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    • 专利摘要:

    公开号:SU906362A3
    申请号:SU782694552
    申请日:1978-12-08
    公开日:1982-02-15
    发明作者:Вундер Фридрих；Арпе Ханс-Юрген；Хахенберг Хорст；Инго Лойпольд Эрнст
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

    one
    This invention relates to a process for producing olefins.
    It is known that methanol and / or dimethyl ether at temperatures above 2 ° C and total pressures from 0.5 to 100 atm on molecular sieves (zeolites) is converted into a mixture of different alkanes, alkenes and aromatics. It is necessary not only to choose a molecular sieve according to numerous physical and chemical criteria, but also to take some measures to increase the selectivity for olefins, such as reducing the conversion, which, however, reduce productivity. one .
    The closest to the proposed technical essence and the achieved result is the method of lower olefins half-melt by converting methanol and / or dimethyl ether at 300-500 ° C in the presence of an aluminosilicate catalyst, which is modified by phosphorus compounds, for example trimethyl phosphate, which allows to increase the selectivity of methanol conversion dimethyl ether 23.
    5 Preparation of phosphorus-modified catalysts is expensive, requires anhydrous conditions and the use of expensive phosphorus compounds. In addition, the life of these catalysts
    10 is limited: they must be regenerated almost every three weeks. Olefins selectivity is still low, as significant amounts of saturated and aromatic hydrocarbons are formed. The conversion reaches no more than 87, the selectivity is on the order of 40-5.
    The aim of the invention is to increase the selectivity of the process.
    权利要求:
    Claims (2)
    [1]
    This goal is achieved by a method of producing lower olefins by converting methanol and / or dimethyl ether at 300-500 ° C in the presence of an aluminosilicate catalyst containing 0.1-10.0 wt.% 3 manganese. The process is preferably carried out at a pressure of 1-100 atm using a catalyst that additionally contains magnesium. The essence of the proposed β-method consists in the following. The use of a manganese-modified catalyst makes it possible to conduct this process more selectively, aliphatic and aromatic compounds boiling in the region of gasoline boiling or even higher are not formed or are formed in minute quantities. In addition, the redox properties of manganese facilitate the oxidation process and allow the catalyst to be regenerated under milder conditions, without significant disruption of its structure, by burning the coke deposits with air or oxygen and melting it in an atmosphere of water vapor. As an aluminosilicate, conventional amorphous acidic cracking catalysts can be used, which contain from 13 to 25% by weight of aluminum oxide and from 75 to Q7 of silicon oxide, natural or Si-1tetic crystalline aluminosilicates (photite, zeolite, chabazite, analcite, jismondin, gmelinit, natrolit, mordenin and erionite or also substances known as molecular sieves). From crystalline molecules, pbH | X sieves with different pore diameters are preferred with large pores, for example, 5R or more. The modification of the catalyst is carried out by applying from 0.1 to 10% by weight of manganese in the form of a solution of manganese salt on aluminosilicate, while the alumino silicate can be impregnated with a solution of salt and then dried. As solvents, water, methanol, formamide, dimethylformer amide or their mixtures are preferable. Manganese can be applied by prolonged exposure to aluminum silicate with a solution of manganese salt, followed by washing with a clean solvent and drying. By using molecular sieves, conventional sieving techniques can be applied with a solution containing a metal cation. This may be the exchange of the cation initially present in the molecular sieve for manganese and also the preliminary conversion of the molecular sieve into a proton form, followed by treatment with a solution of manganese oli. Other catalytically active metal