DE1965239A1 - Process for the production of carboxylic acids and their esters - Google Patents

Description

PATENT LAWYERS
8 MUNICH 2. HILBtESTRASSE 2O

Dr. Berg Dhl.-Iig. Siapf, 8 Mjnch «n 2, HüblestrjSa M

Our sign Date * * »*" »2 · 1969

Attorney's file 19 198

B / A

Monsanto Company St. Louis (USA)

"Process for the production of carboxylic acids and their esters"

This invention "relates to a process for the preparation of carboxylic acids and their esters. In particular, it relates to a vapor phase process for the reaction of alcohols and carbon monoxide in the presence of catalyst preparations which essentially contain activated carbon, including Oase Tj-483 00SS29 / 188S. " -2-

Process carried out in the presence of a halide promoter will, v / o by selectively and efficiently produced carboxylic acids and their esters.

Carbonylierun-sverfahren for the production of carboxylic acids from alcohols are well known and are especially in the production of acetic acid by the carbonylation of! .. ethanol aligned _o The ütand art provides the use of a number of catalysts for the "i.vntlisve of Garbonsäuren by The reaction of alcohols r.:i carbon monoxide at elevated temperatures and pressures so './ ohl in the gas phase in plague bed reactions as well as in ElOigphase reactions. It -. It is reported that catalysts v / ie heavy metal salts, such as zinc and Zupf er (l) -chlori - 3, silicates of various metals and boron trifluoride in various stages of hydration in the production of acetic acid by the reaction of diethyl alcohol and carbon monoxide at elevated ¹ I ¹ loads and pressures of the order of 4 ° G and 700 ata (10,000 psig) will work, however, even under such severe conditions, acid yields are essentially low and therefore inhospitable nomic Slightly less severe reaction conditions of temperature / or pressure and are described in the literature, s B, 260 to 36O ⁰ G and 196 to 1050 ata. (2800-15000 psig) when specific catalyst compositions, namely, metal carbonyls v / ie iron, Cobalt and nickel along with

009829/1866

1.965238

their halides or free halogens in the liquid Pha ^ e used. Even when using this specific Catalyst preparations under these less severe reaction conditions iEi significantly lower yields of the desired carboxylic acid and significantly lower reaction rates received than this at your inventions according to the procedure of EaIl.

Certain! Disadvantages that are involved in the carbonylation process, as they are described according to the prior art occur, are cataljSatoriiiStabilitLLt, lack of product selectivity and poor performance in catalyst reactivity and in processes involving a liquid Phase is used, the need for large and expensive recovery, catalyst regeneration and catalyst cycling to the reaction vessel. A particular disadvantage of the prior art carbonylation processes is their dependence on the use of lletall containing catalysts, the highly volatile carbonyls or ketallcarbonyl, including eikobaltoctacarbonyl, Iron carbonyl and nickel carbonyl uilden, these altogether make the use of high partial pressures of carbon monoxide necessary to make among those necessarily used to remain stable at high reaction temperatures. For example Dicobalt octacarbonyl requires carbon monoxide partial pressures of 21; up to 703 ata (5,000-10,000 psig) below normal

009829 / UiB

1985239

paint Oarbcnyiieruiigsbedingungen at 175 to 3OC ⁰ O _s In (Jegensats dc.13, ;; is the present Ocuupfphasenv & riaren "at lower Diüekeii, Z; B ₅ down to a total pressure of; ■ atmospheres _?

A v-'siterer "? .E3r!, Eil -Jsr O ^ r ^ onylierurLgsverfahreii nach, -iem Stö.-Ai of the TechniJi: is their relatively small extent of Sectionsfiiliigka-i.tf Dic-r? ~ Low? Auame, !? επ Rsnktioriufahigksit requires higher Eatalysatorkcr.sentrationen, lär ^ ors Eesk ~ tionczsitGK. unfi higher T ^ npereturen, ιιγχϊ '-' sortliche P.esktionagerohv / inciglTfsiter vrsl Urav ^ ndlur.gon? u örlialteru% are. rolialteru Dens ^ tpnieli ^ ore procedure devices erf oröcrlri ο I? ...

