CN1435405A - Process for synthesis of isobutanoic acid - Google Patents
Process for synthesis of isobutanoic acid Download PDFInfo
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- CN1435405A CN1435405A CN 02148562 CN02148562A CN1435405A CN 1435405 A CN1435405 A CN 1435405A CN 02148562 CN02148562 CN 02148562 CN 02148562 A CN02148562 A CN 02148562A CN 1435405 A CN1435405 A CN 1435405A
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- isobutyric acid
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- isobutyraldehyde
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Abstract
A process for synthesizing isobutyric acid is characterized by the reaction of vaporized mixture of isobutyraldehyde and water at 200-350 deg.C in the presence of catalyst prepared from Cu, Zn, Al and one or more chosen from La, Ce and Y. Its advantages are high selectivity and safety and no pollution.
Description
Technical Field
The invention belongs to the technical field of preparation of fine chemical products.
Technical Field
Isobutyric acid is an important organic acid, used mainly in synthetic esters, cellulose flame retardants, synthetic resins and other organic syntheses. In industry, isobutyric acid is synthesized mainly by isobutyraldehyde liquid-phase oxidation and methacrylic acid gas-phase catalytic hydrogenation (see Xuke' handbook of Fine organic chemical raw materials and intermediates, chemical publishers, 1998, 1-233), wherein methacrylic acid gas-phase catalytic hydrogenation has high cost, and isobutyraldehyde liquid-phase oxidation, i.e., isobutyraldehyde is synthesized into isobutyric acid by oxidation reaction with oxygen or air, is currently used in industry. The isobutyraldehyde oxidationprocess has the disadvantages of low reaction selectivity, generally less than 85 percent of selectivity, more than ten byproducts and high raw material consumption. In addition, a certain amount of isobutyraldehyde is often carried in the vented tail gas, so that the explosion danger exists, and the environmental pollution is large. In addition, because of the generation of peroxide in the reaction process, certain explosion hidden trouble exists.
Disclosure of Invention
The invention aims to develop a pollution-free, high-selectivity and safe isobutyric acid synthesis process, namely a technology for synthesizing isobutyric acid by heterogeneous catalysis of isobutyraldehyde. The technology replaces oxygen or air with water, has the characteristics of no pollution, safety and high selectivity, and the main byproduct of the technology is isobutanol, so that the technology is easy to separate and can be recycled.
Specifically, the invention is realized by the following method: isobutyraldehyde and water are gasified respectively and then mixed to synthesize isobutyric acid by the action of a catalyst, the catalyst is a heterogeneous catalyst consisting of Cu, Zn, Al and an oxide of one or more elements selected from rare earth La, Ce and Y, and the reaction temperature is 200-350 ℃. The reaction equation of the process is as follows:
the synthesis reaction is completed by the following two steps:
in order to improve the yield and reduce the cost, the reaction conditions of the invention can be further controlled as follows:
the optimal reaction temperature is 250 ℃ to 320 DEG C
The reaction pressure is 0.1-1MPa, preferably normal pressure
The mol ratio of isobutyraldehyde to water is 1: 1-10
The weight space velocity of the isobutyraldehyde fed is 0.5-5 kg of isobutyraldehyde/kg of catalyst/h
The catalyst comprises the following metal elements in percentage by weight:
Cu 20-45％
Zn 15-35％
Al 25-45％
Zr 5-20％
1 to 10 percent of rare earth
The isobutyric acid synthesis reaction of the invention can use a fluidized bed or a fixed bed, and the technological process is as follows:
1. and (4) reducing the catalyst. The catalyst is loaded into the reactor with 1-10% H2/N2The temperature is programmed to 280 ℃ from room temperature for 20 hours, maintained for 5 hours and then adjusted to the reaction temperature;
2. gasifying isobutyraldehyde and water in a certain ratio respectively, mixing, preheating to the temperature of 200 ℃ and 250 ℃, introducing into a reactor, and carrying out catalytic synthesis under the control of the reaction conditions;
3. condensing reaction tail gas, rectifying condensate to separate isobutyric acid, and returning unreacted isobutyraldehyde and a small amount of by-products to the synthesis system.
