GB2265368A

GB2265368A - Production of carboxylic acids

Info

Publication number: GB2265368A
Application number: GB9205742A
Authority: GB
Inventors: Ying-Chih Lin; Yeong-Cheong Lee
Original assignee: China Petrochemical Development Corp
Current assignee: China Petrochemical Development Corp
Priority date: 1992-02-24
Filing date: 1992-03-17
Publication date: 1993-09-29
Anticipated expiration: 2012-03-17
Also published as: GB2265368B; GB9205742D0

Abstract

A carbonylation process for the production of carboxylic acid comprises contacting an alcohol with carbon monoxide in the presence of a catalyst consisting of (1) a rhodium compound (2) a halogen providing component (3) an iodide salt, and (4) a trihaloacetic acid promoter component. The catalyst used in the present process enhances the rate of carbonylation.

Description

IMPROVED PRODUCTION OF CAR30XYLIC ACIDS FROM CAR30NYLATION OF ALCOHOL BACKGROUND OF THE INVENTION AND PERTINENT PRIOR ART 1. Field of the Invention: This invention relates to an improvement of a process for synthesizing carboxylic acids by the carbonylation of alcohol. lore particularity, this invention relates to the addition of trihaloacetic acid to the rhodium catalytic system to promote the reaction rate. The alcohol used in this reaction system has the formula of R3H, where R is a saturated hydrocarbonyl radical having 1 to 4 carbon atoms.

2. Description of the Prior Art : The use of group VIII transition metals as the carbonylation catalysts for the production of carbonylation products are known in the art, with many of such catalysts being based on cobalt and using a halide promoter. However, the rhodium system has become the most important one in the recent years. So far as we know, there has not heretofore been a disclosure of a rhodium based carbonylation catalyst system containing trihaloacetic acid as the pro, noter used in the generation of carboxylic acid such as acetic acid by the carbonylation of alcohol such as methanol with carbon monoxide at mild pressure and temperature conditions. The rhodium catalytic systems that have been disclosed will be described in the following paragraphs and the relationship between those procedures and this invention will be discussed.

Among processes for synthesizing acetic acid, the one that is the most comlnercially useful is the carbonylation of methanol with carbon monoxide as taught in USP 3, 769, 329 and. in US ? 4, 590, 912 both issued to Paulik et al. on Oct. 30. 1973. and Sep. 1, 1937 respectively.

The reaction was carried out at 130oC and 35-70Kg/cm2 Co. The '''.'

catalyst system comprises rhodium. either dissolved or otherwise dispersed in the liquid reaction medium or else supported on an inert solid, along with a halogen-containing catalyst promoter such as methyl-iodide. The patents teach that the preferred solvent and liquid reaction medium for tho process is the desired carboxylic acid itself, i. e. , acetic acid when methanol is being carbonylated to produce acetic acid. The selectivity is exceptionally high, typically greater than 95%. However, the rate of carbonylation has been highly dependent on water concentration in the reaction medium. when the water concentration is reduced to below about 14-15 wt, the rate of reaction declines. Reducing the water content also leads to the formation of by-product such as ester. It is taught in European Patent No. 0055618 that typically about 14-15 water is present in the reaction medium of a typical acetic acid-producing system using carbonylation technology ; In a paper written by Hjortkjaer and Jensen [Ind. Eng. Chem., Prod. Pes. Rev. 16, 231 (1977)], it is shown that the reaction rate of methanol carbonylation is increased with the increasing of water content from 0 to 14 wt. Above 14 wt%, the reaction rate is unchanged. The catalyst also becomes more susceptible to inactivation and precipitation when carbon monoxide partial pressure and/or water content is/are low. These prior arts disclose an important message that water must be present in the reaction system to obtain a satisfactory reaction rate.

US Patents 110. 606730 and trio. 699525, both issued to Celanese Corporation, disclose that using high concentration of LiI as the stabilizer for the rhodium catalytic system under a limited amount of water, it will be necessary to add methyl acetate as the promoter in order to obtain a productivity almost the same as the one which was obtained from a system with high concentration of water. The purpose

of the Celanese patent is to reduce the amount of water but this also reduces the reaction rate.

