JPS59176228A - Manufacture of carboxylic acid by carboxylation of alkanol by carbon catalyst - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] Acetic acid has long been known as an industrial chemical.
It is used in large quantities in the production of various other chemical products. Various proposals for producing carboxylic acids by the action of carbon monoxide (carbonylation) on alcohols have been disclosed as prior art.

The carbonylation of methanol is performed using cobalt iodide or carbonyl as a catalyst and an organic or inorganic iodide such as methyl iodide, hydrogen iodide or potassium iodide as cocatalyst (promoter), respectively. It is carried out industrially in the liquid phase under high pressure (approximately 40 MPa). More recently, nickel carbonyl or other nickel compounds have been used to perform the carbonylation of methanol in the presence of iodide at low pressures such as BMPa when organic amines or bosphines are included in the liquid reaction medium. It has been reported that it is an effective catalyst for
No. and Special Publication No. 54'-5921-1).

Roth and paraphrase (Rothemal, (::hemt)
ech1971.600; osu Chom, Com
Mun., 1968.1578) found that carbonyl complexes of rhodium exhibit excellent activity in carbonylating methanol in the presence of an iodide cocatalyst. Koera's compound shows sufficient activity under atmospheric pressure and selectively produces methyl acetate and acetic acid. A mechanism consisting of oxidative addition of methyl iodide to rhodium, insertion of co, and reductive decomposition of the resulting acyl complex with methanol or water was elucidated by extensive studies of catalytic reactions with rhodium (Forster J. ,km,
Cbom, Soc, 197698846; Hjor
l, kjaer and +Jonsen, Ind.
Eng, Chem, prod.

Pas, Dev, 1976 1.546). Rhodium can be supported on activated carbon or metal oxides by impregnation methods (5chultz and Montgomery et al.
ry J, Catal, 196913, lQ5
', l'1 obinson et al, J, C
atal, 197227, 380: or Kr
zywicki and MarozewsiJ, M
ol, Catal. 1979 6, 431) or supported on zeolite by ion exchange method (
Yasbima et al., J. Catal.
197959 53: Andersson and
5ourrel J+Ca, tal, ]97959
゜340; or 5curr'all and How
e J, Mo1. Catal.

1980 7.535) is also an effective catalyst for the gas phase carbonylation of methanol.

French Patent (FR-A) No. 2030118 discloses that on an activated carbon bed a temperature of 200-500°C and a temperature of 0.
Carboxylic acids, In particular, a method for producing acetic acid is disclosed. According to this method, activation of the carbon, which may be washed with HF (hydrofluoric acid) or HNO, (nitric acid) solutions, if desired, brings the carbon to 0.1 MPa
This is accomplished by heating in a stream of air for 1 to 2 hours.

The disadvantages of this catalytic system are that fairly high temperatures are generally used, that the catalytic system is deactivated after a relatively short period of time, and that the carbon bed must be activated by snowmine for best results. Furthermore, no significant differences in the results obtained using various different types of carbon beds have been reported so far.

Indian Journal of Teohnol
ogy, v'o1.5, 266 (1967), discloses a method for synthesizing methyl formate from methanol and carbon oxide in the presence of an alkali-activated charcoal catalyst. It has been reported that increasing the pressure increases the conversion rate, but when the temperature exceeds 150°C, the conversion rate decreases.

The purpose of the present invention is to provide a methanol carbonylation catalyst for high conversion from methanol, high selectivity to acetic acid, long catalyst life and continuous production of carboxylic acid. It is said that the system will be provided. Another object of the invention is to provide a catalyst system that provides economic advantages by operating at relatively low temperatures, especially without the addition of metal catalysts. Yet another object of the invention is to obtain optimal results by using a special type of activated carbon bed with a special pore size.

The present invention requires a temperature of 150-400°C and a temperature of at least 3.5°C.
In a method for continuously producing carboxylic acids and esters by reacting carbon monoxide with alkanol in the presence of a halogenide cocatalyst and a solid carbon catalyst at a pressure of MPa, solid carbon has a specific surface area. This porous activated carbon contains cobalt, ruthenium, iron,
A transition metal selected from nickel, rhodium, palladium, osmium, iridium and platinum, at least I
The present invention provides a production method characterized in that the reaction is carried out in the presence of preferably 25 to 150 ppm of PP.

The activated carbon is preferably derived from coal or peat, with a density of 003 to 252 m and a specific surface area of 200 to 2000 m'
/f, pore diameter is 0. jl ~200 nm.

According to a preferred embodiment of the present invention, the reaction is carried out in the presence of a halogenide, carboxylate, nitrate or carbonyl of said transition metal at a temperature of 200-400°C and a temperature of 5-40°C.
It is carried out under a pressure of MPa.

According to another preferred embodiment of the invention, the reaction comprises 15
The transition metals are obtained from reactions carried out in reactors made of nickel or cobalt alloys, carried out at temperatures of 0 to 400° C. and pressures of 3.5 to 21 MPa.

