 DEG C, is 1.0mol/L by the mixed solution of step (1) gained and concentration
Na
2cO
3solution drip are surely and constantly stir and obtain suspension, the process of titration keeps the pH value of suspension to be 7.8, then under the condition stirred, continue reaction 1.5 hours, stop stirring aging 2.5 hours, filter rear deionized water washing sediment until cleaning solution pH value is 7;
(3) by step (2) wash after drying precipitate after under the condition of 520 DEG C roasting 5.0h, then the sediment after roasting being put into concentration is carry out drying again after the cobalt nitrate solution of 1wt% floods 48h, finally again under the condition of 260 DEG C, obtains 20 ~ 40 object low C catalyst Cat4 sample after roasting 2.3h, granulation.Twice drying is all dry 10h at 114 DEG C of temperature.
Embodiment five: the method for the present embodiment hydrogenation of carbon dioxide formate low-carbon alcohol catalyst is:
(1) Cu (NO is configured
3)
2, Zn (NO
3)
2with Zr (NO
3)
4mixed solution, the mol ratio of Cu, Zn and Zr in mixed solution is 0.5:0.45:1, the concentration of copper ion is 3.8mol/L;
(2) keeping reaction temperature to be under the condition of 60 DEG C, is 1.0mol/L by the mixed solution of step (1) gained and concentration
Na
2cO
3solution drip are surely and constantly stir and obtain suspension, the process of titration keeps the pH value of suspension to be 8, then under the condition stirred, continue reaction 1.2 hours, stop stirring aging 4 hours, filter rear deionized water washing sediment until cleaning solution pH value is 7;
(3) by step (2) wash after drying precipitate after under the condition of 490 DEG C roasting 5.5h, then the sediment after roasting being put into concentration is carry out drying again after the sodium nitrate solution of 7wt% floods 48h, finally again under the condition of 200 DEG C, obtains 20 ~ 40 object low C catalyst Cat5 sample after roasting 2.0h, granulation.Twice drying is all dry 15h at 110 DEG C of temperature.
Embodiment six: the method for the present embodiment hydrogenation of carbon dioxide formate low-carbon alcohol catalyst is:
(1) Cu (NO is configured
3)
2, Zn (NO
3)
2with Zr (NO
3)
4mixed solution, the mol ratio of Cu, Zn and Zr in mixed solution is 0.3:0.3:0.4, the concentration of copper ion is 4.2mol/L;
(2) keeping reaction temperature to be under the condition of 90 DEG C, is 0.5mol/L by the mixed solution of step (1) gained and concentration
Na
2cO
3surely and constantly stir and obtain suspension, the process of titration keeps the pH value of suspension to be 10, then under the condition stirred, continues reaction 1 hour, stops stirring aging 4 hours, filters rear deionized water washing sediment until cleaning solution pH value is 7 for solution drip;
(3) by step (2) wash after drying precipitate after under the condition of 550 DEG C roasting 6.0h, then the sediment after roasting is put into the Al (NO that concentration is the 5wt% of Al, Cs and Fe
3)
3, CsNO
3with Fe (NO
3)
2mixed solution in flood 24h after carry out drying again, finally again under the condition of 300 DEG C, after roasting 2.5h, granulation, obtain 20 ~ 40 object low C catalyst Cat6 sample.Twice drying is all dry 10h at 120 DEG C of temperature.
Embodiment seven: the method for the present embodiment hydrogenation of carbon dioxide formate low-carbon alcohol catalyst is:
(1) Cu (NO is configured
3)
2, Zn (NO
3)
2with Zr (NO
3)
4mixed solution, the mol ratio of Cu, Zn and Zr in mixed solution is 0.3:0.5:0.2, the concentration of copper ion is 4.2mol/L;
(2) keeping reaction temperature to be under the condition of 50 DEG C, is 1.0mol/L by the mixed solution of step (1) gained and concentration
Na
2cO
3solution drip are surely and constantly stir and obtain suspension, the process of titration keeps the pH value of suspension to be 7.9, then under the condition stirred, continue reaction 2 hours, stop stirring aging 24 hours, filter rear deionized water washing sediment until cleaning solution pH value is 7;
(3) by step (2) wash after drying precipitate after under the condition of 510 DEG C roasting 6.0h, then the sediment after roasting is put into the Fe (NO that Fe, Ce and Co ion concentration is 7wt%
3)
3, Ce (NO
3)
2with Co (NO
3)
2carry out drying again after flooding 48h in mixed solution, finally again under the condition of 300 DEG C, after roasting 2.0h, granulation, obtain 20 ~ 40 object low C catalyst Cat7 sample.Twice drying is all dry 13h at 120 DEG C of temperature.
