SA96170151B1 - A method for producing acetic acid by carbonyl addition - Google Patents

Abstract

Abstract: - In a method for the production of acetic acid by adding the carbonyl group to methanol or its active derivative or both in the liquid state in the presence of iridium as a catalyst for the addition of carbonyl, and methyl iodide as a catalyst and booster, the beneficial effect of the booster is enhanced by the permanent preservation of the following things in the liquid reaction structure, The weight of water does not exceed 6.5%, the weight of methyl acetate is from 1 to 35%, and the weight of methyl iodide is from 4 to 20%. ,

Description

Y _ _ method for producing acetic acid by carbonyl addition Full description BACKGROUND - The present invention relates to a method for producing acetic acid and in particular; It relates to a method for producing acetic acid by adding a carbonyl group in the presence of iridium as a catalyst and methyl iodide as a catalyst. oo - The processes for the preparation of carboxylic acids by the addition of a carbonyl group catalyzed by iridium are well-known processes and described 'as an example in GB —A - VY 1171 3 US Patent 738502 Lahm-N1-1H-H-H-N-N-N-N-N-N-N-H-N-H-N-N-N-N-N-N-H-N-TVAVAE « EP — TYAN AY -EP —A and EP —A - 0 1 OYYAR EP —A 1. Patents YY YY describe JQQN? suffixed DE-A-YYiVYo. —US « . The patent describes enhancers as in the present invention 0 a method of adding carbonyls to produce carboxylic acids EP —A = DAYAL — or their esters or both in the presence of iridium as a catalyst. The composition of the reaction is characterized by the ratio; and a percentage of the halogen catalyst between zero fluid 791 of water between zero inhibitor and ; and a ratio of the solvent ester and the solvent carboxylic acid between 7 460 and 78; Do not describe 70 and . Enhanced Use EP - Patent 5181484 AD vo A carbonyl addition process for the production of carboxylic acids; BP —A = VIAVAT The patent describes - . For example acetic acid; In the presence of iridium and rhodium compounds

YY

_ + _ - Patent 1717 << EP describes a method for preparing a solution containing iridium catalyst and using it in a carbonylation reaction to prepare 1-lactic acid. - The patent EP A= VEY YE describes a method for carbonylation of methanol, an active derivative thereof, or both in the presence of acetic acid; iridium as a catalyst; methyl iodide, a limited concentration of at least 0 water, methyl acetate, and a booster selected from ruthenium and osmium. Operational trials and continuous trials are described in this patent. The water concentration in the continuous lanl is low, reaching 771.8 by weight. Therefore, there is still a need for an improved iridium-catalyzed carbonyl addition process. GENERAL DESCRIPTION OF THE INVENTION 0 - Accordingly, the lap of the present invention provides a method for acetic acid production comprising (1) continuous feeding of methanol or an active derivative thereof or both and carbon monoxide to a carbonyl group addition reactor which contains a liquid reaction composition Including iridium as a carbonylation catalyst, methyl iodide as a catalyst, a limited concentration of water 3, acetic acid, methyl acetate, and at least one (7) promoter the contact of methanol or its active derivative, or both, with ve carbon monoxide on the liquid reaction composition to produce acetic acid; and (¥) = recovery of acetic acid from the liquid reaction composition. The invention is distinguished by the fact that the following components are kept in the liquid reaction composition continuously through the course of the reaction: (00) - Water with a concentration not exceeding 771.59 by weight. (b) - Methyl acetate with a concentration within the limits of 1 to 775 by weight Te (C)- methyl iodide with a concentration in the range from 4 to 7780 by weight.

- - The present invention solves the technical problem defined above by permanently preserving the liquid reaction composition containing the defined concentrations of water; methyl iodide; and methyl acetate. This provides a number of technical advantages. - Accordingly, in the present invention, the rate of the carbonyl addition reaction increases whenever the water concentration decreases in the liquid reaction composition as long as the water concentration is greater than 75.8 by weight; Mara has the largest reaction rate when the water concentration does not exceed 10 pounds by weight, and then the reaction rate decreases when we approach very low water concentrations. Accordingly, the rate of the carbonyl addition reaction in the process of the present invention will generally be greater than the reaction rate when the water concentration is greater than 77.5 by weight (all other variables are equal; except for the difference in the weight of water which is displaced 0 - by the difference (in The concentration of acetic acid). - Also, it was found that the reinforcing effect of any promoter according to Jal's invention, such as ruthenium, increases whenever the water concentration decreases according to the present invention. The water concentration which gives the maximum limit of the carbonyl addition rate at any known concentration of methyl acetate or dial iodide of the present invention; that concentration of water does not exceed 77.8 by weight Lad- in the process of the present invention when it is operation at a water concentration not exceeding 79.5 of 0 _ weight; This makes it easier to recover the acetic acid from the reaction composition that is withdrawn from the carbonyl addition reactor, because the amount of water that must be separated from the acetic acid is reduced. Where YU

Ceo Separation of water from acetic acid is a very energy-intensive part of the recovery process (it consumes a lot of energy) and reducing the concentration of water causes a reduction in manufacturing difficulty, costs or costs. Both Increasing the rate of carbonyl addition at a lower water concentration in the present invention - can allow operation at a lower concentration of iridium catalyst while maintaining a product yield rate of 0 . Propionic acid Jie secondary Water can be formed in the reaction medium in the liquid reaction composition; as an example; By a reaction - Lad esterification (ester formation) takes place between the reactant methanol and the resulting acetic acid. Small amounts of water can be hydrogenated by methanol to produce methane and water. can enter the water. From the other components of the liquid reaction composition Sadie to the carbonyl addition reactor with OR 0 can separate water from the other components of the liquid reaction composition withdrawn from the reactor and can be recycled in controlled quantities to maintain the required concentration of water in the liquid reaction composition. The concentration of water in the liquid reaction composition shall not be greater than 77.5 by weight, where it is; Less than or equal to 776.59 of the weight, preferably not greater than 77 of the weight. Preferably focus. of at least 71 g of weight; and more preferably Te) ve water in the process of the present invention; Suitable reactive derivatives include methyl acetate, di-methyl ether, and methyl iodide. A mixture of methanol and its active derivatives can be used as reactants in . The process of the present invention. It is preferable to use methanol or methyl acetate, or both, as reactants. At least part of the methylol or its reactively active derivative, or both, will be converted to methyl acetate, and therefore it will be present as methyl acetate in the liquid reaction composition, and this transformation will be a result of the reaction with The resulting acetic acid or solvent. In the process of the present invention preferred