The halide cocatalyst is preferably an alkyl halide, an alkyl halide, an acyl halide or a dihalomethane.

The reaction is carried out in the presence of a solvent, if desired.

According to a further embodiment of the invention, the activity is preferably selected from among mineral acids, inorganic sulfur compounds, alkali metal or alkaline earth metal chlorides, hydroxides and oxides. in the presence of a activating agent (activator) for 1 to 25 hours,
Temperature of 500-1500℃ and 0.1-0.5 MPa
Reactivation (reactivation) by contacting with water vapor at a pressure of

Catalysts suitable for the practice of this invention contain soluble transition metals that are either added neat or derived from the materials that make up the reactor. A carbon bed is also necessary to the invention, which is preferably
It can be activated and washed if desired. Soluble metal catalysts can be selected from a wide variety of organic or inorganic compounds, complexes, and the like, as described below. It is only necessary that the catalyst precursor actually used contains the Group 1 metal in soluble form.

It has been found that a halide cocatalyst is required for carbonylation to occur through the general reaction mode outlined above.

The actual catalytically active species are unknown, but are believed to include metals of the group 2, which are complexed with the halogenide cocatalyst and cooperate with the activated carbon of the carbon bed.

The soluble metal catalyst precursors described above can take many different forms. The metal S used is generally the first
Group transition metals (Co, Ru, Fe.

N1XRhX Pa, Os, Ir and pt). The soluble Group 1 metal catalyst is a carbonyl, such as triruthenium dodecacarbonyl, dicobalt octacarbonyl, iron pentacarbonyl, nickel tetracarbonyl, diiron nonacarbonyl, or tetracobalt dodecacarbonyl. Alternatively, group VM metals can be prepared using salts of mineral acids, such as ruthenium trichloride, iron iodide@), iron nitrate (
cobalt(II) nitrate, cobalt(II) chloride, cobalt(II) chloride
) or added as nickel(II) iodide or as a salt of a suitable organic carboxylic acid, such as cobalt acetate(''), cobalt(1) acetate, nickel(II) propionate or iron naphthenate([). You can do it. It's a trench.
It may also be added to the reaction zone as a complex with a trisubstituted phosphorus compound or as an enolate salt. Suitable examples include cobalt(ho)2,4-pentanedionate and dichlorotris(triphenylphosphine)-ruthenium(6).

Preferred Group 1 soluble transition metal catalysts include carbonyl and chlorides. Particularly preferred are ruthenium chloride, ruthenium dodecacarbonyl and dicobalt octacarbonyl. The utility of these Group 1 transition metal precursors for acetic acid synthesis is particularly illustrated by Examples 1-12 below.

The amount of soluble transition metal used in this embodiment of the invention is not critical and can vary over a wide range.

The concentration of this metal is 5 ppm depending on the activity of the metal.
It can be set from less than m (for example, l'ppm) to more than 1000 ppm. The process according to the present invention is characterized in that the desired moieties are present in the presence of a catalytically effective amount of an active metal species in combination with a halogenide cocatalyst and in the presence of a solvent to provide the desired product in reasonable yield. , it is desirable to implement it. Based on the total weight of the reaction mixture, 0.1 to 50 weight -
Only about 0.0001% by weight with halogenide cocatalyst
The reaction will proceed if a group metal catalyst of 1 or less is used. The upper concentration limit may vary depending on a variety of factors, including catalyst cost, partial pressure of carbon oxide, operating temperature, and others. Based on the total moles of the reaction mixture, 0 metals
．． A suitable group metal catalyst concentration of 0.002 to 0.02 wt.% and an alkyl rogenide cocatalyst concentration of 5 to 15 mole are generally desirable values for carrying out the reaction according to this example.

According to another embodiment, either the reactor or the piping system for conducting the liquid to the reactor is manufactured from a cobalt alloy, a nickel alloy or a mixture of cobalt, nickel and other metals. According to this example, the reactor contains an inert material,
For example, if made of tantalum or glass, the tubing should be manufactured from a cobalt alloy, a nickel alloy, or a mixture of cobalt and nickel alloys.

According to this embodiment, no metal catalyst is physically added to the catalyst system, but trace amounts of metal catalyst entering the reaction system from the reactor wall or feed piping system are shown below in Examples 9-10. As such, it obviously increases the catalytic activity. Although these metals are not specifically added to the reactor, they may be present in trace amounts within the reactor, and when using a reactor with an inert lining, such as tantalum, the conversion of methanol to acetic acid may be affected. It was observed that the conversion could not be carried out with such high efficiency. Metal catalysts also require an activated carbon bed with pores that provide a high surface area, and this bed is optionally washed so that carbonylation activity is developed. at least lppm, for example 100-200ppm
The soluble metal catalyst present in an amount greater than or equal to that amount may be an inorganic compound and a complex of an inorganic compound, and is preferably a compound containing a Group 1 metal in ionic form. It has been found that a halide cocatalyst is required for the carbonylation to take place according to the reaction scheme outlined above. In addition to performing its normal function of promoting carbonylation, the halide cocatalyst is believed to also help dissolve traces of the active carbonylated metal from the metal surfaces it contacts.

