SA96170152B1 - Method for adding a carbonyl group to alkyl alcohols or their reactive derivatives, or both - Google Patents

Abstract

Abstract: In a method for adding a carbonyl group in the liquid phase to an alkyl alcohol such as methanol or an active derivative thereof or both to yield the corresponding carboxylic acid or the corresponding ester or both, in the presence of an iridium catalyst and an alkyl halide and water, the reaction is enhanced by at least one promoter selected from cadmium, mercury, zinc, gallium, indium, and tungsten, and selectively with a co-promoter selected from ruthenium, osmium, and rhenium. rhenium

Description

Y — __ a method for adding a carbonyl group to alkyl alcohols, their reactive derivatives, or both Full Description

background of the invention

The present invention relates to a method for adding a carbonyl group and dala relates to a method for de sana carbonylation to alkyl alcohols or their reactive derivatives or both in the presence of an iridium catalyst.

° The methods of carbonylation in the presence of iridium catalyst are well known and described 'eg' in US Patent L, EP Publication No. BP 15187868 « and UK Patent No. 08 17767736; 08756 and 174347 08.

The process of carbonylation in the presence of iridium catalyst 0 and a co-enhancer selected from ruthenium and osmium is described in European Patent Publication No. 647074 - a. General Description HAM It has been found at present that the enhancer selected from the group consisting of cadmium; mercury; and zinc zine and gallium; Iridium (vo) and tungsten (A) tungsten had a beneficial effect on the carbonylation rate of an alkyl alcohol or a reactively active derivative thereof, or both, in the presence of iridium catalyst. Y YAY

—_ y —_ and so on; According to the present invention, it provides a method for producing a carboxylic acid by adding a carbonyl group to an alkyl alcohol or a reactively active derivative thereof, or both. This method includes contact with the said alcohol or its reactively active derivative. Or both inside a carbonylation reactor with carbon monoxide in a liquid reaction composition that includes: - iridium catalyst. b- an alkyl halide with at least a limited concentration of water. d- A booster derived from a group consisting of cadmium and mercury; 0 and the pure zine; gallium; Indium and tungsten. Also, according to the present invention, it is provided with a catalyst system to add the carbonyl group to the alkyl alcohol, a reactively active derivative thereof, or both. This system includes: a. iridium catalyst. . Alkyl halide b. Alkyl halide 0 C - a booster that is selected from a group consisting of cadmium, mercury, zine, gallium, indium, and tungsten. In general the promoters of the present invention are not cheaper than promoters such as ruthenium and osmium only. But it is also believed that at least cadmium and mercury

YYAY

Mercury, zine, gallium, and iridium are less likely to form volatile compounds in the carbonylation reaction. Suitable alkyl alcohols include alkyl alcohols with 1-01 carbons and preferably 0-alcohols with 1- to +7 carbons The most preferred are those alkyl alcohols that contain a number of carbon atoms from one atom to; atoms and still the most preferred methanol. The alkyl alcohol is preferably a primary or secondary alkyl alcohol; The product (ddl) is the carbonylation of an alcohol that contains n number of 0 carbon atoms or its derivative is a carboxylic acid that contains n + 1 carbon atoms or an ester of a carboxylic acid that contains It has n + 1 carbon atoms and an alcohol has n carbon atoms or both. Je This is the product of adding carbonylation to methanol or its derivative acetic acid or methyl acetate or both. Vo The suitable reactive alkyl alcohol derivatives include the corresponding alkyl ester and the corresponding product carboxylic acid; Dialkyl ethers and alkyl halides are preferred, iodides and bromides are preferred. Suitable reactive derivatives of methanol include methyl acetate 0 2061816; And dimethyl ether Ju and methyl iodide. YYAY

m name —

A mixture of alkyl alcohol and reactively active derivatives thereof may be used as reactants in the process of the present invention. It is preferable to use methanol or methyl acetate or both as reactants.

It will convert some of the alkyl alcohol or its reactive derivative or both

0 is at least to and is therefore present as an alkyl ester in the liquid reaction composition

By reaction with ZW carboxylic acid or the solvent.

The appropriate alkyl ester concentration in the composition of the liquid reaction is in the range from 1 to 79760 by weight. Preferably who? to 750 by weight and still more preferable to have concentrate from © to 7705 by weight.

Water can be in the reaction medium in the liquid reaction structure by, for example, the esterification reaction between the alkyl alcohol reactant and the resulting carboxylic acid Water can enter the carbonylation reactor with or separated from the other components of the liquid reaction composition.

Water can be separated from the other components of the reaction composition drawn from reactor 1 and can be recycled in controlled amounts to maintain the required concentration of water in the liquid reaction composition. It is appropriate that the concentration of water in the liquid reaction composition be in the range of 1 to 716 by weight; preferably in the range of 1 De to 701 by weight; It is preferable not to exceed the weight.

