SE452609B - PROCEDURE FOR CARBONYLATION OF OLEFINES THROUGH REVERSE WITH CARBON MONOXIDE IN THE EXISTENCE OF ANTI-FREE ACID - Google Patents

Description

10 ZS 452 609 2 phase, which is preferably saturated with carbon monoxide and which is rapidly reacted in a second reactor with an organic compound described herein, to which one may add carbon monoxide, e.g. propene, under reaction conditions of a liquid phase, thereby forming it an acylium anion product, e.g. isobutyryl fluoride, essentially change. The acylium anion product, e.g. isobutyryl fluoride, is reacted further with excess water to form carboxylic acid, for example isobutyric acid. The acid can be oxide dehydrogenated to an unsaturated acid, e.g. methacrylic acid, as described herein.

DETAILED DESCRIPTION OF THE DRAWING Pig. 1 is a graph of the solubility of carbon monoxide in free hydrogen fluoride. 4 Pig. 2 is a schematic diagram of a reactor for process according to the present invention.

DESCRIPTION OF THE INVENTION The present novel process for producing an acylate lium anion product comprises the following steps: (a) formation in a first reactor of a liquid mixture comprising carbon monoxide dissolved in an anhydrous acid described herein, for example hydrogen fluoride; preferably the anhydrous acid is saturated »With carbon monoxide, (b) liquid phase reaction in a second reactor below such conditions under which an acylium anion product is formed, by it the liquid mixture from the first reactor of CO dissolved in the anhydrous acid with a liquid mixture comprising an olefin, which is described herein, e.g. propylene, to form a product mixture comprising the acylium anion product, e.g. isobutyryl fluoride.

The acylium obtained in the process according to the invention the anion product e.g. isobutyryl fluoride, can be hydrolyzed to formation of the corresponding carboxylic acid, e.g. isobutyric acid, under conditions under which the carboxylic acid is formed and the anhydrous the acid is regenerated. Preferably the carboxylic acid is separated from the hydrolyzed mixture, and the remaining hydrolyzed the mixture, which is free from any harmful amounts of water and other harmful materials and which include anhydrous acid, for example hydrogen fluoride, and / or carbon monoxide and / or unreacted , 452 609 acylium anion product. for example isobutyryl fluoride, is recycled to the liquid mixture of anhydrous acid and carbon monoxide.

Acrylic acid and / or methacrylic acid can be prepared from the pionic acid and / or the isobutyric acid by oxide hydrogenation such as described herein in vapor phase, in the presence of an oxygen-containing gas, air or oxygen itself, water, at a temperature of from 300 to 500 ° C and at a pressure of from 0.5 atmospheres to 2 atmospheres in the presence of a catalyst described herein comprising iron, phosphorus and oxygen and defined by the empirical formula FePx0z, where in relation to an atom iron x represents from 0.25 to 3.5 atoms of phosphorus and z represents the number of oxygen atoms required to satisfy the valence of the catalyst needs. Methyl or other alkyl esters of acrylic acid and / or methacrylic acid is formed by esterification of acrylic and / or the methacrylic acid.

REACTORS The carbon monoxide can come from any source but must be substantially free of water, ie contain less than 1,000 ppm water. The carbon monoxide may be diluted with other sub- punches that do not interfere with the reaction. For example, dry synthesis gas be used as well as dry coal combustion gases. It is however It is advisable to use dry carbon monoxide as such.

The organic compound capable of reacting with carbon monoxide and the anhydrous acid may contain other compounds and / or very small amounts of water, e.g. less than 1,000 ppm water, which does not interfere with the liquid phase reaction and / or causes it double phases arise. More specifically, according to the invention, an olefin having up to 20 carbon atoms with at least a double bond to which carbon monoxide can be added, such as ethylene, propylene, butenes, dodecene, 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene. Ethylene and propylene are preferred, and propylene is special preferred. The alkenes may be substituted with alkyl or arylcycloalkyls or other substituents which do not interfere with horizontal procedure. Although all of the organic compounds described herein may used in the present process, however, propylene is preferred.

The acids used in the preferred process for the acylium anion, should be substantially free of water, i.e. vat- TS 452 609 4 tenfria. The term "anhydrous", as used herein cases, refers to acids that are substantially free of water, e.g. less than 1,000 ppm of water, or for which, if water is present, it do not interfere with the reaction to form the acylium anion or the boxyl acid ester thereof.