A '.veiterer -acj.iteil aer C rbonyli ^ ^ run sverfanren after Stan α of' ϊιργΛχρΑ '.--: i.- ic + their _";;; &ei;;;; ttheit, a · high selectivity in the ^? . ewimsonter Oerboi ^..;; -'ure at temperatures 2U = deliver that i'lir · high;. & Un.w r.dlunrjsov.sjncjja and high RefaxZtior.äveriiälöiiitiKe erforaerlic ^ :: ;; o "rei these higher Iempvrit . «Ren are uiierv / Unscnte ..eüoi.pro-jukte, which essentially consist of: aldehydes, higheri Jarborr ^ luren, carbon dioxide and LIet:, & n bectenen, £; ebilaet, v."". Dar jh," I weekly Losses ar. Yield surrender, u ;. * ts necessary, a zuc ^{; /} tzli 2: ve PrcäUÄtreii.igun ■. ;: ':. ur: ex.:., eii and return steps partly. Veriihrer-tablaui oinzufü:; - 3 /. _O

00S829 / 186S

BATH

A particular disadvantage of the carbonylation processes according to the state of the art is their dependence on the use of liquid phase catalyst systems or certain modified cobalt carbonyls, dissolved in a liquid heat transfer system, _or additional phase systems necessary for the separation of the products from the catalyst solutions, and this leads to losses in handling and the catalyst. This handling of the catalyst solution in liquid phase processes requires the "use of large and costly process equipment to remove the Yerfalaren product for the recovery of the catalyst and the return of the catalyst to the reaction zone. Losses of the metallic component in the handling of the catalyst solutions are also costly because the metals as such are very expensive For example, the carbonylation reaction according to the prior art when using a cobalt catalyst in the liquid phase suffers from the serious disadvantage, which is attributable to substantial losses of the cobalt component during the separation, since the cobalt is plated out as an inactive coating on the walls of the reaction vessels and lines is a heavy.

The present invention using a solid activated carbon catalyst overcomes the above in the handling and implementation of a liquid

009829 / 188S

Difficulties encountered in reaction mediwas * because they are a Provides system for the continuous separation of the products from the solid catalytic phase.

It is one of the components of the present invention to provide a structure in which the catalyst is maintained in a solid phase such that the handling and losses of the catalyst are eliminated or reduced. A further object of the present invention is to provide a more effective, stable and selective catalyst which enables the production of the desired carboxylic acid in higher yield with minimal formation of ethers, aldehydes, higher carboxylic acids, carbon dioxide, methane, and other undesirable by-products has consequence.

Another aspect of the present invention is an improved carbonylation process that is efficient and effective selective production of carboxylic acids or their esters by reacting alcohols and alcohol derivatives with carbon monoxide in the presence of an improved and more stable catalyst, thus also the use of a lower catalyst concentration, lower temperature, pressure and contact time than this Up to now it has been generally possible, and continues to be, the separation of the Process product, catalyst recovery and recycle

-7-009829 / 1885

stages and solvent recovery is also ruled out.

ix of the present ^ i-xind-an .: apply ^ ikoliole with i. Carbon atoms (n = 1 to 20) su a mixture umirev / La.uelt, which is an acid with η -t- 1 carbon atoms and the eater of the iieO ^ Gbe ^ en alcohol with the nn ^ t- flat acid .-. '. -iilo, for which the alcohol or an Ikoiiolderivut with Kor.lorir.onoxid at 5empert.turen from 250 to pOö ΰ and 3? artir.ldrUo.: en of carbon monoxide from 3 »5 to t.030 ata (50 - 15.0Ou: -; ia), preferably from 7 to 211 ata! 100 - 3,000 psia) and in particular 14 to 70 ata (200 - I ₁ OUO p-ia)? obgleicr. :. : ere pressures are used. lccniien _s ir. 3 -: - '.. nwert ei :: -. · I' ^ ia - / ■■ · torrste ": ^, the ic v; esentliehen m ;; Al: ~ ivkohle bt ^ ■■ ■ *; ■. ·, Sets. Li «r AI: tivlcc: iie, the ir. Äeu present ICuta ;, · u: .- · is used, ordered from a .; rorC'sen JrestGfoif oinor size which in Fest- oder Virbelüefrrealr ^ orsn verv? ^: ·· - *; · .-. · ■■■■: '- der. Ki.rr,: _t b. Of approx. 4Ö llikror. (400 nesh / inen} ι : :: "1-, 7 - '·"; \ V ^ inoh) particles ^ rl?, - e: .. Da? Pore volume ■■ -:.: ■. 7 ^ rliältnis :: un:? Eststoif ^ e -vicl: t .Ii-dert.: iJ :. ii ^ iierei. ^ :: ü, (c cii ^. ":, Γ e :: i" / ~ der vorozer. I. "; - v, ciei ei : o; v. ■ ~ .:

Yi'i <? c-'oen cereirs ar. given is the : ' ^: .'. y ax Zv / eolce d ·: ■ v;: - licrG ,. .. .. -.π'ί — ΰΛίπ ^ intended Sat: ._ "eator A ^^ ivkoh ^ e. Z, * ¹ : ·: · Katal;" ijuter k; iii * - a'.is "'- "ei verej.ii-ccLner. Kosiponenxen: ucr.: ..-

009829/1886

: - S - .. ■ - ■■■■■ '. - ■ '. ■ ■■ *

be set, namely from the activated carbon component part and a halogen promoter part ₉ which is dispersed as a second component and which may or may not be catalytically active, but supports the reaction in various ways, such as by facilitating the cleavage of the carbon-oxygen bond in the alcohol "the reaction is also carried out with the HsIagenpromotor ₉ is as part of the reaction mixtures in the ¹ ^ _s present ampfpharae

Modifying treatments of the present Iktirkoiilen-V "'component, which became obon"beech.t'iebsn, feönnan. can also be used, μ den. halogen part acting as a pronotor or a second component to be incorporated into the catalyst system ο Such components acting as a promoter include halogen and / or halogen compounds such as hydrogen halide j alkyl or aryl halide, ammonium _? Phosphonium, arsonium, stibonium halide etc. '' Halogen or V halide variants are suitable as promoter part of the catalyst, although those containing iodine and bromine are preferred of this invention, the following preferred halogen- and / or halogen-containing compounds can be selected. -

009829/1-tiS:

BATH ORIGINAL

EX where E is any alkyl, alkylene or aryl group, e.g., B ₀ GH ₅ J, G ₆ H ₅ Br, CH ₅ GH ₂ J, JGH ₂ GH ₂ JVV '.

(n 1 to 3). ,: - \ \ _

and X = Cl, Br or- J,

X ₂ or X ₅ -, where X = Gl, Br? Or J, e.g. B. Br ₂ , J ₂ , J ₅ where

HX wherein X = Gl, Br or J, Z is _O, HBr, HJ is

EGX
β 'where E = an alkyl or aryl group, e.g.

CH ₅ CJ USWo

and X = Cl, Br or J, E.MX, E ₄ MX ₅ or E ₅ MX ₂

where E = hydrogen or any alkyl or aryl group, e.g. Bo IH.J, PH ₄ J ₅ , PH ₅ J ₂ , PH ₅ Br ₂ , M = Ή, P, As or Sb (CgH ^ KPJg and / or combinations - 'ions of E, M and X, and X = Cl, Br or J is ...; ■

The halogen promoter part or the second component of the catalyst The reaction vessel can be separated from the active catalyst or the first component, or it can be incorporated into the active component, for example by impregnation on the catalyst. Activated carbon or .first component of the "catalyst system can be prepared in a separate activation process before charging into the reaction vessel or in that.

009829718 ^ 6 ^ ⁰ "

1965219

~ 10 ■■ -

Reaction vessel are formed. As a result, after the first component in the reaction vessel is the promoter or the second component of the catalyst in the package as a gaseous or liquid compound or as a solution be fed in a suitable solvent, -However, the Eromotorteil of the catalyst can also the Active catalyst or the first component either

• at the end of the activation or during the in situ formation of the ■ active yene catalyst be incorporated.

, Suitable feeds are alcohols, although alcohols together with ether, alkyl halide or ester as noted above, can be loaded. Preferred alcohols have one less carbon atom than the desired carboxylic acid. These feeds include halides, esters, and others Derivatives of the desired alcohol charge.

Examples of preferred feeds used in the carbonylation reaction of the present invention "include the group of aliphatic alcohols having from 1 to 20 carbon atoms and aromatic alcohols having from 6 to 10 carbon atoms including methanol, ethanol, propanol and isopropanol, the butanols , Pentanols, benzyl alcohol, phenol and hexanols, as well as the higher alcohols such as the deeanols, including the isomeric form », however, an alcohol is the preferred charge» if ~

"For example, acetic acid is the desired product, the feed may be the same of methyl alcohol or derivatives * as dimethyl ether, methyl acetate, methyl _s j ο did and / or combination" - nations of these consist _e