(Sa) that the iridium component of the catalyst in the liquid reaction composition includes any compound that contains iridium and is soluble in the liquid reaction composition. The iridium component of the catalyst can be added to the liquid reaction composition for an addition reaction carbonylation in any suitable form that is soluble in the liquid reaction composition or convertible to a suitable form Examples of suitable iridium-containing compounds that may be added to the liquid reaction composition include iridium chloride (In Cly); iridium iodide (Ir I); iridium bromide (Ir Bra); iodo dicarbonyl iridium dimer and [[ICON]. (COMBI; 0 iridium dicarbonyl diiodo ion + 11- [Ir (©0): LB] iridium dibromodicarbonyl ion + [Ir (CO) Br —H iridium dicarbonyl diiodo ion + 11- Ir (CO) I] dicarbonyl ion; triiodomethyl iridium + 11- [ (CO) and a [Ir (CHa) ¢ iridium carbonyl 00(1)a; aqueous iridium chloride 311: 0 IrCl.; Aqueous Iridium Bromide 311:0 IrB3.; iridium carbonyl (1:00); iridium metal; iridium trioxide (1::0; 1:02 iridium dioxide; iridium dicarbonyl acetate; Ir(acac) (CO) iridium triacetate ¢In(acac)s iridium acetate; iridium acetate Iridium oxide hexaacetate trihydrate IO(OAC)(H20)] [OAC] and hexachloroiridic acid. (HICH) It is preferable to use 0:8 iridium complexes that do not contain Jie chloride acetate; And oxalates 65 and acetoacetate 5, which are soluble compounds in x. One or more of the components of the carbonyl addition reaction (Jie carbonylation) water or alcohol + alcohol or carboxylic acid are all of the above. a

_Vv_

A particularly preferred compound is green iridium acetate which can be used in acetic acid or sl acetic acid solution.

It is preferred that the concentration of the iridium catalyst in the composition of the liquid reaction be within the range of 001 to 0001 parts per million in relation to the weight of iridium

° The enhancers can be cadmium, mercury or zine

or gallium or gallium iridium or tungsten contained in any compound containing cadmium or mercury or zine or gallium or indium or tungsten and soluble in in the composition of the liquid reaction.

The booster may be added to the liquid reaction composition for the carbonylation reaction

0 in any suitable form that is soluble in the liquid reaction composition or convertible into a soluble form

to melt.

Examples of suitable cadmium-containing compounds include Als cadmium Cadmium acetate CA(OAC) and cadmium iodide Cdl can be used; cadmium bromide: 008; and cadmium chloride, CdCl, cadmium hydroxide, Cd(OH), 4-acetyl cadmium acetonate

.cadmium acetylacetonate ‘eo

Examples of suitable mercury-containing compounds that can be used as mercury acetate include Hg(OAC), mercury; mercury iodide Hg I, mercury, mercury bromide ©1188, mercuric chloride HeCl; mercury monoiodide.118:1; and mercury monochloride and 0 with 1].

‎YYAY

m - REY includes suitable zine-containing compounds that can use Zn acetate (OAC); zinc hydroxide 010 (2) Zn ; zinc iodide, Zl; zinc bromide, ZnBry; and zinc chloride O 200; zinc acetylacetonate . Examples of suitable gallium-containing compounds that can use gallium acetylacetonate include gallium acetylacetonate; gallium acetate 56; gallium chloride, GaCly; gallium bromide 3:683; gallium iodide 06813; gallium chloride YL0820; and gallium hydroxide .Ga(OH); Examples of suitable indium-containing compounds that can 0 include indium acetylacetonate; indium acetate; , indium chloride In Cl , indium bromide In Bry ¢ , indium iodide Inky ¢ , indium iodide 101 ¢ , indium hydroxide , (011) 11 . Examples of suitable tungsten-containing compounds that can use hexacarbon include tungsten(17(00) ; Tungsten Chloride WC, » Tungsten Chloride 10 17016 ; tungsten bromide 5 + tungsten iodide 712; tricarbonylation 0 nonan tungsten Hip W(CO); C and any compound tungsten chloro or bromo or iodo-carbonyl. It is appropriate that the ratio Malaria for each selective catalyst booster to iridium catalyst Limits (from 1 to 1:01) preferably within 0 Limits (from 1.59 to 0:01) More than one reinforcer can be used

A selective co-enhancer can also be used selected from a group consisting of ruthenium, osmium and rhenium and the co-enhancer may include any compound containing ruthenium, osmium and rhenium and soluble in the reaction composition the questioner. The selective co-enhancer may be added to the liquid reaction composition of the carbonylation reaction in any suitable form that is soluble in the liquid reaction composition or convertible into a soluble form. Examples of suitable ruthenium-containing compounds that can be used as selective catalysts include: 0 ruthenium (Y) chloride, ruthenium chloride (¥) trihydrate ¢, and ruthenium chloride ruthenium chloride (¢); ruthenium bromide (¥) and ruthenium metal ¢, ruthenium oxides and ruthenium formate (7); + H - [:A:(8:)00] ; Sl carbonyl diiodo 1 _ ruthenium (Y) « [2:(00):1] ; ruthenium tetracarbonyl diiodo ( 7) [Ra,(00)S[; diiodotricarbonyl ruthenium (Y) dimer: [F(00:1)Ru] and tetra(sad)chlororuthenium 0 (Y¢ Y) tetra) aceto)chlororuthenium and ruthenium acetate (7) ¢ ruthenium propionate 0 (09 ruthenium propionate) ruthenium butyrate (7); ruthenium pentacarbonyl “and ruthenium tricarbonate 0 eighteen trirutheniumdodecacarbonyl halo carbonyls ruthenium 5 mixed as dimer ALD chlorothalates ruthenium carbonyl