The species that are actually catalytically active in this embodiment are trace amounts of CO or l'Ji complexed to the norogenide in combination with the high specific surface carbon of the carbon bed derived from peat or coal. It is thought to be made of metal.

Alloy composition is nickel 0~75qb1 cobalt O~75
% and the balance may be iron or other metal.

To improve the conversion of alkanol to carboxylic acid, the total amount of cobalt and nickel should be as high as 4%, 11). Common metal alloys that make the present invention possible include Type 316 stainless steel, No. 1 Steroid C and UM
There is Co-50f. To explain these compositions, the composition of type 316 stainless steel is Ni 10~
14%, Cr 16-18%, MO2-3%, Mn
2%, Si 1%, less than c, p and Si, balance Fe. The composition of No Steroid C is: Ni 56%, MO
17%, Cr 16.5%, W 4.5%, Fe 6%. UMCo-50 contains 0.049%, 28% Cr and 21% Fe. The amount of Group ■ transition metals is 5 to 2.
Good female results are obtained when the concentration is 0.00 ppm or higher. The preferred amount of metal has been found to be between 25 and iso ppm.

These trace metals are introduced into the reactor as a solution along with other reactants including methanol, a gas consisting essentially of carbon monoxide, and a halogenide cocatalyst on a bed of activated carbon. It has been found necessary to carry out the carbonylation of . A particularly preferred concentration of the norogenide cocatalyst is 5
Rinse with ~15 mulch. This cocatalyst component in the catalyst system can be introduced into the reaction zone in liquid or gaseous form or dissolved in a suitable solvent or reactant. Examples of preferred no-rogenide cocatalysts include no-rogenide (e.g., hydrogen iodide), gaseous hydriodic acid, alkyl norogenide having 1 to 12 carbon atoms, and no-rogenide. Aryl iodide (e.g. methyl iodide, ethyl iodide, 1-propane iodide, 2-butane iodide, 1-butane iodide, methyl bromide, ethyl bromide, benzene iodide, benzyl iodide), iodide Acyls (eg, acetyl iodide). Quaternary ammonium and phosphonylam halides (eg, tetramethylammonium iodide and tetrabutylphosphonium iodide) are also suitable as halogen components. Additionally, alkali metal and alkaline earth metal halides (eg, cesium iodide) may be used.

Alkyl iodides and alkyl bromides having 1 to 6 carbon atoms are also preferred reagents for the carbonyl reaction of the present invention. Most preferred are methane iodide, hydrogen iodide and methyl bromide.

The gas reacted with the liquid feed and passed over the activated carbon in the manufacturing process of the present invention is essentially -carbon oxide.

Carbon monoxide may be used with up to 90 volumes of one or more other gases. These other gases include one or more inert gases (eg, nitrogen, argon, and neon). Although hydrogen gas may be present, it is desirable not to be present since hydrogen reacts with carbon monoxide and reduces the efficiency of the carbonylation process.

The activated carbon bed over which the liquid feed stream is passed can be a fixed bed or a fluidized bed and is prepared from a porous solid.

The density of the solid is preferably 003 to 2. S c! t
/ymN Particularly preferably 0.05 to 1.5 r7r
It should be L/d. Fixed carbon beds can be prepared from porous carbon obtained by high temperature decomposition of amorphous activated carbon. The specific surface area of this type of activated carbon is 200-20
It is 00i/2. The carbon can be preformed from compacted granules, powders or particles. Powdered raw materials are not preferred. Materials derived from animals, plants or petroleum may also be used.

In the process of the present invention, contrary to the discussion in the prior art, it is clear that the pore size of the carbon source and the carbon in the carbon bed make a large difference in the selectivity of acetic acid, and that the temperature and temperature used in the prior art It has been found that by using lower temperatures the lifetime of the catalyst is significantly improved compared to prior art manufacturing methods.

In particular, contrary to the conventional wisdom that a limited activated carbon source that does not use crude oil as a feedstock does not make a difference in the behavior of the catalyst system, the present invention shows that It has been found that carbon sources derived from peat and coal offer particular advantages for the effectiveness of catalyst systems.

Not only is the efficiency improved by using a specific activated carbon source, but if the activated carbon has a specific pore size consisting of (
This pore size was observed in the production method of the present invention.
It has been found that better results are obtained with activated carbon from peat or coal sources. Best results are obtained when the pore size of the carbon source allows a higher specific surface area. A wide pore size in the range of 06 to 2 Q Q nm may be used, with pore sizes in the range of 2 to 12 Onin being preferred.

The activated carbon bed can be cleaned if desired.

The cleaning treatment is carried out using HF (hydrofluoric acid) solution or I (NO3
Nitric acid) solution is used in an amount of 5002 equivalents of carbon and 32000 equivalents of 9HNO, and the concentration of HNO in water is 2 to 30%.

When using an HF bath, the concentration in water is 10-55%. The cleaning time may range from 5 minutes to 24 hours, and the acid-washed carbon may be further washed with I(,O) to remove excess acid.

