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    • 专利摘要:

    公开号:SU1042609A3
    申请号:SU792746997
    申请日:1979-04-03
    公开日:1983-09-15
    发明作者:Вундер Фридрих；Арпе Ханс-Юрген；Инго Лойпольд Эрнст；Шмидт Ханс-Йоахим
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

    i The invention relates to a method for producing acetic acid, ethanol, acetaldehyde and their derivatives, which are used to obtain resins, rubbers. A known method for producing acetic acid, ethanol, acetaldehyde and their derivatives by reacting carbon monoxide with hydrogen in the presence of a catalyst containing metallic rhodium on a carrier with C and 1 ,, atmosphere Performance.  process 250-275, selectivity for Cg, -products - ki, 2% lj.  The disadvantage of this method is low selectivity and productivity of the process.  The closest technical solution to the proposed method is to obtain acetic acid, ethanol, acetaldehyde, and their derivatives by reacting carbon monoxide with hydrogen in the presence of a catalyst containing metallic rhodium and manganese, at 150-ii50 ° C and 20-200 atm.  The productivity of the process is 2 0380 gl-h, only at the maximum amount of manganese (5) it has reached. e. 32 g / LHP, Selectivity of the process according to C Products 60% 2 The method differs in these drawbacks. The purpose of the invention is to increase the selectivity of the process. The goal is achieved by the method of producing acetic acid, ethanol and acetaldehyde and their derivatives by reacting carbon monoxide with hydrogen in the presence of metals. -.  rhodium as a catalyst on support J.  additionally containing magnesium halide or its mixture with titanium oxide or zirconium or silicon, or with acetylacetonate, or with magnesium silicate, or magnesium aluminate, or magnesium salt with calcium chloride or tin, or chro. MER or cerium with a magnesium-halo-alkaline complex compound, or magnesium-halo-alkaline compound. Preferably, a magnesium salt or magnesium compound as well as a hydrogen halide or organic halide compound is continuously or periodically supplied with the starting components. in the conditions of the process, hydrogen halide B as magnesium salts is used with SjTOT chloride bromide 3 nitrate 5 c |) ormiat and acetzt, and trichlorohranium magnesium salt, magnesium hexaamine dichloride or magnesium acetyl acetonate as complex with 09 mg of magnesium.  Preferred are magnesium compounds with oxides of elements of the L – U1 groups of the Periodic System, for example, natural or artificial magnesium aluminates, al-.  mosilicates, metasilicates, orthosilicates, titanates, tsikonaty and chromites, and these compounds can also be used as carriers of rhodium at the same time. But magnesium can be bound on cation exchanger by ion exchange, which is stable under the reaction conditions and used as a carrier of rhodium, for example natural or artificial aluminosilicates (molecular sieves | "Chlorides, bromides, or metal iodides of 1-UH groups of the Periodic System are used as suitable halides.  Preferred are the halides of magnesium or rhodium, which can be formed, for example, also by the reaction of the oxides, hydroxides or carbonates of these two elements, on carriers, with organic compounds that release hydrogen halides, for example 1,1-dihydrate. Catalysts are used as catalysts. conventional carriers with different specific surface areas, most preferred are carriers with a specific surface area of 50-1000.  Cream, for example, are suitable.  Nyeva acid, natural or synthetic silicates of elements of the C-UTsG groups of the Periodic System (silicates of magnesium, calcium, aluminum, rare earths, silicates of titanium, zirconium, manganese), further aluminum oxide, zirconium oxide, thorium dioxide, vanadium pentoxide, zeolites and spinels the method makes it possible to increase the selectivity of the process to 7.6-82.21 (60% in the known method), as well as to achieve a more stable performance within g / l. The method is carried out as follows.  To prepare the catalyst, the support is wetted or prescribed either directly or in two successive stages with active components, after which the catalyst is reduced.  When using oxides of elements of the W-U1 groups of the Periodic System as carriers, catalysts, the preparation of the catalyst is carried out as follows.  Magnesium compound and halide (which may be ideal) are applied to the carrier, then, by calcining at high temperature, the impregnated carrier is transferred partially or completely into mixed magnesium oxide and elements of the W-VI group of the Periodic System, for example magnesium silicate, and. immediately after this, the rodi compound is impregnated.  The reduction of the introduced rhodium compound to metallic rhodium is carried out by treatment with reducing agents, for example hydrogen or carbon monoxide or their mixtures or methanol, at temperatures above 300 ° C, preferably at temperatures in the range of 350-550 ° C.  It is advisable to perform the reduction not with pure reducing agents, but with a share of inert gases, such as nitrogen, carbon monoxide, or also noble gas.  The concentration of rhodium, magnesium and halides in the catalyst can vary widely. In general, the concentration value is in the range of 0.1-20% by weight for rhodium, 0.1-25% by weight for magnesium and 0.01-201 by weight for halogen  Most preferred are catalysts with a concentration of 1.0-10% by weight for rhodium, 0.1-20% by weight for magnesium, and 0.05-15% by weight for halides. About gas mixtures consisting entirely of or more some of the oxide of hydrogen and hydrogen, and in some cases other components, such as nitrogen, argon, carbon dioxide or methane, are passed through the catalyst.  The molar ratios of carbon monoxide and hydrogen vary within wide limits.  These ratios are preferably in the range of 5: 1 and 1: 5, especially 3: 1 and 1i3.  The reaction temperature is in the range of 175 and 375 ° C, preferably 200 and 350 ° C, the reaction pressure is in the range of 1-300 atm, preferably 20-200 atm. It is advisable to maintain the temperature and pressure at such a level to ensure high selectivity for the oxygen-containing compound. m and a slight exotherm.  