salts can be applied simultaneously with the manganese salt, for example by mixing its solution with one or more solutions of other metal salts and applying this mixture. Suitable salts include alkali metal compounds (especially lithium, sodium, potassium), alkaline earth metals (especially magnesium and calcium), zinc, lanthanum, rare earths (for example, praseodymium, neodymium, smarium, gadolinium or their mixture, beryllium) . The catalytically active salts can be deposited: on the silicate sequentially. As manganese salts, all soluble manganese salts are suitable: chloride, sulfate, nitrate, formate, acetate, propionate, butyrate, lactate, citrate, manganese tartrate and salts of malic acid. The same applies to the other active components of the catalysts. If combined solutions of manganese and another catalytically active element are used, then the opposite effect of solubilities must be taken into account, for example, when using calcium or barium, the use of sulfate as an anion is impractical. In addition, when using natural crystalline aluminum silicates, it is often recommended to rinse with water before impregnation with salts of manganese or other active components of the catalyst, so that metal salts cannot prematurely precipitate as oxyhydrates. After impregnation, the catalysts can be dried at normal pressure, under vacuum or under excessive pressure, at normal or elevated temperature. Typically, the drying temperature is lower, preferably from 100 to 200 ° C. When methanol is used as a starting material, methanol can be immediately passed under a catalyst or first converted by dimethyl precursor to a conventional dehydration catalyst, for example, alumina or silica-alumina, into dimethyl ether and the latter passed over the catalyst. 5 Despite the two stages of the reaction, some of the water is removed already in the first stage. As a starting material, a mixture of methanol and dimethyl ether or one dimethyl ether can be used. The components used methanol and / or dimethyl ether can be supplied to the reaction also with dilution with an inert gas. For example, nitrogen, carbon dioxide, alkene and also water are suitable for reducing the partial pressure. For this purpose, the reaction can also be carried out under reduced pressure (up to 0.1 atm). However, it is preferable to conduct at pressures of 1-100 atm, and especially preferred pressure area of 150 atm. The reaction temperature is usually in the range of 300-500 ° C, more preferably C and particularly preferably C. If the reaction conditions are chosen such that only incomplete conversion of methanol and / or dimethyl ether occurs, the unreacted fraction can be separated and returned. The olefins obtained according to the proposed method can be by conventional methods, for example distillation, separated from alkanes formed as by-products and from each other. Example 1. 100 ml of a commercially available molecular sieve, titled 1 × (total formula Nag5, (A2 (05) g (Si02W) 276, pore diameter 10 A, water absorption capacity 36, the zeolite lattice structure) is washed with water at 25 ° C until reaching wash water pH 7.3-Wet molecular sieve is mixed with 100 ml of a saturated aqueous solution of manganese acetate, left for 48 hours, then washed with water and dried at 120 ° C This catalyst contains k, k wt.% manganese. Above it is passed 7 dimethyl ether per hour at normal pressure and. With a conversion degree of 5.9, 3.3 liters of a mixture containing, by weight .: Ethylene, 31.6 Propylene, 29.1. Butene 11.3 Methane, 16.6 Ethane, 3.7 2 Propane, 1, 6 Butane, 6.1 Thus, saturated and unsaturated C-Sf hydrocarbons are obtained total selectivity 83, ethylene selectivity 31.6%; propylene 23.1 and butene 11.31. Example 2. 