Suitable activated carbon sources that can be used in the production method of the present invention include N0RIT-RB-1 or 5ORBORNORIT
B-3 activated carbon X-Cal (NORIT and 5ORBOR
NORIT is a registered trademark of American Frit Company). Other activated carbon used is CARBOR
UNDUM GAC-616GA (CAR)
BORUNDUM is a registered trademark of Kennecott Corporation).

These activated carbons, manufactured by these manufacturers using the processes developed by them, are in the form of granules or pellets, and have a specific surface area of 100 to 1200 d/? It is explained. The method for producing activated carbon is Activated
Carbon, Manufacture an
dRegeneration.

A, Yehaakal, Noyes Dat
a Corporation, Park Ridg
E, New Jersey, 1978.

US Pat. No. 4,032,476 describes a method for producing granular activated carbon from sub-bituminous coal.

Coal is crushed and sieved into granules of 8 to 30 mesh, then mixed with phosphoric acid or other mineral acids, ground into powder, pressed into pellets, and then Granulate the mixture into 20 mesh pieces. The obtained granules were heated to 450° C. and heated at 800 to 900° C. for 4 to 5 hours in an atmosphere of nitrogen and water vapor to obtain activated carbon. The specific surface area of activated carbon granules is 9
00～] 050m'/liter, apparent retention is about 0.50
crt/? It is. Granules produced in this way are suitable for the practice of the invention. In order to obtain activated carbon granules that are better suited for the practice of the present invention, the steam activation treatment period can be extended to 5 hours or more.

Extending the steam treatment period in this way produces the desirable results of lower density, larger pore size, and larger specific surface area of the carbon granules compared to the values described in the aforementioned U.S. Pat. No. 4,032,476.

Elsevier publishing Co.
New York (, N, Y,.

1974 describes a general process for producing activated carbon in the form of pellets, for example from peat (which is also suitable for the practice of the invention). According to this manufacturing method, powdered peat is carbonized by heating to 300 to 500°C. The carbon powder is mixed with a binder (eg coal tar or pitch) and extruded through an orifice to obtain a solid extrudate. The extrudates are heated at high temperatures (600-1000<0>C) with controlled amounts of steam, air or carbon dioxide to produce extruded carbon with a high specific surface area, which is preferred for fixed bed applications of the present invention.

When carbonylation is carried out using methanol, acetic acid is obtained in good yield, with methanol conversion of 10-100%,
The selectivity to acetic acid is as high as 100%.

Solvents are generally not necessary for the practice of this invention. This is because the reactant, a low molecular weight alcohol, serves as a satisfactory solvent. However, if the transition metal compound or the norogenide cocatalyst is only partially soluble in the alkanol, a solvent may be used. In other cases, a solvent may be used to aid in product separation, for example, by forming an insoluble product layer or by co-distillation. In still other cases, a solvent may be used to aid in the dissipation of heat during the formation of the carboxylic acid by the exothermic reaction of -carbon oxide and alkanol. Solvents that can be used include compounds that are inert to the reaction conditions and do not interfere with the desired reaction.

Examples of suitable solvents include aliphatic or aromatic hydrocarbons such as pentane, 2-methylhexane, cyclohexane, benzene, toluene, o-, m- or p-xylene and ethylbenzene, and aromatic or aliphatic ethers, such as Eva, diphenyl ether, diethyl ether,
These include p-dioxane and tetrahydrofuran. Other solvents include aliphatic or aromatic ketones such as evaporation, acetone, 4-methyl-2-pentanone and acetophenone. Further suitable solvents are esters of carboxylic acids, such as alkyl acetates, alkyl propionates or alkyl octoates. Particularly preferred solvents are the small amounts of co-products obtained when carrying out the invention normally, such as methyl acetate, obtained as a co-product during the reaction of methanol with carbon monoxide, or -carbon oxide. and ethyl propionate obtained as a co-product during the reaction with ethanol. Other solvents include acetic acid, propionic acid, octanoic acid and isobutyric acid. Water may also be used as a solvent.

The temperatures useful for these syntheses are variable and are themselves a function of the composition of the reactor and feed piping, among others, the selection of the particular species of Group I soluble metal catalyst;
It depends on other experimental parameters including concentration and pressure. The operable range is 150-400°C, preferably 200°C using carbon monoxide pressure of 1 atm or more.
~400°C. The preferred temperature is 240-350°C,
A particularly preferred temperature is 240-300°C. By using activated carbon sources derived from peat or coal of special pore size - together with lower temperatures compared to the prior art,
Yields and selectivities are improved and catalyst system lifetimes are longer than any recorded in the prior art. Example j2
．． 16, the lifetime of the catalyst is between 96 and 218 hours, but the longest lifetime recorded for a conventional catalyst system is according to French Patent No. 2030118, which
It is as short as 4 hours (Example 14).