- 11. V) dichlorotricarbonylruthenium dimer and other SLB (Y) dibromotricarbonylruthenium dimers such as organoruthenium ruthenium SD and tetrachlorodi(benzene) ( (7) tetrachlorobis(4-cymene)diruthenium diene) -1,5- dichloro(cyclo-(Y) tetrachlorobis(benzene)diruthenium 0) and tri(acetyl polymer) (7) dichloro(cycloocta-1,5-diene)ruthenium (7) tris(acetylacetonate)ruthenium which can include osmium Examples of suitable aqueous osmium-containing compounds (7) Osmium chloride is used as selective catalysts for the following osmium chloride, osmium tetraoxide, osmium metal tetraoxide and hydration; Y) diiodo dimer osmium tricarbonyl . And [”halo pentachloro-.mu.-nitrododiosmium chloro-no-nitro diode osmium dimer thalachy carbonyl di Jie mixed osmium halocarbonyls osmium carbonyls 10 and osmium complexes ¢ (Y) tricarbonyldichloroosmium dimer. Other organic organoosmium that can rhenium include Examples of suitable compounds containing rhenium and (0)00m1; rhenium rhenium SL used as a decacarbonyl selective catalyst; Re(CO)sBr ; bromomochloroquinylrhenium Re(COYCl), chloropentacarbonylrhenium 00. iodo pentacarbonylrhenium O(06)00; and aqueous trichloro rhenium L110, 2001.

YYAY

— 1 \ _ tetraiodo dimer [Re(COMI Ly) and tetraiodo dimer ion +11-[ [Re (CO)4ly « and pentachlorrhenium ReCls. 0 od! . It is appropriate that The molar ratio of each selective catalyst to iridium catalyst is in the range (from 0.1 to 0 (Yo) and preferably in the range of (from 8 to CY () 0) preferably not to contain iridium or the selective catalyst or promoter on any impurities which in the reaction medium may provide or produce ionic iodides which may inhibit the reaction, for example, any alkali metal, alkaline earth or any other metal salts. For example: chromium and chromium iron; iron nickel and especially nickel corrosion metals - 00 and or nitrogen ligands or nitrogen-containing compounds phosphines B - phosphines that can It sits in the middle of the reaction.It must be kept in the lowest concentration in the liquid reaction composition, as it will have an opposite effect on the reaction by generating iodine-1 ions in the liquid reaction composition, which in turn have an opposite effect on the reaction rate. It has been found that some minerals 1. 1 - polluted quot; For example, molybdenum is less likely to generate JST. OST minerals, which have an opposite effect on the reaction rate, can be reduced by using suitable materials that resist OST in the composition. likewise; Pollutants such as alkali metal iodides must be preserved. For example, lithium iodide 100106, lithium, in the lowest possible concentration.

VYAY

yy - - corrosive metals and other ionic impurities can be reduced by using a suitable ion exchange resin substrate to treat the reaction composition; Alternatively, a recycled catalyst stream is preferred. Such a process of removing corrosive metal is described in US Patent No. 400971706 ; It is preferable to maintain the ionic pollutants at a concentration in which 9000 ppm of iodide-1 is generated, and it is preferable to maintain the concentration so that less than You generate ppm of iodide-1 in the liquid reaction composition. Suitable alkyl halides have alkyl groups corresponding to the alkyl groups of the reactant alkyl alcohol and preferably have 0 carbon atoms from 1 to 01 atoms. It is more preferable that the number of carbon atoms be from one to 7 atoms. It is still more preferable to have the number of carbon atoms from one atom to 4 atoms in alkyl halides. It is preferable for the alkyl halide to be ke alkyl halide over iodide or bromide, and it is more preferable for it to be iodide. The preferred alkyl halide is methyl fodide Yo. It is preferred that the concentration of the alkyl halide in the composition of the liquid reaction be in the range from 1 to 770, preferably from * to 713 by weight. The reacted carbon monoxide can be basically pure, or it can contain inert impurities such as carbon dioxide; methane; and nitrogen; the noble gases; water and paraffinic hydrocarbons | 0 containing a number of carbon atoms from one to ; atoms

