CN1295028A - Gas phase catalytic formic acid-dewatering process for preparing high-purity CO - Google Patents
Gas phase catalytic formic acid-dewatering process for preparing high-purity CO Download PDFInfo
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Abstract
The gas phase catalytic formic acid dewatering process as one small-scale high-purity CO preparing method in laboratory is effected at reaction temperature of 150-350 deg.c and space velocity of 0.1-1.0/hr and in the presence of catalyst including acid ceramic ring, active carbon, Al2O3, ZrO2, MgO, etc. It has a formic acid converting rate higher than 95%, and a CO purity higher than 99.5%. The catalyst is easy to prepare, low in cost and long in service life, and the process has less corrosion of equipment and less environmental pollution.
Description
The invention relates to a method for preparing high-purity CO by gas-phase catalytic dehydration of formic acid. Specifically, after formic acid is heated and vaporized, CO is generated by dehydration through a catalyst at 300 ℃, the purity of the obtained CO gas is more than 99.5%, and the conversion rate of the formic acid is more than 95%.
With the development of carbon-one chemistry, organic synthesis based on CO is becoming increasingly attractive. For example, methanol is oxidized and carbonylated to synthesize dimethyl oxalate, allyl oxide or benzyl chloride is carbonylated to prepare butenoic acid or styrene, olefin is hydrogenated and esterified to synthesize various organic acids (esters), and halogenated and carbonylated to synthesize the corresponding ketols. Therefore, how to conveniently and economically obtain high purity CO gas (greater than 99.5%) to meet the needs of laboratories and small scale production is an interesting topic for carbon-chemical researchers. A formic acid liquid phase dehydration method is commonly adopted in a method for acquiring CO in a laboratory, namely formic acid is dripped into concentrated sulfuric acid heated to a certain temperature to be dehydrated to generate CO, and the method generates a large amount of waste acid, has low utilization rate of methanol and has the problem of equipment corrosion. The literature reports a method for preparing high-purity CO from formic acid gas phase by using a Cu/ZnO catalyst or a JM solid catalyst, but the service life, the cost and the formic acid conversion rate of the catalyst have problems. (encyclopedia of chemical technology, Volume 4, 782-&783; T, Guezalsk; et al, J.catal.1980, 63(1), 94-101)
The invention aims to provide a formic acid gas-phase catalytic dehydration method, which has the advantages of simple preparation of the used catalyst, low cost, long service life, high formic acid utilization rate, conversion rate of more than 95 percent and high CO purity of more than 99.5 percent.
The invention provides a method for preparing high-purity carbon monoxide by formic acid gas-phase catalytic dehydration, which is characterized in that the formic acid gas-phase catalytic dehydration reaction comprises the following steps: (1) an acidic supported catalyst is used, and the catalyst carrier is ceramic ring, active carbon and Al2O3、ZrO2One of MgO, soaking the carrier in sulfuric acid or sulfate solution, stoving and roastingForming a catalyst;
the preparation conditions were as follows: concentration of the solution: 20-98 percent
Dipping time: 2-8h
Drying temperature: 80-100 deg.C
Drying time: 2-4h
Roasting temperature: 300 ℃ and 500 DEG C
Roasting time: 2-4h
(2) Passing the formic acid gas phase over a catalyst;
the reaction conditions were as follows: temperature: 150 ℃ and 350 DEG C
Space velocity: 0.1-1.0h-1。
The main reaction for synthesizing high-purity CO is as follows:
the side reaction is as follows:
the above synthetic reaction is optimizedThe reaction temperature is 300 ℃ and 350 ℃, and the optimal space velocity is 0.40-0.71h-1Space velocity = mass of formic acid/mass time of catalyst (h)-1)。
The catalyst carrier is preferably ceramic ring, activated carbon, Al2O3The dipping solution is sulfuric acid.
The synthesis provided by the present invention is further illustrated by the following examples.
Example 1 preparation of acidic alumina catalyst Al2O3The carrier (particle size: diameter 3-4mm, bulk density: 0.96Kg/l) is dipped in sulfuric acid solution with sulfuric acid concentration 98% for 8h, dried at 100 deg.C for 3h, and calcined at 400 deg.C for 3h to obtain the acidic alumina catalyst.
