JPH0327543B2 - - Google Patents

Description

[Detailed description of the invention]

Acetic acid has long been known as an industrial chemical and is used in large quantities in the production of a variety of other chemical products. Various proposals for producing carboxylic acids by the action of carbon monoxide on alcohols (carbonylation) have been disclosed in the 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 shown to perform the carbonylation of methanol in the presence of iodide at low pressures such as 3 MPa when certain organic amines or phosphines are included in the liquid reaction medium. It has been reported that it is an effective catalyst for the reaction (Federal Republic of Germany Publication No. 2749955 and Japanese Patent Publication No. 54-59211). Roth and Pawlik (Roth et al.Chemtech 1971,
600; Ross Chem.Commun. 1968, 1578) found that carbonyl complexes of rhodium exhibited excellent activity in the carbonylation of 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 through extensive research on catalytic reactions with rhodium (Forster et al. J.
Am.Chem.Soc.1976 98 846; Hjortkjaer and
Jensen.Ind.Eng.Chem.Prod.Pes.Dev.1976 15
46). Rhodium can be supported on activated carbon or metal oxides by impregnation methods (Schultz and
Montgomery J. Catal.1969 13, 105; Robinson
et al.J.Catal.1972 27., 380; or Krzywicki
and Marczewsi J.Mol.Catal.1979 6, 431) or supported on zeolite by ion exchange method (Yashima et al.J.Catal.1979 59 53;
Andersson and Scurrel J. Catal.1979 59, 340;
or Scurrell and Howe J.Mol.Catal.1980 7,
(535), the methanol gas phase is also an effective catalyst for carbonylation. French patent (FR-A) No. 2030118 discloses that on an activated carbon bed, the
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 _HNO3 (nitric acid) solutions if desired, involves heating the carbon in a nitrogen stream at 0.1 MPa for 1-2 hours. This is achieved by doing. The disadvantages of this catalytic system are that fairly high temperatures are generally used, that the catalytic system deactivates after a relatively short period of time, that for best results the carbon bed must be activated with nitrogen; Furthermore, no significant differences in the results obtained using various different types of carbon beds have been previously reported. Indian Journal of Technology, Vol.5, 266
(1967) disclose a method for the synthesis of methyl formate from methanol and carbon monoxide in the presence of an alkali-activated charcoal catalyst. It has been reported that increasing the pressure increases the conversion rate, but at temperatures above 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. The aim is to provide a system. Another object of the present 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 is characterized in that monoxide is produced under high temperature and pressure in the presence of a halide cocatalyst, activated carbon and at least 1 ppm of a transition metal selected from cobalt, ruthenium, iron, nickel, rhodium, palladium, osmium, iridium and platinum. In the method for continuously producing carboxylic acid and its ester by reacting carbon and alkanol, the activated carbon is derived from coal or peat and has a density of 0.03 to 2.5 g/cm ³ ,
It has a specific surface area of 200 to 2000 m ² /g,
And the reaction temperature is 240~300℃ and the pressure is 3.5
This is a method for continuous production of carboxylic acids and their esters, characterized in that the process is carried out at ~27.5 MPa. According to a preferred embodiment of the invention, the reaction is
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 27.5 MPa. According to another preferred embodiment of the invention, the reaction is carried out at a temperature of 150 to 400 °C and a pressure of 3.5 to 21 MPa, and the transition metal is obtained from the reaction carried out in a reactor made of nickel or cobalt alloy. . The halide cocatalyst is preferably an alkyl halide, a hydrogen 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 activator is preferably selected from mineral acids, inorganic sulfur compounds, halides, hydroxides and oxides of alkali metals or alkaline earth metals. agent)
for 1 to 25 hours at a temperature of 500 to 1500°C and
Reactivation (reactivation) by contacting with water vapor at a pressure of 0.1 to 0.5 MPa. 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, but it is preferably activated and can be cleaned 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 a metal of the group in soluble form.