It can be seen from the prior arts mentioned above that those systems either have the disadvantage of requiring high water content or have the disadvantage of the reduced reaction rate if the amount of water therein is reduced. Those literatures have never mentioned the use of trihaloacetic acid. Therefore, the main purpose of this invention is to find a suitable additive which can both reduce the amount of water and increase the reaction rate. Using the catalytic system of this invention, a very high productivity can be obtained under the reduced water content of 4 to 11% so that the problem resulting from water can be avoided. The catalytic system of this invention, even though dissolved in the system containing low amount of water, is still resistant to precipitation. Furthermore, in view of the separation of the acetic acid froh) low amount of water, the consumption of energy during distillation can be reduced when compared with the separation of them fro. n high amount of water. The other procedures, such as solvent extraction, can also be simplified and thus the expansion of equipments can be avoided. The accomplishment of this invention, i. e. , achieving high productivity and reaction rate under low water content by the incorporation of trifluoroacetic acid into the catalytic system, can not be overmatched by the prior art. According to the present invention, the reaction rate in the environment of low water content and in the absence of methyl acetate is even higher than that of the prior art in which methyl acetate is used.

DETAILED DESCRIPTION AIID PREFERRED ENBODIHENTS The catalyst system of this invention was employed in carbonylation reactions operated as a batch process. The reactor employed for the carbonylation reactions in this example consists of a corrosionresistant main reaction vessel and a CO reservoir connected to the main reaction vessel with a regulator between them to keep a constant pressure in the main reaction vessel. The main reaction vessel was equipped with a magnetic drive stirrer and a methanol reservoir on the top of a sample inlet. Heat was provided by heating mantle wrapping on the reactor walls. An inlet valve for liquid reactants was provided on the top of the reactor and the gaseous reactants enter the reactor through the sa, le inlet. The effluent from the reaction was withdrawn through a dip tube.

The temperature at which the reaction is effected is in the range from 50 C to 30QoC with higher temperature favoring higher reaction rates.

The preferred temperature range is fro : n 125 C to 225 C. The reactor temperature was between about 190 C dnd 195 C. Reaction pressure may vary over a wide range. Partial pressure of carbon monoxide from 1 to 70 kg/cm2 or even higher can be employed. However, the process is particularly advantageous in that it can be carried our at a lower carbon monoxide partial pressure ranging from 1 to 2i kg/cm2 or even more preferably at carbon monoxide partial pressure ranging from 3 to

71 kg/cm2. The liquid reaction medium used in the reaction system 71 kg/cl, was acetic acid.

In this operation, the reactants are charged into the reactor that contains the liquid catalyst system which is then subjected to the

desired temperature and pressure conditions. To make quantitative comparison on tht reaction rate. the rate data is reported as space time yield as suggested by Smith. G. l. et a1. in J. no1. Cataly. 39,

115, 1937. The space tins yield (STY) is expressed in gram-moles of acetic acid produced per hour per liter of reaction medium contained in the carbonylation reactor, the volume of reaction medium being measured at ambient temperature and in the unaerated state.

The present invention is illustrated in the following examples which, however, are not to be construed as limiting the invention since various changes and modifications within the spirit of the invention will become apparent to those skilled in the art.

Comparative Examples 1 and 2 In order to compare this invention with those prior arts to show the superiority of this invention, the prior arts are repeated. The results are shown in Table I as the Comparative Examples. In these two examples, no trifluoroacetic acid was used. In Comparative Example 2, 14% LiI was added. The experimental procedures for both Comparative Examples are similar to those for Example 1 and will be described below.

Table I

Comparative Comparative Example 1 Exaliple 2 lligh water Low water REAGENTS o TFAA No TFAA fJo Lil < 'ith LiI water 14 8 TFAA % 0 0 Li 1 7 0 14 Mel 14 14 Rh 409 ppm 400 ppm STY 10.79 12. 77

Examples In the following examples, the main reactors used in the experiment-is Hastelloy B. The 7. represents weight percentage.