The anhydrous acids which can be used for the present process farande, är; hydrogen fluoride (hydrofluoric acid) (HF) hydrogen chloride (hydrochloric acid) (HCl) hydrogen fluoride - boron trifluoride (HF-BF3) or mixtures thereof but preferably the individual acids.

Preferably, the anhydrous acid for the process is selected from anhydrous hydrogen fluoride and anhydrous hydrogen chloride. The most preferred However, the anhydrous acid of the present process is hydrogen fluoride (hydrofluoric acid).

Reaction conditions for the preparation of the acylium anion product The reaction between carbon monoxide and an organism described herein technical compound and a described anhydrous acid can be performed at a temperature of from 0 ° C up to 90 ° C, the upper temperature the tour is determined by the by-product formation. For the turnover between the preferred reactants described herein may be temperature from 40 ° C to 60 ° C, but preferably it is at about 50 ° C.

The carbon monoxide pressure can vary from 34 bar to 340 bar, and typically it is from 170 bar to 136 bar. The pressure increases after what required for the solubility of carbon monoxide in the anhydrous acid, such as e.g. shown in Fig. 1, which shows the increase of that amount carbon monoxide dissolved in anhydrous hydrogen fluoride when the pressure and temperature the temperature increases.

The molar ratio of anhydrous acid to the organic described herein compound should be from 1: 1 to 100: 1, but usually it is from 10: 1 to 20: 1 and preferably about 15: 1. The molar ratio of carbon monoxide to organic compound is from 1: 1 to 5: 1 or higher, but preferably it is from 1.5: 1 to 1: 1, and the maximum value corresponds to the saturation limit of carbon monoxide in the reaction mixture during and at the end of the reaction.

All carbon monoxide (CO) and anhydrous acid, e.g. anhydrous hydrogen fluoride to be reacted with the organic compound, for example propylene, should be mixed thoroughly in the first reactor to formation of a liquid mixture in which CO is dissolved, 452 609 wherein the liquid mixture is preferably saturated with CO before the reaction with the organic compound, e.g. propene.

Thereafter, the organic compound is brought into the liquid phase to react. quickly, while mixing it with the carbon monoxide and the acid in the other reactor. Usually happens the reaction, depending on the pressure and temperature, within a few nuts to form an acylium anion product, e.g. isobutyryl- fluoride. The organic compound itself can be diluted with carbon monoxide or other inert diluents, e.g. methane, ethane, propanol, etc., in the liquid phase to form a liquid formal mixture comprising the organic compound, e.g. pro- pen, and CO and / or inert materials before reaction with it the liquid mixture of anhydrous acid diluted with carbon monoxide. The second reactor can be a so-called semi-batch reactor, a plug flow reactor, a so-called back mix reactor (CSTR) or any other reactor known to those skilled in the art, but the preferred reactor tower is a plug flow reactor.

When the reaction for the preparation of the acylium anion is complete boarded, which depends on the reaction conditions as known the expert in the field, is separated from 1 to 100 percent of it formed the acylium anion product from the product mixture. Preferred separated from 80 to 100% of the acylium anion product, and the remaining product mixture is recycled to it the first or second reactor, i.e. carbon monoxide, anhydrous acid and the organic compound described herein. Alternatively, separate from 1 to 100 percent (preferably from 80 to 100 percent] of the anhydrous acid from the product mixture containing acy- the human anion product, when the reaction to form acylium anion is completed, and the separated anhydrous acid is recycled. back to the first reactor for further mixing with carbon monoxide.

The separation may be any of the known separations. methods such as distillation.

The hydrolysis process for the production of the corresponding carboxylic acid The hydrolysis reaction of the acylium anion addition product, for example isobutyryl fluoride, with excess water can occur at a temperature of from 20 ° C to 150 ° C and at pressures of from 1 to 340 bar, but normally it takes place at a temperature of from 40 ° C to 70 ° C and at a pressure of from 34 to 204 bar. The temperature and 452 609 6 the pressure is chosen so as to avoid decomposition of the intended ones the products.

The total amount of water to be added can be injected in the reaction mixture when the reaction to form acylium anion is complete. The hydrolysis step is exothermic, and thus cooling may be required.