The formation of methane occurs at elevated temperatures.  Therefore, high pressure and temperature as low as possible is preferred.  The degree of carbon monoxide conversion should not exceed 50%, since with a higher degree of conversion, the amount of by-products can easily increase, along with carbon dioxide and gaseous carbon with hydrogen can also occur high-molecular liquid hydrocarbons and oxygen-containing products.  It is preferable to carry out the process in a gas phase. In the process, conventional fixed bed reactors are used, and the catalyst bed should be thin for better heat removal.  In addition, moving catalyst or fluidized bed reactors are also suitable.  Synthesis gas conversion reactions (CP and H2 can be carried out in the presence of a solid and finely divided catalyst suspended in inert solvents and / or reaction products.  It is preferable to conduct the reaction in a circulating apparatus in the gas phase, when, after condensation of the target reaction product, the unreacted gas mixture goes back into the reactor.  This variant of the method is the most economical.  By mixing the fresh gas with the exhaust gas, which is returned to the circulation loop of the apparatus, it is possible to maintain high temperatures in the reactor and, at the same time, a high degree of utilization of the reactor volume with constant selectivity. Devices with both internal and external gas are considered as circulation apparatus. contour.   When carrying out the method, the catalysts have a high initial activity And an excellent selectivity for the conversion of carbon monoxide to oxygen-containing C2 compounds, but with long-term catalyst operation (over 500 hours), its activity and selectivity gradually decrease.  Consequently, the catalysts have a limited service life.  The service life of the catalyst can be increased if during the synthesis gas reaction the magnesium salts or magnesium compounds are continuously or periodically added together with gaseous reagents to the reaction zone, which, under the existing reaction conditions, evaporate. on the basis of rhodium, magnesium and halides, the activity and selectivity of which remains approximately unchanged after 1000 hours of work, as magnesium salts or a compound. Magnesiums that evaporate under the reaction conditions and which are introduced into the reaction zone together with one or more reapents can be used, for example, magnesium chloride, magnesium bromide, magnesium iodide, acetylacetonate, ethylate-isopropylate, magnesium aluminum ethyl acetate, magnesium isopropyl and magnesium salt of monocarboxylic acid with carbon atoms in the molecule.  Magnesium chloride and magnesium acetate should preferably be used.  Such salts of magnesium and its compounds are also used, which are converted into halides or by reaction with aliphatic monocarboxylic acids into the corresponding carboxylates, for example, oxide, hydroxide or carbonates of magnesium, by reaction with hydrogen halide.  The supply of volatile magnesium salts or its compounds to the α-reaction zone together with the gaseous components of the reaction is carried out using various methods of MIO. Thus, magnesium compounds can be made into 8 types of solutions, for example, in water, ethanol or acetic acid, as well as injected into the hot gas flow before the catalyst. Further, it is possible to mix the solution or melt of the magnesium compound with the gas reagent at an elevated temperature before the reaction zone or to feed the gas reagent through this solution or melt.  The advantage of this process is that the high temperature reaction components pass either partially or all completely volatile magnesium compounds that are in solid form 5, while the magnesium compounds are transferred to the vapor phase without changing additional solvents. Magnesium compounds can be used media, for example, with silica, alumina or carbon.  Magnesium compounds in vapor state I 09 can be either inside or outside the reactor; It is preferable to arrange them in such a place that the heated reaction components first pass through the reactor zone with the catalyst.  In principle, both of these zones can be located in one another or can be combined.  Volatile magnesium compounds may be introduced to the reaction zone continuously or intermittently. , With continuous feed amount of magnesium. Compounds of 0.01–200 ppm, preferably 0.1–5 ppm of the weight of the gas stream passing through the catalyst. During batch feeding, the amount of blended magnesium compounds depends on the batch duration.  The amount administered is controlled by the temperature and volume of the gas transporting the magnesium compounds.  The gas stream containing volatile magnesium compounds, carbon monoxide and hydrogen then passes through a catalyst containing rhodium, magnesium and halogen-D in a circulation apparatus, in which, after separation of the condensed reaction mixtures. Unreacted gas mixture with added fresh synthesis gas is returned to the reactor. Magnesium compounds can be introduced either into the circulation loop, or into fresh syngas, or into the mixture of two gases. The life of the catalyst can also be increased without the addition of magnesium compounds.  At the same time, during the reaction of the synthesis gas flowing in the reaction zone, hydrogen halide or volatile organic halogen compounds, which do not contain sulfur or nitrogen in their molecules, are continuously or periodically supplied with or through the conditions maintained in the reaction zone. , the hydrogen halide is cleaved off.  As with the introduction of magnesium compounds, in this case, the activity and selectivity of catalysts based on rhodium, magnesium, and halides after 10,000 hours of their use and remain more unchanged. Hydrogen chloride, hydrogen bromide or hydrogen iodide or their mixture can be introduced as hydrogen halides. be obtained by reacting halogens with a water source, as well as with synthesis gas, in a reactor. The most recommended halogenated hydrogen is hydrogen.  