EXAMPLE 2 preparation of acidic activated carbon catalyst
The active carbon (5-10 mesh, bulk density: 0.5-0.6Kg/l) carrier is dipped in sulfuric acid solution with sulfuric acid concentration of 98% for 8h, dried at 100 deg.C for 3h, and roasted at 4000 deg.C for 3h to obtain the acidic active carbon catalyst.
EXAMPLE 3 gas phase Synthesis of high purity CO from formic acid
The formic acid is vaporized in a certain amount (while the formic acid is vaporized, the formic acid is continuously dripped at a speed equivalent to the vaporization speed of the formic acid), the vapor is decomposed by the acidic alumina catalyst and then passes through a condensing tube to condense the water generated by the reaction and the unreacted formic acid, and the gas is subjected to CO removal2After drying, the acid is measured by a rotameter and collected.
Example 4 Effect of decomposition temperature of formic acid on formic acid conversion
The experiment of example 4 was carried out according to the experimental procedure described in example 3. The change of the conversion rate of different catalysts in the decomposition temperature range of 270-310 ℃ of formic acid is examined, and the results are shown in Table 1. As can be seen from the results in Table 1, the decomposition temperature of formic acid is in the range of 270 ℃ to 310 ℃, and the conversion rate increases with the increase of the temperature. At temperatures below 290 ℃ the formic acid conversion is less than 95% and at temperatures above 300 ℃ the formic acid conversion is close to 100%, so increasing the temperature is advantageous for the formic acid conversion.
TABLE 1 formic acid conversion as a function of temperature
| Catalyst and process for preparing same | Decomposition temperature of formic acid | Formic acid conversion% |
| Acidic alumina (particle size: diameter 3-4mm, pile Density: 096Kg/l) | 270 280 290 300 310 | Is composed of 85 93 99 100 |
| Activated carbon (5-10 mesh, bulk density: 0.5-0.6Kg/l) | 250 270 300 | 63 88 100 |
example 5 Effect of formic acid decomposition temperature on side reactions due to side reactions in addition to the main reaction . The experiment of example 5 was carried out as described in example 3, investigating the extent to which the side reactions proceed by the change in hydrogen content when formic acid decomposes at different temperatures, the catalyst being acidic alumina. The results are shown in Table 2. From the results in Table 2, it is understood that the increase in the hydrogen content at an elevated temperature is advantageous for the side reaction. As can be seen from the results of tables 1 and 2, the temperature is too highAlthough low, very pure CO can be produced, the conversion rate of formic acid is very low, and although too high temperature can improve the conversion rate of formic acid, the content of hydrogen is also increased, so that the purity of CO is reduced. According to the relationship between the temperature and the content of hydrogen and the relationship between the temperature and the conversion rate, the decomposition temperature of formic acid can be adjusted to meet different requirements.
TABLE 2 variation of hydrogen content with decomposition temperature
| Decomposition temperature of formic acid | Hydrogen content% |
| 280 290 300 330 | 0.105 0.165 0.210 0.410 |
EXAMPLE 6 Effect of space velocity on formic acid conversion
The experiment of example 6 was performed according to the experimental procedure described in example 3. The reaction temperature is controlled at 300 ℃, and 0.4-0.73h is considered-1The space velocity of (a) has an influence on the formic acid conversion, and the catalyst is acidic alumina. The results are shown in Table 3. As can be seen from Table 3, the space velocity was in the range of 0.40 to 0.73h-1Within the range, there was no significant change in conversion.
TABLE 3 Effect of space velocity variation on conversion
| Space velocity h-1 | Formic acid conversion% |
| 0.40 0.50 0.58 0.73 | 100 99.80 96.50 98.67 |
Example 7 catalyst Life
According to the examples3, the reaction temperature is 300 ℃, and the space velocity is 0.7h-1A catalyst life test was conducted with the catalyst being acidic alumina and the results are shown in Table 4.
TABLE 4 catalyst Life test
| Cumulative reaction time h | Percent conversion of CO% | CO satin% |
| 153-193 233-246 260-270 293003 342-377 | 100 95.43 100 96.43 98.67 | 99.78 99.82 99.83 99.86 99.79 |
According to the above examples, it can be seen that the synthesis method of the present invention is adopted, at normal pressure, at a decomposition temperature of 300 ℃, at a space velocity of 0.43-0.7h-1The catalyst of the present invention has methanol converting rate over 95%, long service life and stable activity. The method for preparing the high-purity CO gas has the advantages of high utilization rate of formic acid, good CO purity, low cost of the catalyst, long service life and small corrosion to equipment and environmental pollution, and is an ideal method for producing the CO gas in a laboratory and on a small scale.