200 ml of molecular sieve 1X (characteristic in example 1) are washed with water in a tube with a diameter of 2.5 cm to Achievement in wash water pH 7.0. Then, aOO, ml of a saturated solution of magnesium propionate and manganese butyrate are passed through for 2 hours. Excess manganese and magnesium salts are washed with water. The resulting catalyst contains 6, manganese and 1.3 ma1-ni. After drying with Nzd, this catalyst passes 27.5 g / hrO of methanol at 40J C and a pressure of 1 atm. With a conversion degree of 90.15, 11 g / h of water, 13 g / h of dimethyl ether and 2.57 nl / h of a mixture of hydrocarbons containing, by weight,: Ethylene, 6 Propylene 29.2 Buten5.3 Methane12.3 Ethane3.7 Propane 0.5 Butane2.1 Since the formed dimethyl ether is recycled, the selectivity for ethylene is, for propylene 2E, 2% and for butene, 5.3, i.e. these three olefins are formed with a total selectivity of 81.5X. Example 3 (comparative). The preparation of the catalyst is carried out according to Example 2, only a saturated solution of magnesium propionate, not containing manganese butyrate, is used. After 200 ml of this 13x molecular sieve, 27.5 g / h of methanol are passed at a pressure of 1 atm and 400 ° C. In the exhaust gas is only 0.1 o6,%, ethylene, the rest is dimethyl ether. At 500 ° C, the ethylene content increases to 1.3 ° and again decreases to 0.1%. Example k (comparative). Over 200 ml of the 13x molecular sieve (characterization in example 1), without any pretreatment, pass 27.5 g / h of methanol at a pressure of 1 atm and 400 ° C. Exhaust gas; does not contain ethylene, but only almost one d methyl ester with traces. carbon monoxide and hydrogen. Example 5 (comparative). The operation is carried out as in Example 2, only the 1Zx molecular sieve is washed with water before use until the washing water is neutral. The exhaust gas has the same composition as in Example 2. EXAMPLE 6. 200 g (500 ml) of commercial amorphous aluminum silicate containing, by weight, I: A82.0j25; ,five; Na 0.05; Fe 0.03; Ca 0.03 BET 325 MVr surface, pore volume О, 5 ml / g проп impregnated (according to the pore volume) with a solution consisting of 23.2 g of manganese formate and 77 ml of water and dried at 120 ° C. The catalyst contains 3.8 weight. manganese. Over this catalyst I pass at 380 ° C and a pressure of 0.5 atm 46 g / h of methanol. This gives 13.5 liters of waste gas per hour, containing, wt.% Ethylene Propylene Propane Carbon monoxide Hydrogen Dimethyl ether 11.4 Forms 26 g of condensation water with 13.3 wt.% Methanol. This corresponds to a degree of conversion of 92.5 and selectivity for saturated and unsaturated hydrocarbons,%: from 13.1 C to 22.7 Cj. 23.7 C 0.0 if unconverted, methanol and the formed dimethyl ether are recycled back to the reaction. Hydrocarbons Sp-C (saturated and unsaturated) are formed with a selectivity of 86, a selectivity for olefins Sp-C. 58.3. Example 7. Over 300 ml of the usual commercially fine-porous (with a small pore diameter) aluminosilicate catalyst containing, weight .. 15 ,; 0.028; 0.007j, 3, BET 485MV surface, pore volume 0.55 ml / g, which is treated with a 20% aqueous solution of ace2 .. 8 manganese tata and contains 1.3 manganese, is passed at a pressure of 15% ATM 200 g / h of methanol. The resulting reaction product contains, by weight: Methanol Dimethyl Ethylene Propylene Methanol conversion degree 3.1%, hydrocarbon selectivity (saturated and unsaturated) 89, il, ethylene selectivity 35, propylene 15.6 and butene 12.5%. Olefins are formed with a total selectivity of E,%. Example 8. 50 ml of commercially available (trade name AGZ) molecular sieve catalyst containing, weight: .0% 30; rare earth oxides 2.57; SOVO, Naf2.0 0.29; SiOfj. 66.6; BET surface for 3 h heating at 538 C 290 MVr; pore volume 0.3 ml / g; average bulk density 0.6 g / l; the average particle size is 68 μm, stirred with a saturated aqueous solution of Mirganz chloride and Mn2 chloride for 10 hours, then washed with water and dried at 110 ° C. The resulting catalyst contains 0.5 wt.% Manganese. Above this catalyst, 20 nl of dimethyl ether are passed per hour at a pressure of 1.5 atm. The reaction product contains, Ethylene 21.6 The degree of conversion is 9b, the selectivity for ethylene is 36, for propylene is 32.9, for butenes 2k, (%, Ole was formed with a total selectivity of 9 hours, h |. Example 9. 