In a typical Garbonylierungsver £ _s Ahren selective for acid, one mole of carbon monoxide reacts with each hydroxyl group (molar basis) "More or less carbon monoxide over the designated stoichiometric amount may, however, be present," Kohlenmonoxidströmej the inert impurities contains en ₉ v / ie _{Zohleiidioxid?} Methane, nitrogen gas _s, water and paraffinic hydrocarbons with from 1 to 4 carbon atoms ^ can _s . if desired, be used, for example from available gas plants with good effect _ö However, the total pressure of Eeaktionsgefäßes should be increased in such cases to achieve the desired carbon monoxide to obtain ^ partial pressure * The carbon monoxide concentration in the feed gas mixture is from 1 vol. $ to 99.9 VoI.-56, with a preferred range of 80 to 99.9 VoI. ^.

In carrying out the invention described above for Production of a high proportion of acid, 2. B «acetic acid, The charge to the reaction vessel can be used as the desired product be pure, or it can remove by-products those used with the alcohol charge in the circuit

'V ■ .- .. ■■ -12-

■ - 12 -

v / earth. The purification system can therefore be a distillation plant to obtain acetic acid by means of "distillation, while the remaining low-boiling components be fed back into the cycle.

The activated carbon catalysts of the present invention, exhibit an unusually high degree of specificity for the Carbonyl oxidation reaction, d. H. for the reaction of alcohols with carbon monoxide to form a carboxylic acid. Such a control over various competing reactions with the formation of carboxylic acid in high yield is surprising because most of the catalysts "at this reaction does not show such specificity. The ferrous metal group, such as iron, cobalt and hiekel, is different The activated carbon catalysts used here are characterized by the fact that the metals of the iron group simultaneously undergo side reactions catalyze. Therefore belong to the products from Eiseny Cobalt or nickel catalysts both the next higher Alcohols as well as aldehydes and also carboxylic acids with more than 2 carbon atoms than the starting alcohols · In addition The catalysts of the iron group, especially cobalt, require a fairly high carbon monoxide partial = pressure to stay active. If the pressures are moderate, for example, less than about 140 ata (2,000 psig) carbon monoxide partial pressure at a temperature of 175 0 was used found that the cobalt catalyst is plated or

• -13-

009829/1886

. BATHROOM 0RI6INAL

disintegrates to the free metal, which on the walls, of the reaction vessel plated and so to act as a catalyst Loss goes.

Another difference between the active carbon catalysts of the present invention over the cobalt catalysts is the El chtauftreten undesirable gaseous by-products, including carbon dioxide and methane "which are obtained as a result of the catalysed by cobalt water gas shift reaction, ·. Furthermore, equally significant amounts of the undesirable by-product dimethy lather are also formed in the presence of the cobalt catalyst system. This ether compound achieves a very high partial pressure under the reaction conditions used and requires the use of a reaction system for a high total pressure in order to maintain the necessary partial pressure for carbon monoxide in the reaction to form carboxylic acids, for example 140 ata (2,000 psig) total pressure at 52 ata (750 psig) Carbon monoxide partial pressure at a reaction temperature of 175 ⁰ O. -

The activated carbon catalysts used in the present invention are also platinum as one for the platinum group superior to typical catalyst. For example, the present activated carbon catalysts cooperate Yields which in the case of carboxylic acids and esters are greater than

-H-009829/1886

In contrast, a catalyst produced by means of thermal degradation of platinum nitrate supported on carbon shows only 55% of the activity of the activated carbon catalyst used here under comparable reaction conditions. The designation ¹¹ KoIiIe ¹¹ is used here in its general meaning and denotes the class of activated carbons. The activated carbons useful in catalyst preparation for the purposes of this invention can be any porous carbons formed by pyrolytic reactions of amorphous carbonaceous materials at high temperatures. The activated carbons of this type generally have a surface area of about 400 square meters, the 2000 square meters per gram. cm / g of the porous phase, a preferred range being from 0.05 to 1.5 cm / g. These coals may be in the form of compact masses such as granules, flake powder, etc., although the powder form is not preferred. The activated carbons can be of animal or vegetable origin or come from petroleum processing. For example, coconut charcoal, general charcoal, and charcoal-derived coke can be used, while natural, untreated charcoal by itself is not an effective catalyst for use in the present invention. Process