That the concentration of methyl acetate in the liquid reaction composition be within the range of 1 to 770 by weight; The most preferred would be from © to 775 by weight. It has been found that the higher the concentration of methyl acetate. The rate of the carbonyl addition reaction increases and the selectivity of the by-products, Je propionic acid and carbon dioxide, decreases. However, as the concentration of methyl acetate increases, 0 increases the amount that must be recycled to the carbonylation reactor in the acetic acid recovery stage. Lad, the excessive concentration of methyl acetate can adversely affect the phase separation of the aqueous phase from the methyl iodide phase during the acetic acid recovery phase. Also, the excessive concentration of methyl acetate can negatively affect the rate of the carbonylation reaction by reducing the partial pressure of carbon monoxide to a defined total pressure in the 0 carbonylation reactor. - in the process of the present invention; It is preferable that the concentration of Saad catalyst, methyl iodide, in the composition of the liquid reaction be in the range from © to 717 by weight. The higher the concentration of the catalyst rising upward is methyl iodide; This reduces the production of by-products, Jue: peronionic acid, carbon dioxide, and methane. An increase in the rate of carbonyl addition occurs by increasing the concentration of 1-methyl iodide, where that increase is greater in the case of lower water concentrations than in the case of a higher water concentration. also ; The higher the concentration of methyl iodide, this can cause a negative decrease in the partial pressure of carbon monoxide at a certain total pressure in the carbonyl addition reactor. - in the process of the present invention; Preferably, the iridium carbonyl addition catalyst should be present in the liquid reaction composition at a concentration in the range from 50660 to 95086 ppm measured ys as iridium; It is more desirable that the concentration be in the range of 70001 to Tove ppm measured as iridium. In the process of the present invention; The rate of carbonyl addition reaction increases with increasing iridium concentration.

Dr" -

Any soluble iridium-containing compound in the liquid reaction composition could include iridium catalyst in the liquid reaction composition? The iridium catalyst may be added to the liquid reaction formulation for a reaction in the liquid reaction formulation or convertible to a soluble form. Examples of suitable iridium-containing compounds that may be added include:

to the composition of the liquid reaction. iridium chloride TrCLs iridium iodide A:1 and iridium bromide Ir

+ an iridium dicarbonate iodo dimer (0 117 sense [Ir (COR) chlorodicarbonyl iridium [Ir (CO) CL 2 (D) and a bromodicarbonyl iridium dimer [Ir (CO) Br] ; a binary ion iridium dicarbonyl iodo0 [Ir (COR To] irr), iridium dicarbonyl dicarbonyl ion [Ir (CO) BIH (I), iridium dicarbonyl iodo 0 HT (I)

[Ir (CO) Ba (00)2 1711 (II) triiodomethyl iridium carbonyl JB and [1(060(1] 0] ion and X [Ir (CA) Ty (CON HY) ion Dicarbonyl triiodomethyl iridium; Aqueous iridium chloride 311:0 .12015; Irg bromide (CON) tetra-iridium carbonyl; Metal 1:8 (CON) and tetra-iridium dicarbonyl Bra. 311:0 hydrated iridium and iridium oxide 10:11 and dicarbonyl acetoacetyl 1505 (I) iridium and iridium oxide

vo iridium Ir (aCaC) (CO) and triacetoacetyl iridium “Ir (aCaC)s and iridium acetate and acetate (trihydrate hexaacetate iridium trioxide) [no] [remote IrO (OAC) ] For hexachloroiridic acid [Hy Ir CL] it is preferable to use iridium complexes that do not contain chloride such as acetate and oxalate; and acetoacetate, which are soluble

in one or more components of a carbonylation reaction such as water, alcohol, or acid (ind).

0 or all of the above. It is especially preferred to use green iridium acetate, which can be used in

acetic acid or an aqueous solution of acetic acid. YY

M - In the process of the present invention at least one promoter is present in the reaction structure. It is preferable to select suitable enhancers from the group consisting of ruthenium; osmium; rhenium and cadmium; And Zabak 0 and Al-Zarqin; gallium; and indium, and testosterone, and the most favored selection of ruthenium; osmium; The most preferred would be ruthenium. 0 Preferably the presence of the promoter in an amount significant up to the solubility limit in the liquid reaction composition or in any liquid process streams recycled to the carbonylation reactor from the acetic acid recovery stage or both. It is appropriate for the promoter to be present in the liquid reaction composition with a molar ratio of the promoter to iridium (from 1.5 to (Vo). As indicated, ruthenium is the largest possible at the water concentration which gives the greatest rate of carbonyl addition at any given concentration of methyl acetate and iodide To 500 860 ppm 4010 Methyl The suitable concentration of the booster is from 0 The booster can include any suitable compound that contains the metal of the promoter and is soluble in - the liquid reaction composition The booster may be added to the liquid reaction composition For the carbonyl addition reaction in any suitable form that is soluble in the liquid reaction composition or convertible to the soluble form Examples of suitable ruthenium-containing compounds that can be used as booster sources include ruthenium chloride! 00 hydrate, ruthenium metal, ruthenium oxides, TIT, ruthenium bromide IV, ruthenium chloride, [Ru[or(0)H™ (I), ruthenium triiodide ion TL, formate Ruthenium and quaternary diiodo [Ru (COR 15 [ » (ID) and ruthenium diiodo dicarbonyl polymer

Ru J; (I) Ruthenium triiodo dimer [Ru (COL) (I) ruthenium carbonyl, ruthenium acetate (111), propionate (LI), tetra(aceto)chlororuthenium (CO) 17 Ye, pentacarbonyl ruthenium; Ruthenium Manne TIT Ruthenium Butyrate TIT Ruthenium Dimer Dichlorotricarbonyl Jie Tenth Carbonyl Halo Carbonyl Mixed Ruthenium

YT)

EP

Ruthenium-1 dibromotricarbonyl dimer ruthenium-1 and other organic ruthenium complexes such as tetrachlorodi(;-cymene) diruthenium-1 and dichloro(IIdiene) ruthenium-1 polymer and tri(acetylacetone) ruthenium- 51 Examples of suitable osmium-containing compounds that can be used as reinforcement sources include osmium chloride IT, anhydrous and anhydrous; osmium metal 0, osmium tetroxide and osmium tricarbonyl 0; and osmium diiodo4[05D] [(CON), osmium triiodotricarbonyl dimer (COX Bh 05], osmium triiodotricarbonyl ion (CO) TB) THT (ID) 05], osmium pentachloroUs GHB; osmium halocarbonyls Mixed compounds such as Fld tricarbonyl dimer Chloroosmium I. and other organic osmium complexes 0 - Examples of suitable rhenium-containing compounds that can be used as reinforcement sources include decacarbonyl dirhenium (00) Rey and chloropentacarbonyl rhenium Re (CO)s CL, bromopentacarbonyl rhenium Re (CO)s Br, iodo pentacarbonyl rhenium (1) -1 (CO)s, []rhenium chloride aqueous 11:0 ReCLy. a tetraiodo dimer (TH 0) and a diiodo tetracarbonylalenium ion [Re (CON Th (D) rhenium carbonyl 1 ). And rhenium chloride? Aqueous [Re(CO) I] - Examples of cadmium-containing compounds that can be used include cd cadmium diacetate (OAC), cadmium iodide cd LIT, cadmium bromide cd Bry (IT) and cadmium chloride ,. Cadmium acetytones cd (OH), (ID) and cadmium hydroxide ed CL, (ID) are oy. Examples of suitable mercury-containing compounds that may be used include -