Volatile organic halo compounds that do not contain sulfur or nitrogen in their molecules, which, under the existing reaction conditions, are cleaved off, are alkyl, aryl and aralkyl halides with one or more halogens in the molecule, such as, for example, dichloromethane , carbon tetrachloride, ethyl iodide, 1,1-dichloroethane, tert-butyl chloride or allyl chloride, or benzyl chloride, then saturated or unsaturated halogencarboxylic acids, aldehydes, are alcohols, ketones or aliphatic, cycloaliphatic esters, or, Cesky row e.g., mono-, di- or trichloroacetic acid, acid yodistouksusna, bromoacetone, 0, P) -dihloretilEfir 3 hlorkrotonova acid (cis or trans), and p-chlorobenzoic acid.  Carboxylic acid halides, such as acetyl chloride, bromide and iodide, or MONO-, di-, or trichloroacetyl chloride, are also suitable, which, under the influence of water, which is produced during the conversion of synthesis gas, are very easily removed by hydrogen halide. The most preferred halogen compound is acetylchloride It is not necessary that the removal of hydrogen halides from volatile organic halogen compounds is quantitative, since the lifetime of the catalyst is catalyzed. congestion increases even an insignificant amount of split hydrogen halide. Hydrogen halides or organic compounds, from which hydrogen halide splits off, are introduced into the reaction zone along with the reagents by any available method.  For example, hydrogen halides or organic halogen compounds can be introduced in the form of solutions, for example, in the form of an aqueous solution, in the form of a solution in ethanol or in acetic acid, as well as in addition to a hot gas stream.  In addition, it is possible to pass the entire reaction gas stream or only a part of this stream through halogen compounds in a solid or liquid state.  The amount of compound injected is set according to its vapor pressure 09, depending on the amount of gas, its pressure and temperature. In addition, organic halogen compounds can be applied as impregnation on inert carriers such as silicic acid, alumina or coal through which the reaction components then pass, t, eo CO and hydrogen halides or organic volatile halogen compounds are introduced, continuously or periodically into the reaction zone.  With a preferred continuous supply, their concentration is 0.01500 ppm, preferably 0.1-100 ppm, relative to the weight of the gas flow through the catalyst.  In the case of a periodic feed, the amount of feed depends on the duration of the feed cycle.  At the same time, the added amount of reactants is inversely proportional to the duration of their supply to the gas. The gas flow, containing carbon monoxide, hydrogen and hydrogen halide or volatile halogen compounds, is converted on a catalyst containing rhodium, magnesium and halide.  In a preferred form, isp.  After the separation of the condensing agent, the unreacted mixture, together with the fresh gas added to it, is returned to the reactor after the separation of the condensing agent.  At the same time, halogen, hydrogen or volatile organic halogen compounds are introduced either into the circulating gas, or into fresh artificial gas, or into a mixture of these two gases.  Increasing the life of the catalysts by supplying magnesium compounds and hydrogen halides and organic halogen compounds in the same way can be used together.  The oxygen-containing products Cj obtained by the proposed method are acetic acid, ethanol and / or acetaldehyde and, in addition, products that can be obtained in subsequent reactions, for example, at this stage. Verification or condensation of these compounds. These subsequent products include, for example, ethyl acetate and acetaldehyde diethyl acetate.  The proportion of oxygen-containing compounds with three or more carbon atoms in the molecule is small and is usually 10 mol.  from reacted carbon monoxide.  The overall selectivity for oxygen-containing C2 Products, including products converted into ethyl acetate and acetaldehyde diethyl acetate 5, is more than 75% relative to the amount of carbon monoxide, participating in the reaction. The remaining carbon monoxide, other than carbon compounds with three or more carbon atoms in the molecule, is converted to mainly methane and other gas hydrocarbons and, to a small extent, carbon dioxide.  The proposed method allows to increase the selectivity of the process to 658 jO against 60% in the known method. General description of the experiments.  The apparatus consists of a heated reaction tube with a length of 1 mm and an inner diameter of 16 mn with coaxially placed thermometers for thermometers with an outer diameter of 6 mm, made of stainless steel, a series-connected condenser, a condensate collector, and a compressor for returning the uncondensed gas to the reactor circulating gas).  Each time, the apparatus is loaded with 100 ml of the congestion indicated below.  After purging the apparatus with nitrogen, synthesis gas is first supplied to it: 49-OBD CO; 9 OBD, OBL CO, 1 ob N and a small amount of other components, under a pressure of 80 bar, then the reactor is heated to ZPO C.  During heating and. then during the whole experiment, 500 nl of synthesis gas of the specified composition are fed into the circulation loop of the exhaust gas every hour and together with it are passed through the catalyst. The gas mixture leaving the reactor is cooled in a condenser to + 5 ° C and the condensed portion are in the condensate trap.  The uncondensed gas, after being mixed with fresh synthesis gas, is fed back to the reactor using a compressor.  To maintain the pressure and discharge the exhaust gas by-products, it is discharged through a check valve.  Thus, catalysts are tested.  1 shows data on the duration of the experiment, the performance of oxygen-containing C-products per 1 liter of catalysts B h at the beginning and at the end of the experiment, the percentage of acetic acid, acetaldehyde and ethanol with respect to G2 compounds c. the condenser, as well as selectivity to these compounds (in molo CO, relative to converted CO), Minor.  A quantity of presently ethyl acetate or acetaldehyde dizethyl acetate is included in acetic acid, ethanol or acetaldehyde, and the preparation of catalysts.  