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    • 专利摘要:
    1. A METHOD FOR OBTAINING A MIXTURE OF ACETIC ACID, ACETIC ALDEHYDE, ETHANOL AND Cr - C OLEFINS with a molar ratio of oxygen-containing compounds and olefins equal to
    公开号:SU1111684A3
    申请号:SU802937846
    申请日:1980-06-20
    公开日:1984-08-30
    发明作者:Вундер Фридрих；Арпе Ханс-Юрген；Инго Лойпольд Эрнст；Шмидт Ханс-Йоахим；Хахенберг Хорст
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

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    four
    I
    The invention relates to a method for producing oxygen-containing compounds C and low-molecular-weight olefins from synthesis gas, in particular a mixture of acetic acid, acetaldehyde, ethanol, ethylene and propylene, which can be used in the chemical industry.
    A known method for producing a mixture of these compounds from synthesis gas, i.e. mixtures of carbon monoxide and hydrogen, - in which catalysts are used, containing mainly manganese, mixtures containing olefins with predominantly 2–4 carbon atoms in the CU molecule are obtained, however, much of the carbon monoxide is oxidized during the reaction to carbon dioxide, in addition, the content of oxygen-containing compounds in the resulting mixture is very small P.
    There is also known a method of obtaining a mixture of oxygen-containing compounds and olefins by reacting synthesis gas with a catalyst, containing 2.5 wt.% Rhodium, at 70 atm and a pressure of only 3.4% of the total carbon dioxide in the reaction goes into saturated and unsaturated hydrocarbons with or more carbon atoms, 43.1% in an oxygen-containing Cj compound and 52% in methane C2J.
    By using catalysts, which, along with rhodium, also contain promoters (magnesium or manganese), oxygen-containing compounds such as acetic acid, acetaldehyde, and ethanol can be obtained with a high B4 selectivity.
    The production of pismolecular olefins of technically important initial products of heavy chemical synthesis is of great importance. This is important in cases where, with an increase in the yield of olefins, the yield of methane, which is a by-product, simultaneously decreases.
    The closest to the proposed essence is a method of obtaining oxygen-containing compounds from synthesis gas at 150,450 ° C, a pressure of 1.05-700 atm and a molar ratio of H.,: CO equal to 20: 1-1: 20, in gas phase in presence 116842
    VII of the catalyst containing 2.5-5% rhodium, mainly on the carrier З,
    However, carrying out the process according to this method leads to the formation of g low olefin content.
    The purpose of the invention is to increase the olefin content.
    The goal is achieved by the fact that according to the method of obtaining
    About a mixture of acetic acid, acetic aldehyde and Cj-Sc-olefins with a molar ratio of oxygen-containing compounds and olefins equal to Cl-2.5): 1, from synthesis gas by
    5 The interaction of carbon monoxide and hydrogen in the gas phase at 150-350 ° C, a pressure of 1-300 atm in the presence of a rhodium catalyst, as a rhodium catalyst is used
    0 catalyst containing 0.1–15 wt.% Rhodium and 0.1–5.0 wt.% - alkali metal compounds selected from the group of sodium, lithium or potassium acetates, sodium or cesium chlorides,
    5 nitrates of sodium or rubidium, the rest is silicic acid as a carrier.
    Preferably sodium is used as an alkali metal.
    As a result of the process, olefins are formed, mainly ethylene, propylene and small amounts of butenes, and oxygen-containing products such as acetic acid, acetaldehyde and ethanol.
    5 The presence of small amounts of alkali metal ions in catalysts promotes the formation of olefins, leading to a decrease in the degree of conversion of synthase gas to methane
     and, moreover, significantly increases
    total catalyst activity. The selectivity of the process is 70-90% based on the reacted carbon monoxide. Oxide residue
     carbon is converted to alkanes, including methane, carbon dioxide, and to a small extent oxygen-containing compounds with three or more carbon atoms.
