Method for obtaining @@@ olefins

专利摘要:
The invention of mercury is related to light olefins, in particular to the production of olefins. The goal is to improve the economy of the method. Production is carried out by converting synthesis gas containing carbon monoxide and hydrogen, not a copper-containing catalyst into a mixture of alcohols, which contains methanol and higher alcohols with a mass ratio of 0.6-5.6, preferably 0.6-1.5. The process is carried out followed by contacting the mixture of alcohols with a catalyst with a pentasil structure at 250-600 ° C. 1 hp f-ly.
公开号:SU1657478A1
申请号:SU877774399
申请日:1987-01-14
公开日:1991-06-23
发明作者:Венер Клаус；Дердулла Ханс-Еахим；Штриеглер Хэлмут；Тимм Диетер
申请人:Феб Леуна-Верке "Валтер Улбрихт" (Инопредприятие)；
IPC主号:

专利说明:

The invention relates to a process for the production of olefins from mixtures of alcohols, which were obtained from gases containing carbon monoxide and hydrogen.
From gases containing carbon monoxide and hydrogen, as synthesis gas, is obtained using catalysts containing copper, a mixture of alcohol that contains methanol and higher aliphatic alcohols, in particular ethanol and propanol, is dehydrated on the dehydration catalyst to the corresponding olefins (FGD application No. 3005550, c. C 07 C 1/20, 1981).
The proposed method has the disadvantage of consuming a great deal of energy, since methanol is completely separated from the alcohol mixture before the dehydration of the alcohol, and the energy for endothermic dehydration of the higher alcohols is introduced from the side. In addition, the methanol content of the original alcohol mixture is not used to form olefins. It is also known to convert a mixture of alcohol on zeolite catalysts to olefin-containing hydrocarbons. The removal of the heat of reaction produced in this way is carried out in various ways.
This conversion of lower alcohols, esters, also in a mixture with other compounds, such as higher alcohols or carbonyl compounds, is known, in which methanol is converted into a mixture of dimethyl ether, methanol, water in the first stage, the intermediate product is indirectly cooled. and is further converted into a hydrocarbon mixture upon indirect cooling of the second catalyst zone (U.S. Patent No. 4,052,479, CL 585-640, 1978). Work is carried out only at a maximum 25% conversion of the initial product and high methanol recovery.
Heat removal is carried out only by indirect cooling with corresponding heat losses and significant technical costs for cooling equipment.
The heat liberating from the conversion of oxygen-containing compounds cannot be directly
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used for chemical reactions, it is diverted.
A known method for producing lower olefins (German Application No. 3437698, Cl, C 07 C 11/04, 1984), mainly ethylene, monoaromatic hydrocarbons and carburetor fuel, by catalytic conversion of methanol (or mixtures of oxygen-containing organic compounds) and hydrocarbons, boiling areas of gasoline and gas oil, in a ratio of 10: 1 to 1: 5 on zeolite catalysts, with a high content of silicic acid at 600-800 ° C, due to which the described disadvantages are eliminated,
The exothermic conversion of methanol with endothermic splitting of hydrocarbons, although leading to a better mastery of exothermia, however, the method has the disadvantage of additional hydrocarbons in water for the conversion of methanol. The known method (US Patent No. 4,067,761, class C 07 C 15/09, 1978) for the preparation of olefins, one of the variants of which involves the conversion of alcohols obtained from synthesis gas on a copper-containing catalyst, on catalysts having a tape-strength structure, for example ZSM -five.
The aim of the invention is to improve the economy of the process for the production of Cs-Cz olefins from mixtures of alcohols.