Hg, mercury bromide HL (ID) and mercury iodide Hg (OAc) as sources of mercury diacetate enhancer. Hg CL, (I), mercuric chloride 118 Ih gp, mercuric iodide HgCLy (ID), mercury chloride ( Examples of suitable zinc-containing compounds that can be used as reinforcer sources include zinc diacetate (©20)04 (©20)04, zinc hydroxide 11, iodide 5 (2001:11) and zinc bomide [1]: 2003 Zinc Chloride 11 200012 and Acetyl.Zin acetones Examples of suitable gallium-containing compounds that can be used as reinforcer sources include acetyl gallium acetone; gallium acetate; Gallium iodide 111, Gallium chloride 08201.11, Gallium hydroxide TT Gallium 0 Examples of suitable indium-containing compounds that can be used as booster sources include indium acetone (indium acetate; indium chloride [11] and bromide)

In Indium iodide (1) [10], indium III hydroxide, and indium III iodide indium . 1 The examples include suitable tungsten-containing compounds that can be used - chloride WCly 17 and chloride of tungsten W(C)g as sources of the tungsten hexa-enhancer three Ji sis 171:11 and iodide of tungsten 171 5: (V) Tungsten Lubomide WCLg 16 Tungsten. Chloro, Bormo, or Iodocarbonyl Tungsten Compound Co Hyp 177 Tungsten Carbonyl and (©) Iridium-containing compounds and promoter-containing compounds are preferably free from - Impurities that provide or generate ionic iodides in the reaction medium where they can For those iodides that inhibit oy. . interaction; as an example; Alkali metals, alkaline earth metals, or salts of other metals

- 11 -

- Ionic pollutants such as; As an example (a) - corrosion metals; especially nickel; iron; chrome; and (b) phosphines or nitrogen-containing compounds or ligands that can sit in the reaction medium; All these pollutants must be kept as little as possible in the liquid reaction composition, as these compounds have a negative effect on the reaction by generating 1 iodine ions in the liquid reaction composition, which have a negative effect on the reaction rate. It has been found that some corrosion metal pollutants ia, such as molybdenum, are less likely to generate 1 corrosive metals that have a negative effect on the reaction rate can be reduced by using an appropriate composition of anti-corrosion materials. Likewise contaminants such as alkali metal iodides must be conserved; For example, lithium iodide 0 at the lowest possible level. Corrosion metals and other ionic impurities may be reduced by the use of a substrate of 0 ion exchange resin for the reaction synthesis coefficient; Or it is preferable to treat the recycled catalyst stream. Such a process is described in US Patent No. 400971946-US. It is preferable to keep ionic impurities at a concentration at which 50,000 ppm 1 is produced.

Below the concentration at which J of You is produced is 1 ppm in the liquid reaction composition. - The reacted carbon monoxide can be basically pure or it can contain inert impurities 1 _ such as carbon dioxide and methane; nitrogen; the noble gases; and water; and ddl hydrocarbons containing a number of carbon atoms from one to ; atoms It is preferable to keep the hydrogen level in the carbon monoxide feed and that hydrogen generated in the reaction medium by gaseous water displacement reaction at a low level as the presence of hydrogen can cause the formation of hydrogenated products and so; Preferably the amount of hydrogen in the reacted carbon monoxide is less than 1 mol 7 ; It is more preferable to be less than 85 mol 7 and it is still more preferable that the quantity J be of 01.7 mol 7 or it is preferable that the partial pressure of hydrogen in the carbonyl addition reactor be less than 1 bar and the most preferable to be 1 # Bar and still

- 11 -

It is preferable for the pressure to be less than 1.7 bar or both. It is appropriate to have pressure

Partial carbon monoxide in a reactor is in the range of 1 to Ve bar; Preferably from 1

to ©bar; It is more preferable for it to be from 1 to 15 bars.

- It is appropriate that the total pressure of the carbonyl addition reaction be in the range of 01 to Yoo 0 towers; It is preferable that it be from 15 to 001 constellations, and the most preferable is that it be from 11 to 000 constellations.

It is appropriate that the temperature of the carbonyl addition reaction be within appropriate limits

The temperature of the carbonyl addition reaction is in the range from 100 to 7080 °C; Preferably in

Limits 151 to AY . a

It is preferable to implement the process of the present invention as a continuous process.

0 - The acetic acid produced from the liquid reaction synthesis may be recovered by drawing vapor, liquid, or both from the carbonylation reactor and recovering the acetic acid from the calculating material. It is preferable to recover the acetic acid from the liquid reaction synthesis by continuously withdrawing the liquid reaction composition from the carbonylation reactor and recovering acetic acid from the reaction composition by one or more methods, either by the flash or by the fractional distillation stages, or both, whereby the

vo acetic acid from other components of the liquid reaction synthesis such as the iridium catalyst; dale catalysis methyl iodide; and enhanced methyl acetate; Unreacted methanol, water and solvent acetic acid, as these components can be recycled to the reactor to maintain their concentrations in the liquid reaction composition (where the flash point is defined as the lowest temperature at which the volatile liquid is given the lowest vapor percentage sufficient to ignite a flame). to maintain factor stability

Ys iridium catalysis during the resulting acetic acid recovery phase ¢ should retain the water in

Yi

Incorporating process streams containing iridium carbonyl addition catalyst for recycling in Jeli carbonyl addition should be kept at a concentration of at least 70.5 by weight. - The reaction composition of the preferred liquid especially includes about 75 by weight water; and about 797 by weight of methyl iodide as a catalyst; and about 719 by weight methyl acetate; 0 iridium catalyst with a concentration in the range of 500 to 70006 ppm measured as iridium to give a rate of carbonyl reaction in the range from 01 to 400 mol/l/h at a carbonyl reaction temperature of about VAS m. and pressure for the carbonyl addition reaction of 11 to Te tower and partial pressure of carbon monoxide from ; to 1 bar and the concentration of enhanced ruthenium is in the range from 500 to hen ppm measured as ruthenium to give a molar ratio of ruthenium to iridium of about 0.7:1 and the equilibrium in the reaction composition actually includes acetic acid. Higher or lower catalyst concentrations, higher or lower temperatures, or higher or lower partial pressures of carbon monoxide can be used to obtain higher or lower reaction rates. A brief explanation of the drawings - and the invention will now be explained by examples only and by reference to the following examples and drawings vo where figures from 1 to 1 represent the effect of water concentration on the rate of carbonyl addition in experiments that are in the form of batches in the sterilizer. Figure 1 shows schematically the apparatus used to illustrate the process of the present invention in a continuous process. Bray Figure A. The effect of water concentration on the rate of carbonyl addition in a continuous reactor. Detailed Description Y. - The following batch experiments were carried out to illustrate the present invention and then the reaction components were charged to a pressure and heat sterilizer with an amount of carbonyl additive reactant (acetate)