The esterification process for the preparation of the carboxylic acid esters The esterification reaction between the acylium anion product, e.g. isobutyryl fluoride, and an alcohol, in particular, may occur at a temperature temperature of from 20 ° C to 150 ° C and at a pressure of from 1 to 340 bar, but normally it takes place at a temperature of from 40 ° C to 70 ° C and at a pressure of from 3.5 to 7 bar. The temperature and the pressure is selected to avoid decomposition of the desired ones products and to facilitate product separations.

It is convenient for the reactants to be stirred during esterification. the ring. In many cases, when rapid mixing is used, reaction with the simultaneous regeneration of the aqueous tenfria syran, e.g. HP, completed in a few seconds minutes.

From 1 to 100 percent (preferably from 80 to 100 percent cent) of the anhydrous acid is separated from the esterification product the mixture and recycled back for reaction to form of additional acylium anion product. The recirculation current can be contain small amounts of unseparated, unesterified acylium anion pro- product and / or carboxylic acid ester and / or unreacted organic Association.

The separation may be any of the known separations. methods such as distillation or solvent extraction.

Preferably distillation is used.

Formation of acrylic acid and a methacrylic acid The carboxylic acid of propionic acid or isobutyric acid formed by acylic anion product, e.g. propionyl fluoride or isobutyryl fluoride, after the hydrolysis described herein, oxide hydrogen by the process described in U.S. Patents 3 S85 248, 3 S85 249, 3 585 250, 3 634 494, 3 652 654, 3 660 S14, 3,766,191, 3,781,336, 3,784,483, 3,855,279, 3,917,673, 3,948,959, 3,968,149, 3,975,301, 4,029,695, 4,061,673, 4,081,465 and 4,088,602 and in British Patent Specification 1,447,593. 452 609 REACTOR FOR THE MANUFACTURE OF THE ACYLIUM ANJON PRODUCT The reaction can be carried out in any reactor which is provided with means for forming a liquid phase mixture of carbon monoxide and anhydrous acid, e.g. a pressurized mixing tank, and a means for separately bringing the liquid phase mixture off carbon monoxide and anhydrous acid in contact with a liquid phase include an organic compound and for reaction (eg a tube reactor) to form a product mixture containing an acylium anion product. It may further comprise either a means for securing parry the acylium anion product from the product mixture, e.g. one distillation column, or a means for separating the acylium the anion product from the product mixture and hydrolyze separately or esterify the separated acylium anion product from the product the product mixture to a carboxylic acid or ester (eg a des- column connected to a reactor) or a means for to separately hydrolyze or esterify the acylium anion product in the product mixture to a carboxylic acid or ester. An organ to separate the carboxylic acid or ester may be attached the reactor (eg distillation column). Means for entering the reactants to the reactor (eg pumps) can be connected to the tower.

Fig. 2 shows a schematic diagram of a typical reaction systems for use in accordance with the present invention. A so- such a system should include sources of the acid, e.g. hydrofluoric acid 10, a source of carbon monoxide II and a source of the organic units, e.g. propylene 12. The carbon monoxide is dosed using a dosing means, such as a dosing valve 13, through line 14 in in a pressurized mixing tank 15, which is kept under pressure. Syran, for example hydrofluoric acid, is injected into the mixing tank via line 16 by means of input means, such as a pump 17. The pressurized the mixing tank 15 should also be equipped with stirring means, such as a stirrer 18. The pressurized mixing tank can be have a liquid phase 19 and a gas phase 20, wherein it is carbon monoxide which are not dissolved in the acid, e.g. hydrogen fluoride, is maintained.

The liquid phase comprises a mixture of carbon monoxide and hydrogen fluoride. This mixture is transferred through line Z1 under pressure to the inlet to a reactor, such as the plug flow or tubing reactor 22.

The organic compound, such as propylene, is transferred via a ZS 452 609 8 line 23 into the reactor inlet via a liquid-liquid mixing nozzle. A metering pump 24 should also be used for injection of the organic compound at the desired rate and at the pressure of the reaction.

The reactor of the present invention must be able to maintain pour the hydraulic pressure for the system and must enable maintaining sufficient residence time for the reaction shall be done. The reaction time usually varies with the reaction temperature. raturen. Increased temperature increases the reaction rate. Usually should the reaction time should not be longer than about 120 seconds, even if It is easy for a person skilled in the art to determine exactly what drawn reaction time should be for special reagents, temperatures and press.