It is necessary to develop a method for the production of C2-C4-olefins from mixtures of alcohols, in which the technological costs of the entire process will be reduced. This is achieved by converting gases containing carbon monoxide and hydrogen, for example synthesis gas, on a copper-containing catalyst to an alcohol mixture and converting higher aliphatic alcohols on pentasil-type zeolite catalysts at 250-600 ° C and pressures higher than 100-200 kPa, in an alcohol mixture a mass ratio of methanol to higher alcohols is set to 0.6-5.6, preferably a mass ratio of methanol to higher alcohols is set to 0.6-1.5.
The simultaneous presence of varying water content in the starting product does not affect the synthesis gas of olefins and the further separation processes required
With the establishment of a mass ratio between methanol and higher alcohols, when a mixture of alcohol is converted on a conversion catalyst, a significant equilibrium between the exothermic conversion of methanol and the endothermic dehydration of higher
alcohols, which leads to almost thermoneutral reactions. Thus, the energy for dehydrating the alcohol is obtained by converting methanol with the simultaneous formation of additional olefins.
The determination of a certain mass ratio of methanol to higher alcohols occurs predominantly by
0 distilling off a part of methanol from the alcohol mixture obtained during the synthesis of alcohol, but it can also be carried out so that the synthesis of alcohol is carried out under conditions that allow one to obtain such a mixture or so that
5 C2 alcohols, which are obtained in other ways. Methanol obtained by distillation can be returned to the synthesis of alcohol.
Suitable transformation catalysts are pentazil-type zeolites, for example
0 obtained on the basis of zeolite LZ 40 (GDR patent Mg 219639, C 07 B 33/26, 1985). Such catalysts can be used in a mixture with dehydration catalysts, for example with alumina. Transformation
5 occurs at a pressure of 100-200 kPa. The catalyst load with organic product is 0.3-5.0 l / l of catalyst per hour, preferably 0.5-1.5 l / l of catalyst per 1 hour. Works can be carried out in the presence of an inert gas, such as hydrocarbons or carbon dioxide. Full conversion of the alcohol is achieved. The transformation is carried out in a fixed or fluidized bed. Used for
5 (the transformations of the alcohol mixture contain besides methanol C2; to Syu-n- and iso-alcohols. As well as esters, esters, carbonyl compounds and, if necessary, hydrocarbons with the corresponding content
0 to 5 wt.%. A mixture of alcohol can have a water content of up to 800 wt.%. The method is also suitable for mixtures of alcohols that are dehydrated.
The transformation product is cooled.
E to a temperature of less than 313 K. In the separator, the product is divided into a lower aqueous, upper hydrocarbon phase and a gas phase. The aqueous phase is discharged as process water. It does not contain
0 alcohol. After separation of the carbon dioxide from the gas phase, methane and Cr-to C4-olefins are separated in the usual way. The remaining components of the gas phase, as well as Cs + hydrocarbons of the liquid phase, can be returned to the transformation reactor or to
5 additional reactor for thermal decomposition to olefins.
Example 1. From 1000 g of a mixture of alcohol obtained by converting carbon monoxide and hydrogen on a copper-containing catalyst and containing May. %: methanol 53; ethanol 17; propanol 7; butanol 3,5; higher alcohols 1.0; hydrocarbons 0.5, water 18, 320 g of methanol was distilled off. The remaining mixture of alcohol has a methanol to higher alcohol ratio of 0.74. The mixture containing water obtained after distillation of a part of methanol is converted at 250 ° C and a pressure of 200 kPa and a load of 0.8 ml (in terms of organic, oxygen-containing components of the product) per 1 ml of catalyst per 1 hour on a catalyst of 70% by weight zeolite with the structure of pentasil (LZ40), containing 2.6 wt.% magnesium, and 30 wt.% alumina, the catalyst is in a tubular reactor and is heated by a heating current of 3 amps before loading the starting product. With the start of catalyst loading with a mixture of alcohol, the heating current is disconnected. The product of conversion consists in terms of used CH2 from 28.5 wt.% Of ethylene, 20.4 wt.% Of propene, wt.% Of butene, 11.9; 37.7 May. % C4 + - hydrocarbons (without butene) and 1.5 wt.% Ci-Cz-paraffins.