EXAMPLE 1 The reactor was charged with a solution containing rhodium iodide,

methyl iodide. water, acetic acid and trifluoroacctic acid (TFAA) in proportions to provide 400 ppm rhodium, 14. 0 methyl iodide, 14. 0% water and 20. 0% TFAA. The reactor was sealed, pressured to approximately 28.14 ! (g/cn of carbon monoxide partial pressure which was checked at 25 C. The reactor was then slowly vented of its carbon monoxide and then flushed twice with carbon monoxide (7 Ky/cI1l2). The reactor was then pressured to 14 Kg/cm2 with carbon monoxide and hedted to 120 C for 2 hours, after which the agitator was turned on to stir at medium speed (100-200 rpm). The reactor was then further heated to 194 C, stirred at high speed (500-500 rpm) and pressured with carbon monoxide to 29 Kg/cin2. The reactor was maintained at a temperature of 194 C when methanol was fed into the solution and carbon monoxide was introduced continuously at a rate to maintain the pressure in the reactor at about 29 Kg/cm2. The rate of reaction was determined by monitoring the amount of carbon monoxide consumed over a period of time, assuming that the ideal gas law can be applied to carbon monoxide. The rate of CO consumption approximates to the rate of acetic acid production since the formation of by- products is small as shown by products analysis.

The analysis of the carbonylation product recovered showed that all the methanol was converted to acetic acid. Selectivity for the formation of carboxylic acid product is greater than 95%. No substantial amounts of by-products such as alo'ehydes, dimethyl ether. high boiling point carboxylic acid, Methane and carbon dioxide are

detected by gas chromatography. It took about 13 minutes to convert 50 % of methanol to acetic acid. The results are listed in Table II. Compared with Comparative Example 1, it is clear the STY value of Example 1, wherein 20% trifluoroacetic acid is added, has been increased about 50%.

Table II

High water REAGENTS High TFAA No LiI water Z 14 TFAA 20 Lil % 0 MeI% 14 Rh 400 ppm STY 15. 08

EXAMPLE 2 Acetic acid was prepared by the method of Example except that the water concentration was reduced to 8X and 14% LiI was added. The rate of reaction was again deter, nined by monitoring the amount of carbon Monoxide consumed over period of time. No substantial amounts of by-products are detected by gas chromatography. The results are listed in Table III. It is clear that the STY value of this example is higher than those of Comparative Examples and is also higher than that of Example 1. It can be learned from this example that if both Lil and trifluoroacetic acid are added to the reaction system, not only water content can be reduced, but also reaction rate is increased.

Table III

Lo'. v water REASENTS High TFAA with LiI water : 8 TFAA % 20 LiI % 14 Mel % 14 Rh 400po) ppm STY 19.79 EXAMPLES 3-5 Acetic acid was prepared by the method of Example 1 except the molar ratio of trifluoroacetic acid to acetic acid was varied. The rate of reaction was again determined by monitoring the amount of carbon monoxide consumed over a period of time. fJo substantial amounts of by-products are detected by gas chromatography. The results are listed in Table IV. As can be clearly seen in the Table IV, the rate of formation of acetic acid is increased with the increasing of the wt% of trifluoroacetic acid. The STY value was almost. doubled when the wt% of TFAA is increased from 10% to 25%. The solution remained clear after exposed to air for about 2 weeks, no precipitation was observed. The amount of soluble rhodium metal was determined by atomic absorption as described in EXAMPLES 13-17 below.

Table IV

Comparative Example 3 Example 4 Example 5 Example 6 Example 2 watery 8 8 8 8 8 TFAA % 0 10 15 20 25 Lui 1 7. 14 14 14 14 14 Mel % 14 14 14 14 14 Rh 400 ppm 400 ppm 400 ppl71 400 ppli1 400 ppm STY 12.77 13. 33 13. 15 19.79 23.17 EXEMPLES 7-12 The purpose of these examples is to test the activity of the catalytic syste. after consecutive use. A batch reactor was charged with appropriate amounts of rhodium iodide, methyl iodide, LiI and trifluoroacetic acid. The solvent is acetic acid. The reaction was operated under the conditions as described in Example 1. The rate of reaction was again determined by monitoring the amount of carbon monoxide consumed over a period of tinte. The STY values are listed in Table V as STY1. After methanol was all consumed and CO pressure of the reservoir renamed constant, a second aliquot of methanol was