S preferred to keep the presence of hydrogen in carbon monoxide and the hydrogen generated in the reaction medium by the gaseous water displacement reaction at a low level; For example, with a partial pressure of less than 1 bar ; As the presence of hydrogen can cause the formation of hydrogenated products. It is appropriate that the partial pressure of carbon monoxide in the reaction be in the range from 1 to Ve: h. preferably 1 to bar Yo ; It is more preferable for it to be from 1 to 16 utf. It is appropriate that the total pressure of the carbonylation reaction be in the range from 0 to Yoo 8:59, preferably from 01 to 001 charg, and most preferably from 0 to 50 at; It is appropriate that the temperature of the carbonylation reaction be 0 in the range from 100°C to 0107°C; Preferably, it should be within the range of 1001 pm to 17 pm. The carboxylic acid or esters (or both) obtained from the reaction may be used as solvents in that reaction. The process of the present invention may be accomplished in batches or as a continuous method; The continuous method is preferred. (Se) Removal of the SI carboxylic acid or its resulting ester (or both) from the reactor by withdrawing the liquid reaction composition and separating the zl carboxylic acid or the resulting ester (or both) by one or more flash or fractional distillation stages (or both) of other components of the liquid reaction composition Jie iridium catalyst and enhancers cadmium, mercury 0, or zine or gallium or indium or tungsten and auxiliary reinforcement as

eclectic; Alkyl halide, water, and reactants that were not consumed can be recycled back into the reactor to maintain their concentration in the liquid reaction composition.

The resulting carboxylic acid, ester, or both may also be removed as steam from the reactor.

The flash point is defined as the lowest temperature at which a volatile liquid vaporizes

can give a flame). Detailed description:

The invention will now be illustrated by example only with reference to the following examples: reinforcements of cadmium, mercury and zinc.

2 of the No. Vou 1051 dims (3. Then using an autoclave (pressure and heat sterilization device 01 (registered trademark) and a Magnedrive (registered trademark) equipped with a Hastelloy stirrer and 3 carbonylation facilitators for injection Liquid and cooling coils for a series of carbonyl addition batch tests

A gaseous feed is supplied to the aid device from a ballast vessel; The gaseous feed is provided to keep the sterilizer at a constant pressure. The rate of gas taking at a particular point in the experiment was used

vo to calculate the carbonylation rate; as the number of moles of reactant consumed per liter of ungasified cold reactor installation per hour (mol/l/h); At a specific installation of the reactor (where the installation of the reactor is based on the volume that was not supplied with cold gas).

The concentration of methyl acetate was calculated during the course of the reaction starting from the coral composition assuming that 1 mole of methyl acetate is consumed for every mole of monoxide

And 1 - carbon monoxide consumed. No organic components are allowed into the top of the autoclave. The results were recorded at the following calculated concentrations of methyl acetate 777 and Gao 1/ which correspond to ideal concentrations in the liquid reaction composition in the continuous process.

At the calculated 715° concentration of methyl acetate in such a continuous process the concentration of the other components of the same composition for that liquid reaction is: methyl iodide is about from © to 78 and ideally about from © to 776; Water is about + to 78 and acetic acid is balanced.

For each operational experiment, carbonylation is added; The sterilizer has been charged with one of 0 boosters cadmium, mercury or zine; the selective auxiliary reinforcer; And the liquid components of the liquid reaction composition, with the exception of part of the water charge (10 grams), which is the part in which the iridium catalyst was dissolved (see Table No. 1). Washing the sterilizer twice with mitogen nitrogen and once with carbon monoxide (where the device compressed JS gas to about (arg Yo) and then heated by ve electric heating coils to a temperature 9801 m at a pressure of 1 bar) for carbon monoxide A fast and consistent stirring rate (Vere revolutions per minute) was used. Once the temperature has stabilized; An aqueous iridium catalyst was injected as a solution into the autoclave; At the same time ; Sterilizer pressurized to 77 barg by feeding carbon monoxide from the holding vessel; The inlet pressure of carbon monoxide was not measured but was thought to be less than bar VO; The temperature was kept within + 1 °C of the desired reaction temperature (9 Cp) a

The rate of taking gas from the stent vessel during the course of the reaction was measured and used to calculate the rate of carbonylation; After the withdrawal of carbon monoxide from the restraining vessel was interrupted, the sterilizer was isolated from the gaseous feed and cooled to room temperature by means of cooling coils. The sterilizer was opened for ventilation and samples of the liquid and gas reaction composition present in the upper part of the sterilizer were analyzed by gas chromatography. The main product in each batch of the Js SI carbonylation addition experiment according to the present invention was acetic acid. The secondary products are compared in Table (1). Examples 1 to 01 and experiments A to I : 01 The results given in Table No. (7) show that cadmium does not act as a catalyst for carbonylation under reaction conditions (Experiment D).The results in Table (Y) also show that cadmium It enhances the process of adding carbonylation to methanol and iridium dipped (compare examples ©-1 with experiments a-d), the results in Table No. (7) show that the rate of adding ve carbonyl increases The higher the concentration of cadmium, the results in Table No. (Y) show that mercury and zinc are also enhancers of iridium as a catalyst in the process of adding carbonylation to methanol (examples ;-7) But they are not as effective as cadmium Y YAY