The conversion of alcohol was complete.
PRI mme R 2. 1000 g of a mixture of alcohol. which is obtained by converting carbon monoxide and hydrogen on a copper-containing catalyst and containing, in wt.%: methanol 82.0; ethanol 0.1; propanol 4.1; butanol 4.3; 1,4 higher alcohols; hydrocarbons 0.1 (and the mass ratio of methanol to higher alcohols was 4.58) were converted at 370 ° C, a pressure of 200 kPa and a load of 1.5 ml (in terms of oxygen-containing organic components of the product) per 1 ml of catalyst per hour on the catalyst from 80 May. % zeolite with the structure of pentasil (HS30) and 20 wt.% Bemio. The catalyst is in a tubular reactor and is heated by a heating current of 3 amps before loading and the input product. With the start of catalyst loading with a mixture of alcohol, the heating current is disconnected. The conversion product is based on the used CH2 of 20.2% by weight of ethene,
34.2 wt.% Propene, 19.6 wt.% Butene,
24.3 wt.% C4 - hydrocarbons (without butene) and 1.7 wt.% Ci-Cz-paraffins.
The conversion of alcohol was complete.
Example 1000 g of a mixture of alcohol, which is obtained by the conversion of carbon monoxide and hydrogen on a copper-containing catalyst and containing, in wt.%: Methanol 84.5; ethanol 6.7; propanop 3.9; butanol 3.4; higher alcohols 1,1; hydrocarbons 0.4 (moreover, the mass ratio of methanol to higher alcohols was 5.6) were converted at 350 ° C, a pressure of 200 kPa and a load of 1.1 ml (in terms of oxygen-containing organic components of the product) per 1 ml of catalyst per hour for catalyst of 65 wt.% zeolite with the structure of peptazil (LZ40) and 35 May. % boehmite. The catalyst 5 is in a tubular reactor and is heated by a heating current of 3 A before loading the starting product. With the beginning of the catalyst load with a mixture of alcohol conducts off the heating current. The conversion product is based on the used CH2 of 24.3% by weight of ethene. 27.7% by weight of propene, 18.4% by weight of butene, 28.0% by weight of C4 + hydrocarbons (without butene) and 1.6% by weight of Ci-C3 paraffins. 5 The conversion of alcohol was complete.
Example 4. From 1000 g of a mixture of alcohol obtained by the conversion of carbon monoxide and hydrogen on a copper-containing catalyst and containing, in mass%: methanol 57;
0 ethanol 14.3; propanol 7.2: butanol 5.1; higher alcohols 1.0: hydrocarbons 0.4; water 15: 404 g of methanol is distilled off. The remaining, water-containing alcohol mixture has a weight ratio of methanol to higher
5 alcohols 0,6. The mixture is converted at 570 ° C, a pressure of 100 kPA and a load of 1.5 ml (in terms of organic oxygen-containing components of the product) per 1 ml of catalyst per hour on the catalyst
0 75 wt.% Zeolite with the structure of pentasil (ZSM 34) and 25 wt.% Alumina. The catalyst is in a tubular reactor and before the product is loaded, it is heated by a heating current of 3 A. At the beginning of the loading of the catalyst with a mixture of alcohols, the heating current is turned off.
The conversion product is based on the used CH2 from 26.2% by weight of ethene, 27.1% by weight of propene, 18.1% by weight of bute0 on, 25.2% by weight of C4 + hydrocarbons (without butene) and 3J% by weight Ci-Cz-paraffins.
The conversion of alcohol was complete. PRI me R 5. 1000 g of an alcohol mixture which is obtained by the conversion of an oxide
5 carbon and hydrogen on the copper-containing catalyst and containing, wt.%: Methanol 54, ethanol 18.3; propanol 10.6; butanol 6, higher alcohols 1.1, hydrocarbons 0.5, water 9.5 (and the mass ratio