-15-

009829/1885

and is also not activated carbon. Other suitable coals include those marketed under various trade names for the purpose of making catalysts. Examples of activated carbons that are commercially available include Pittsburgh ¹¹ BPL "," CAL "," OL "and" SGL "from Pittsburgh Activated Carbon Co., Girdler" G-32-C ", and" G-32 -E "from Chemical Products Division, Chemetron Corp. and Barnebey-Cheney Company's" EE-I "," EH-I "and other activated carbons. The activated carbons can be washed or unwashed. If the charcoal is to be washed, a typical wash treatment looks like this washing the coal with aqueous hydrofluoric acid or with aqueous nitric acid, for example a dilute nitric acid solution, using, for example, about 600 to 1000 ml of nitric acid per 500 g of charcoal to 30 wt. # in water. Similarly, the hydrofluoric acid can have a strength of 10 to 55 wt. # in water. Contact times of the acid and charcoal of about 5 minutes to 24 hours are sufficient washing the coal. After the acid wash step, the acid-treated charcoal can be washed with water to remove the excess acid from the surface.

The inventive method can be used both in batches

-16- 009829/1885

1365239

can also be carried out continuously. That
fäß can «in a fluidized bed or one of them
double-sided arch beds: g between cL-caa. .öattsn
have, or cei "catalyst can be in tubes with sinem
Heat from tiä.u & ohüiödiim uxl dl «pipe <m aZigfeordaet. Those the catalyst anthaLte ^ you tubes can par & llel oa © r in series ang & orc & jst hvLu. It is possible whether & n & o in
of the invention aife Eiö ^ ions ^ ar'sner by cL & si ^
Vessel either upwards or downwards fli & ßön jsu laaö & ü, furthermore a * pürioaiücho üaköhr
share »wife ,, die i ^ cfrwchtoriiÄ
bettee, au true. iäevora; * g ^ becomes the HaAo ^^ aproaiotor after the S

Is J) ie Eatalycü "5orhfeir & * cer way iss eilung. Carried out by e & s C> 454 kg (1 lb) verwt 48 ^ Institute of Environmental Sciences wäflrigö Pluorwasberttoffsäure, Nd-Fe," AöR 200 g IPIR-Kohie, Pittsburgh Activated Carbon oc, zugegeoen It is left (in a polyethylene beaker) at the same temperature for two hours while stirring easily. The excess of hydrogen fluoride is decanted and the process is repeated three times, each for 16, 6 and 16 hours . The
Coal is then washed with 500 ice 1000 ml portions of water until the water has a pH of 4 after washing.

-17-009829 / 1885

BATH

1985239,

The coal is dried in a vacuum oven for 8 hours at 130 ⁰ C and 50 mm pressure, yielding 177 g "ashless" charcoal. Analysis: ashes before leaching 5 »57 $ j ash after leaching $ 0.38.

The activation of the coal catalyst (either leached or not) is carried out in such a way that the coal is heated to 275 to 300 ^° C. in a nitrogen stream of 1 atm. Heated pressure for 1 to 2 hours. ^

Example 2

The HF-leached carbon catalyst (10 ecm) is placed in a stainless steel reaction vessel (5/8 "outer diameter χ 8" long) in a heated fluidized bed sand bath. The system is brought with nitrogen to 14 ata (200 psig) pressure and heated to 35O ⁰ C. When this temperature is reached, allowed to flow to carbon monoxide and shuts off the flow of nitrogen. Methyl iodide and methanol feeds are then introduced. The feed ratio "methanol: methyl iodide: carbon monoxide" is 0.25: 0.02: 0.50 mol / hour.

The effluent from the reactor contains the desired carboxylic acid product including the ester of the acid product and alcohol charge, water and unreacted alcohol, carbon monoxide and promoter. The selectivity of alcohol conversion to the desired carboxylic acid

-18-

^009829/1885

and their ester is essentially $ 100 on one cycle procedure in which the ether is guided in the cycle will. The chromatographic analysis shows that essentially no by-products such as aldehydes, higher boiling points Carboxylic acids and / or alcohols, methane or carbon dioxide were formed.

The conversion obtained in this example is 17 »2 mol # based on methanol. The isolated products have the following analysis in% by weight on.:

Methyl ether 5.5 Methanol 42.5 Methyl iodide 18.6 Methyl acetate 20.1 acetic acid 6.3 water 7.0

100, Q

If methyl acetate and water are used in equimolar amounts as feed to the reaction vessel, substantial amounts of acetic acid are formed from the methanol from the hydrolytic equilibrium reaction of methyl acetate and water.