Detailed Description
Example 1
Preparing a catalyst: 80ml of 1M copper nitrate solution, 40ml of 1M zinc nitrate solution, 180ml of 1M aluminum nitrate solution, 30ml of 1M zirconium oxychloride solution and 4ml of 1M ammonium ceric nitrate solution were measured by a measuring cylinder, and mixed uniformly in a dropping funnel. In a further dropping funnel 500ml of a 1M sodium carbonate solution were added. Under the condition of stirring, the solutions in the two dropping funnels are simultaneously dropped into a beaker for precipitation reaction, the PH value is controlled to be about 10 by adjusting the relative dropping speed of the two solutions, the reaction temperature is 80 ℃, and the precipitation time is 30 minutes. After the dropwise addition, the mixture is aged for 1 hour at 80 ℃, filtered and washed by deionized water until the filtrate is free of Na+And NO3 -Drying at 120 deg.C, calcining at 400 deg.C for 15 hr, cooling, crushing to 100 meshes, and tabletting to obtain particles of 4X 4mm in diameter, where the weight ratio of Cu to Zn to Al to Zr to Ce is 32: 16: 31: 17: 4.
Pretreatment of a catalyst: 50 g of the catalyst prepared in the above-mentioned manner are charged into a reactor having an internal diameter of 20mmIn, 5% H is introduced2/N2Programmed heating from room temperature to 280 ℃ over 20 hours and maintaining for 5 hours;
and (3) synthesis reaction: isobutyraldehyde (30 g/h) and water (30 g/h) are gasified and mixed respectively, namely the molar ratio of isobutyraldehyde to water is 1: 4, the mixture is preheated to 250 ℃, the mixture enters a reactor, the reaction temperature is 260 ℃, the reaction pressure is normal pressure, products are condensed and divided into an oil layer and a water layer, the oil layer and the water layer are weighed and analyzed respectively, and the result is shown in table one.
Example 2
The catalyst preparation and catalyst pretreatment were carried out as in example 1, except that the synthesis reaction temperature was 280 ℃ and the results are shown in Table I.
Example 3
The catalyst preparation and the catalyst pretreatment were carried out as in example 1 except that the synthesis reaction temperature was 300 ℃, the isobutyraldehyde feed rate was 60 g/h, and the water feed rate was 50 g/h, i.e., the molar ratio of isobutyraldehyde to water was 1: 3.33, and the results are shown in Table I.
Example 4
Preparing a catalyst: the procedure is as in example 1, except that the amounts of the respective solutions are: 80ml of 1M copper nitrate solution, 100ml of 1M zinc nitrate solution, 370ml of 1M aluminum nitrate solution, 20ml of 1M zirconium oxychloride solution, 15ml of 1M cerium ammonium nitrate solution and 900ml of 1M sodium carbonate solution, the weight ratio of the metals in the catalyst obtained being approximately Cu: Zn: Al: Zr: Ce-20: 26: 39: 7: 8.
The catalyst pretreatment was the same as in example 1.
And (3) synthesis reaction: the isobutyraldehyde was fed at 100 g/h and water at 50 g/h, i.e., the molar ratio of isobutyraldehyde to water was 1: 2, the reaction humidity was 280 ℃ and the reaction pressure was atmospheric pressure, and the results are shown in Table I.
Example 5
The catalyst preparation and the catalyst pretreatment were carried out as in example 4 except that the isobutyraldehyde was fed in an amount of 50 g/hr and water was 100 g/hr in the synthesis reaction, i.e., the molar ratio of isobutyraldehyde to water was 1: 8, the reaction humidity was 280 ℃ and the reaction pressure was 0.5MPa, and the results are shown in Table I.