fl p and me 1.  "About g of silicic acid with a specific surface of 270, a pore volume of 1.22 ml / g, a bulk weight of 0 kg / l, with a pH of 7, a granule size of 2-3 mm in diameter, as well as a content of P5 by weight of SiO and 0.2% by weight of Na is moistened with a solution of 10.4 g of magnesium chloride in kS ml of water.  Further produced. drying for 2 h at 75 ° C and for 2 h at -150 With After that, the mass is sintered for 30 min at 900 ° C.  After calcination, they are moistened with a solution of 5.3 g of RhCl X N20 (37 wt. % Rh) in S ml of water and dried as indicated.  The catalyst is restored in a pipe made of glass by passing hydrogen through it for 3 hours 30 nl / h at 450–500 C at atmospheric pressure.  After reduction, it contains 2 secolRh 3.1 weightL 1.1 weight,% C1o Volumetric yield by the beginning of the experiment 15 g of oxygen-containing C2-compounds per liter of catalyst per hour.  Of this amount, 52.3 wtD of acetic acid, 3.6 wt. % acetaldehyde and C / on-ethanol.  Example 1 (comparative), Catalyst without My halogens.  5.6 g of Rh (NO) v2H20 (31.3 wt. The% Rh) is dissolved in ks ml of water and impregnated with these.  a solution of silicic acid carrier described in example I.  After 2 hours, the catalyst was dried at 80 ° C and 260. ATM by passing through it 1 nl / h of nitrogen.  The catalyst is restored according to example 1 and it contains 4.2 weight. % give birth  Example 2 (comparative).  The catalyst does not contain halogens.  4D g of silica carrier is moistened with a solution of 14.5 g of MgCNO) x X 6H20 in 43 ml of water.  The wetted carrier is dried at -120 ° C, then calcined at.  After calcination, it is impregnated with a solution of 5.9 g of YAN (NO) s 2H, jO (31.3 wt. % Rh) in 45 ml of water, dried in vacuum at a vacuum of 2bO atm and by passing 1 nl / h and restored by the method described in example 1-.  After reduction, the catalyst contains 1.2 ppm of Rh and 3.1 ppm of MD.  Example 2 (reduction in the reactor) About As a carrier, natural magnesium silicate of the usual type is used, which, after washing and drying, has the following composition: 65.5 wt D Si () 2; 3.6 weight D A120; 0.5 weight1 FejOg and.   weight MDO.  The bulk density of its 537 g / l and a pore volume of 0.99 ml / g, g of the carrier is moistened with a solution of 6.3 g of CCCH B7.8 wtD Rh) in +9 ml of water and dried at 150 ° C.  The catalyst is introduced into the reactor in an unwrought form, heated under vacuum to (by passing a stream of nitrogen and then reduced at a temperature of 60 nl / m of a mixture of carbon monoxide and hydrogen at a volume ratio of 1: 1. Unlike all experiments, the catalyst is cooled ; up to 225 ° (, o Into the apparatus, synthesis gas is supplied under a pressure of 80 atm and the catalyst n is heated to the reaction temperature, o The catalyst after reduction contains k, 2; 7.8 ppm D and 0.95% by weight C1.  .  . Example 3  Separately prepared solutions of 1.  g.   in 20 ml of water, 8.6 g of I RhBr - 27.2 wt D of Rh) in It ml of water are mixed and immediately applied to +0 g of the carrier of silicic acid described in measure 1.  After that, the catalyst is dried at 80 ° C and 2bO atm and reduced as in Example 1 o Example ko Solutions are prepared separately: 13, + in 20 ml of water and 8.9 rRh, jO (27.2 wtL, Tb) in 23 ml of water .  Both solutions are cooled to, at this temperature they are mixed with one another and immediately applied to 40 g of the silica carrier described in example 1a. After this, drying is carried out in vacuum 2bO atm at 90 ° C with nitrogen and reduced, as in Example 1 An example of a silicic acid carrier of the same composition as in example 1 is impregnated with a solution of 13.3 g of KMdSCbN O and 5.6 g of KhClj-HjO (37, -8 Å) iRh and 28 ml of water, and dried at 120 ° C pressure and then restore. according to the method described in example 1.  Example 6o Pyrogenic titanium dioxide (obtained by hydrolysis from) is mixed with kaolin, moistened with water, dried, and crushed into particles of 0.1–1 mm.  After that, tablets with a diameter of about 3 mm are pressed and then sintering is carried out at 80 g (corresponding to 100 ml) of these tablets is impregnated with a solution of 20 g of MDS-nHO (56%) and 7.5 g of CdSC.  HjO (37.8 wt.  Rh) in +5 ml of water, dried at 15Uc and restored.  The process is described in example 1 “The catalyst contains 3 wt. %  Rh, 3 1.03 wt. ; C1.  Example 7 Finely crushed zirconia is tableted according to Example 1.85 g of these tablets (100 respectively. ml) lobsters. The solution is made up of 22 g of N50 (56% MgCl2 and 16.5 g of RhCl3-H20 (37.8% Rh) in ml of water O. The catalyst is dried and recovered in the manner described in Example 1  The results of the experiments are presented in tabLo 1 on Table 1
     4.2 3.1 SIOjit 215 comparative Jt, 2 SIOj 2 cpai. Yitelnymy k, t ZI SIOj 19,256, 3, 6, 1 82.28.5 "ta1.5.5" 8.7 35.8 5t, 135.6 238 58.6 28.8 12.6 66.7 | 8.9 PRIMVvvvie. Example 8c. A natural commercial type of magnesium silicate is used as a carrier, which, after washing and drying, has the following composition: b5.5 Bec.SiOj .; 3.6 dB Al20j; 0.5 weight D and 1A all% MrfO. The bulk density is 537 g / l and the pore volume is 0.99 ml / g. 108 g of this carrier (200 ml) are soaked with a solution of 12.6 g of Rh N20, (37.8 wt.% Kh) and 98 ml of water and dried at 150 C. The catalyst is reduced in a glass tube for 3 hours while passing through it 75 nl / h of hydrogen with temperature C and atmospheric pressure. After recovery, it contains k, 2 Bec.Rh; 7.8% by weight of Mg and 1.05% by weight of C1. 100 ml of the recovered catalyst are placed in a vertical pipe made of corrosion-resistant steel with an internal diameter of 1 mm and a length of 1 m. The reactor relates to an installation that includes a hot salt bath, a thermometer, a condensate collector, an expansion valve and a compressor for feeding gas for circulation. A 100 m carrier of silicic acid, impregnated with a solution of 15 g of magnesium acetate in 40 g of water, is loaded into the heater and dried after that.