- 1 p

methyl) which was consumed during the course of the reaction. In batch carbonylation experiments, water is reduced during the progression of the reaction, where carbonyl addition to methyl acetate and water consumption are corresponding.

to add carbonyl to methanol. - by monitoring the rate of the carbonyl addition reaction and calculating the concentration of the reaction components during the experiment; 0. It is possible to determine the rate of the carbonylation reaction that would be expected if the carbonylation process was run in a continuous manner while the liquid reaction composition was maintained under steady state which is the same as the overall reaction composition calculated at any given point in the batch experiment. Reaction composition" in batch experiments to the total composition of the components in a cold-state autoclave that is not exposed to gas. in continuous experiments down; The composition of the reaction 0 liquid was analyzed. The main avenue between batch experimentation and a continuous process is that in batch experimentation; No allowance was made in calculating component concentrations for dividing the reaction components between the liquid and gaseous states because of that division; The concentration of reaction components present in the liquid state in the batch reaction under reaction conditions was similar but not identical; to concentrate the total reaction components. Especially the more volatile components in the reaction composition, such as methyl iodide and methyl acetate; ve is slightly lower in concentration in the liquid reaction composition; Lee is present in the overall reaction composition; Where the water concentration was compared between the two. And on that; The rate calculated in the batch experiment at a given JS concentration for the reaction will be similar to the composition in the continuous process running with a liquid composition identical to the composition of the total batch Jeli. in addition to ; Trends observed in batch experiments were compared by changing process variables; such as water concentration; With the © directions observed in continuous experiments, then carry out all carbonyl addition experiments (batch experiments) using an autoclave Jolie of zirconium with a capacity of 060 ml and equipped with a Dispersimax (registered trademark) stirrer and a soft pass For injection of liquid catalyst agent yy

And 1 - and cooling coils. then supply a gas source to the brazier from a braking vessel; Gas feeding is provided to keep the roaster at a constant pressure level. Then using the rate of taking gas at a specific point in the reaction process to calculate the carbonyl addition rate as the number of moles of reactant consumed per liter of cold reactor composition that is not exposed to gas per hour (mol/l/h) at a specific reactor composition (0 builds) Determine the total composition of the reactor On the cold volume not exposed to gas).

- The concentration of methyl acetate during the course of the reaction was calculated from the starting composition; Assuming that every mole of methyl acetate is consumed for every mole of carbon dioxide consumed. No components are allowed

Membership in the upper part of the body. - for each carbonyl addition batch experiment; The catalyst (0-hexachloroiridic acid) was dissolved in part of the liquid charge acetic acid/water of the lye and then charged to the liquid injection tract. if a booster is used; It was placed in the coal with part 01 (gram) of the charge of acetic acid. After that test the acid by nitrogen; Then breathe through the gas sampling system and wash with carbon monoxide a number of times (© times at a pressure of * to 01 bar). Then, the remaining liquid components to form the liquid reaction were charged to the acid through the liquid addition hole. The pulverizer was then compressed with carbon monoxide (ideally 7 towers) and heated with stirring (100 rpm) to a reaction temperature of 090 °C. The total pressure was then patched to about * tower under the desired operating pressure by feeding carbon monoxide from the braking vessel once the temperature had stabilized (about 11 minutes) injecting the catalyst using excess pressure of carbon monoxide between quoting the iridium concentrations in those batch experiments On the effectiveness of the introduction of Jalal catalyst 7957 and then Lia v. the reactor pressure at a constant value (+ 1.6 tower) by gaseous feeding from the braking vessel during the experiment. Then measure the gas intake from the ballast vessel using a data log facility during the course of the experiment. Then the reaction temperature was maintained at + 1 °C above the temperature

1 - The desired heating tender connected to a control system of the type Eurotherm (registered trademark). In addition, the excess reaction temperature was removed by cooling coils. Each trial was continued until gas intake was interrupted. After that, the braking vessel was isolated and the reactor was cooled abruptly by the use of cooling coils.

0 - Hexachloroacetic acid, Hy IrCLe (777:7 w/w idium aqueous solution) was supplied by Johnson Matthey. Acetic acid was obtained from the carbonylation of a mixed feed stock of methanol/methyl acetate that contained very small amounts of propionic acid and its subcompounds (compounds that yield probiotic acid by certain reactions). Methyl acetate (1 4,144?) and water (?- 00 (FY,) were supplied.

0 and methyl iodide (—Y) 85-]) by 5M and diiodotetracarbonyl ruthenium [1 [Ru (CO)Lo] was synthesized from diiodotetracarbonyl ruthenium (STREM) RU; (CO); and iodine (Aldrich 77,365 —A) weighed under carbon monoxide in a Schlemk tube freezer before use. Examples 1 to 11 show the effect of water concentration, which is expressed as 78 by weight. on rate

1 Carbonyl addition reaction using iridium as a catalyst and reinforcing it with ruthenium (the molar ratio of rhenium: iridium is about ?: 1) at 198 m and a total pressure of YA tower. bel Charge composition in Table 1 and rate data are given for the following calculated concentrations of methyl acetate in the total reaction composition (as expressed by the top of the cold, gasless liquid) dogo ce 770 7758 AY by weight in Table number SY

0 Calculating the rate of carbonyl addition at different concentrations of methyl acetate and water, and the data were separated according to the present invention (the water concentration does not exceed 77.0 of the total weight of the reaction composition; the cold liquid that does not contain gas) from the comparison data by a thick solid black line in schedule;

_ Bah _ it is clear from the data that the continuous carbonyl addition process can be operated under steady state conditions with the composition of the liquid reaction as in the composition of the total reaction calculated in the batch experiments in coal with obtaining a rate similar to the addition of carbonyl. Table 1 © Charge compositions for ruthenium-enhanced reactions in zirconium batches of 000 mL example.> Reference 1 Methyl acetate | acetic acid | Methyl iodide 1 g water | hexachloro | tetraiodo diiodo gram gram gram areric acid carbonyl ruthenium (g) gram B Te, Y £0.710 nit EY YAY MR oY At Ta, change to 0/7 GREY [vey |W love YF,Aan OA, + A a EY Ye, av 6; 1Palak Lakr ATA Lamka Vey GUEY van TY, ee [YY oo Lamthalunla lie Ma tee] n but 71 nit yE GREY 1 adma no 17 I adjure you to tyn A EY 1 ‎Tae) yo A yakhi 3 ‎EN yy, ve 1 1 4 cups 1 qt | .4,0 | yen leo yi

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VEY | Cut | v, an bards |, Seay [eA] 0 ra 0 EY 1.40 cr Tv, Teo VY 10) 11 164 LEY | Blind investigation wan L.L. [Ted | VY

V,67V LEY (68 00,0) TY TEA} 01 vio. LTE) YAY | 4 pm | with Tet |e] 6k ¥,10. Lge Lav Tare Rakha eet [a | 5 view. CATA supplies an inventory ed,A0 04,4A | FY | 1a- The weight is expressed as pure hexachloroiridic acid.