     The molar ratio of oxygen-containing Cj-compound and olefins is (1-2-, 5): 1 and the molar ratio means the ratio of the sum of moles of oxygen5 containing Cj-compounds, i.e. acetic acid, acetaldehyde and ethanol, to the sum of moles of olefins with 2-4 atoms C. The process in this method allows to obtain a mixture of oxygen-containing Cj compounds and olefins with a molar ratio of (1-2.5): 1. Example, Seri A. (use of carriers containing various amounts of sodium). In each case, 52 g (120 ml) are given in table. 1 silica-based carrier is impregnated with a solution of 1.08 g of magnesium chloride hexahydrate in 66 ml of water at room temperature and then dried for 2 hours at and for 2 hours at. Next, the sintering process is carried out for 30 minutes at 800 ° C. The sintered carrier is impregnated with a solution of 4.0 g of rhodium (III) chloride X (37.4 wt.% Rh) in 66 g of water at room temperature and dried in the manner described. Then the catalysts are placed in a glass vessel and reconstituted by passing through them for 3 h hydrogen at a rate of 30 nl / h at 225-27 and normal pressure. The resulting catalysts contain 2.7 wt.% Rh and 0.24 wt.% Mg. 100 ml of catalyst are placed in a stainless steel reaction tube with a length of 810 mm and an inner diameter of 16 mm, equipped with a thermometric tube with an outer diameter of 6 mm. The desired temperature is maintained using a water bath. A gas mixture of carbon monoxide and hydrogen is passed through the catalyst in a volume ratio of 1: 1 at a pressure of 20 atm and a temperature inside the reactor of 275 ° C, at a rate of 70 nl / h. The reaction mixture is cooled and depressurized non-condensing components. The gaseous components and condensed reaction products are analyzed by gas chromatography. The results are shown in Table. 1. Reaction conditions: pressure 20 bar, temperature 275 ° C; source gas CO: Hj 1, speed 70 nl / h; catalyst volume 0.1 l, composition 2.7% Rh, 0.24% Mg on SiOj; AcOH-acetic acid, AcH-acetic aldehyde, EtOH-ethanol. Seri V. (use of carriers doped with various alkali metal salts). Given 4 2 the amount of alkaline salt in the table. metal (which corresponds to 8.16 mmol of anhydrous compound) is dissolved each time ij 66 g of water. Each of the solutions obtained is impregnated with 52 g (120 ml) of silicic acid as a carrier in accordance with comparative example 1 of series A. After impregnation, the carriers are dried for 2 hours at 80 ° C, then for 2 hours at and finally sintered for 30 minutes at . Then, each of the carriers is impregnated with a solution of 1.08 g of hexahydial magnesium chloride in 66 g of water, after which they are dried and the process of sintering is carried out in the manner described. The carriers thus treated are impregnated with a solution of 4.0 g of rhodium (III) chloride — X H ,, 0 (37.4 wt.% Rh) in 66 g of water, dried for 2 hours at 150 ° C and reconstituted in a glass vessel. Hydrogen flowing through it for 3 hours at a rate of 30 ml / h at 225-275 C and normal pressure. The resulting catalysts; contain 2.7 wt.% Rh and 0.24 wt.% Mg. Testing of the obtained catalysts is carried out in the reactor described in series A and under the same conditions. The results are shown in Table. 2. Seri S. (gas circulation facility). The installation consists of a heated tubular reactor with a tube of stainless steel with a length of 1 m and an inner diameter of 24.4 mm, with a thermometer sleeve with an outer diameter of 12 mm, connected in series with a condenser reactor, a condensate collector and a compressor to return a portion of unreacted gas (circulating gas in the reactor). In each of the experiments in the reactor load 250 ml of the specified catalyst. After purging the unit with nitrogen, the initial synthesis gas of the composition, vol.%: 49 CO, 49 Hj, 1 COj, 1 Oj (gas also contains minor amounts of other components) is fed under a pressure of 100 bar and the reactor is heated to 275 ° C. During the heating process and further throughout the whole experiment, 1000 nl / h of synthesis gas of the specified composition is added hourly through the suction line of the compressor and the mixture is passed over the catalyst. The amount of circulating gas returned to the reactor is 5000 l / h. The gas mixture leaving the reactor is cooled in a brine cooled condenser to 5. ° C and the condensed products are captured in a collection. The uncondensed circulation gas, after mixing with fresh synthesis gas, is returned to the reactor with a compressor. In order to maintain the pressure in the system and to separate the olefins and by-products, part of the circulating gas is discharged through the stop valve. According to the described method, the processes are carried out in accordance with comparative example 3 and 11-13. The results are presented in. Table. 