A halide cocatalyst is required for the carbonylation to take place according to the general reaction scheme outlined above. The actual catalytically active species are unknown, but are believed to include group metals that are complexed with the halide 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 species used are generally group transition metals (Co, Ru, Fe,
Nu, Rh, Pd, Os, Ir and Pt). The soluble group metal catalyst is a carbonyl, such as triruthenium dodecacarbonyl, dicobalt octacarbonyl, iron pentacarbonyl, nickel tetracarbonyl, diiron nonacarbonyl, or tetracobalt dodecacarbonyl. Alternatively, the group metal can be added as a salt of a mineral acid, such as ruthenium trichloride, iron iodide (2000), iron nitrate (2018), cobalt nitrate (2018), cobalt chloride (2019) or nickel iodide (2018), It may also be added as a salt of a suitable organic carboxylic acid, such as cobalt acetate (), cobalt acetate (), nickel propionate () or iron naphthenate (). 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(2,4-pentanedionate) and dichlorotris(triphenylphosphine).
-Ruthenium (). Preferred Group soluble transition metal catalysts include carbonyls and halides. Particularly preferred are ruthenium chloride, ruthenium dodecacarbonyl and dicobalt octacarbonyl. The utility of these group 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 varies from less than 5 ppm (for example 1 ppm) depending on the activity of the metal.
It can be 1000ppm or more. The process according to the invention is carried out in the presence of a catalytically effective amount of an active metal species in combination with a halide cocatalyst and, if desired, a solvent that provides a reasonable yield of the desired product. is desirable. The reaction proceeds with as little as about 0.0001 weight percent or less Group metal catalyst, based on the total weight of the reaction mixture, with 0.1 to 50 weight percent halide cocatalyst. The upper concentration limit may vary depending on a variety of factors, including catalyst cost, carbon monoxide partial pressure, operating temperature, and others. Suitable Group metal catalyst concentrations of 0.002 to 0.02 weight percent metal and alkyl halide cocatalyst concentrations of 5 to 15 mole percent, based on the total moles of the reaction mixture, were used to carry out the reaction according to this example. This is generally a desirable value. 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 embodiment, if the reactor is made of an inert material, for example tantalum or glass, the tubing should be made 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 that enter the reaction system through the reactor wall or feed piping system are
As shown later in Example 8, it clearly increases the catalytic activity. Although these metals are not specifically added to the reactor, they are present in trace amounts in the reactor and can inhibit the conversion of methanol to acetic acid when using a reactor with an inert lining, such as tantalum. It has been found that this does not occur with very 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 1ppm, e.g. 100
The soluble metal catalyst present in an amount of ˜200 ppm or more may be an inorganic compound and a complex of inorganic compounds, preferably a compound containing a group 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. In this embodiment, the actual catalytically active species consists of trace amounts of Co or Ni metals complexed with halides in combination with the high specific surface carbon of the carbon bed derived from peat or coal. it is conceivable that. Alloy composition is nickel 0-75%, cobalt 0-75%
75% and the balance may be iron or other metal. For good conversion of alkanol to carboxylic acid, the total amount of cobalt and nickel should be greater than 4%. Common metal alloys that enable the practice of this invention are Type 316 stainless steel, Hastelloy C, and UMCo-50. To explain these compositions, the composition of type 316 stainless steel is Ni 10-14%, Cr 16-18%, Mo 2-
3%, Mn 2%, Si 1%, P and S less than 1%,
The remainder is Fe. The composition of Hastelloy C is Ni 56
%, Mo 17%, Cr 16.5%, W 4.5%, Fe 6%
It is. UMCo−50 contains 49% Co, 28% Cr and Fe
Contains 21%. Group transition metal amount from 5 to
Good results are obtained when the concentration is 200 ppm or more. The preferred amount of metal has been found to be between 25 and 150 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 halide cocatalyst on a bed of activated carbon. Generally, 1 to 20 mole percent of the halide found necessary to effectuate the desired carbonylation should be present. Particularly preferred halide cocatalyst concentrations are from 5 to 15 mole percent. 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 halide cocatalysts include hydrogen halides (e.g.