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71. - —- Cost of Table No. Y Example Reference Water 7 Rate/mole JAAN Rate/mole w/w L/hr 77.5 w/w L/hr/Methyl acetate Methyl acetate 1 (vr) 1 4 1 (TTY 5,1 ed m 018 (Te Y)Y a no YY Y,. q,v \,Y (1 ,5 1074 = all reactions are at pressure Total YA tower and temperature 0: with de yu for stirrer YOu rpm - at a calculated concentration of methyl acetate 776 the composition was calculated as follows / about 7854 0-methyl iodide and 8001 ppm iridium and 0050 ppm ruthenium.- At a calculated concentration of dial acetate 776, the composition was calculated as follows: 78.0 methyl iodide; Calculated concentration of methyl acetate 715 Composition OSs were calculated to be approximately 7030 methyl iodide 0 - Between the calculation of methyl iodide concentration based on the approximation that for each mole of iridium consumed; a mole of methyl iodide at most to give Ir (CON I] Y.A

- Synthesis of iridium on the basis that the efficiency of the input catalyst is 97. Figures (Vo) show some of the lly of Table No. Y in curved form and show the effect of water concentration on the rate at 7700 and 7169 w/w methyl acetate, respectively, for the iridium/ruthenium catalyzed carbonylation process to methanol. 0 - Figure shows a number? information from table no. at different concentrations of methyl acetate 0,5; Ne 01 » 5 of the weight. Additional experiments were carried out without the enhanced ruthenium. Experiments a to z show the effect of water concentration (expressed as 75% of the total weight of the reaction composition of the cold liquid that was not exposed to gas); On the rate of carbonyl addition reaction using only 0 iridium catalyst without enhanced ruthenium at 098 m and total pressure YA tower. The charge composition is given in Table 7. Information for the rate is given at calculated concentrations of methyl acetate AR’ / 01 + / 1001 + 1 0.0. 7 2 7" 0 'm ¢ by weight (expressed as m by the total weight of the cold liquid reaction composition that was not exposed to gas) in the table;

YY — _ table number ? Charge composition of reactions in zirconium batch chambers of 01 mL capacity. Experiment | Ref | Methyl acetate 1 acetic acid | Methyl iodide | water | Hexachloro (g) (g) (g) (g) Uridic Acid (g) A 17 A / 6 | Hat B 1.4 04,44 Yo) VY,AY oo, YY ki 1 86 Tee) 153 z takha VE Tae Y lov 5 a 1 each for GVEY ha amoh 04, 44 4 YY,4Y ra VED and “1 Ba 151 VE 11,4 VY, TY) 3 4 7114 7, 1 McKay z 7 M1 1714, 7 edited by REL 4 46 YBY 5.0 (Ee 3,0) \Y,4V Y | 9 Tae) mi hand CE q,0Y TY “47 8 4 7 A 7 J 4 ye 0/4 4 tqla a- The total weight was expressed as pure hexachloroiridic acid.

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J

3 < — — . a NY WY 4 wT] d- =

J 1 =~ 2X 1 2lzxaxd 232 Z. = 22813125528388 3 3 p you are for Ze LL Sunni ara dah nick aab b 2° ~ I ~~ v t rsi f3 3 5 : 3 2 Add this oe lm amd cm ss name > x TY 7 << < ad a ak a ww la 4 2 a 4 od = - MN ty 4 3 : . A for =~ A wT > = ow > a ~ > a ~ a - 3 _— “3 - ws > 4 - a « — a bad > bod ro 3 9 3 > 22 x a > together ah ho S3 »

J 3 3 ] 75 — 3 3 and 2 3

Pa 3 J < ~ - * a w pa li Lal La a Lal Via > x hat a > > maha mama ww» lo cw 0 . . “A, ~ 3 9 3 1 3 0 - — 71 = . 0 1 5 3 3 I 3 0 ~ > - cor we a to the > 1 > Q Sw Q > > > > > 9 ~ ben »A 3, J > LA ee Sr . 33 2. J 4 d º nN hae | - - 5 and << H 3 3 3 3 Se <> Ld | << Bah Jah M Dah had 3, + 3 Am Najat oo Voy ْ و ْ و SS 3 ~ 3

J x = — >

F745 9 _ > 3 3 . aw < - . < < o. ~~ 3 3 Sr l n ww Ba J - 0 | for 3 J < ZZ return Sa em. T - 0D 4 = 2 3 3 2 he - a a . 0 0 0 0 su | . > 3 jos > Sue - . > > > > Mia Neb

A ~~ 3 3 0 — 33 o L 3 = 2 Tr ~ WA > and Q > a. ao a 7 << mia 7 ~~ 3 in 1 b > L.M. 3, 3 : a shar amser al-li — — 3 3 : : 2 3 1 2 - 13 3 > 1 2 esds ae a 0 ~ ~ ~ - . - - oy Q 3 3 0 x . - - 1 8 3 — 1 + 6 = - 4 4 3 rr rr rah say it next to it 2 a l d 324 3 3 3 : h < > > to ao a 0 neighborhood a s + 2 J

Y $ — -_ cost table number; Experiment Reference Water / rate / mole of water / rate / mole weight / weight. Liters/hour 7217.6 | w/w l/h/methyl acetate methyl acetate qv 1, Ye (iv) 7 b( 0') 8,1 ¢,° 0,lb v,4 c41 Y,1 ,1 7 1 8 0 1.4 Y, V (lov). The composition is as follows/about AE iridium VAs die 0 ppm - At a calculated concentration of methyl acetate 0 70 the composition was calculated as follows: 77560 methyl iodide; At a calculated concentration of methyl acetate 719, the composition was calculated and it was about 70731 methyl iodide.

Yo — - - methyl iodide concentration was calculated based on the approximation that each mole of iridium is consumed; moles of methyl iodide at most to give iridium tetraiodo dicarbonyl ion [Ir (CO), Li} (IID). - The concentration of iridium on the basis that the efficiency of the catalyst for the introduction of the catalyst is 7/97. 0 - shows the combinations of the table data; For iridium only with table data? for iridium/ruthenium in the form of a curve in Figs. 4; © . - Anak comparison of the reinforcing effect of ruthenium; at 7700 w/w methyl acetate at different water concentrations in Table © below (comparing experiments ST RR iMK with awning Ct 7 No 3 11 1). Table 1 * Water concentration 7 Carbonyl addition rate mol/l/h Reinforcement rate of Ara or Lio yoy Ja YY,Y 14 04 IVA vY,¢ YAY AY YY 8.1 m LAY VA Vv, YY, 2 0 and ara /Yo 1,1 11 YY

