• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 法律状态
  • 优先权
    • 专利摘要:
    A method of producing ethanol by reacting hydrogen and carbon monoxide at 200-375 s and a pressure of 20-200 atm in the presence of a metal-containing catalyst, characterized in that, in order to increase the selectivity of the process, the latter is carried out in the presence of a catalyst on siliconic acid, element selected from the group of: zirconium, hafnium, lanthanum, platinum, chromium, mercury, or a mixture of zirconium with magnesium. WITH
    公开号:SU1064865A3
    申请号:SU792834356
    申请日:1979-10-23
    公开日:1983-12-30
    发明作者:Инго Леупольд Эрнст；Шмидт Ханс-Йоахим；Вундер Фридрих；Арпе Ханс-Юрген；Хахенберг Хорст
    申请人:Хехст А.Г.(Фирма)；
    IPC主号:
    专利说明:

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    The invention relates to a method for producing ethanol, which can be used as a solvent, from synthesis gas.
    A method of producing ethanol is known by reacting methanol with hydrogen and carbon monoxide at 100-350 ° C, pressure 7 ° C-1050 atm. In the presence of cobalt carbonyl and a rhenium metal cocatalyst as a catalyst as a catalyst. Conversion of raw materials. 20-30%. The output of ethanol is 25-29%.
    The disadvantage of this method is the low yield of the target product (25-29%)
    The closest in technical essence to the present invention is a method for producing ethanol by reacting hydrogen and carbon oxides at 150-400 ° C and a pressure of 20-250 atm in the presence of a catalyst containing more than four metals selected from the group: copper, cobalt, metal (M ) - chromium, iron, vanadium, magnesium, metal fM) - alkali metal, formula CcjCo McJ l, where а 0 „1-1,, 1-1, с-0,2-1, el 0,001-0,2, a + b + c OtO, 5. The selectivity of the process to ethanol is 33.141%, the catalyst productivity is 0.104-0.341 g of ethanol with 1 g of catalyst per hour .2.
    The disadvantage of this method is the low selectivity of the process to ethanol.
    The purpose of the invention is to increase the selectivity of the process.
    The goal is achieved by the fact that according to the method of producing ethanol by reacting hydrogen and hydroxide oxide at 200-375 s and a pressure of 20-200 atm in the presence of hydrogen on a silica acid promoted by an element selected from the group: zirconium, hafnium, lanthanum, platinum , chrome mercury, or a mixture of zirconium with magnesium
    The composition of the reaction product is shifted towards the formation of ethanol, while simultaneously increasing the degree of feedstone variation, through the use of these elements.
    Along with ethanol, oxygen-containing products with two carbon atoms: acetaldehyde, acetic acid, as well as products that can be formed in a sequential reaction, such as esterification, acetalization, or condensation reactions from other products: ethyl acetate and acetaldehyde diethyl acetal, are also formed. The proportion of other oxygen-containing products with three or many carbon atoms in the molecule is very small and lies in normal conditions below 5 mol.%, In terms of converted carbon monoxide. Remaining oxide
    carbon is transformed, in addition to the named products with three and many atoms. carbon, mainly to methane and other gaseous hydrocarbons, and to a small extent to carbon dioxide.
    When preparing the catalyst for the proposed method, one can proceed from the salts or complex compounds of rhodium.
    For example, PO.DIUM chlorides, bromides, and iodides are suitable, as well as double salts of rhodium with alkali metal halides such as potassium trichloride.
    As an additional component of catalysts in accordance with the invention, one of the elements is applied to the support: zirconium, hafnium, lanthanum, platinum, chromium and mercury in the form of their salts or complex compounds. Zirconium, hafnium, lanthanum, chromium or mercury are used mainly, especially hafnium, chromium or mercury. Simple inorganic and organic salts of the named elements such as chlorides, bromides, nitrates, formates, acetates are suitable. Chlorides are preferably used. .
    For the manufacture of the catalyst, the support is simultaneously or sequentially impregnated with the active components. When using salts of bivalent rhodium, subsequent treatment with suitable reducing agents, such as hydrogen carbonate or methanol, is preferable. This reduction can be carried out in a separate apparatus or in the reactor itself. In general, temperatures suitable for this are lower, mostly in the range of 100-275 C. It is often advisable to carry out the reduction with gases containing impurities of inert gases, for example, nitrogen, carbon dioxide, and noble gases.
    It is also possible to manufacture the carrier in the presence of active ingredients, for example, by co-precipitating the active components with silicates.