Similar results are obtained when using equimolar amounts Dimethyl ether and water can be used.

If these experiments are repeated using benzyl alcohol, substantial amounts of phenyl acetic acid

-19-

009829/1885

PAD ORIGINAL

1S65239

acid isolated.

Examples 3 to 10

Examples 3 to 10 are shown in Table I

sums up and show the beneficial effect of the i-Ionlen catalyst in carrying out the carbonylation reaction and likewise the additional beneficial effect of building leaching of the coal catalyst. The reaction temperature is

these tests in the range from 300 to 400 ⁰ C.

If these attempts with other coals, finally HoIakohle (Darco), carbon black, activated carbon powder vegetative (I ^ Cru A) and Kokosnussholakohle in the original Fors or säureausgelaugt used werden- _v similar results are obtained.

If these attempts are made using an impure charge, those made up of 6G ^ carbon dioxide and $ 20 carbon dioxide is repeated, similar results are obtained. The use of carbon dioxide in the present Coal catalyst has the same effect as if additional Carbon monoxide would be added to the reaction "

When changing the promoter, the use of Methyl bromide has a similar promoter effect as methyl iodide.

009829/1835

ο Example* Catalyst or Reaction
temperature Table I. Pr oduct distribution
CH ₃ OH CH ₃ COOH 0.4 CH ₃ COOCH • 3 ^CH 3 ^X CD
OO 3 no 300 ° Methanol
conversion 81.8 5.6 0.3 17.7 KJ
«Ο 4th no 400 ° 0.2 ·· 77.7 5.1 0.3 21.8 «Ο 5 BPL carbon 300 ° 0.1 66.1 0.4 3.5 16.0 σι 6th BPL carbon 350 ° 2.0 51.7 6.3 10.6 20.3 7th BPL carbon 400 ° 10.4 64.9 9.7 9.1 15.5 8th HF drained
BPL carbon 300 ° 8.5 59.4 13.2 15.4 **
O 9 HF drained
BPL carbon 350 ° 7.5 42.5 20.1 18.6 , 10 HF drained 400 ° 17.2 57.4 7.3 20.5, Footnote:
a. Procedural conditions
was changed 13.0 S.
I.
. as in Example 2, except that the Temperatures like specified, ε b. Catalysts as in Example 1 described 8th
ο I.
.-a
I. • ■ l Τι
O

Ca) CO

Examples 11-18

The results of Examples 11-18 are summarized in Table II and show the beneficial effect increased alien monoxide pressure in the carbonylation reaction.

-22-

00.9829 / 1886

Table II

Eeaktions- Heaktions-

Example print ata

ο
ο
co
co
κ>
«Α

11th

12th

13th

15th

16

17th

18th

O (O)

7 (100)

14 (200)

19.3 (275)

35.2 (500)
0 (0)

7 (100)

14 (200)

19.3 (275) 35.2 (500)

temperature

rc)

300 300 300 300. 300 350 350 35ο 350 350

Methanol conversion (Molfl)

0.1 3.8

7.5

10.1

24.4

0.1

6.2

17.2

20.7

46.4

Product distribution (

CH, OH CH-COOH CH _x COOCH, CH_I 3 3 3 3

72.8 67.6 59.4 49.9 25.0 74.8 63.7 42.5 37.6

0.1 0.7 0.4 1.9 9.8 0.1 0.7 6.3 7.9 23.4

0 23.7 6.0 18.5 13.2 15.4 15.9 18.9 26.7 21.9 0
8.5 21.0
19.9 * 20.1 18.6 19.0 21.4 23.8 22.4

Footnote:

Feed ratios as in Example 2 using 10 ecm HF leached BPl coal as a catalyst in the reaction vessel described.

t *

cn ro co co

Examples 19 to 24

Examples 19 to 24 are summarized in Table III, to the effect of the throughput speed to show the carbonylation reaction.

009829/1885

Table III

ο
ο
<ο
οο

Example*

19th
20th
21
22nd
25th
24

Throughput speed °

0.5
1.0
2.0

0.5
1.0
2.0

Heating methanol

temperature

ro

300 300 300 350 350 350

Conversion (Molfl)

11.3 7.1 2.6

22.3 9.9 5.6

Product distribution (wt.