3. In Example 3, 250 ml of the catalyst described in Comparative Example 1 is used as the catalyst. In the Example, 250 ml of the same catalyst as in Example 4 is used. In Example 12, 250 ml of the same catalyst is used as in Example 5; In Example 13, 250 ml of catalyst are prepared as follows. 120 g of a silica-based carrier described in Comparative Example 1 with a Na content of 0.04 wt.% Is impregnated with a solution of 2.49 g of magnesium chloride and 1.55 g of sodium acetate in 152 g of water and dried for 2 hours at 80 ° C. 2 hours at 120 ° C and 2 hours at 150 ° C. The carrier is then impregnated with a solution of 9.24 g of rhodium (III) chloride (37.4 wt.% Rh) in 152 g of water and dried again in the manner described. The catalyst is then placed in a glass vessel and hydrogen is passed through it at a rate of 50 nl / h at 225-275 ° C and normal pressure for 3 hours. The resulting catalyst | 5 contains, wt%: 2.7 Rh, 0.24 Mg, 0.37 Na and 1.9 C1. The results are given in Table. 3. Reaction conditions: gas circulation setup, 1OO bar pressure, temperature, source gas CO: H2 1, speed 1000 nl / h, catalyst volume 0.25 l, catalyst composition,%: 2.7 Rh, 0 , 24 Mg per SiOj; AcOH - acetic acid. 4 Ace acetaldehyde, EtOH - ethanol. Seri D. (the use of other catalysts of different composition). A tube with a length of 500 and an inner diameter of 16 mm, equipped with a thermometer coaxially located with an outer diameter of 6 mm, connected together with a condenser, a condensate collector and a pressure regulator is used to carry out the reaction. The temperature in the reactor in accordance with Example 14 was maintained with an oil bath, and Examples 15-19 with molten salt. Charged to the reactor 50 ml of catalyst, washed with nitrogen and then passed over the catalyst specified in the table. 3 the amount of synthesis gas (a mixture of carbon monoxide and hydrogen in a volume ratio of 1: 1) at the values indicated in this table. 3 pressure and temperature. The condensate collected in the collector and the uncondensed gases discharged through the pressure regulator are subjected to gas chromatographic analysis. Given in Table. 4 results are average values for 5 hours of reactor operation, catalyst volume 50 ml. In examples 14-19 in the preparation of the catalyst used granular media with a particle size of 1.2--3.0 mm PRI and meR 14. 26 g (60 ml of used as a carrier) of silicic acid with a sodium content of 0.04 wt.% Is impregnated with a solution of 0.54 g of magnesium chloride hexahydrate and 0.5 potassium bromide for a further 2 hours at 150 ° C, after which they are sintered for 30 minutes at 750 ° C. The sintered carrier is impregnated with a solution of 2.0 g of rhodium (III) chloride x X HjO (37.4 wt.% Rh) in 33 ml of water and dried in the manner described. Then the catalyst is restored by passing hydrogen over it for 3 hours 30 nl / h at 225-275 ° C and normal pressure. Poluchennym ka-. The catalyst contains 2.7 wt.% Rh, 0.23 wt.% Mg, 0.57% K, 1.1% Br, and 0.8% Cl. Example 13. The process is carried out as in Example 14, but instead of 0.5 g of potassium bromide, 0.1 hydro-, lithium oxide is used. The resulting catalyst 7,%: 2.7 Rh, 0.22 Mg, 0.1 L contains and 1.2 C1. P p and M e p 16. Natural magnesium silicate is boiled in 50% acetic acid, then washed with water and dried. After this treatment, the carrier has the following composition, wt%: SiO 65.5, AljGj 3.6, FejOj 0.5 MgO 14.0%. 30 g (6Q ml) of the resulting wipe is impregnated with a solution of 0.8 g cesium acetate in 25 ml of water and dried for 2 hours at 80 ° C, and then another 2 hours at 150 ° C, after which the sintering process is carried out for 30 min at 750 ° C. The sintered carrier is fed, as in Example 14, with a solution of rhodium (III) chloride (37.4% Rh) in 25 ml of water, dried and reconstituted. The resulting catalyst contains 2.3 Rh, 7.8 Mg, 1.7 Cs and 1.5 C1. Example 17 The process is carried out in the same manner as in the example, but instead of 0.7 g of cesium acetate, 1.0 g of rubidium carbonate is used. The resulting catalyst contains,%: 2.3 Rh, 7.9 Mg, 2.3 Rb, and 1.2 C1. Example 18: 42 g (60 ml) used as a carrier for alumina with a specific surface area of 250 is impregnated with a solution of 0.25 g of sodium metasilicate (water content: 0.1%) and g of magnesium chloride hexahydrate in 29 ml of water. and then dried and dried. The sintered carrier was impregnated as in Example 14 with a solution of 2.0 g of rhodium (III) chloride (37.4 wt.