Hydrogen iodide), gaseous hydriodic acid, 1 carbon atom
~12 alkyl and aryl halides (e.g., methyl iodide, ethyl iodide, 1-propane iodide, 2-butane iodide, 1-butane iodide,
Methyl bromide, ethyl bromide, benzene iodide, benzyl iodide), acyl iodide (e.g. acetyl iodide)
There is. Quaternary ammonium and phosphonium 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 iodide and alkyl bromide cocatalysts containing 1 to 6 carbon atoms are also preferred reagents for the carbonyl reactions of this 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 monoxide. Carbon monoxide may be used with up to 90% by volume of one or more other gases. These other gases include
There is 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
0.03 to 2.5 g/cm ³ , particularly preferably 0.05 to 1.5 g
It should be m/ ^cm3 . 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 between 200 and 2000 m ² /g. 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, the pore size of the carbon source and the carbon in the carbon bed makes a large difference in the selectivity of acetic acid, and the temperature is lower than that used in the prior art. It has been found that the use of temperature significantly improves catalyst life compared to prior art manufacturing methods. In particular, the activated carbon source does not make any difference in the behavior of the catalyst system unless crude oil is used as a feedstock.
Contrary to the dogma of the prior art, the present invention specifically provides
It has been found that carbon sources derived from peat and coal offer particular advantages for the effectiveness of catalyst systems, as shown by 10, 11, 12. Not only is the efficiency improved by using a specific activated carbon source, but also if the activated carbon has a specific pore size, which is It has been found that even 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 range of pore sizes ranging from 0.6 to 200 nm may be used, with pore sizes ranging from 2 to 120 nm being preferred. The activated carbon bed can be cleaned if desired. Cleaning treatment is performed using HF (hydrofluoric acid) solution or
HNO ₃ (nitric acid) solution HNO ₃ 2000ml per 500g of carbon
The concentration of _HNO3 in water is 2-30%. When using HF solution, the concentration in water is 10-55
%. The cleaning time may be between 5 minutes and 24 hours.
Further, the acid-washed carbon may be further washed with H ₂ O to remove excess acid. A suitable activated carbon source that can be used in the production method of the present invention is NORIT-RB-1 (density 0.42-0.45
g/cm ³ , specific surface area 900-1000m ² /g) or
SORBORNORITB-3 (density 0.38-0.42g/ ^cm3 ,
It is activated carbon with a specific surface area of 1050 to 1200 m ² /g (NORIT and SORBORNORIT are American
(Registered trademark of Noritz Company). Other activated carbon used is CARB ORUNDUM
GAC-616GA (density 0.32g/cm ³ , specific surface area 1000~
1200 m ² /g) (CARBORUNDUM is a registered trademark of Kennekotsu Corporation). These activated carbons produced by these manufacturers using processes developed by them are in the form of granules or pellets. The method for producing activated carbon is
Activated Carbon, Manufacture and
Regeneration, A. Yehaskel. Noyes Data
Corporation, Park Ridge, New Jersey, 1978
It is described in. US Pat. No. 4,032,476 describes a method for producing granular activated carbon from sub-bituminous coal.
The 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 Make it into granules so that it has 20 mesh pieces. The obtained granules were heated to 450℃ and heated to 4-5
Activated carbon was obtained by heating at 800-900° C. for hours in an atmosphere of nitrogen and water vapor.
The specific surface area of activated carbon granules is 900 to 1050 m ² /g,
The apparent density is approximately 0.50 g/cm ³ . 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. This extended period of steaming produces the desirable result of lower density, larger pore size, and larger specific surface area of the carbon granules compared to the values described in US Pat. No. 4,032,476. M. Smisek and S. Cervy, Active Carbon,
Manufacture, Properties and Applications;
Elsevier Publishing Co., New York, NY;
1974 describes a general process for producing activated carbon in pellet form, for example from peat (which is also suitable for the practice of the invention). According to this production method, powdered peat is produced at temperatures of 300 to 500℃.