    Continued table. 1 Reaction Conditions: 80 atm., 300 ° C., 500 nl / h m3 CO; H2 1: 1 catalyst volume of 0.1 l (AcOH - acetic acid, AcH - acetaldehyde, EtOH - etheiop) After purging with nitrogen while passing synthesis gas (9 vol% 1 vol.% C02; traces M-g) are set The pressure of 120 atm and the catalyst are heated to 280 Co. During heating and after it, when conducting the test, 300 nl synthesis gas is fed to the circulation gas circuit hourly from the compressor through its suction inlet, which, together with the circulation gas, is heated in the heater before and then into the reactor. The gas mixture leaving the reactor is cooled in a refrigerator to about + 5 ° C, the condensate thus formed is directed to. condensate tank The uncondensed part of the exhaust gas, after being mixed with fresh synthesis gas, is sent back through the compressor to the heater and then to the reactor. To maintain a constant pressure and remove by-products, a portion of the exhaust gas is discharged through a stop valve. Kg of oxygen-containing C2 compounds is obtained: 22 g of ethanol, 12 g of acetic acid, 7 g of acetaldehyde) as a solution, which corresponds to +10 G / L1HC catalyst. The CO conversion averages 31% of the total starting CO and the selectivity for oxygen-containing C2. products of 8.3% relative to the reacted carbon monoxide Productivity, CO conversion and selectivity remain unchanged after 1500 hours. A small amount (about 7.% of the amount of {; 2-compounds} ethyl acetate or acetaldehyde diethyl acetate is taken into account in acetic acid, ethanol or acetaldehyde The same applies to the following examples. EXAMPLE 3 (comparative). The experiment is carried out according to Example 8, but pure non-wetted silicic acid is placed in the heater. Under the conditions of experience identical to Example 8 and using 100 ml cat The catalyst indicated in example 8 and using 100 ml of the catalyst specified in example 8 is the output of oxygen-containing S-products in the first 500 hours. It is iOO g / l catalyst per hour, after h the yield of these products is Zb5, after 1000 h t / After 1680 hours, only 312 g / lh (the percentage composition of the omesis products as in Example 3 —CO-conversion decreases from 31 to 29.9 in the same period of time and the selectivity to oxygen-containing C2-products from B to 72.5% relative to converted carbon monoxide. Example 9–100 g of silicic acid with a specific surface of 270, a pore volume of 1.27 ml / g, a bulk weight of 0, 4 kg / l, pH 7 ,, granule size 2-3 mm in diameter, and also with a content of 99.35 wt. % 0.2 all%. The mixture is moistened with a solution of 18.75 g of magnesium chloride (3 112 ml of water and then dried for 2 hours at 70 ° C and for 2 hours at. Thereafter sintering is carried out for 30 minutes at 900 ° C. After calcination, silicic acid is moistened with a solution of H, 25 g Rh SC-Hg.0 (37.8 wt.% Rh) and 112 ml of water and then dried as indicated. The catalyst is reduced in a glass tube with 75 nl / h of hydrogen flowing through the tube for 3 hours. with a temperature of + 00–50 ° C at atmospheric pressure. After the reduction, o contains i, 6 weights D Rh, 2.3 weights D MB and 0.7 weights D 01. 100 ml of catalyst are placed in a reactor The device is described in example B. However, unlike compressor B, there is no compressor here.After purging with nitrogen, 235 hl / h of gas mixture 0916 with a temperature and pressure of 120 atm, which contains 9 OBD of hydrogen, OB of carbon monoxide, 1, is passed through the catalyst. carbon and a small amount of nitrogen, and circulation is not carried out. 10 ml / h of aqueous 0.07% magnesium acetate solution is injected into the hot gas mixture in the heater. After the reactor, the reaction gas is cooled in a refrigerator to a temperature of about + 5 ° C and non condensation The ovated part is discharged. 28 g of acetic acid, 8.5 g of acetaldehyde and 3.5 ethanol are extracted as condensate per hour. Conversion of CO is 35.1 selectivity for oxygen-containing C02-products 81% relative to reacted carbon oxide Production of RPODS CO and selectivity unchanged after 1000 hours. Example. (comparative. The experiment was carried out analogously to example 9, but instead of an aqueous solution of magnesium acetate, 10 ml of distilled water was supplied to the heater. The output of oxygen-containing C2 products was after 200 hours 395 g / lh, after 600 hours 360 g / lh, after 1000 hours 290 g / lH. The percentage composition of the C2-products as in Example 9 The conversion of CO over the same period of time instead of 35% is 32.5% and the selectivity to oxygen-containing C-products from 80% takes up to 63.5%. Example 10. 