It can be seen from Tables oF 4; 0 and Figures 1 through © that when the water concentration was reduced from greater than 77.5 wt.; carbonyl addition rate increased; passing through a great degree; Then it decreased when very low water levels 0 were approached for both catalyzed systems, one with iridium and the other catalyzed with iridium/ruthenium. It is clear, Lad, that ruthenium becomes more effective as a booster as the water concentration decreases, and the effect of ruthenium reaches its maximum degree. Concerning reinforcement when the maximum rates are observed at a water concentration of not more than 776.9 by weight. at lower water levels; At 776 methyl acetate the rate decreases and the reinforcing effect of ruthenium decreases. - Figure © and Table + at the bottom (comparing experiments A; Ba Da Ha with OY) 0 © 7) show the same point, but at a lower concentration of methyl acetate 711 by weight. Table 6 Water concentration/carbonyl addition rate mol/l/h enhancement rate w/w 0 ruthenium/iridium catalyst | Iridium catalyst only and ruthenium promoter Ra Labla Lg 01 LAN YX 17 Yoo oY) AREA Yo,0 VY,Y £,0 ml YA 1 11 YI

-vy-

Shows the figure? That the lower the concentration of methyl acetate in the process of the present invention from 710 through

And up to 75% of the calculated weight of the methyl acetate concentration in the total reaction composition, the concentration

ideal for waterproof; Regarding the rate; moves to a lower concentration.

It is also clear from the two tables »; that at 75% by weight calculated for the concentration of 0-methyl acetate in the total composition of the reaction and a relatively low water concentration 77% by weight (see example “)

A relatively high carbonyl addition rate of 11.7 mol/L/hour was observed compared to experiment (D).

booster; Which gave a rate of 5.4 mol/L/h, which means that the ruthenium reinforcement is below that

conditions was significant (71197 enhancement rate) even at a concentration of 77 by weight of water. similar to that;

At 77.7 by weight water and 1071 by weight methyl acetate, a relatively high rate of 715.7 mol/hr (Fe) was observed.

- Experiments were carried out for other batches from 1 to 11, and the charge compositions are not shown in Tables 1.

The results of experiment l are shown in the table; ; And the results of Example 1 in the table? ; and example results from VE

to 11 in the CV table

o - p 0 via = = = ~- ,3 = pn = a + . ZZ 2 4 3 3 — h ~~ ~ ~~ 3 — - 1 ho ~ - _ s rr ~ > — 3 3 3 - - - b his Q < 7 3 b 3 : 3 > - a4 Lf S| 5 T 3 l 3 + 204 O Jh pi 3 3 ~~ 3 3 03 4 Q ¥ 1 and He 2 — C 2 > 2 — <Low 3 3 2 nb > B Rma > a ,= 30 7 a and 1 < > > 3 3 ,4” x > 4 3 3 2 1 713 3 e 3 3 and 0 : d hat < > a - : a 3 i a 3 3 in — ~~ 3 3 > J = .oo i 3 = \ a 2 < 3 T a > 3+ 3 3 ~~ — > — 3 J 4 3 3 a — 7 3 3 4 J bd 0 . tmr + + |5 : 403 yt Aly sr J = 2a| 34 1 l + 3 3 y 3 . + > 3 3 9 a - = x 0 a and ~ + k 3 4 .34 in a ~ 5 3 3 31 > a — 3 3 ~~ = a 9 3 k 4 t 2 4 b km : 1 yi

Y q — _ - all reactions take place at a total pressure (TA) tower of 5 40 aa) with a stirrer speed of 150,800 rpm. - At a calculated concentration of methyl acetate 8177, the composition was calculated as 7/854 methyl iodide; And 8060 ppm iridium and 9080 ppm ruthenium, and at a calculated concentration of methyl acetate 715, the concentration was calculated to be about 78.0 methyl iodide 1706 ppm

Million iridium EAT ppm ruthenium. - The concentration of methyl iodide was calculated on the approximate basis that each mole of iridium can be consumed; moles of methyl iodide at most to give iridium tetraiodo dicarbonyl ion [Tr (CO), Li] - .

,. 797 The concentration of iridium is based on the introduction efficiency of the catalyst - 0 The experiment shows the effect of increasing the catalyst methyl iodide on the reaction catalyzed with iridium - only without a booster; By comparison with experiment h in Table 4; It can be noted that . Increasing methyl iodide has a beneficial effect on the reaction rate, especially at a low concentration of water. The effect of increasing the concentration of the co-catalyst is methyl iodide by about Y (Table 1 shows the example -

10 28 wt to IVY wt on the iridium-catalyzed ruthenium-reinforced process in comparison with Example No. 7. It is clear Lad in comparison with experiment L that at a low water concentration; The reinforcing effect of ruthenium increased when the concentration of methyl iodide was raised from 8 to 717 by weight (compare experiment H with Example 7); As shown in Table No. below. The effect of 70 methyl acetate on a curved shape is shown in Figure 6.

- A. Table No. A: concentration of iodide, catalyst, rate of reinforcement reaction. Methyl (7 mol/L/h) | In ruthenium Experiment (mol/l/h) m weight) A 7 iridium YA yo,v and ruthenium VY VY iridium YE, 1l and ruthenium CD Comparison between experiment z and experiment J ( No 7" increase in the reaction rate when the concentration of methyl iodide is increased from + to 777) and a comparison of Example 7 with Example 710A (VT) increase in the rate of the reaction when the concentration is increased from 8 to 707 methyl iodide) that under those conditions; was a factor Iridium 0 catalysis enhanced with ruthenium is more sensitive to the concentration of methyl iodide than the unreinforced catalyst. - Examples from VE to 11 show the effect of water concentration at different concentrations of methyl acetate using a molar ratio of ruthenium: iridium about *: 1 at JA's concentration of methyl iodide.These examples also illustrate the additional benefit on the reaction rate of increasing the molar ratio of ruthenium:iridium from about ?:1 (examples 1 to 11) to 1:8 . YT

trampled

Examples of a continuous carbonylation reactor

Experiments were carried out to illustrate the present invention using a continuously operating carbonyl addition reactor

When setting up a steady state liquid reaction. A schematic diagram of the device is given in the figure.

The apparatus included a stirred carbonylation reactor (1), flash tank (Y), and distillation column (7£).

0 and the whole device is made of zirconium YoY The device Lad contains two packages of gas cleaners

They are a selective acetic acid cleaner (not shown) and a methanol (0) cleaner, made of stainless steel.

- When used, the carbonyl group was added to the industrial grade of methanol; And who

Use to clean out gas; In a 6 L reactor (1) in the presence of 0 iridium carbonyl addition catalyst and booster at a pressure of YE to 90,050 towers and a temperature of MAM - AVA

The reactor was connected to a stirrer/fan (1) and a gas stopcock (not shown) to ensure mixing

Complete liquid and gaseous reactions. Carbon monoxide was supplied from an industrial unit or from

pressure piping to the reactor through a perfusion tube (V) installed under the stirrer (1) to reduce the amount of inlet

Iron to the reactor as much as possible the carbon monoxide was passed through a carbon filter (not shown). 1 There is a casing (not ABA (One) that was circulating the alu oil as it was allowing the reaction liquid in

The reactor is to be kept at a constant reaction temperature. The composition of the liquid reaction was analyzed by

Near infrared or gas chromatography analysis.