Claims (3)
1. A method for preparing high-purity carbon monoxide by gas-phase catalytic dehydration of formic acid is disclosed
A reaction characterized by:
(1) an acidic supported catalyst is used, and the catalyst carrier is ceramic ring, active carbon and Al2O3、
ZrO2One of MgO, soaking the carrier in sulfuric acid or sulfate solution, stoving and roasting
Forming a catalyst;
the preparation conditions were as follows: concentration of the solution: 20-98 percent
Dipping time: 2-8h
Drying temperature: 80-100 deg.C
Drying time: 2-4h
Roasting temperature: 300 ℃ and 500 DEG C
Roasting time: 2-4h
(2) Passing the formic acid gas phase over a catalyst;
the reaction conditions were as follows: temperature: 150 ℃ and 350 DEG C
Space velocity: 0.1-1.0h-1。
2. The process for the preparationof highly pure carbon monoxide by gas phase catalytic dehydration of formic acid as defined in claim 1 wherein
The method comprises the following steps: the carrier is ceramic ring, activated carbon, Al2O3The dipping solution is sulfuric acid.
3. The process for the preparation of highly pure carbon monoxide by gas phase catalytic dehydration of formic acid as defined in claim 1 wherein
The method comprises the following steps: the reaction temperature is 300 ℃ and 350 ℃, and the space velocity is 0.4-0.7h-1。
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| CN99113399A CN1295028A (en) | 1999-11-03 | 1999-11-03 | Gas phase catalytic formic acid-dewatering process for preparing high-purity CO |
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| CN99113399A CN1295028A (en) | 1999-11-03 | 1999-11-03 | Gas phase catalytic formic acid-dewatering process for preparing high-purity CO |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993075A (en) * | 2010-10-09 | 2011-03-30 | 宜兴市创新精细化工有限公司 | Method for rapidly reducing water content in carbon monoxide (CO) |
| CN105084359A (en) * | 2015-09-18 | 2015-11-25 | 北京环宇京辉京城气体科技有限公司 | Method for industrially preparing high-purity carbon monoxide through formic acid dehydration |
| CN113509938A (en) * | 2020-04-10 | 2021-10-19 | 绿菱电子材料（天津）有限公司 | Catalyst for preparing carbon monoxide and method for preparing carbon monoxide by using catalyst |
| CN116273143A (en) * | 2023-02-22 | 2023-06-23 | 中船(邯郸)派瑞特种气体股份有限公司 | Catalyst for preparing high-purity carbon monoxide by formic acid dehydration and synthetic method and application thereof |
-
1999
- 1999-11-03 CN CN99113399A patent/CN1295028A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993075A (en) * | 2010-10-09 | 2011-03-30 | 宜兴市创新精细化工有限公司 | Method for rapidly reducing water content in carbon monoxide (CO) |
| CN105084359A (en) * | 2015-09-18 | 2015-11-25 | 北京环宇京辉京城气体科技有限公司 | Method for industrially preparing high-purity carbon monoxide through formic acid dehydration |
| CN105084359B (en) * | 2015-09-18 | 2018-05-08 | 北京环宇京辉京城气体科技有限公司 | A kind of method that formic acid dehydration industry prepares high-purity CO |
| CN113509938A (en) * | 2020-04-10 | 2021-10-19 | 绿菱电子材料（天津）有限公司 | Catalyst for preparing carbon monoxide and method for preparing carbon monoxide by using catalyst |
| CN113509938B (en) * | 2020-04-10 | 2022-07-08 | 绿菱电子材料（天津）有限公司 | Catalyst for preparing carbon monoxide and method for preparing carbon monoxide by using catalyst |
| CN116273143A (en) * | 2023-02-22 | 2023-06-23 | 中船(邯郸)派瑞特种气体股份有限公司 | Catalyst for preparing high-purity carbon monoxide by formic acid dehydration and synthetic method and application thereof |
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