100 g of silicic acid with a specific surface area of 270, a pore volume of 1.27 ml / g, a bulk density of 0.4 kg / l, pH 7, (pa measures granules of 2-3 mm in diameter), as well as content of 99.35 wt., and 4.2 wt.% of Na are moistened with a solution of g of magnesium chloride (56%) in 112 ml of water and then dried for 2 hours at 70 ° C and 2 h at. After that, it is sintered for 30 minutes at 800 ° C. After calcination, the silicic acid is moistened with a solution of 1 g of RhCl N50 (38.0 Bec.% Rfi) in 112 ml of water and then dried, as indicated, the Catalyst is restored in a glass a pipe with hydrogen passing through it for 3 hours 75 nl / h with a temperature of A00-50 ° C at atmospheric pressure. After reduction, the catalyst contains 5 wt.% Rh; 1.8 wt.% M and 0.6 wt.% C1. 100 ml of reduced catalyst are placed in a reactor, which is a vertical pipe made of corrosion-resistant steel with an inner diameter of 16 mm and a length of 1 m, which is equipped with a salt bath, a thermometer with a heater, a condenser, a condensate collector and an expansion valve. The gas mixture is passed through the catalyst with nitrogen. at 100 atm and in the amount of 250 nl / which consists of 9% of the volume of carbon monoxide J 49 of the volume of hydrogen, 1% of the volume of carbon dioxide and a small amount of nitrogen. Into the hot gas mixture 10 ml / h 0, 1% aqueous hydrochloric acid solution is injected into the heating device. After the reactor the gas is cooled to a refrigerator, the non-condensed part is ejected. The condensate is separated per hour: acetic acid 27 g , acetaldehyde and ethanol 2s5 g, which corresponds to the performance of the target products of 360 g / l h. CO conversion of 28.9, selectivity to oxygen-containing C products 82.5 relative to the reacted carbon monoxide, CO conversion efficiency and selectivity remain unchanged and after 1000 h „Minor quantities (about 3 weeks of the amount of cl; products) appearing ethyl acetate or dehydrated ethyl acetate acetal are converted to acetic acid, ethanol or dehydro acetal. This applies to all subsequent examples. Example 5 (comparative). The test was carried out similarly to that of Example 10, but instead of dilute hydrochloric acid, 10 ml / m of distilled water was supplied to the heater. After the release of 600 hours and 315 grams and after 1200 hours - g / l catalysts per hour. The percentage composition of the C products, as in Example 10, the CO conversion decreases at this time, from 2.8 to and selectivity to oxygen-containing C-products from 81 to 6ii. Example 11 "As a carrier, use is made of a natural commercial type of magnesium silicate, which, after washing and drying, has the following composition: 65.5 3.6 wtL A1205; 0.5 weight; k ° 4 Mboo The bulk density is equal to fc 537 gUl, the pore volume is 0.99 ml / g 108 g (20) ml of this carrier is moistened with a solution of 12.6 rRhCli (37j8 weight Rh) in 98 ml of water and dried at 150 s: o Catalyst is restored in a glass tube through which 8 hydrogen flow is passed in an amount of 75 nl / h at 375,425 C at atmospheric pressure for 8 hours. After recovery, the catalyst contains J weight Rh, 7.5 weight MB and 1, 12 weight % SC .... 100 ml of catalyst are placed in the reactor described in Example 10, but with a compressor for feeding part of the exhaust gas to the circulation. After flushing with nitrogen using The pressure of the synthesis gas is set to 100 atm (gas composition: HL CO; 49% by volume Hj; 1 HL CO2, traces NI) and then the catalyst is heated to, During the heating and during the run 300 nl / h of synthesis gas is pumped through the compressor Together with part of the exhaust gas, through the heater, where the mixture is heated to, is sent to the reactor. 10 ml / h every hour of a 0.1% solution of 1,1-dichloroethane in methane is injected into the heater. The gas mixture leaving the reactor is cooled in a refrigerator to + 5 ° Cj and the condensate formed is trapped in the condensate. collector. The uncondensed gas, after being mixed with fresh gas in the compressor, is fed back through the heater to the reaction zone. A shut off valve is used to maintain a constant pressure and exhaust part of the exhaust gas to remove any by-products. The output of oxygen-containing C products is 38 g / h (21 g of ethanol, 10 g of acetic acid and 7 g of acetaldehyde) as an aqueous solution, which corresponds to 380 g / l of catalyst per hour. The CO conversion averages 28.6% of the starting material and the selectivity for oxygen-containing C-products is 83.3% relative to the reacted carbon monoxide. The productivity of the target product, CO conversion and