Embodiment eight: the method for the present embodiment hydrogenation of carbon dioxide formate low-carbon alcohol catalyst is:
(1) Cu (NO is configured
3)
2, Zn (NO
3)
2mixed solution, the mol ratio of Cu, Zn in mixed solution is 0.3:0.3, the concentration of copper ion is 3.5mol/L;
(2) keeping reaction temperature to be under the condition of 50 DEG C, is 0.8mol/L by the mixed solution of step (1) gained and concentration
Na
2cO
3surely and constantly stir and obtain suspension, the process of titration keeps the pH value of suspension to be 7, then under the condition stirred, continues reaction 1 hour, stops stirring aging 2.5 hours for solution drip, is 7 by deionized water washing sediment to cleaning solution pH value after filtration;
(3) by step (2) wash after drying precipitate after under the condition of 550 DEG C roasting 6.0h, then the sediment after roasting being put into concentration is carry out drying again after the cesium nitrate solution of 10wt% floods 48h, finally again under the condition of 200 DEG C, obtains 20 ~ 40 object low-carbon (LC) catalyst samples after roasting 2.5h, granulation.Twice drying is all dry 15h at 110 DEG C of temperature.
The catalyst that above-described embodiment mode one to seven prepares carries out CO at the micro-reactor of urging of fixed bed
2hydrogenation synthesizing low carbon mixed alcohol activity rating, is loaded on 2.0g catalyst in stainless steel reaction pipe, reduces with hydrogen through temperature programming to 280 DEG C, and heating rate is 1 DEG C/min, and reducing gases flow velocity is 10mL/min, and whole reduction process continues 6h.After catalyst reduction terminates, reducing gases is switched to unstripped gas, carry out activity rating.Evaluating catalyst condition is 250 DEG C, 3.0MPa, and air speed is 3000h
-1, unstripped gas consist of V (H
2): V (CO
2)=3:1, reaction end gas gas chromatograph on-line analysis, TCD, FID detect.Product liquid uses gas chromatographic detection after cold well condensation is collected.Evaluation result is in table 1.
Table 1 catalyst activity evaluation result
Below by reference to the accompanying drawings the specific embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (5)
1. a method for hydrogenation of carbon dioxide formate low-carbon alcohol catalyst, is characterized in that step comprises as follows:
(1) Cu (NO is configured
3)
2, Zn (NO
3)
2with Zr (NO
3)
4mixed solution, the mol ratio of Cu, Zn and Zr in mixed solution is 0.3 ~ 0.5:0.3 ~ 0.5:0 ~ 0.4, the concentration of copper ion is 3.5mol/L ~ 4.2mol/L;
(2) reaction temperature is kept to be under the condition of 50 ~ 90 DEG C, by the mixed solution of step (1) gained and Na
2cO
3
Solution drip are surely and constantly stir and obtain suspension, the process of titration keeps the pH value of suspension to be 7 ~ 10, then under the condition stirred, continue reaction 1 ~ 2 hour, stop stirring aging 2 ~ 4 hours, filter rear deionized water washing sediment until cleaning solution pH value is 7;
(3) roasting is carried out after the drying precipitate after step (2) being washed, then the sediment after roasting being put into concentration is carry out drying again after the nitrate solution dipping 24 ~ 48h of 1 ~ 10wt%, obtains 20 ~ 40 object low-carbon alcohol catalysts after finally again carrying out roasting, granulation;
Nitrate refers to any one or a few the arbitrary proportion mixture of Fe, Co, Ni, Li, Na, K, Cs, Al or Ce;
Low-carbon alcohol catalyst refers to the catalyst of mix products preparing methyl alcohol, ethanol, propyl alcohol, butanols.
2. the method for hydrogenation of carbon dioxide formate low-carbon alcohol catalyst according to claim 1, is characterized in that: described Na
2cO
3the concentration of solution is 0.5 ~ 1.0mol/L.
3. the method for hydrogenation of carbon dioxide formate low-carbon alcohol catalyst according to claim 1, is characterized in that: in described step (3), twice drying is all dry 10 ~ 15h at 110 ~ 120 DEG C of temperature.
4. the method for hydrogenation of carbon dioxide formate low-carbon alcohol catalyst according to claim 1, is characterized in that: in described step (3), first time roasting is roasting 5.0 ~ 6.0h under the condition of 480 ~ 550 DEG C.
5. the method for hydrogenation of carbon dioxide formate low-carbon alcohol catalyst according to claim 1, is characterized in that: in described step (3), second time roasting is roasting 2.0 ~ 2.5h under the condition of 200 ~ 300 DEG C.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018215943A1 (en) * | 2017-05-24 | 2018-11-29 | Sabic Global Technologies B.V. | Copper-zinc-zirconium-based catalyst for direct hydrogenation of co2 to methanol |
| CN110433813B (en) * | 2019-07-11 | 2022-07-15 | 盐城工学院 | Copper-indium alloy catalyst for synthesizing methanol by carbon dioxide hydrogenation and preparation method and application thereof |
| CN110465302A (en) * | 2019-07-30 | 2019-11-19 | 武汉大学 | A kind of CO2Hydrogen is added to prepare low-carbon alcohol catalyst and its preparation method and application |
| CN110947386A (en) * | 2019-11-21 | 2020-04-03 | 太原理工大学 | Preparation method of catalyst for synthesizing low-carbon alcohol by carbon dioxide hydrogenation |
| CN112237916B (en) * | 2020-10-16 | 2021-10-15 | 西南化工研究设计院有限公司 | Preparation method of high-activity methanol synthesis catalyst |
| CN115672341B (en) * | 2022-11-18 | 2024-04-16 | 中国科学院山西煤炭化学研究所 | Double-function composite metal oxide catalyst and preparation method and application thereof |
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