% Rh in 29 ml of water, dried and reduced. The resulting catalyst contains,%: 1.7 Rh, 0.14 MR , 0.25 and 1.1 C1. PRI me R 19. 45 g (60 ml) of aluminosilicate with a specific surface area of 100 is impregnated with a solution of 0.6 of anhydrous sodium iodide and 0.54 g of magnesium chloride hexahydrate in 17 ml of water and then dried, sintered, the sintered support of Example 14 is impregnated with a solution of 2.0 g of rhodium (III) chloride (57.4 mAh Rh) in 17 ml of water, dried and reduced. The resulting catalyst contains,%: rj 1.6 Rh , 0.13 My, 0.2 l and 1.0 C1. 4 PRI me R 20. 52 g (100 ml) of silica-based carrier indicated in Comparative Example 1 are impregnated with a solution of 1.08 g of magnesium chloride hexahydrate and 0, 5 g of sodium chloride in 66 g of water at room temperature are then dried for 2 hours at room temperature and 2 hours at room temperature, then calcined at 650 ° C for 30 minutes. The calcined carrier is impregnated with a solution of 0.15 g of chloride (III) X HjO ( 38.1 wt.% Rh) in 66 g of water at room temperature and dried in the same manner as described above. The catalyst is reduced in a glass vessel by 30 hl / h of hydrogen at 225-275 ° C at normal pressure in 3 hours. The resulting catalyst contains, wt%: 0.1 Rh, 0.24 Mg and 0.6 Na. Under the conditions of reaction mentioned in the series A, the results given in Table 2 are obtained. 5. Example 21. 52 g (100 ml) of silica-based carrier indicated in Comparative Example 1 are impregnated with a solution of 0.5 g of magnesium chloride hexahydrate and 5.7 g of sodium chloride in 66 g of water, dried for 2 hours at 80 ° C and 2 hours at 150 ° C and thereafter for 30 minutes at 650 ° C. The calcined carrier is then impregnated with a solution of 26.8 g of rhodium (III) chloride X (38.2 wt.% Rh) in 66 g of water and dried in the same manner as described above. The catalyst is reduced according to example 14. It contains wt.%: 15.0 Rh, 0.1 Mg and 5.0 Na. The results are shown in Table. 5. Reaction conditions: 20 bar, 275С, introduced gas 70 nl / h, CO: H2 1, volume of catalyst 0.1 l, AcOH acetic acid, AcH - acetaldehyde, EtOH - ethanol. Thus, the proposed method allows to obtain a mixture of oxygen-containing Cj compounds and C-C α-olefins with olefin content, which is characterized by a molar ratio of products (1-2.5): 1.
    1111684
    10 Table 1
     Ethyl acetate and acetic acid diethyl acetate, acetic aldehyde and ethanode Amount of moles AcOH, AcH, EtOH
    The sum of moles of CjHj (, Cj H, Includes 0.04% of Na contained in the sales in the added alkali metal is
    .Table 2 aldehyde recalculated and acetic carrier; in each case the amount of 8, 16 mmol. 110,439.2 A52 31.518.3 120.433.9 428 37.4 12.3 130.37 34.6 410 32.6 15.3
    Table 3 3.7 9.624.1 0.8 3.8.2.05 2.1 11.5 23.6 1.0 4.11.86 1.5 12.2 25.1 1.1 3.21.68
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    CNI 200.1 3.210.0 21.0 8.5 3.5 2115.0 TO, 663, A 25.3 13.8 3.8
    Table 5 8.5 21.2 1.3 18.0 1, A 9.0 15.6 2.5 21.0 2.1
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING A MIXTURE OF ACETIC ACID, ACETIC ALDEHYDE, ETHANOL AND C 2 - C ^ OLEFINS at a molar ratio of oxygen-containing compounds and olefins equal to (1-2.5): 1, from synthesis gas by the interaction of carbon monoxide and hydrogen in gas phase at 150-350 ° C, pressure 1-300 atm in the presence of a rhodium catalyst, characterized in that, in order to increase the olefin content, a catalyst containing 0.115 wt.% rhodium, 0.1-5 , 0 wt.% Alkali metal compounds selected from the group of sodium acetate, lithium or a potassium, sodium or cesium chloride, sodium nitrite or rubidium rest - silicic acid as the carrier.
    [2]
    2. The method of pop. 1, characterized in that sodium is used as the alkali metal.
    SU "1111684
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    优先权:
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