    The method is preferably carried out in the gas phase. To do this, use traditional fixed bed reactors, and for a better heat removal, it is preferable to pour a small catalyst bed. Also suitable are reactors with a moving catalyst bed or a fluidized bed of catalyst.
    The synthesis gas conversion can also be carried out in the presence of a solid and highly dispersed catalyst suspended in inert solvents and / or reaction products. The method is carried out as follows. The transformation is carried out in an apparatus with a closed cycle in the gas phase, in which, after the separation of the condensing reaction products, the unconverted gas mixture is returned to the reactor. This embodiment is very economical and allows the benefit of diluting fresh gas with returning into the cycle, containing little hydrogen with residual gas, to maintain a higher reaction temperature and, thus, leads to a higher degree of conversion of the raw material. Example 1 (Comparative). 40 g of silicic acid with a BET surface of 270., a pore volume of 1.27 ml / g and a bulk weight of 0.4 kg / l are impregnated with a solution of 5.2 rRbce x HjO (38 May.% Rhodi) in 50 ml water and 1.5 hours at 80 ° C; 1.5 hours at and 1.5 hours at 150 ° C. This catalyst is used for comparison experience. For examples 2-8, depending on the circumstances, the catalyst is impregnated with another aqueous solution (or alcoholic of the following chlorides in 50 solvents and dried for 2 hours at 2 hours and at 150 ° C (see Table 1.). .L 8 ZrCI + MgCl26H203.4 + 0., 3 Then, the catalysts according to examples 2-8 are heated in a glass column under reflux with 50 m acetic acid for 5 hours at 1.5 hours at and then 3 hours at 150 ° C and dried for 1 hour at atmospheric nitrogen atmosphere. The composition of the catalysts is given in Table 2. The reduction of the catalysts for examples 2-8 is carried out in a glass flow tube After 30 liters / hr of hydrogen flow for 3 hours at 225-275 C and normal pressure. Table Example Rhodium chloride Promoter The rest of the carrier is the carrier material (. Examples 2-8. The apparatus consists of a heated reaction tube with an internal diameter of 16 mm and a length of 1 m, made of corrosion-resistant steel, with a thermometer sleeve with an outer diameter of 6 mm coaxially mounted, in series cond; connoisseur, condensate receiver and compressor for returning part of the uncondensed gas to p actor (circulating gas) Each time the reactor was filled with 100 ml portion of the catalysts of Examples 2-8. After purging the apparatus with nitrogen, first of all, the synthesis gas of the composition, vol.%: CO 40, H240, CO21, From, is supplied (and minor amounts of other components), pressure is set at 100 atm and the reactor is heated to 275 ° C. During heating and with the further course of the process, 450 l / h of synthesis gas of the above-mentioned composition is supplied, the circulating gas is fed through the suction inlet of the compressor and is passed through with the catalyst. The mixture leaving the reactor is cooled in a brine-cooled condenser before and the condensed portion is collected in a receiver. The uncondensed residual gas, after mixing fresh synthesis gas, is re-injected into the reactor via a compressor. To maintain the pressure at a given level (and to separate the by-products), a part of the residual gas is discharged | through the stop valve as exhaust gas. The catalysts of the examples are tested by this procedure. 2-8. Table 3 presents the time of pro- cess, the process, the degree of conversion of the raw material to oxygen-containing compounds C2g selectivity to ethanol, acetaldehyde, acetic acid {mol%). Minor amounts of ethyl acetate or acetaldehyde diethyl acetal are converted to acetic acid, ethanol and acetaldehyde.
    Example 9. The catalyst of Example 2-is applied at and at a pressure of 200 atm, all other conditions being equal. The output of oxygen-containing compounds with two carbon atoms
    95 g / lh and 70 g / lh ethanol. Selectivity to ethanol, 68.6%.
    Example 10. The catalyst of example 2 is used at 375C and a pressure of 20 atm, all other conditions being equal. The output of oxygen-containing compounds with two carbon atoms is 60 g / l-h, etonola 40 g / l "h. Selectivity to ethanol is 66.7%.
    Table 3
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING ETHANOL by reacting hydrogen and carbon monoxide at 200-375 ° C and a pressure of 20-200 atm in the presence of a metal-containing catalyst, characterized in that, in order to increase the selectivity of the process, the latter is carried out in the presence of rhodium on silicic acid as a catalyst, promoted by an element selected from the group: zirconium, hafnium, lanthanum, platinum, chromium, mercury, or a mixture of zirconium with magnesium.
    §
    1sl □ about the joint venture
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    同族专利:
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    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19782846148|DE2846148A1|1978-10-24|1978-10-24|METHOD FOR PRODUCING ETHANOL FROM SYNTHESIS GAS|
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