CH ₃ Oh CH ₃ COOH CH-COOCH-
3 3 ΟΗ, Ι
3 32.1 3.5 15.0 19.2 43.0 2.4 9.6 24.6 58.4 1.0 3.6 21.2 23.5 12.8 17.5 22.0 35.6 4.6 10.1 28.7 50.5 1.8 7.3 24.7

Footnotes: · "*

a. All examples ran at 17.6 ata (250 psig). Charge ratio as in example 2

b. Throughput rate is expressed as ml liquid feed / cc catalyst / hour.

c. In all cases the conversion, expressed as g HOAc / g cat / hour, is essentially unchanged. At 300 ^° C.: 0.10-0.12; at 350 ° C: 0 * 22 - 0.26

ro

VJl

Claims (1)

- 25 claims : Iy process for converting an alcohol with n-carbon atoms into a mixture which contains an acid with η + 1 carbon atoms, where η is a number from 1 to 20 and the ester of this alcohol with the specified acid, characterized in that one the alcohol brings an activated carbon catalyst in contact with carbon monoxide in the presence and the upper guide in the presence of a promoter substance * bromine, iodine and / or compounds of the halogens listed at a temperature of 25O ⁰ O performs as up to 500 ° 0th 2 · Process with reactants and products in the vapor phase for converting an alcohol with n-carbon atoms into a mixture which contains an acid with η + 1 carbon atoms, where η is a number from 1 to 20 and the ester of this alcohol with the specified acid , characterized in that the alcohol in vapor form is brought into contact with carbon monoxide in the presence of an activated carbon catalyst and the conversion is carried out in the presence of a promoter substance such as bromine, iodine and / or compounds of these halogens at a temperature of 250 ^° C. to 500 ^° C. 3. The method according to claim 1, characterized in that -26- 009829/1885 _BA0 a promoter consisting of iodine and / or its compounds is used. 4. The method according to claim 1, characterized in that a promoter which is an alkyl iodide is used in which the alkyl radical has from 1 to 20 carbon atoms. 5. The method according to claim 1, characterized in that the carbon monoxide as a gas mixture with a content of 1 vol # Carbon monoxide up to 99.9 vol. # Carbon monoxide is supplied and the balance of the gas mixture of nitrogen, noble gases, Carbon dioxide, water and / or paraffinic hydrocarbons with from 1 to 4 carbon atoms. 6. The method according to claim 1, characterized in that a carbon monoxide partial pressure of 5 »5 ata (50 psia) to 1050 ata (15,000 psia) is used. 7. The method according to claim 1, characterized in that a carbon monoxide partial pressure of 7 ata (100 psia) to 211 ata (3,000 psia) is used. 8 · The method according to claim 1, characterized in that ι a carbon monoxide partial pressure of 14.1 ata (200 psia) to 70 ata (1 OQO psia) is used. -27-009829 / 1885 BATH ORIGINAL Process for the preparation with reactants and products in the vapor phase of at least one compound, namely acetic acid and / or methyl acetate, characterized in that a steam charge of at least methanol, methyl acetate, dimethyl ether and / or methyl iodide is brought into contact with carbon monoxide in the presence of an activated carbon catalyst brings and the process in the presence of a promoter substance is selected from bromine, iodine and / or compounds of the halogens listed carried out at a temperature of 250 ⁰ C to 50O ⁰ C. 10. The method according to claim 9, characterized in that methanol is used as the charge. 11 · The method according to claim 9, characterized in that a charge is used which also ent ent holds. 12. The method according to claim 9, characterized in that that a feed is used which also contains methyl acetate. 13. The method according to claim 9, characterized in that iodine and / or its compounds are used as the eromotor will. -28- 009829/1885 14. The method according to claim. 9 characterized in that the promoter used is alkyl iodide in which the alkyl radical Clay has 1 to 20 carbon atoms. 15 · The method according to claim 1, characterized in that alkyl iodide is used as a promoter, in which the alkyl radical has the same number of carbon atoms as the alcohol. 16. Carbonylation process with reactants and products in the vapor phase, wherein alkyl and aryl alcohols, halides, esters and / or ethers are used as reaction partners and these reaction partners are reacted in the vapor form with carbon monoxide, characterized in that the carbonylation is carried out performs 5-1050 ata (50 to 15,000 psia) | in the presence of an activated carbon catalyst and in the presence of a promoter substance selected from halogens and / or halogen compounds at a temperature of 25O ⁰ U The 500 ⁰ U and a Kohleumonoxid partial pressure of the third 009829/1885 BATH ORIGINAL