selectivity remain unchanged even after 1800 hours. Equally concentrated solutions of monochloroacetic acid in methanol are used in three subsequent identical experiments instead of Oyl-Horo solution of 1,1-dichloroethane in methanol. benzyl chloride in methanol and acetyl chloride in diethyl ether. The results are the same as in this experiment. Example 6 comparative The experiment was carried out as in Example 11, but 10 ml of pure methanol was injected into the heater every hour. With other conditions being equal to the reaction and with the use of 1O ml of the catalyst of composition 11 given in experiment 11, the yield of oxygen-containing C2 products per liter of catalyst per hour is in the first 600 hours, 360 g, after 1000 hours, 315 g, after 1500 hours 80 g, and the percentage composition of the mixture is as in Example 11. The CO conversion at the same time and the same time falls from 27.9 to 2.1%, the selectivity for oxygen-containing (2-products from 81.2 to 72.6 relative to of the reacted carbon monoxide Example 12. AO g of the silica-acid carrier described in the example is impregnated with a saturated with 0.5 MOC 6H20 and 0.5 g of magnesium acetylacetonate in 5 ml of aqueous ethanol (50 CgHgOH) and dried for 2 hours at and 2 hours at, then calcined at 800 ° C for 30 minutes. After cooling, the mixture is impregnated with a solution of 5.3 g RhC N5.0 (37.8 wtD Rh) in kS ml of water and dried as indicated.The catalyst is restored, in a manner similar to the example, by passing hydrogen through it at a rate of 30 norms of about 1 / h at 450-500 ° С and atmospheric pressure. After reduction, the catalyst contains A, 7 0.27% by weight of Mtf, and 0.8% by weight of C1. Example 13. 5 g described in example 2 of the carrier - silicate magSiO
    - |
    21
    eight
    12
    17 neither, is impregnated with a solution of k g of trichloride - potassium hexahydrate-magnesium () and 6.3 rRhCl3-H, 0 (37, B wt.% Rb) in 9 ml of water and dried for 3 hours at 150 ° C. The catalyst is reduced for 3 hours in a flow tube reactor with hydrogen, which is supplied at a rate of 30 l / h at kSO-500 C and atmospheric pressure. After reduction, it contains k, weight. Rh; 8, And a weight loss of Mtf and 0.8 weight loss of C1. Example of GA. Repeat with, measure 13; however, instead of potassium trichloride, magnet use 3 g. Reduced catalyst:, 1 wt.% Rh; 8.5 wDM and 0.7 wDD C1. Each 100 ml of the following catalysts is placed in a tubular reactor with an inner diameter of 16 mm. 1 m long, heated indirectly by means of a salt melt bath and equipped with a device for temperature measurement, then series-connected refrigerators, a condensate collector and a device for relieving overpressure. After blowing nitrogen through the catalyst, per hour, 170 nl of the carbon monoxide gas mixture hydrogen in a 1: 1 volume ratio under the conditions prefixed in Table. 2. Condensate and off-gas are analyzed by gas chromatography. Table 2 contains information on the composition of the catalyst, the conditions of the reaction, the volumetric outputs per unit of time and the selective effect (with respect to the reacted carbon monoxide). Table 2 ,
    21
    Example 15. (20 atm, 350 ° C,}% rhodium. 50 g of silicic acid with a bulk weight of 0.2 kg / l and a VE T 270 surface is impregnated with a solution of 1.1 MffCI 6Н20 in 55 ml of water, dried 7. h at 80 ° C and 2 h at 150 ° C and then sintered for 30 min. After cooling, the carrier is impregnated with a solution of 1.3 g of Rh SC H20 37.8 weight of rhodium in 55 ml of water and dried as indicated. The catalyst is regenerated in 3 hours transmission of 30 nl / h of hydrogen at 420–50 ° C at atmospheric pressure.
    Example 16 (200 atm, 20 °, about 10 times). The catalyst was prepared as in example 15 but using 15 rRhCI-j. N20 (37.8 wtL rhodium) in 55 ml of water.
    Example 17. (addition of calcium chloride to a catalyst not containing halogen), 0 n halogen-free catalyst described in comparative example 2, after reduction, is impregnated with a solution of 3.0 g of calcium chloride in ml of water and dried for 2 hours at 80 ° C and h at,
    22
    10 42609 Continued table. 2
    Example 18 (addition of H F to a halogen-free catalyst. AO g of a halogen-free catalyst described in Comparative Example 2, after reduction, is impregnated with a solution of 5 ml of hydrofluoric acid in S ml of water and heated for 2 hours at.
    Example 19 (low concentration of halogen. Conducted according to examples 17 and 18, but the halogen-free reduced catalyst (AO g) is impregnated with a solution of 2.5 ml of 1% hydrochloric acid in A5 ml of water, then dried for 2 hours at 80 ° C and 2 hours at.