Since the added to test the activity of the catalyst system. Since the concentration of rhodium catalyst decreased when the formation of acetic acid increased, a lower STY value was expected and listed in Table V as STY2. The STY2* velues are the STY value after correction for the concentration of Rh (STY2"= STY1 x correction factor). Gas chromatographic analysis showed that the resultant reaction fixture contains acetic acid and methyl iodide. It is obvious from the table, the activity of the catalyst system after the first aliquot of tnethanol was completely converted was almost the sain2 as its initial

activity, which can be verified by the small difference between STY2 and STY2". Table V

Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 waler % 8 8 2 8 8 8 TFAA 0 20 0 15 25 30 Lis% 0 0 14 14 14 14 Mel % 14 14 14 14 14 14 Rh 400 ppm 400 ppm 400 ppm 400 ppn 400 pp. ii 400 ppm STY1 9.67 10.42 12.61 18. 15 24. 26 21.93 STY2 6.65 6.92 8. 95 11.17 13. SO 11. 70 STY2 8. 23 7. 39 8.68 10. 08 13.13 11. 78 The theoretical STY value after correction of rhodium concentration reduction and volume increase.

EXAMPLES 13-17 The purpose of this experiment is to test solubility of the rhodium catalytic system. The results showed that a reaction system consisting of suitable concentration of trifluoroacetic acid and LiI still has the same solubility after settled for a period of time.

The experimental procedure are as follows : A lixture of 8 H2O, 14% Mel, 25Z trifluoroacetic acid and Rh, in which the concentration of Rh was always kept at 400 ppia, was charged into the reactor and the reactor was sealed and heated to 194 C for one hour and then allowed to be kept at room temperature. The solution in the reactor was then removed and then sealed in a flask for 5 to 10 days. The concentration of Rh in the clean solution was then determined by using the atomic absorption spectrum. The results listed in Table VI

showed that the concentration of Rh was in the range from 394 to 342 ppm. It is seen from this table that the extent of precipitation is very low.

Table VI

Example Original Rh New Rh Concentration Concentration 13 400 ppr, 394 puni 14 400 pp m 371 ppm 15 400 ppm 342 ppm 16 400 ppm 330 ppm 17 400 ppm 353 ppm In a word, with the addition of trifluoroacetic acid and Lil, this invention not only increases the rate to almost twice as fast as that of the prior art, but also allons the reduction of the water content.

Another advantages of this invention are that the catalytic system has high solubility and is very stable even at high temperature, making it resistant to precipitation.

Claims

What is claimed is: 1. A carbonylation process for production of carboxylic acid, which comprises contacting an alcohol of formula ROH wherein R is a saturated hydrocarbonyl radical having from 1 to 4 carbon atoms, with carbon monoxide in the presence of a catalyst system consisting essentially of (1) a rhodium compound, (2) a halogen providing component, (3) an iodide salt, and (4) a separately added trihaloacetic acid promoter component.
2. The process of claim 1, wherein said halogen providing component is an iodine providin'j component.
3. The process of clai. n 2, \/herein said iodine providing component is ethy1 iodide.
4. The process of claim 1, wherein said trihaloacetic acid component is trifluoroacetic acid.
5. The process of claim 1, wherein said iodide salt is lithium iodide.
6. The process or claim 1, wherein said alcohol is methanol.
7. The process of claim 1, wherein said process is carried out at a temperature form about 180 C to 220 C.
8. The process of clai, n 1, wherein the partial pressure of carbon monoxide is in the range from about 1.4 to about 60 kg/cm2.
9. The process of claim 4, wherein the concentration of trifluoroacetic acid is from 2 to 40 weight percentage.
10. The process of claim 5, wherein the concentration of lithium iodide is from 2 to 40 weight percentaga.
11. The process of cl#im 1. wherein said process is carried out at a water concentration from 4 to 11 weight percentage.

<Desc/Clms Page number 13>
12. A process for the production of carboxylic acid according to claim 1 and substantially as hereinbefore described.
13. A process for the production of carboxylic acid substantially as hereinbefore described with reference to the Examples.
14. A carboxylic acid formed according to a process as claimed in any one of the preceding claims.