It is carbonized by heating to . The carbon powder is mixed with a binder (eg coal tar or pitch) and extruded through an orifice to obtain a solid extrudate. This extrudate is heated at high temperature (600°C) with controlled amounts of water vapor, air or carbon dioxide.
~1000° C.) to produce a high specific surface area extruded carbon preferred for fixed bed applications of the present invention. Carbonylation using methanol gives acetic acid in good yield, with methanol conversion of 10
~100%, and the selectivity to acetic acid can be as high as 100%. Solvents are generally not required for the practice of this invention. This is because the reactant, low molecular weight alcohol, serves as a satisfactory strength agent. However, if the transition metal compound or halide 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 exothermic reaction of carbon monoxide and alkanol to form the carboxylic acid. 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,
These include 2-methylhexane, cyclohexane, benzene, toluene, o-, m- or p-xylene and ethylbenzene, as well as aromatic or aliphatic ethers such as diphenyl ether, diethyl ether, p-dioxane and tetrahydrofuran. Other solvents include aliphatic or aromatic ketones such as 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 and carbon monoxide, or carbon monoxide and ethanol. Ethyl propionate is obtained as a co-product during the reaction with Other solvents include acetic acid, propionic acid, octanoic acid and isobutyric acid. Water may also be used as a solvent. The temperatures that can be usefully used in these syntheses are variable and depend on the selection of the particular species of Group soluble metal catalyst, concentration and pressure, which themselves are a function of the composition of the reactor and feed piping, among other things. and other experimental parameters. The operable range is 150-400°C, preferably 200-400°C using carbon monoxide pressures of 1 atmosphere or more.
Preferred temperatures are 240-350°C, particularly preferred temperatures are 240-300°C. By using a special pore size, peat- or coal-derived activated carbon source, and lower temperatures compared to the prior art, yields and selectivities are improved and are higher than any recorded value for the prior art. A long service life of the catalyst system is obtained. According to Examples 10, 12, 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,
This is shorter than 24 hours (Comparative Example 4). Pressure higher than atmospheric pressure, i.e. at least 3.5MPa
substantially increases the yield of carboxylic acid by the production method according to the invention. The preferred operating pressure range is
Pressures between 3.5 and 27.5 MPa, but 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 reactivated by the following step, for example after use for 10 to 300 hours or more. If desired in the presence of an activator or activator,
1 to 25 hours, preferably 1 to 15 hours, at 500°C or higher,
The deactivated carbon bed is contacted with steam, preferably at a temperature of 500-1500°C and a pressure of 0.1-0.5 MPa. 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 carbonates of alkaline earth metals;
Included are alkaline earth metal oxides, alkaline earth metal hydroxides, and alkaline earth metal halides. Also suitable are oxides, hydroxides, carbonates and halides of alkali metals. Effective compounds include _K2O , NaOH, KOH, Ca(OH) ₂ ,
Included are MgCl ₂ and BaO, with KOH 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 ZnCl ₂ and Na ₂ SO ₄ and inorganic sulfur compounds, typically K ₂ S and KNCS, also
Suitable as an activator. Various other suitable activators known in the art and expected to function in accordance with the present invention are set forth in A. Yehaskel, supra. The temperature range that can be usefully used in the activation process is
It 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 catalyst bed geometry. The operable range is
The temperature is 500-1500℃. A narrower range of 650 to 800°C is preferred. When the pressure is 0.01~0.5MPa or more,
The deactivated catalyst is substantially reactivated. The preferred operating range is 0.1-0.5MPa, but 0.5MPa
Reactivation also occurs with higher pressures. The time required for the steam to contact the deactivated carbon catalyst for reactivation is variable; for example, if the steam temperature is 705°C, it will take at least 3 hours to reactivate the catalyst. Contact 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 major by-products of these acetate-ester syntheses 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 can be used 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 given in parts by weight, all temperature values in degrees Celsius (°C), and all pressure values in MPa. The invention will now be further explained by way of example. Example 1 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 metal-containing catalysts than in prior art processes. In this example, a 25 ml capacity Hastelloy C down-flow tubular reactor was filled with NORIT RB-1 activated carbon
Wash with aqueous nitric acid solution at 100 °C, then with deionized water,
Finally, it was filled with vacuum-dried material. 2432g methanol, 1197g iodized methane and RuCl ₃ H ₂ O
A solution consisting of 0.200 g was fed continuously at 6 ml/h and CO at 700 ml/h to the reactor (held at 275° C. and 20.78 MPa). Analysis of the effluent after 32 hours revealed 97% acetic acid, 2% methyl acetate, and 1% water.