The results in Table (Y) also show that cadmium and zinc zine enhance the process of carbonylation of methanol catalyzed by iridium / ruthenium (experiment E compared to examples) 01 3 eA . No evidence of precipitation is observed in Examples 1 to 7 which indicates that cadmium oo, mercury and zine are soluble. Table (1) Sterilizer charges Experiment System Catalyst (molar ratio) Irely agent Selective co-enhancer 0 aqueous | 203(00)12 (g) (g) Experiment A Ir 20 Experiment B Ir | 10 Experiment C 0 YY 1 Ir Experiment D Cd (2) - Cdl, 7 Ex (1) (1:2) 1/00 LY Ex LT Ir/Cd (1:5) ( Y) Example (10:4) (7) 1/00 CTE nT Ir/Hg (1:5) (£) Joe Example LT Ir/Hg (1:5) (o) Example ) 1( (1:5) 1/20 Ba e.g. LY Ir/Zn (1:5) (V) YYAY

- 1 acetic methyl Experiment augmented Amount of water amitate acid 1001086 G3322 9 (g) 4i o Yo YoY YALA - = Experiment A go, YY 0.71 010 YA AS — — Experiment (B) £6, 1,v1 YoY YA, A — - 1 Experiment (C) 81 014 YAA | «TA Cd (2) - Cdl, (2) Experiment 1 89 YoY YAM | oA Cd (2) - Cdl (0 eg a mata YoY YAACIY YY cd 2) - Cdl (Y) eg £1.4Y 0,¢¢ Yo 0A YALA | 1711 og (2) - Cdl (¥) Ex. EY, 7) o, YY 07 a | 0 Hel, (4) Joe £Y,0V | 1.10 Yo A YA AY, 84. Hg(OAC)» (0) Example $Y AE o,Yo Yor YA ACT E49 Zn, (1 ) Ex. EY, 70 1,10 YoY YAAY | ak ZnCl, (V) Ex. Y YAY

And 1 - follow Table (1) Charges of the sterilization device Experiment Catalyst system (ratio | factor Ire, co-enhanced AE) 7 molar) 0 aqueous 2 (g) (g) Experiment — (1:2 Experiment 6 I/Ru 1 and (1:5) Ir/Ru 7 440 Experiment g (5:1) G1 7 0705 g Rez(COYI0) Experiment H (1:2:3) 06 SP Darken and check grams 00 (12) Os Experiment I (1:2:2) I/RwRe - 8 and 117 grams Example I/RwCd (1:2:2) (A) - F Example (4( LE) LIT I/RwCd Example LE) - I/Rw/Cd (V+) Follow Table (1) Sterilizer shipments Follow Table (1) Sterilizer shipments Enhanced Experiment | Amitate quantity Water MEL | Enhanced 1 Methyl Acid | (g) | (g) didd) 1 g 8 (g) Experiment (e) ] ~ Term o, AY Ye NA 1 Experiment (f) l - LY YOY YALA 64 Experiment (5) ] - £1,A0 VY Vet YALA Experiment YA YA,AY - _ (z) Mar 771 Experiment (i) L - YALA 4 14 P Example VOY YALA | 4 cdl, (A) 8 a Example (9) cdl Then EY, VY 8/1 Yo Ny YA,AY (yy 1,74 Voy YANN Yel ZnCl, (V+) Joe YAY )

Cy. Information on rate, stability and by-products (Y) Methyl acetate table | The average is at 76 « 10 | Joliall's iodide Al-Dora pressure at 71 from | and 79 by weight of (ppm) Methyl Concentration | Weight Methyl acetate (z) acetate (mol/l/h) Experiment A 7 | 46 | 7 884 BL

YA \ YA AY | 4,4 77,1 Experiment (b) for | AY | 44 YY, A (z) Experiment No >7 ve B (YY,Y) (2) Experiment vol 11) ve [Avy 1 m YY, 1 Example YY Noy 0.11 | Labach VALS 71 example?

Yoo 174 4.11 VY, 7 Example? M 7 M L OV 4.17 Example ¢ 171 A

YYV ¥.o TY Kh 1 YY, A o Example YY OYA Bella Libr 7 YY A 6 Example YAQ Feb 1 Hm 11 YY,4 Vv Example Y YAY

- “1 Table (¥) continued Information about rate, stability and by-products Appearance of the reaction structure at the end of carbon methane Cycle acid Experiment Propionic dioxide ppm No orange solution 1 At (1) Experiment orange solution o,A AE 01 Experiment B Experiment C Orange solution whitish solution +4 Y,.oo (3) Experiment orange solution 4,3 18 A 1 Example Orange solution Yo, VV, No Y Example Brown-green solution Yoo VV VY Y Example ? Orange solution AA YA, YY Example E Orange solution 4 VAY Xa + Example Brownish orange solution A,0 VV, ¢ 01 V Example Y YAY