A pressure higher than atmospheric pressure, ie at least 3.5 MPa, substantially increases the yield of carboxylic acid by the process according to the invention. The preferred operating pressure range is 3.5-27.
5 MPa, but pressures higher than 27.5 MPa also provide useful yields of the desired acetic acid. The most preferred operating range is 7-17.5 MPa.

According to a preferred embodiment of the invention, the carbonylation catalyst used can be activated (reactivated) by the following step, for example after use for 10 to 300 hours or more.

W + 1 to 2 in the presence of an activator or activator if desired
5 hours, preferably 1 to 15 hours, at a temperature of 500°C or higher, preferably 500 to 1500°C and 01 to 0.5 Mp.
The deactivated carbon bed is contacted with steam under a pressure of a.

Activators can be selected from a wide range of organic and inorganic compounds. It is only necessary that these compounds help regenerate the pore structure of the deactivated carbon.

Generally, the activators used are alkali metals, alkaline earth metals and inorganic acids.

Suitable compounds containing alkali metals and alkaline earth metals include alkaline earth metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides and alkaline earth metal nologides. is included. Also suitable are oxides, hydroxides, carbonates and halides of alkali metals. Effective compounds include K2OXNaOH, KOH
Included are Xca(oH)2, M, CZ2 and BILO, with KOI being preferred.

Examples of suitable inorganic compounds for use as activators according to the invention are phosphoric acid, sulfuric acid and boric acid.

Metal salts, typically ZNCT and Na25o, and inorganic sulfur compounds, typically S and KNO2, are also suitable as activators.

Various other suitable activators known in the art and expected to function in accordance with the present invention include A, Ye
This is shown in the above-mentioned book by Haslcel.

The temperature range that can be usefully used in the activation process is variable and depends on other experimental parameters such as pressure, flow rate, contact time of deactivated catalyst with water or steam, type of catalyst used in the carbon bed or Depends on catalyst bed geometry. The operable range is 500°C to 1500°C. A narrower range of 650 to 800°C is preferred.

Pressures of 0.01 to 0.5 MPIL or higher substantially reactivate the deactivated catalyst. The preferred operating range is 0.1-0.5 MPa, but 0.5
Reactivation also takes place with pressures higher than MPa.

The time required for contacting the steam with the deactivated carbon catalyst and the reactivation reservoir is variable; for example, if the steam temperature is 705°C, a contact period of at least 3 hours is required to reactivate the catalyst. time is considered desirable.

It is expected that a relationship exists such that the higher the temperature and flow rate, the shorter the contact time required.

According to the production method of the present invention, the amount of carbon monoxide present in the reaction mixture should be a value sufficient to at least satisfy the stoichiometric relationship of the desired carbonylation reaction.

The main by-products of cholera acetate-ester synthesis are most commonly methyl propionate, propionic acid and its derivatives, and these compounds are of course also useful and important commercial products. Propionic acid and other products can be easily separated from each other by conventional means (eg, fractional distillation).

The products presented herein are suitable for gas-liquid chromatography (GLC), infrared analysis (IR), mass spectrometry,
Identified by nuclear magnetic resonance (NMR) and elemental analysis, one or more analytical techniques, or a combination thereof. Most analytical values are in parts by weight and all temperature values are in degrees Celsius (°C).
Furthermore, all pressure values are respectively indicated in MPa.

The invention will now be further explained by way of example.

EXAMPLE This example describes the use of ruthenium chloride as a soluble transition metal catalyst in combination with an activated carbon bed and an iodide methane cocatalyst. The effectiveness of the components used in the process of the present invention, as discussed above, allows for the use of significantly lower concentrations of soluble Group 1 metal-containing catalysts than in prior art processes.

In this example, N0RIT RB-1 activated carbon (100°C
nitric acid water bath solution, then deionized water, and finally dried under vacuum). Methanol 24329, iodized methane 1197? and Ru CL.

A solution consisting of 0.20 Or of H2O was fed continuously at 6-/h and 70001 nt/b of separated CO into the reactor (held at 275 DEG C. and 20.78 MPa). Analysis of the effluent after 32 hours revealed that it contained 97% acetic acid, 2% methyl acetate, and 1% water. Dimethyl ether was hardly detected.

Comparative Example IA The liquid supply flow rate was 12rn1. /h, Co flow rate is 1
2000rn1. The operation was carried out in the same manner as in Example 1, except that the operating conditions were changed so that /h. The typical acetic acid content of the effluent under these conditions was 96%.

Comparative Example IB Liquid supply speed is 20 m/h, CO supply speed is 20 tn
It was operated in the same manner as in Example 1 and Comparative Example IA, except that the operating conditions were changed so that the ratio was 1/h.

Analysis of the liquid showed a cyacetic acid content of 11%. The feed solution was collected. Black ruthenium-containing precipitate (]66.0%R
u was seen and no detectable l'iu was contained in solution (<ippm). By analyzing the initial solution,
Ru26PPm was shown.

Example 1 and Comparative Examples IA and IB show that the productivity of the catalyst system increases when low concentrations of Ru are used and that activity decreases as ruthenium is removed by precipitation.