It was %. Dimethyl ether was hardly detected. Example 2 Liquid supply flow rate is 12 ml/h, CO flow rate is 12000
The operation was carried out in the same manner as in Example 1, except that the operating conditions were changed so that the flow rate was ml/h. The typical acetic acid content of the effluent under these conditions was 96%. Example 3 The procedure was essentially the same as in 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. Table 1 below shows the acetic acid content of the effluent under the conditions indicated.

[Table] The operation time was 169 hours, and the final activity showed a high value as shown in the last column of the table. No precipitation of ruthenium was observed during storage of this feed under atmospheric conditions for three months. Example 4 The procedure was substantially the same as in Example 1, but
A cobalt-containing catalyst _Co2 (CO) ₈ was used instead of _RuCl3 . The acetic acid contents in the effluents shown in Table 2 were obtained under the conditions shown in this table.

[Table] The operation time was 150 hours, and the catalyst activity at the end of the operation was as shown in the last column. Comparative Example 1 This is an example showing the unsuitability of using a silicon-containing compound instead of a carbon bed in the production method of the present invention. The same procedure as in Example 4 was carried out, except that commercially available tablet silica (Calisicat E-361) was used in place of the carbon bed. pressure
20.78MPa, liquid space velocity 0.24ml/h/ml, 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%. Comparative Example 2 The same operation as in Example 4 was performed except that commercially available alumina (United CS.331-3) was used as the filler. The maximum content of acetic acid during 20 hours of operation is
It was 0.6%. Example 5 In this example, Co ₂ (CO) ₈ was used as in Example 4, but the carbon was not washed.
SORBONORIT B-3 was loaded into the reactor in the same condition as received, but without cleaning.
Pressure 19.75MPa, temperature 265℃, liquid space velocity 0.24ml/
Operating at h/ml, the maximum content of acetic acid in the effluent is
It was 97.2%. Example 6 The same procedure as in Example 1 was carried out, except that the feed solution consisted of 1.48 g of Fe(CO) ₅ , 1218 g of methanol and 593 g of iodized methane. The packing was unwashed SORBONORIT B-3 carbon (as received). After 115 hours of operation, the following results were obtained.

EXAMPLE 7 This is an example showing how soluble cobalt used as a catalyst compound is recovered for recycling to the feed stream. Lot of effluent from Examples 4 and 5 (440.8
g) were combined into one. The cobalt content of the combined sample before distillation was 20.2 ppm. The sample was distilled at normal pressure until 35.74 g of a homogeneous dark colored liquid remained.
Analysis shows a Co content of 287 g, which can be recycled to the feed solution if desired. The final distillation conditions were: pot temperature 117℃;
The top temperature was 117°C and the pressure was 0.1 MPa. The composition of the liquid part of the residue is 99.3% acetic acid and 0.2% propionic acid.
% and water 0.5%. Comparative Example 3 The reactor was operated in the same manner as in Example 5, except that the reactor was made of tantalum instead of Hastelloy C. Also, no soluble metals were added to the feed solution. Analysis of the feed stream taken at a point just upstream of the reactor showed 5.6 ppm nickel and 0.7 ppm cobalt. Operating at a temperature of 285°C, a pressure of 13.89 MPa, and a feed space velocity of 0.40 ml/h/ml, analysis of the effluent revealed that the acetic acid content was between 24 and 34% during 55 hours of operation.