TABLE-reaction results (gas chromatography)
| Fruit of Chinese wolfberry Applying (a) to Example (b) | Oil layer Weight (D) (gram) | The water layer is heavy Volume (gram) | Oil layer analysis result wt% | Analysis of the aqueous layer results in wt% | ||||||
| Chinese medicinal composition Aldehydes | Chinese medicinal composition Acid(s) | Chinese medicinal composition Alcohol(s) | Water (W) | Chinese medicinal composition Aldehydes | Chinese medicinal composition Acid(s) | Chinese medicinal composition Alcohol(s) | Water (W) | |||
| 1 | 27.3 | 32.2 | 69.35 | 19.15 | 4.00 | 7.5 | 7.29 | 3.97 | 0.29 | 88.45 |
| 2 | 26.7 | 33.0 | 58.71 | 25.97 | 7.04 | 8.28 | 6.78 | 4.34 | 0.33 | 88.56 |
| 3 | 53.5 | 55.2 | 71.58 | 22.12 | 3.19 | 3.11 | 7.76 | 4.10 | 0.32 | 87.82 |
| 4 | 96.8 | 52.7 | 79.51 | 11.26 | 7.19 | 2.05 | 8.23 | 2.85 | 0.65 | 88.28 |
| 5 | 48.3 | 100.3 | 75.14 | 17.45 | 5.25 | 3.15 | 7.96 | 3.25 | 0.54 | 88.24 |
Claims (8)
1. A process for synthesizing isobutyric acid features that the isobutyric acid is synthesized from the gasified mixture of isobutyraldehyde and water under the action of catalyst, which is composed of Cu, Zn, Al and the oxide of one or more elements chosen from La, Ce and Y, and the reaction temp is 200-350 deg.C.
2. The method for synthesizing isobutyric acid according to claim 1, wherein the optimal reaction temperature is 250-320 ℃.
3. The process for the synthesis of isobutyric acid according to claim 1, characterized by the reaction pressure being comprised between 0.1 and 1 Mpa.
4. The process for the synthesis of isobutyric acid according to claim 1, wherein the optimum reaction pressure is atmospheric pressure.
5. A process for the synthesis of isobutyric acid according to claim 1, wherein the molar ratio of isobutyraldehyde to water is from 1: 1 to 10.
6. The process for the synthesis of isobutyric acid according to claim 1, wherein the isobutyraldehyde feed weight space velocity is from 0.5 to 5 kg isobutyraldehyde per kg catalyst-hour.
7. The method of claim 1, wherein isobutyric acid is obtained by condensing, rectifying and separating the tail gas from the catalytic synthesis.
8. A process for the synthesis of isobutyric acid according to claim 1, wherein the catalyst comprises the following metal elements in weight percent:
Cu 20-45％
Zn 15-35％
Al 25-45％
Zr 5-20％
1 to 10 percent of rare earth
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02148562 CN1238327C (en) | 2002-12-13 | 2002-12-13 | Process for synthesis of isobutanoic acid |
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| CN 02148562 CN1238327C (en) | 2002-12-13 | 2002-12-13 | Process for synthesis of isobutanoic acid |
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| CN1435405A true CN1435405A (en) | 2003-08-13 |
| CN1238327C CN1238327C (en) | 2006-01-25 |
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| CN 02148562 Expired - Fee Related CN1238327C (en) | 2002-12-13 | 2002-12-13 | Process for synthesis of isobutanoic acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079705A (en) * | 2019-06-12 | 2020-12-15 | 中国石油化工股份有限公司 | Process for the preparation of isobutyric acid |
| CN113185395A (en) * | 2021-04-09 | 2021-07-30 | 润泰新材料股份有限公司 | Process for the production of isobutyric acid |
| CN114702377A (en) * | 2022-04-14 | 2022-07-05 | 华东理工大学 | Continuous flow synthesis of isobutyric acid |
-
2002
- 2002-12-13 CN CN 02148562 patent/CN1238327C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079705A (en) * | 2019-06-12 | 2020-12-15 | 中国石油化工股份有限公司 | Process for the preparation of isobutyric acid |
| CN113185395A (en) * | 2021-04-09 | 2021-07-30 | 润泰新材料股份有限公司 | Process for the production of isobutyric acid |
| CN114702377A (en) * | 2022-04-14 | 2022-07-05 | 华东理工大学 | Continuous flow synthesis of isobutyric acid |
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| CN1238327C (en) | 2006-01-25 |
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Owner name: YIXING CITY HENGXING FINE CHEMICAL CO., LTD. Free format text: FORMER OWNER: ZHONGGANG FINE CHEMICAL PLANT, YIXING CITY Effective date: 20130315 |
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Effective date of registration: 20130315 Address after: 214203 Yongning Road, Yixing Economic Development Zone, Jiangsu Patentee after: Yixing City Hengxing Fine Chemical Co., Ltd. Address before: 214223, Jiangsu City, Yixing Province Lake Town, City Ze Patentee before: Yixing Zhonggung Fine Chemicals Factory |
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