Analysis of the effluent showed an average Ru content of 6 ppm, which was recovered if desired by concentrating the effluent and adding the concentrate to a fresh MeOH/MeI feed stream. Analysis of the used catalyst bed revealed that Ru
The electrical charge was about 0.6%.

Example 2 Essentially the same procedure as Example 1, except that the ruthenium source was changed to triruthenium dodecacarbonyl (Ru 3 Co) 12 and the concentration of ruthenium used was 18 ppm. I did it.

Table 1 below shows the acetic acid content of the effluent under the conditions indicated.

Table J 275 20.78 0.24 95.427
5 13.89 0.24 97.3275
10.44 0.24 97.6275 2
0.78 0.48 63.3290 8, 3
7 0.24' 76,. 1 operation time is 169
As shown in the last column of the table, the final activity showed a high value.

During storage of this feed for 3 months under atmospheric conditions,
No precipitation of ruthenium was expected.

Example 3 The procedure was essentially the same as in Example 1, but a cobalt-containing catalyst co, (co)8 was used instead of RuC1°.

The acetic acid contents in the effluents shown in Table 2 were obtained under the conditions shown in this table.

Table 2 Temperature Pressure Liquid hourly space velocity Acetic acid (tj (MPa) (rnl/h/ml reactor volume) (~) 285 20.7B 0,24
96.0285 13.39 0.24 93.
7285 13.39 0.48 63.7285
10.44 0.24 46.8 Operation time is 15
The catalyst activity at the end of the operation was the same as shown in the last sample.

Example 4 This is an example showing the unsuitability of using a silicon-containing compound as a substitute for the carbon bed in the production method of the present invention. Commercially available tablet-form silica (Caliaicat E-36
The same operation as in Example 3 was performed except that 1) was used instead of the carbon bed. Pressure 20.78MPR1 Liquid hourly space velocity 0.24 rrl/h/'+n/, temperature 285
The operation was carried out for 20 hours at °C. The maximum acetic acid content of the effluent during this period was 0.7%.

Example 5 Commercially available alumina (TJnited, C8,331-3
) was used as the filler, but the same operation as in Example 3 was carried out. Maximum content of acetic acid after 20 hours of operation is 0
It was 6%.

In the example, co2 (co)8 was used as in Example 3, but the carbon was not washed. 5ORBONORT
TB-3 was loaded into the reactor in the same condition as when it was received, but without washing. Pressure 19.75 MPIL.

Operating at a temperature of 265 DEG C. and a liquid hourly space velocity of o24y/h/-, the maximum content of acetic acid in the effluent was 972%.

Example 7 Feed liquid was Fe(Co)s 1.48 g, methanol 12
18′? and iodized methane 593? The same operation as in Example 1 was performed except that The filling was unwashed 5ORBONORIT B-3 carbon (with the receiver in place). After 115 hours of operation, the following results were obtained.

Temperature Pressure mg/h/ml HOA” (℃) (
MPa) Excellent) 285 20.78
0. ．． 24 92285 ], 0.44
0.40 85 Example 8 This is an example illustrating how soluble conolt used as a catalyst compound can be recovered for recycling to the feed stream.

Lots of effluents from Examples 3 and 6) (440,87)
combined into one. The cobalt content of the combined sample before distillation was 20.2 pPm. Uniform dark liquid35.
The sample was distilled at normal pressure until 749 remained. The analysis showed a CO content of 287v, which, if desired,
Can be recycled to the feed solution. The final distillation conditions were a pot temperature of 117°C, a top temperature of 117°C, and a pressure of 0.1 MPa.

The composition of the liquid portion of the residue was 99.3% of acetic acid, 0.2% of propion, and 0.5% of water.

Comparative Example 9 The reactor was operated in the same manner as in Example 6, except that the reactor was made of Hastelloy C and made of tantalum. Also, no soluble metals were added to the feed solution. Analysis of the feed stream taken at a point just upstream of the reactor revealed 5.6 ppm nickel,
Kobal) 0.7 ppm was indicated.

It was operated at a temperature of 285 °C, a pressure of 13.89 MPa and a feed space velocity of 0.40 rrl/h/me, and analysis of the effluent showed that the acetic acid content was 2 during 55 hours of operation.
It was shown that the value was within the range of 4 to 34.

Example 10 Soluble nickel 8i (Nil
The procedure was as in Comparative Example 9, except that 2) was introduced into the feed solution. Analysis of the feed solution immediately upstream of the reactor revealed 3 ppm cobalt and 111 ppm nickel.
It has been shown. The acetic acid content of the effluent was generally 85-90%.

Example 11 The same procedure as Comparative Example 9 was carried out, except that dicobalt octacarbonyl was added to the feed stream 27507. The acetic acid content of the effluent was generally 94-96%.

Example 12 This demonstrates the use of activated carbon derived from peat at temperatures lower than those used in the prior art to produce an effluent with an acetic acid content of over 90% after 4 days of continuous operation. This is an example in which an effluent with an acetic acid content of 90% or more is produced even after 4 days of continuous operation.