VV

Rate, stability and by-product information (Y) Ethyl acetate iodide table 10 (YY cycle) Modified reactor pressure at 716 by 77 by weight of 1 ethyl acetate (part by weight methyl acetate methyl) (ppm) (z) acetate (mol/L/h) million) Experiment They are YY) AQ 1,A 3 Vo 1 Experiment and VY, Eva) YY, o Free for 4 Experiment g IN| ry YY,A L B 7179 Experiment z Kard YAN 17 | Mark £1¢ YY¢ Experiment I 7 Transition 6 0 §AY Example YT,0 0 YAN YY o (A) A 111 19 6 Example (3) Y £1 141 YY) VY, eb YAY YY Ex. Vov [hee] VY YY,4 (Ve) .04 with Y YAY

Table (7) information on the rate, stability and by-products of the methane acid cycle Appearance of the carbon-propionic reaction composition at the end of the experiment ppm carbon dioxide experiment (e) 4” vr VY, Y experimental orange solution (f) 1101 l, 8 orange precipitate in experimental orange solution ( g) 4 1 b orange solution Experiment (h) VE, Vo 4 Experiment (i) YA 1 vo Example Vor VAT A l orange solution + cloudy orange precipitate Example 9 11 q 72 orange solution + Cloudy orange precipitate Example V'Y,4 YY ¢ 01 1,8 a- From the volume of measured gases (carbon monoxide and methane; carbon dioxide 0) and the balance is carbon monoxide .YYAY

Y ¢ —_ — b- no carbonylation occurs - therefore the reactor pressure was not measured at a concentration of 719 by weight of 0 methyl acetate c-- the calculated concentration of methyl acetate [XT methyl acetate] ; 719 and 71 by weight - corresponding water concentrations of 74.7, 79.0 and 4.1, respectively; The amount of methyl iodide 100106° is about ee to 0 and ideally about from © to at « specifies the error rate at + ZY.

,. methyl acetate = MeOAc : 14 to 11 and iridium nicks as enhancers; Examples are gallium gallium

The same method and device were used as reinforcements for cadmium, mercury, and zine. The shipments of the sterilizer are given in Table (©) and are given

,. 04 to 11 results in table (;) for examples from 0

The main product in each batch in the carbonylation experiment according to the present invention was acetic acid.

The results given in table (€) show that both gallium and indium enhance iridium, which catalyzes the process of carbonylation of methanol

,. with experiments A to C) VY; 11 (compare the two examples methanol vo

Lad results in Table No. (4) show that gallium and indium enhance iridium / ruthenium catalysts for the process of adding carbonylation Juss SI to methanol (experiment E compared to the two examples ( VE601

a

Aja - No evidence was observed that precipitation occurred in Examples 11-VY, which indicates that gallium and indium are soluble. Table ) 0 Charges of Sterilizer Experiment Catalyst Agent System 1 Agent 34.0:1:1 Aqueous Co-enhancer (molar ratio) (g) Selective Ru3(CO)12 (g) Experiment A CYT Ie ~ Experiment B 7171 Ir = Experiment C 0 YT - Example YT 1/08 (1:5) (11) = Example $I Win (1:5) (V7) - Experiment (E) | LE) AA wRu(12) BE $Y 110/0 (12:2) | (OF) Joe Example Ee all WRwIn (1:2.2) | (V8) (YAY)

Follow table (¥) Sterilizer shipments Enhanced Experiment Quantity of acetic methyl water (g) Acid iodide (g) (g) Experiment (1) - - ovo Yoox YALA Experiment 0 (b) - - to, YY 0,71 YoYo YA A Experiment (z) - - spray to the other in ex 0 Gals (0 V) Mar 71 2,01 ex ny (VY) What is outside 8 01 AA Experiment (E) ~ - ¢Y o,AY 01 AH Y AA £4 Ex. ARE 0. AA Voy YA AY YYAY

Table No. (;) Information on rate, stability and by-products Experiment (1) 1 Modified reactor pressure at 156 YY and 776 by weight of MEOAC concentration at 715 MEOAC concentration mol/L/h Experiment (1) 111 YY, 5 5 Experiment B 1 YA A) 4,4 YY Experiment AY 4,4 YY A (z) 5 Example VV, ¢€ Yvan 11 A IY Ex 11 7 M 4 P Experiment E for 1 11 4 Ex q,¢ V1, V4,V YY,0 11 Ex 101 7, Ve for 0

Table No. (;) Information on rate, stability and by-products Liquid by-products Gaseous by-products Methanic acid iodide a/dioxide | Form of constituents ethyl (JAY) propionic carbon 1 Reaction at a carbon 3 : : “dl | 7 0 0 0 0 ay - ay part of | part in | oxide GER end A million sata million Experiment (A) 5 y At Y vy 7 1" orange solution Experiment (B) 1 01 Yo No 1 0,A Orange solution Experiment (C) - - - - - -- Orange solution Example 11 pcs VEY Yoo Pad 01 Orange solution Example AVY VY M yor M Yeo L Orange solution Experiment (E A ) 1 TY 7 14 711 FAS Orange Solution Example (\Y) 7V VY,” Yet 10 Orange Solution Example (1) 1 RR 11 74 TAY | Orange Solution with Cloudy Suspension A of Volume The measured gases (carbon monoxide and mechane; carbon dioxide; the balance is carbon monoxide. b- The calculated concentration of methyl acetate 7789; 715 and 776 by weight - the corresponding concentrations of water are M 78.7 710.0 and 1, respectively; the amount of methyl iodide is about * to 78; ideally about 0 to 79; sets the error rate at +701 YYAY