    EXAMPLE 20 (high halogen concentration). 50 g of the silicic acid described in Example 15 is impregnated with a solution of 2A g of 6H20 in 50 ml of V0% hydrochloric acid and dried for 2 hours at 80 ° C and h at 150 s. Then, it is impregnated with a solution of 4.0 g of KISC-HgO (37.8 wt. L rhodium) in 55 ml of 10% hydrochloric acid, dried kec is indicated and reduced by passing a three-hour transmission of 30 nl / h of a gas mixture consisting of 9IJ vol. h about hydrogen and 5 vol. including hydrogen chlorine with ijOO Co Example 21 (carrier variant, 50 g of magnesium aluminate in the form of balls with a diameter of. -C mm, a surface of 100 m2 / g and a bulk weight of 0.8 kg / impregnated with a solution of 4 g of Rh (37.8 wt. Rhodi) in 23 ml of water, dried for 2 hours at then 2 hours at 150 Co Catalyst is reduced by passing 30 liters / h of hydrogen at 3 hours. Example 22 o (carrier variant 1 50 g of alumina in the form of balls 2-5 mm in diameter 350 and a bulk weight of 0.77 kg / l is impregnated with a solution of 2.5 g in 23 ml of water, dried for 2 hours at 2 hours and at 150 ° C, then sintered at 800 ° C for 30 minutes. After cooling The mixture is impregnated with 4 rRhCI -HO solution (37.8 wtD rhodium and dried as indicated. Finally, the solution is reduced by passing 3 hours to 30 nl / hr of hydrogen at 420-450 ° C. Example 23 (carrier variant) the difference is that they use 50 g of aluminum silicate containing 13.0 wt. of alumina and 86.5 wt. of L. two-sided silicon: surface area 100, bulk density 0.75 kg / l. To prepare solutions of MdCl2 or trichloride rhodium, each time they take 14 ml of water. Example 24 (carrier variant) The catalyst was prepared as described in example 22 with the difference that 50 g of zeolite in the form of rods containing pores with a radius of 4-5 A, with a flat surface of 420 and a bulk density of 0.7 KG / -L, 10,924 fl p and m and p 25 (addition of ShClj to a halogen-free catalyst). 40 g of the catalyst described in comparative example 2, after reduction, are impregnated with a solution of 6 g of 5hCl2 2H20 in 45 ml of water and dried for 2 hours at 2 hours at 120 ° C. The resulting catalyst contains 4.1, 2.0% Mg and 0, 7 C1. Example 26 (addition of chloridions in the form of CgSC). 40 g of silica-based carrier are impregnated with a solution of 10.6 g) l6H20 and 7.2 g of CgSC-6H20 in 45 ml of water and dried for 2 hours at 80 ° C and 2 hours at, after which they are sintered for 30 minutes at . After cooling, the carrier is impregnated with a solution of 6.3 rRh (NO,) -2H20 (31, -8 Bec.lRh) in 45 ml of water and dried under vacuum at 200 mbar, passing nitrogen at a rate of 1 nl / h. Then the reduction is carried out by passing hydrogen at 450-500 ° C for 3 hours at a rate of 30 nl / m (the catalyst obtained contains 4.3 wt. 2.0 M (f and 1.5% C1, Example 27 (addition of chloridions in the form of 40 g of silicon as a carrier, is impregnated with a solution of 1.0 g of magnesium acetylacetonate in 45 ml of hot ethanol and dried for 3 hours at. Then it is impregnated with a solution of 8.0 P cerium chloride (III) (hydrogen chloride) and 4.0 rRh (N03) 2-2H, jO (31.8 wt. D Rh) in 45 ml of water, dried for 2 hours at and 2 hours at 120s. TI is reduced by passing hydrogen at 450-500 ° for 3 hours and normal pressure at a rate of 30 ml / h. The catalyst obtained contains 2.7% wDI, 0.2 Mg and 0.8% C1.
    权利要求:
    Claims (3)
    [1]
    1. METHOD FOR PRODUCING ACETIC ACID, ETHANOL, ACETALDEHYDE AND THEIR DERIVATIVES by reacting carbon monoxide with hydrogen in the presence of a catalyst containing rhodium metal on a support at a temperature of 200-350 ° C and a pressure of 20-300 atm, characterized in that, in order to increase selectivity of the process, use a catalyst additionally containing magnesium halide or its mixture with titanium or zirconium oxide, or silicon, or with magnesium acetylacetonate, or with magnesium silicate, or magnesium aluminate, or a magnesium salt with calcium chloride or ol ova, or chromium, or cerium, or with a magnesium halide alkaline compound, or a magnesium halide alkaline compound.
    [2]
    2. The method of pop. D, characterized in that the magnesium · g magnesium salt or magnesium compound is supplied continuously or periodically to the process together with the starting components.
    [3]
    3. The method according to π. 1, it is different with the fact that, continuously or periodically, together with the starting components, hydrogen halide or organic halide-containing compounds are fed which give hydrogen halide under the process conditions.
    W ^ DT ' l) TiS ί
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19782814427|DE2814427A1|1978-04-04|1978-04-04|Catalyst for acetic acid, ethanol and acetaldehyde mfr. - from synthesis gas, consists of rhodium on support with co-catalyst of magnesium cpd. and halide ions|
    DE19782825598|DE2825598A1|1978-06-10|1978-06-10|Catalyst for acetic acid, ethanol and acetaldehyde mfr. - from synthesis gas, consists of rhodium on support with co-catalyst of magnesium cpd. and halide ions|
    DE19782850201|DE2850201A1|1978-11-18|1978-11-18|Catalyst for acetic acid, ethanol and acetaldehyde mfr. - from synthesis gas, consists of rhodium on support with co-catalyst of magnesium cpd. and halide ions|
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