It was shown that the value was within the range of . Example 8 Supplying Soluble Nickel Species (NiI ₂ ) by Contacting the Feed Stream (Prior to Entering the Reactor) with a Nickel Metal Alloy (Stainless Steel) During Transfer from the Feed Tank to the Reactor The procedure was carried out in the same manner as in Comparative Example 9, except that the sample was introduced into the liquid. Analysis of the feed solution immediately upstream of the reactor revealed cobalt
3ppm and nickel 111ppm. The acetic acid content of the effluent was generally 85-90%. Example 9 The same procedure as in Comparative Example 9 was carried out, except that dicobalt octacarbonyl was added to the 2750 ml feed stream. The acetic acid content of the effluent was generally 94-96%. Example 10 This shows that activated carbon derived from peat was used at temperatures lower than those used in the prior art to produce an effluent with an acetic acid content of more than 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
Washed with _HNO3 50% solution. A tubular reactor made of nickel alloy (Hastelloy C) with a capacity of 25 ml was filled with this carbon. A 90 mol% methanol/10 mol% iodide methane solution was continuously pumped into the reactor at a flow rate of 10 ml/h while CO was metered simultaneously at a flow rate of 12000 ml/h. Reactor temperature and pressure respectively 285
℃ and kept at 13.89MPa. Analyze the effluent after 26 hours of operation and find that acetic acid 94.3
%, methyl acetate 4.3%. The composition of the effluent after 49 hours was 96.4% acetic acid and 2.8% methyl acetate. After 4 days of continuous operation, the acetic acid content of the effluent was still higher than 90%. Example 11 This has a specific surface area of about 10 more than NORIT RB-1.
% activated carbon is used. The procedure was as in Example 10, except that the activated carbon used was SORBONRIT B-3 (as received from the manufacturer). Analysis of the effluent after 18 hours showed 95.1% acetic acid and 2.9% methyl acetate. The composition of the effluent after 42 hours was 95.3% acetic acid and 3.1% methyl acetate. COMPARATIVE EXAMPLE 4 This example compares improvements in the process of the present invention that provide relatively long catalyst lifetimes by using relatively low temperatures and relatively high pressures in combination with activated carbon sources having a range of pore sizes. The same procedure as in Example 11 was carried out, except that reaction conditions more similar to those of the prior art (French Patent No. 2030118) were used to demonstrate. In Comparative Example 4, the same operation as in Example 11 was performed except that the reactor temperature was maintained at 315° C. and the pressure at 8.37 MPa. Table 3 below shows the results of the analysis of the effluent after a given period of time.

[Table] 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 12 This is an example showing the results obtained using wide pore size activated carbon derived from coal. The carbon used is CARBORUNDUM GAC
The same operation as in Example 10 was performed except that 616GA was used. The following table shows the analytical values of the effluent obtained after various continuous operating times.

[Table] It can be seen that high methanol conversion and high selectivity to acetic acid and methyl acetate were achieved even after 218 hours of continuous operation. Example 13 This example demonstrates the initial use of a SORBONORIT 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) Made of nickel alloy (Hastelloy C) with a capacity of 25ml
SORBONORIT B-3 activated carbon (derived from peat, with a specific surface area of approximately 1000
m ² /g of carbon). CO 12000ml/h
90 mol% methanol/10 mol% iodized methane solution, while simultaneously measuring so that the flow rate is .
It was continuously pumped into the reactor at a flow rate of 10 ml/h. The temperature and pressure of the reactor were set to 285℃, respectively.
It was maintained at 13.89MPa. The composition of the effluent after 42 hours was 95.3% acetic acid and 3.1% methyl acetate.
After 88 hours, the catalyst activity decreased and the composition of the effluent was 95% H ₂ O/methanol, 4.7% methane iodide/methyl acetate, and only 0.5% acetic acid. (b) Maintain the reactor temperature at 315℃ and reduce the pressure.
The operation was repeated as above, except that the pressure was kept at 8.37 MPa. After 40 hours of continuous operation, the catalyst activity decreased and only a small amount of methyl acetate was produced.