Reagent mixture comprising acid, hydrogen fluoride - carbon the monoxide solution and the organic compound pass through the reactor and exits through a pressure relief valve or so-called let down valve 25.

This is a simple scheme for a reaction system suitable for the present invention. Different types of reactors can be used for the present invention, and one skilled in the art should do not have any trouble designing a special reactor that is suitable for the specific purpose.

When the reactants have passed said let down valve 25, may be the additional step for hydrolysis or esterification of the acylium anion product, such as an acyl fluoride, e.g. isobutyryl- fluoride, is carried out in a second reactor 26 or in an extension of the tube reactor 22. The hydrolysis is carried out simply by addition of water to the stable organic carbon monoxide-acid anion product ten, e.g. acid fluoride, e.g. isobutyryl fluoride. This gives kar- the boxyl acid, e.g. isobutyric acid, as well as acid, e.g. hydrogen fluoride, which can then be separated by means such as a distillation apparatus 27 and reused, if desired, for manufacture of additional stable organic carbon monoxide-acid anion addition pro- duct. The acid can also be reacted with other compounds, such as an alkane alcohol to form an ester.

It is extremely important according to the present invention to maintain the appropriate amount of carbon monoxide in solution. With help of the diagram in Pig. 1, the amount of carbon monoxide which can be dissolved in anhydrous hydrogen fluoride, is determined. These data were determined empirically, 9 452 609 and a person skilled in the art should likewise be able to determine solubility carbon monoxide in any anhydrous or in the main thing anhydrous acid at a special temperature and a special print. Based on the molar amount of the organic compound which one wishes to convert, the amount of carbon monoxide required for the reaction is determined. For example, as mentioned above, the desired range in terms of molar ratio organic ratio to carbon monoxide to acid lzl-5: 1-100, and the preferred the ratio is 1: 1, 1: 15, especially for propylene, carbon monoxide and anhydrous hydrogen fluoride.

Other required information is the desired reaction conditions. the things, e.g. the pressure and temperature of the reactor. From this, the mole percentage of carbon monoxide dissolved in the acid, e.g. hydrogen fluoride, is determined. From this you can also determine the amount acid-, e.g. hydrogen fluoride, the solution required to maintain a sufficient amount of carbon monoxide to react with it organic compound.

If e.g. the intended reaction conditions are 340 bar and 80 ° C, it appears from Pig. 1, or you can determine the empi- that under these conditions 14 g of carbon monoxide dissolves in 100 g of anhydrous hydrogen fluoride.

More specifically, one can e.g. take the formation of isobutyryl fluoride from propylene, where the desired flow rate of propylene is 103 kg-mol / h. or 4,316 kg / h. This is preferred to have about 10% excess carbon monoxide in order to ensure adequate carbon monoxide availability for the olefin. É Therefore, approximately 112 kg-mol / h is required. (3,146 kg / hr.) Av carbon monoxide. Because the solubility of carbon monoxide in hydrogen fluoride at the reaction conditions are 14 kg CO / 100 kg HF, it is known that 22,560 kg / h. of HF is enough to dissolve the carbon monoxide required to react with propylene. This is equal to 1,128 kg-mol / h, which gives a molar ratio of hydrogen fluoride to propylene of ll: l.

At 204 bar and 80 ° C, 9 g of carbon monoxide would dissolve in 100 g hydrogen fluoride. The minimum molar ratio in this situation should be le is therefore calculated at 17: l as far as HF to propylene is concerned.

When the required proportions of organic compound and acid-carbon monoxide solutions have been determined, the carbon monoxide is injected and the solution in the mixing vessel at the desired reaction conditions. 452 609 elserna. The solution of carbon monoxide in acid, e.g. hydrogen fluoride, which formed in the mixing vessel is metered into the reactor. The mixing vessel must be kept at a sufficiently high temperature and high enough pressure to keep the carbon monoxide in solution. The wished for the amount of organic compound, e.g. propylene, is also dosed into the reaction tower, where it comes into contact and is mixed with the solution of monoxide in acid, e.g. hydrogen fluoride.

The reactants are passed through the reactor during maintaining pressure and temperature. Since this reaction is is exothermic, cooling jackets may be required for the reactor. Thus this is especially important for the reaction carbon monoxide, hydrogen fluoride and propylene, since this reaction should be carried out at a temperature subdued 90 ° C.