0 methanol to higher alcohols 1.5) were converted at 600 ° C. pressure of 100 kPa and a load of 2.0 ml (in terms of the oxygen-containing organic components of the product) per 1 ml of catalyst for 1 hour per
5 catalyst from 70 wt.% Zeolite with the structure of pentasil (ZSM 11) and 30 wt.% Boehmite. The catalyst is in a tubular reactor and heated before the product is loaded with a heating current of 3 A. At the beginning of the catalyst loading with a mixture of alcohols, heating
stopped. The product of conversion consists in terms of the used SN from 26.4% by weight of ethene, 25.3% by weight of propene, 15.8% by weight of butene, 29.8% by weight of C4 + carbohydrates (without butene) and 2, 7 wt.% Ci-Cz-paraffins,
The conversion of alcohol was complete.
PRI me R 6. (comparative). From 1000 g of a mixture of alcohol obtained by the conversion of carbon monoxide and hydrogen on a copper-containing catalyst and containing, in wt.%: Methanol 55.0; ethanol 16.5; propanol 8.3; butanol 4.7; higher alcohols 0,7; hydrocarbons 0.8; water 14.0 was distilled off 490 g of methanol. The remaining mixture of alcohols containing water has a mass ratio of methanol to higher alcohols of 0.2. The mixture is converted at 250 ° C, a pressure of 200 kPa and a load of 0.8 ml (in terms of the oxygen-containing organic components of the product) per 1 ml of catalyst per hour on a catalyst of 70% by weight zeolite with the structure of pentasil (LZ 40). containing 2.6 wt.% magnesium, and 30 wt.% alumina. The catalyst is in a tubular reactor and is heated before the product is loaded with a heating current of 3 A. At the beginning of the catalyst loading with a mixture of alcohols, the heating current increases to 3.5 A and is subsequently held.
The conversion product is calculated on the basis of used CH2, from 25.8 wt.% Ethene, 20.7 wt.% Propene, 16.2 wt.% Butene, 35.8 wt.% C4-hydrocarbons (without butenes) and 1.5 wt.% Ci-Cz-paraffins. The conversion of alcohol was complete.
Example, (comparative). 1000 g of alcohol, which is obtained by converting carbon monoxide and hydrogen on a copper-containing catalyst and containing, in wt.%: Methanol 81.4; ethanol 6.1; propanol 3.3; butano 0.5, higher alcohols 0.1; hydrocarbons 0,2; water 8.4 (and the mass ratio of methanol to alcohols was 8.14) was converted at 590 ° C, a pressure of 100 kPa and a load of 2.6 ml (based on the oxygen-containing organic components of the product) per 1 ml of catalyst per hour with the addition of 30 l / h of nitrogen on the catalyst of 70 wt.% zeolite with the structure of pentasil (ZSM 11) and 30 wt.% boehmite. The catalyst is in a tubular reactor with an external
salt bath and is heated before the load of the product current heating 3 A to 550 ° C. At the beginning of the catalyst load with a mixture of alcohols turn off the heating current and heat of reaction, released by the reaction
the conversion is removed by the addition of inert gas and through the circulation of the external salt bath. The conversion product is based on the used CH2 from 22.6% by weight of ethene, 29.4% by weight, of propene,
13.5% by weight of butene, 30.3% by weight of C4 + hydrocarbons (without butene) and 4.2% by weight of Ci-C3 paraffins.
The conversion of alcohols was complete.

权利要求:
Claims (2)
[1]
1. A method for producing olefins by converting synthesis gas containing carbon monoxide and hydrogen on a copper-containing catalyst into a mixture of alcohols,
which contains methanol and higher alcohols with C 2, followed by contacting the mixture of alcohols with a catalyst with the structure of pentasil at a temperature of 250-600 ° C and a pressure of 100-200 kPa, distinguishing
so that a mixture of alcohols having a weight ratio of methanol to higher C 2 alcohols of 0.6-5.6 is used for contacting with the catalyst.
[2]
2. A method according to claim 1, characterized in that the mixture of alcohols has a mass ratio of methanol to higher alcohols of C 20.6-1.5.

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法律状态:

优先权:

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