The amount was 1.7%, and the amount in the effluent was zero. (c) Maintain pressure at 13.89MPa and operating temperature for 23 hours.
The procedure was as described above, except that the temperature was kept at 250°C and then at 265°C for the next 96 hours. After the end of the operation period, the acetic acid content of the effluent was 10.2%;
Also, the maximum content of acetic acid (over the entire 50 hours of operation) was 46%. (d) The centers of the used catalyst beds from the three operations described above were combined and mixed thoroughly. 45 of these
ml into a quartz tube and heated to 705°C in a nitrogen stream.
heated to. After that, the temperature of the playback area was increased for 7 hours.
The temperature was kept at 710±10° C. and the H ₂ O introduction was further continued at a rate of 0.191 ml/min. Example 14 The reactor temperature was maintained at 285℃ and the pressure was 13.89MPa.
The procedure of Example 13(b) was repeated using the reactivated carbon (25 ml) obtained from Example 13(d), keeping at . Acetic acid selectivity and catalytic activity were high. 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%, 141
The acetic acid content after hours was only 0.8%. Example 15 This is a twice-reactivated SORBONORIT
This is an example showing the use of B-3 carbon. In this example, the carbon lot used in Example 14 was subjected to the same reactivation treatment as Example 13(d). Next, using the twice-reactivated carbon material, Example 22
The operation was repeated. The reactor was operated for 24 hours, and the acetic acid content in the effluent was 92.0% after 18 hours of operation. Example 16 This is an example showing the reactivation process where carbon was used in the presence of a cobalt catalyst. (a) as (Co ₂ (CO) ₈ ) in the feed stream.
Acid washed NORIT with Co111ppm present
The same procedure as in Example 13 was carried out, except that RB-1 activated carbon was used at 285° C. and 13.89 MPa for 112.5 hours. The acetic acid content in the effluent near the start of the operation (e.g., 24 hours after the start of the operation) was 95%, but near the end of the operation the acetic acid content was only 0.7%.
It was hot.

Claims (1)

Claims: 1. In the presence of a halide promoter, activated carbon and at least 1 ppm of a transition metal selected from cobalt, ruthenium, iron, nickel, rhodium, palladium, osmium, iridium and platinum,
In a method for continuously producing carboxylic acids and their esters by reacting carbon monoxide and alkanol under high temperature and pressure, the activated carbon is derived from coal or peat and has a density of 0.03 to 2.5 g/cm ³ and a specific surface area of 200. ~2000m ² /g, and the reaction temperature is 240~300℃, and the pressure is 3.5 ~
A method for continuous production of carboxylic acids and esters thereof, characterized in that the process is carried out at 27.5 MPa. 2 The reaction is carried out in the presence of a transition metal halide, carboxylate, nitrate or carbonyl.
The manufacturing method according to claim 1, characterized in that the manufacturing method is carried out under a pressure of 27.5 MPa. 3. The method according to claim 1, wherein the reaction is carried out in a nickel or cobalt alloy reactor in the presence of a transition metal originating from the reactor and under a pressure of 3.5 to 21 MPa. Production method. 4. The manufacturing method according to any one of claims 1 to 3, wherein the amount of transition metal is 25 to 150 ppm. 5 The halide promoter is an alkyl halide,
5. The production method according to any one of claims 1 to 4, characterized in that hydrogen halide, acyl halide, or dihalogenated methane is used. 6. The production method according to any one of claims 1 to 5, characterized in that the reaction is carried out in the presence of a solvent. 7 The catalyst is heated at a temperature of 500 to 1500°C with a temperature of 0.1 to
The manufacturing method according to any one of claims 1 to 6, characterized in that the reactivation is carried out by contacting with water vapor under a pressure of 0.5 MPa. 8. A patent claim characterized in that the reactivation of the catalyst is carried out in the presence of an activator selected from oxides, hydroxides and halides of alkali metals or alkaline earth metals, inorganic sulfur compounds and mineral acids. The manufacturing method according to item 7.