- » 8 No - MeOAc = methyl acetate. Tungsten promoter Using an autoclave (pressure and heat sterilization device of the type Hastelloy B2 (registered brand) of size 01 cm) equipped with a stirrer of the type Dispersimax (registered trademark) and a soft way to inject the liquid and cooling coils ALL from 8100071210 Carbonylation Experiment Run A gaseous feed is supplied to the autoclave from a braking vessel A gaseous feed is supplied to keep the autoclave at constant pressure The gas intake rate at a point in the experiment is used to calculate the carbonylation rate Where the calculation was made as the number of moles of reactant © consumed per liter of the contents of the cold non-gas fueled reactor per hour (mol/l/h) 0 at certain reactor contents (where the reactor contents are calculated les for the cold non-gas volume). The concentration of methyl acetate was calculated during the course of the reaction starting from the basic composition (the starting composition), assuming that 1 mole of methyl acetate is consumed for every mole of carbon monoxide ve consumed.No tolerance occurred for the organic components in The upper device of the autoclave The information was taken at calculated concentrations of methyl acetate at 711 776 and 76 which ideally correspond to the remaining concentration in the liquid reaction composition in the continuous process At the calculated concentration of 711 methyl acetate the concentrations of the components are Other such 0 compositions for the liquid reaction: methyl iodide of about 75 to IA and ideally of about 75 to 776 ; And water is about 1 to ZA and the acetic acid balance is .

V. = a for each batch in the carbonylation experiment; The heating sterilizer was charged as a booster; the selective co-enhancer and the liquid components of the liquid reaction composition with the exception of part of the water charge Vo AY (gram) in which the iridium catalyst has been dissolved (see Table #).

Washing the sterilizer once with nitrogen to a pressure of about 71 58:8 and twice with carbon monoxide to about barg Yo and then heated ¢ with electric heating coils; to a temperature of 01°C under a pressure of barg A for carbon monoxide.

A fast and harmonious rate of flipping (Vou (rpm)) was used; Once the degree is stable

0 heat; The aqueous solution of iridium catalyst was injected into the sterilization device to barg YY by feeding carbon monoxide from the suppression vessel.

The partial pressure of carbon monoxide was calculated and was about bar A when the calculated concentration of methyl acetate was 711 methyl acetate by weight; The temperature was kept within + 1 C from the desired reaction temperature (1 84 C).

The amount of gas taken from the braking vessel was measured during the course of the experiment and that measurement was used to calculate the rate of carbonylation; After interruption, carbon monoxide, carbon 086, was taken from the restraining vessel, the sterilizer was isolated from the gas source, and then cooled; The sterilizer was opened for ventilation and samples of the liquid reaction composition were analyzed by gas chromatography.

The main product in each batch of the carbonylation experiment according to the present invention was acetic acid 26802; The secondary outputs are compared in Table No. (1). YYAY

Tv \ —_ _ Examples Ye to YY and Experiments Z to N: In the examples Vo to VY additional quantities of methyl iodide (© mole equivalent of tungsten) were added to compensate Possible loss of methyl iodide due to carbonylation of tungsten. > Experiment M shows that the simple direct addition of that extra amount of methyl iodide to an unenhanced iridium reaction does not cause a significant increase in the rate of the reaction. The results given in Table No. (1) show that tungsten enhances iridium, which is used as a catalyst in the process of adding carbonyl 00718808 T: “_ to methanol (compare examples VV Ye, experiments J - L). Additional experiments were carried out (experiment N; and examples (YA) using the same sterilization device that has a volume of 00 ml as happened in the case of tungsten. Cd Examples are from YA to Lil Y. Increasing the amount of zinc (zing) as enhancers. Example No. 7 shows the effect of cadmium cadmium as reinforcement

Copy Table No. (9) Sterilizer shipments Experiment Catalyst system Catalyst agent 1013 Enhanced (equivalents) 2120 Iridium trichloride Aqueous iridium (g) 7 roo Ir Experiment Q 0 7 Ir Experiment K 0 Hoey Ir Experiment L — v,00Y Ir Experiment M d tungsten hexacarbonyl IW (1:5) 10 eg d tungsten hexacarbonyl IW (1:5) 11 eg Tungsten hexacarbonyl Hoey IW (1:5) 11 Example 7 17 Ir:Ru (1:2) Experiment n Zinc iodide “00Y YA, Example Zinc iodide 4” 19 Example of zinc iodide 4 01 Example of zinc iodide 71 Example of YAY