In this example, commercial grade activated carbon derived from peat (NORIT RB-1,) was heated with boiling HNO
Washed with 350% solution. A 25 ml tubular reactor made of a nickel alloy (STEROY C) was filled with this carbon. A 90 molar timethanol 710 molar iodide methane solution was continuously pumped into the reactor at a flow rate of 10 ni/h while CO was metered simultaneously to a flow rate of 12000 me/h. The temperature and pressure of the reactor were set to 285°C and 1
The pressure was maintained at 3.89 MPa.

After 26 hours of operation, the effluent was analyzed and found to be 94.3% acetic acid,
43% methyl acetate was shown. The composition of the effluent after 49 hours was 964% acetic acid and 28% methyl acetate. After 4 days of continuous operation, the acetic acid content of the effluent was still higher than 90%.

Example 13 This is an example showing the results when activated carbon having a specific surface area about 10 cm higher than N0RIT RB-1 was used.

The procedure was as in Example 12, except that the activated carbon used was 5oRBoNRITB-3 (as received from the manufacturer). Analysis of the effluent after 18 hours revealed that it contained 95.1% acetic acid and 29% methyl acetate.
It has been shown. The composition of the effluent after 42 hours was 95% acetic acid.
3%, methyl acetate 3.1%.

Example 14 This example demonstrates the improvement of the process of the present invention in obtaining relatively long catalyst life by using relatively low temperatures and relatively high pressures in combination with activated carbon sources having pore sizes in the range of For purposes of comparison, a similar operation was carried out as in Example 13, except that reaction conditions more similar to those of the prior art (FR 2030118) were used.

In this Example 14, the same operation as in Example 14 was performed except that the reactor temperature was maintained at 315° C. and the pressure was maintained at 8.37 MPa. Table 3 below shows the results of the analysis of the effluent after a given period of time.

Table 3 Time (h) Acetic acid content Methyl acetate content 16
84°4 6.023
3.9 2.840
None 1.7 Initially, a considerable amount of acetic acid is produced, but as the catalyst quickly deactivates, the amount of acetic acid produced drops to zero after only 40 hours of operation.

Example 15 This is an example demonstrating the improved results of the present invention obtained using relatively lower temperatures (i.e. below 300°C and above 250°C) in contrast to Example 14. be.

The operating temperature was increased to 250°C for 23 hours and then to 26°C.
The same operation as in Example 13 was performed except that the temperature was 5°C.

The following table shows the analytical values for the effluent sample.

Table 4 22 250 13.9 7.950 26
5 45.8 19.8 This example and the results of Example 13 indicate that it is desirable to conduct the reaction at a temperature higher than 265°C and lower than 300°C in order to obtain a high selectivity for acetic acid. ing.

Example 1 is an example showing the results obtained using a wide pore size activated carbon derived from coal.

The carbon used is CARBORUNDUM GAC616
The same operation as in Example 12 was performed except that GA was used. The following table shows the analytical values of the effluent obtained after various continuous operating times.

Repetition time Acetic acid content (I) Methyl acetate content (A)
46 94
372 98
1144 98
1164 94
51 88
90 8218
It can be seen that a high conversion rate of methanol and a high selectivity to acetic acid and methyl acetate were achieved even after 70 hours of continuous operation.

Examples 17-20 These Examples 17-20 demonstrate the varying results obtained by reacting carbon monoxide and methanol on various sources of activated carbon.

As shown in the following table, the operation of Example 13 was carried out using a variety of filt-type activated carbons. The following table also shows the composition of the effluent after various operating periods.

17 WiLcarb Columbia
22 4 7 9 JXC (oil source) 63 0219 Carbo
rundum 23 20
520 Arrow briqu
eMomoe 18 78
(activated at 720° C. with 15H, C1) These examples and the results of Examples 12 and 13 show that carbon extracted from peat is superior to other carbons.

Example 21 This example demonstrates the initial use of a 5ORBONORIT B-3 carbon catalyst bed and the effect that use of the reactivation method according to the present invention has on the used catalyst.

a) Capacity 2.5 made of nickel alloy () / Steroid C)
- 5ORBONORIT B-3 activated carbon (derived from peat, with a specific surface area of about 1000 rr)
? /li carbon) was filled. While measuring CO at the same time to a flow rate of 120007/h, methanol 90
A 10 molar solution of mol %/methane iodide was continuously pumped into the reactor at a flow rate of 10 -/h.

The temperature and pressure of the reactor were set to 285°C and 13.89°C, respectively.
It was maintained at MPa. The composition of the effluent after 42 hours was: acetic acid 9
5.3%, and methyl acetate 31%.

After 88 hours, the catalyst activity decreased and the composition of the effluent changed to H2
0/methanol 95 units, methyl iodide/methyl acetate 4.7
Furthermore, the amount of acetic acid was only 0.5%.

b) Maintain the reactor temperature at 315°C and the pressure at 8,37°C.
The operation was repeated as above, except that the pressure was maintained at MPa. After 40 hours of continuous operation, the catalyst activity decreased and the amount of methyl acetate produced was only 17 inches, and the amount of acetic acid in the effluent was zero.