- to clean the entrance; An off-pressurized gas Je was removed from the reactor at a constant flow rate through J

Line (3) where it passed through a condenser (not shown) before the pressure was reduced to 1.48 towers through valve ©01 to feed through the cleaning system.

‎YT)

— M - - The liquid reaction composition from the carbonylation reactor is drawn down into a fixed well (11) and then fed into the flash vessel (Y) under reactor level control. The liquid reaction composition is flashed into the flash vessel to pressure VEN tower Then the steam was separated from the mixed liquid. The catalyst-rich liquid was returned to the reactor by the line (VY) and the pump (VF) and the steam was passed through a remover (14) and then directly to the double-ended light distillation column (©) as steam. The defogger was in two parts. The first part was a gauze defrost section; the second part was a wadded section. That second section was optionally washed with aqueous material from the top of the two light ends of the shaft. A substrate was run to remove corrosion minerals by ion exchange ( YO) to remove corrosion metals from the slipstream of the recycled liquid portion of the flash vessel (sale) catalytic cycling (0) thus maintaining the concentration of corrosion metals below 100 ppm in the liquid reaction composition. The section for the recovery of the resulting acetic acid includes a light-end distillation column and 30 (©) plates and a drying distillation column containing YA plates (4). Both devices are made of zirconium with perforated PTFE tubs. 1 - Distillation column (VF) operated at the same flash vessel pressure (approx. 0.448 tower) with steam feed. The distillation column had “basins under the feeding point.” - The distillation column (;) was operated at a pressure of 0.8 tower at the head with liquid feeding at tray No. 01 except from the base. Pressure was saved by applying bleed (776) of carbon monoxide to the top of the shaft. To reduce heat loss from the columns, they are lined with planks; Where it is heated atheria and then lining. Archaeal heating was controlled to a temperature similar to the process temperature at that point inside the column.

S - I passed the upper parts resulting from the distillation column (7) through a condenser (10) where the low-pressure outgoing gas passes through the line (01) to the cleaning system, and the liquid (asad) falls into a beaker (17). For two phases: the heavier organic phase was pumped directly back to the reactor, while the lighter aqueous phase was divided; some of it was returned to the top of the column as a reflux (D) and some (AY) was optionally used as a wash for the flash vessel and then for the reactor. Repeat the rest of the phase

water to the reactor through the catalyst recirculation pump (VT) electrically preheat the distillation column (©); reboiler heat absorbent (not shown); With a temperature controlled boiling in a reboiling liquid. The crude acetic acid was removed from the reboiler through line VA and flashed to an evaporator (19).

0 - The evaporator was made of zirconium VY and operated at atmospheric pressure with controlled boiling at the level of the evaporator. The majority of the material introduced into the evaporator was removed from the upper section as steam and condensed before being pumped by the pump (Y+) to the drying column (4). It can also be fed to the drying column as steam. The basal bleed from the evaporator was recycled through line (71) to the reaction system.

1- It was also possible to operate the distillation column (7) with steam being taken from the base by means of a bleeding boiler instead of an evaporator. - The drying column was heated and controlled in a similar way to the (?) column, but boiling was controlled by the temperature on the tray 8. Its upper material was a single phase. Some of the top material was used as reflux for the distillation column and the remainder was returned to the reactor.

© The dry acetic acid obtained from the base of the column was removed through the line (TY) The concentration of propionic acid in the dry acetic acid produced from the base of the drying column was a function of the rate

yy

Y ¢ — _ production of probiotic acid as a by-product. Methanol was fed to the column at tray (1) in order to react with the hydroiodic ae. - Pass the low pressure gas produced from the two columns (© 40); first through low cold condensers (baal) of the outgoing gas (TT) and the liquid is returned The condensate to the decanter (COV) 0 - The resulting vapor was associated with the outgoing gas, which reduced its pressure after it was high before entering the base of the methanol cleaner. - The outgoing methanol cleaner (0) contained a gauze nolly pad. Refrigerant methanol was used to remove methyl iodide from the outgoing gas stream. The cleaned methanol from the cleaner was combined with fresh methanol to provide feed to the reactor. The cleaned gas was passed through a control valve (YE) Which 01 controls the pressure of the flash vessel ¢ and is analyzed before it passes through a vent to the atmosphere - The out gas can be either high, low or combined pressure passed through an acetic acid cleaner (not shown) ¢ before a methanol cleaner.This cleaner is similar to a cleaner methanol but contains Noli gauze filler of type 32 Hastelloy and about J of acid product (Sid) is used to clean the off gas. The detergent-washed part is then returned to the flash bowl. If ve use acetic acid cleaner for low pressure out gas; It bypasses the cooling capacitors. The results of the process with different liquid reaction formulations are shown in Table 4.

Yo — - 3 4333 493933494949 04 3 = 4 4 4 4 4 4 4 4 4 4 4 4 1 3 Wb ww 4 + > < a | > s + Pd > << eo 7 v ao — — >» > > > > > > > > 2 3 LE ol * e . > © LE OL FE KEM FE YA YA 5 : 3 = 9 HO - 0 9 DA AA > »> why not > - ry 3 b 3 5” ~ ~ = 3 2 ram > - vir Dy = <> oe ow << - oe = ya 7 la la la um a to um um ow ow or 2 3 . _ say 3 Q , > > b ak l ya ya wm > in lba ha < 3 l + 3 wo oa rr rr rr << << 0 ww a ww ~~ > . 4 0 — : em ee ° to er em am a l l sr el le em to msi lam ~~ 4 3 A Cee eee Le eee | d 42 a f< > b+ + ~~ >» - << ww > + a 0 4 4 3 i 1 . nb > 3 y —- — — — — — — EA 2 — — — — — — — — — — — — — A 73 pal - . . > . . . . . . . . - . A A 3 0g SoS Aw ow DZ iE x 2 ee + =< =< > > + 0 0 a r+ > ~~ 6 } 4 for the secret of the arc of the arc of the arc of the arc of the arc of the arc of the arc of the arc of the arc Ams — 3 wah 2 77 3 ahm lah ah ah tatah > Fr a wa dha jah ah fa 2 4 a ala 2 ra an alam tL ava ava aa ha 3 "= < god + < << << < < Te rr oe ZX 3 4 71 for smr l refer to ler to the secret of my mother's sail = ol lm 31 b and a — ah god bat . + gib bel is ler f ed > 2 p = i 1 3 < << << < << << << >” < << << << << << . l 4 3 1” — Q Via wr > a < > Lad rr 3 a bad > 0 2 3 2 I = Vi Vi Vi = Vi Vi Vi Vi Ya Vi = A ~ So J So . J , . . 5 . 5 141 I 0 0 >» ww 0 ww + eo 0 >» < oo a 3 3 3 rr = 6 a << << > > o> > > > 3 = = 5 a7 power 3 throw Ji 33 wo 3 TG ° 2 a 9 sq 3 . << > >« > sq > « = 3 a l v Ty 1 4 1 > mL mm > a * ow - — - — — - - — — — — — — — 0. p 3 ES 3 — What: A El Tee ee 3 = No b for Mag Sa. »> 2 3 Ji 9 © « I< > 0 rr 0 rr w= © = ,4 d h + 3 :