Table No. (0) Sterilizer shipments Experiment | Amount of booster | Amitate water Methyl acid quantities (g) Methyl (g) sAY ketesella gid Acetic acid (#2) (#2) (g) Experiment S - VLAY | EA) 84 m Vo oA Experiment K - 7 0 m Vo oA Experiment L - EAE I don't know why experiment M - EA) YY,Y¢ 18 Example YVoA | Ye m a 774 64 makhal 11 | Maala "VY VA 11,40 EAL 14,9 Example Y,vov 01 M 1 78 in Experiment N - Vi, oY 9A 148 EAN Example VA 717 and don't use AAR for example 19 m" m 84 m A Ex EA) £ 9A 01 Mtca Y.,09 AAA Ex VE 71 7 M A 17 A

USA Table No. (1) Information on rate, stability, and by-products Catalyst factor system (rewards) rate at calculated concentrations 76; Ir J 6 Arla 4.¥ Experiment M Ir A £,Y A Example Ir:W (1:5) Yo I want 1.1 £,A Example YY, Y 16 Ir: W (1:5) 101 1,4 1 Example VY, Ir:W (1:5) 117 4,4 0 Experiment n (1:2) 101 1 Ir:Ru 8 Example 0 10 Ir: Zn (1:2) YA 1,0 Example AN VY, A 1 Ir:Zn (1:5) 1 Example Yo (1:10) 1:70 RR B Example Ir:Cd (1 2) YY M 11 M 4.6 Continued Table No. (1) Information on the rate, stability and by-products of the experiment Ethyl iodide | SAN acetate) acid appearance composition (part in (part in propionic reaction per million) per million) (part At the end of the experiment a million) Experiment X RE with orange solution Experiment K 1 VY 9 orange solution Experiment for the Y > Yay orange solution Experiment M Y > Va 001 orange solution Example Y > YY Yo 11 Orange solution + Example Y > Y AA FY A 101 blue solid Orange solution + YYAY

dos

Example Y > yo yo 117 blue solid a Yor too Experiment n

Example YA £1 1 18 solution orange

6 Ve Ee A EA 19 eg x VA Ya 71 Yo eg

2 - - - YY Example

2

a- Specifies the error rate at + ye

The water concentration was 74.7 » CIV, 6.0, respectively, at concentrations of 776 ee 76 acetate.

. methyl acetate 0

The concentration of methyl iodide is about © to ZA and ideally about from © to 1 (eg

In M, methyl iodide is about (A YYAY

Claims (1)

Claims 1 1 - Process for carbonylation of an alkyl alcohol and/or one of its reactive derivatives. Where it involves contact; In a reactor to introduce the ¥ carbonyl group ccarbonylation of said alcohol and/or one of its derivatives reacting with carbon monoxide into a liquid reaction composition comprising: ° (1) iridium catalyst « and (b) an alkyl halide and (=—) 1 at least one specified concentration of water; and (d) a promoter selected from the group consisting of cadmium, mercury, zine, and gallium And indium A 00175 and tungsten Y 1 - a process according to claim No. (1) where the molecular ratio between each booster is 7 and the iridium catalyst of A: (01 AY) © 1 - Process of claim (1); wherein a co-promoter selected from Y ruthenium, osmium, and rhenium is present in the liquid reaction composition 7. 1 ¢ - Process according to Claim (Y) 3 wherein a co-promoter selected from 7 ruthenium, osmium and ahenium is present in the liquid reaction composition 3. 1 © - Process according to of protection number o£) wherein the molecular ratio between each Y co-promoter and iridium catalyst is of .1:01 JY) Y YAY elo is a process according to Claim (1) wherein the liquid reaction composition includes 1-1 with an alkylester concentration of 1 to 95 by weight, and an alkyl ester 1 with a concentration of 1 to 1 with a concentration of alkyl halide to 9670 by weight; to 1 alkyl halide of v by wt. 90 ¢ slo wherein the liquid reaction composition includes oY) process according to Claim -V 1 with a concentration of alkyl ester to 9615 by weight; and on the 1 alkyl ester with a concentration ranging from Y to 1 with a concentration ranging from alkyl halide to 9070 by weight; and an alkyl halide of 1 of Y wt. 0 ¢ A 1 - Process of claim No. (0) wherein the liquid reaction composition includes water Y with a concentration of 1 to 9616 by weight, and an alkyl ester with a concentration of V from 1 to 96750 by weight, and on an alkyl halide with a concentration of 1 to 0 by weight. 1 9 - EAN process for Claim 1 ( » where z the partial pressure of carbon monoxide in the reactor ranges from 1 to 19 bar 1 0 - process loka of claim (1)”; Where the partial pressure of carbon monoxide Y in the reactor ranges from 1 to Ve bar, 11 - A process according to Claim No. (A) where the partial pressure of carbon monoxide in the reactor ranges from 1 to 15 bar. ‎YAY Ars - Vv 1 - Process pursuant to any of the foregoing claims; where the alkyl alcohol is methanol ¢ and the alkyl halide is methyl iodide fie v and the reaction product is acetic acid and/or methyl acetate -acetate ¢ Y YAY