Once the reactants have passed through the reactor, they are released they through a let down valve and are further purified and reacted further, if required. A typical reaction such as written previously would be hydrolysis of the stable organic the carbon monoxide and anion addition product, e.g. acid fluoride to formation of a carboxylic acid and the acid, e.g. hydrogen fluoride.

The following examples are intended to illustrate the written procedure and reactor scheme.

Example 1 The reactor of the present example comprises one liter Monel autoclave equipped with a turbine blade stirrer with two inlets and a bottom outlet connected to a reactor. The reactor was one tube reactor comprising a tube with a diameter of 1.3 cm and 12.2 m length and connected at one end to the outlet of the autoclave and at the outlet end of a let down valve. Reaction temperature the temperature was maintained at about 30 ° C and the pressure was maintained at 204 bar overpressure.

In this reaction, propylene is reacted to form iso- butyryl fluoride. The carbon monoxide was injected into the autoclave with a 3.5 g-mol / hr., and the hydrogen fluoride was injected with a speed of 55 g-mol / h. and mixed therein to form a liquid phase of carbon monoxide in hydrogen fluoride, which is injected into the reactor. The flow rate for feeding propylene into the tube reactor was 2.6 g-mol / h. The total flow rate of the reagents is nom tube reactor was l 198 g per hour. While using this method, 2.05 g-mol / h was formed. of isobutyryl fluoride. Remain in eff- the luent was 1.0 g-mol / hr. of carbon monoxide, 52.4 g / mol / h of hydrogen

Claims (9)

452 609 11 'fluoride and traces of propylene. The remaining effluent contained other undesirable organic substances. The selectivity for this reaction to isobutyryl fluoride was approximately 75 percent. Although the invention has been described in connection with concrete details for certain illustrative embodiments, it is not intended that it be thereby limited in any respect other than that set forth in the appended claims. PATENT REQUIREMENTS Process for the carbonylation of olefins by reaction with carbon monoxide in the presence of anhydrous acid, characterized in that (a) in a first reactor at a temperature in the range from 0 ° C: in 11o ° c ooh if : jerks in the range of 14 boron to osz boron form a liquid mixture of carbon monoxide in an anhydrous acid selected from hydrogen fluoride (HF), hydrogen chloride (H61), hydrogen fluoride-boron trifluoride and mixtures thereof; (b) reacting in liquid phase in a second reactor the liquid mixture of carbon monoxide in the anhydrous acid and an olefin having up to 20 carbon atoms and having at least one double bond, to which carbon monoxide can be added for a period of time sufficient to form corresponding acylium anion product, at a temperature in the range from 0 ° C to 9000 and at a pressure in the range from 34 bar to 340 bar, the molar ratio of anhydrous acid to olefin is in the range from 1 mol to 100 mol of anhydrous acid per 1 mol , and wherein the molar ratio of carbon monoxide to olefin is from 1 mole to 5 moles of carbon monoxide per 1 mole of olefin. Process according to Claim 1, characterized in that the olefin is selected from the group consisting of ethylene and propylene. Process according to Claim 2, characterized in that the olefin is propylene. 452 609 12 Process according to any one of the preceding claims, characterized in that the anhydrous acid is hydrogen fluoride. Process according to any one of the preceding claims, characterized in that the acylium anion formed is substantially separated from the reaction mixture. Process according to Claim 5, characterized in that the acylium anion is further reacted with water at a temperature of from ZOOC to 100 ° C and at a pressure of from 1 bar to 340 bar. Process according to Claim 1 for the production of isobutyryl fluoride by carbonylation of propylene with carbon monoxide in anhydrous hydrogen fluoride, characterized in that (a) a first liquid mixture of carbon monoxide is formed in substantially anhydrous hydrogen fluoride and (b) is reacted in a liquid phase reaction the first liquid mixture and propylene in a reactor under conditions in which isobutyryl fluoride is formed in substantial yields at a temperature of from 40 to 60 ° C and at a pressure of from 34 bar to 340 bar, the molar ratio of carbon monoxide to propylene being from 1: 1 to 5: 1 and the molar ratio of hydrogen fluoride to propylene is from 10: 1 to 20: 1. Method according to claim 7, characterized in that the pressure is from 170 to 340 bar. A method according to claim 7, characterized in that the pressure is from 136 to 170 bar.