S - - The results in Table 9 show the effect of varying the water concentration from 797.1 by weight to 77.7 by weight on the carbonyl addition reaction rate and by-products. From the data in Table 9 it can be seen that when he reduced the water concentration from more than 776 by weight to 76,5 or less; This increased the rate of the acetic acid production reaction to a maximum value (as in the 0 batch examples); which under special conditions in examples 11 to 01 the water concentration was about ; to 75 by weight. This is shown in the diagram in Figure 8. Examples 1? to YY were reactions with a liquid reaction composition of about TVA by weight methyl acetate of ; to 701 by weight of methyl iodide as a catalyst and about 177 by weight of water. The examples YE through TY were reactions with a liquid reaction composition of about 219 0 by weight methyl acetate and about 75 by weight water . These two sets of examples show that as the concentration of the catalyst is increased, methyl iodide increases the composition of the reaction liquid; This would lower the temperature or the concentration of the catalyst, or both, required to catalyze a certain reaction rate; With the reduction of the formation of by-products. The two examples, OYA 74, show the effect of varying the concentrations of water and methyl acetate at about 79 by 1 _ weight of the co-catalyst concentration of methyl iodide in the composition of the liquid reaction. Therefore, whenever there is a decrease in the water concentration and there is an increase in the concentration of methyl acetate; The temperature required to maintain the reaction rate was lowered and the by-products were reduced. Batch experiments using zinc as a reinforcer - batch examples performed; As in Examples 1 to 11, but using zinc as a reinforcer instead of 0 from ruthenium 0, the charge compositions are shown in Table 01 and the reaction rate data are in Table 11 below. YI

Table No. 01

Charge compositions for zinc-enhanced reactions in 01 mL zirconium batches

Example Reference Water Iodide Acetate Methyl Acetic Hexachloriodide Jal g | Uridic acid | Zinc gram gram gram (gram) gram yolk | oo, vo Tee) die | ‎AAA VEY Yo‎ £ | Tees 59.51 aq 1 1 1 0 7" a 1 14 TY. oY ry for heat each oyun a- The weight was expressed as pure hexachloroiridic acid. yy

- m - 3 a J 5 Co = 3 | LL x < 3 = = = = = 5 1 3 = = = = 1 ZZ 35 3 > wa 3 ~ > 3133 Fz % 0 and x ~ 3 — 10 * . 3 3 — — > < “ 2333 So; 3 m 5 3, 3 5] — > > — — 1] d 20 4

Ng *- 0 9 and 3 . ; °. a 0 ak as la l l “ b a + 3 o 7 1 = . 20X. 3 — > 4 T1323 Sooo 2 b 1 7 > > he | . 3 > mo 3 3 4 <<

Lg 3 = “J = 2 3 3 3 > < 3 for 5 2 3 < a 3 a 2 3 3 ao “ Via 6133 +42 en 1 Eg “ for 3 - << 35 7 3 or J a ~ aa 3 > = ba pir > 3 - rs 3 Aa 353 o 13a z . << secret. ~~ 3 3 4 ad a ~ l 34 4 1

Wa 3 3 > 3 aT : a ja the 1 > 3 + = 3, — he 5 + z : 3 m 7 4 i 2 3 ~ J , 2 2 m

All reactions take place at a total pressure of YA tower and 1551 m with a stirring device speed of 15080 revolutions per minute. - At a calculated concentration of methyl acetate 715, the composition was calculated as 79,8 methyl iodide; 5601 ppm iridium and 6080 ppm zinc. 1 - The concentration of methyl iodide was calculated based on the approximation that each mole of iridium can be consumed

; Methyl iodide moles at most to give tetraiodo ion JE iridium carbonyl - [ Ir Ma«00) . - The concentration of iridium was built on the basis of the introduction efficiency of catalyst 797. - The data in Table 11 shows that the lower the water concentration, the lower the water concentration. was the reaction rate

0 Addition of carbonyl increases and was at its maximum when the water concentration was not higher than 771.5 by weight of water.

YI

Claims (1)

PE protection alc 1 1 - A process for the production of acetic acid, Jedd acetic acid, on (1) a continuous feed of methanol and/or a reactant derivative thereof and carbon monoxide J. v. The carbonylation treatment reactor contains a reaction composition liquid lef comprising iridium carbonyl curing catalyst; methyl iodide© co-catalyst; limited concentration of water, acetic acid 26606, and 1-methyl zcetate; and at least one promoter; (?) contacts Methanol for methanol and/or its derivative interacting with carbon monoxide A in the liquid reaction composition is characterized by the fact that 9 (a) water is maintained throughout the reaction period at a concentration ranging between 1 and 776.5 by weight + (b) 68 01 methyl acetate 68% to 770% by weight and (c) 1-methyl iodide 1% to 7176% by weight in liquid Jeli formulation ; The concentration of NY water is such that it gives the maximum carbonyl treatment rate at the concentrations of tal methyl acetate VY and methyl iodide as defined. 1 "- A process according to Claim 1, in which the reaction flow is continuously maintained throughout the Y period on methyl acetate with a concentration ranging between 0 Yo Y by weight in the liquid reaction composition. 1 *- A process pursuant to any of the foregoing claims; where at least one promoter Y is selected from the group consisting of ruthenium ¢, osmium 1 ¢ and cadmium; mercury; zinc, gallium, and indium; and tungsten. 1 — $_ 1 ;?- operation according to claim ? ; Where the reinforcer is either ruthenium or osmium. 1 5- A process pursuant to the claim “or”; ; where the molecular ratio of the booster: Y iridium is [ve to 10:15] . 1 - a process according to claim 1; where the old reaction Y is continuously maintained on about 75 by weight of water; and about 797 by weight of iodide; and about Ive YF 0580 of 1 methyl acetate, an iridium catalyst with a concentration of sev 0060 ppm and a ruthenium promoter of 2 between 6 and 06 ppm in the reaction composition The liquid. 1-1 process according to any of the previous protections where the partial pressure of hydrogen in the carbonylation reactor is less than +1 mega(dsr bar). A) a process according to claim 7; Where the partial pressure of hydrogen, hydrogen Y, is less than 1.05 MPa (+0 bar). 1 - a process according to claim 1; Where the partial pressure of hydrogen is less than 0.07 MPa (1.7 bar). -0 1 A process according to any of the previous claims, 0, where the amount of hydrogen Y hydrogen reacted carbon monoxide Y is less than 7 moles. 1-1 process pursuant to claim 01; Where the amount of hydrogen in the reacted carbon monoxide Y is less than 70.5 moles. 1-1 process pursuant to claim 01; Where the amount of hydrogen in the reacted carbon monoxide Y is less than L,Y mol.