C) Maintain the pressure at 13.89 MPa and the operating temperature at 23
The procedure was as described above, except that the temperature was 250°C for one hour and 265°C for the next 96 hours. After the end of the operating period, the acetic acid content of the effluent was 10.2%,
The maximum content of acetic acid (during a total operating period of 50 hours) was 46
It was Chi.

The central part of the used catalyst beds from the three operations described above was combined and optically mixed. 45 ml of this was packed into a quartz tube and heated to 705°C in a nitrogen stream. Keep the temperature of the area at 710±10℃ for 7 hours
20 introduction was further continued at a rate of 0.191 or 117 minutes.

Example 22 Reactor temperature was maintained at 285°C and pressure was 13.89MP
Example 21 (+
)) was repeated. The acetic acid selectivity and catalytic activity were excellent.

The acetic acid content of the effluent after 26 hours was 95.2%. The acetic acid content of the effluent after 120 hours was 11.2 and 14.
The acetic acid content after 1 hour was only 0.8%.

Example 23 This is a twice reactivated 5ORBONRIT B-
This is an example showing the use of 3 carbons. In this example, the lot of carbon used in Example 22 was replaced with the lot of carbon used in Example 21.
It was subjected to the same reactivation treatment as in (d). The procedure of Example 22 was then repeated using the twice reactivated carbon material. The reactor was operated for 24 hours and the acetic acid content in the effluent was 92.0% after 18 hours of operation.

Example 24 This is an example showing the reactivation process when carbon was used in the presence of a cobalt catalyst.

a) CO in the feed stream as (co2(co), )
,lllppm exists, acid washed N0RIT
RB-1 activated carbon at 285°C and 13.89 MPa for 11
The same operation as in Example 21 was carried out, except that it was used for 2.5 hours. Near the start of the operation (for example, 2 after the start of the operation)
The acetic acid content in the effluent at 4 hours) was 95%, but near the end of the run the acetic acid content was only 0.7%.

b) 140&9J'tiJ285℃, 13.89
MPar operation.

After that, the temperature was increased to 310℃ and the liquid flow was increased to 70 (10m1
The procedure of this example was repeated, except that the operation was carried out for an additional 6 hours, with the gas flow reduced to 7000 d/h. The acetic acid content of the effluent after 146 hours of operation was 5.3%.

The carbon described above according to this example remained in the reactor. N20 was introduced at a flow rate of 4 rnl/b for 9 hours, the reactor temperature was maintained at 360'C, and the pressure was 148 MPa.
I kept it. Using this carbon, the pressure was 13.89 MPa.
, when the operation was performed as described above at a temperature of 285°C,
An acetic acid-free effluent was obtained.

d) The centers of the two used catalyst beds of this example were combined, mixed well and placed in a quartz tube. H,O in a N2 stream for 2.5 hours 0.191-7 minutes, then for an additional 1
705 i/min while supplying at a rate of 0.0764i/min.
Regeneration was performed at a temperature of ~710°C. Carbon 32m7! was first charged, and 32- was recovered.

e) The operation of Example 22 was carried out using recycled carbon. The acetic acid content in the effluent collected during the first 16 hours was 14
．． 3%, and the methyl acetate content was 6.896. The effluent collected thereafter contained no acetic acid.

This is an example of how the relatively slow regeneration operation used in Example 21 is not as effective.

Continuation of page 1 @Int, C1,3 identification symbol Internal office reference number C0
7C69/14 6556-4H
Priority claim @March 25, 1983■United States (US)■
478829 @March 25, 1983 [Phase] United States (US) ■4788
30 0 Inventor John Harold Estes New York 12 590 Watupingers Falls Cedar Hill Road RFD 6 0 Inventor Roger George DeJurrenlieu George Town Route 5 Boxes 78626 Texas 78626 United States 87

Claims (1)

[Claims] 1) Temperature of 1.50 to 400°C and at least 35M
In a process for the continuous production of carboxylic acids and esters by reacting carbon monoxide with alkanol in the presence of a halide cocatalyst and solid carbon at a pressure of at least 1 p of a transition metal selected from cobalt, ruthenium, iron, nickel, rhodium, palladium, osmium, iridium and platinum;
A manufacturing method characterized in that the reaction is carried out in the presence of Pm. 2) The reaction is carried out in the presence of a halide, carboxylate, nitrate or carbonyl of the transition metal at a temperature of 200 to 400°C and a pressure of 5 to 40 MPa. The manufacturing method according to item 1. 3) Temperature of 150-400℃ and 3.5-21Mpa
2. A process according to claim 1, characterized in that the reaction is carried out at a pressure of 0.05 to 0.000, and the transition metal results from the reaction carried out in a nickel or cobalt alloy reactor. 4) Temperature of 500-1500°C and 0.1-0.5
4. The production method according to claim 1, wherein the catalyst is reactivated by contacting with steam for 1 to 25 hours at a pressure of MPa.