600 g of 13x molecular sieve are loaded in a vertical tube with an internal diameter of 25 mm and washed with desalted water. Then carbonic acid is added to the wash water and the wash is continued until pH 6 is set in the containing C0 (j wash water after 5 hours contact with the molecular sieve , 8, within a period of +8 h, the concentrated aqueous solution is passed Manganese and Magnesium Acetate (2.5 L). Then rinsing with distilled water until the manganese ions disappears from the wash water. The resulting catalyst contains 6.8% manganese and 1.3 wt.% magnesium. and at a pressure of 25 atm, 2.8 liters (2.2 kg) of methanol per hour are passed in. The reaction product has the following composition, weight: Ethylene Propene Methanol Dimethyl Methanol conversion rate: 98.8 Selectivity for hydrocarbons (saturated and unsaturated) 97) 3%. Selectivity,%: for ethylene 33, for propylene 28.9 ps butene 16.8; methane 7.7; on ethane 4; butane 7.2. The selectivity for hydrocarbons (saturated and unsaturated) is 90.6, the selectivity for olefins SL-Cd is 79.0 °. Example 10. 200 ml (T4b g) of the Habasit-erionite product mixture in the form of a molded product by spraying of the product is washed with acetic acid and then dried. The support thus prepared is impregnated with a solution of 1.0 g manganese acetate hydrate in 80 ml of water for two days and then dried. The finished catalyst contains 0.1, manganese. Through this catalyst, 27.5 g of methanol per hour are passed at + 00 ° C and 1 atm. At a conversion degree of 93%, 16.0 g of condensate with 11.9% of methanol and 8.5 l of a gas mixture containing, weight, are obtained per hour. .%: Ethylene Propylene Propane 2 Butane5.6 Dimethylether 2.5 Selectivity for CQ-C4 olefins 56.7%, for hydrocarbons 82.9%. Example 11. 200 ml of the natural mixture of habazit-erioni in the form of a product molded by spraying are processed in a diameter of 2.5 cm with 400 ml of a saturated solution of manganese acetate for 8 hours, then washed with water and dried. After drying, 100 g of an aqueous solution containing 22.61 manganese acetate hydrate are added and then dried again. This catalyst is kept for 2 hours in an air stream heated to 00 ° C, after which it is fed to AOO ° C and a pressure of 1 atm, 27.5 g of methanol per hour. Get the reaction product containing, Bec. Ethylene8.3 Propylene 6.1 Butene2.2 Methane10.4, Ethane0.5 Propane6.2 Dimethylether 10.5 Methanol 5.8 Water (7.9 This corresponds to the degree of conversion of 80.2 x hydrocarbons and selectivity,%: Ethylene 23.2 Propylene 17.0 Butene6.1 Methane29.6 Ethane1, Propane 17.3 Butane5.9 Example 12. (Methanol + dimethylether - feedstock.) 200 ml of the natural mixture of Habasit-erionite are treated with 300 ml of a saturated solution of manganese acetate, decanted after 48 hours at 25 ° C and washed with water until the traces of manganese disappear in the washing water. After drying, the finished catalyst contains 2.4% Mn. This catalysis is p at 400 ° C and a normal pressure of 25 g of methanol and 2.7 g of dimethyl ether N. A reaction product is obtained containing, in wt%, dimethylether 4.1 Methane2.9 Ethylene18.6 Ethane0.5 Propene15.6 Propane2 9 Buten2.7.7 Butane.2 / 1 Water50 , 6 After condensation of water, half of 9.7 liters of gas is contained, containing: Dimethylether 8.3 Methane5.8 Ethylene37.6 Ethane1.1 Propylene31, 6 Propane5.9 Buten5, Butanit, 2 This corresponds to a conversion degree of 91.7% and selectivity ,%: Ethylene 1, 0 Propylene, 3.5 Butene, 5.9 Ethane, 1.2 Propane, 6 Butane, 4,6 - t. Cn-C4 olefins are formed with a selectivity of 81, ij%, and 4 hydrocarbons with a selectivity of 93.6. 9063 5 10 15 20 25 12 2 Formula of the Invention I-A method for producing lower olefins by converting methanol and / or dimethyl ether at 300-500 ° C in the presence of an aluminosilicate catalyst, characterized in that, in order to increase the selectivity of the process, a catalyst is used that additionally contains 0.110, 0 weight D of manganese. 2. The method according to p. 1, characterized in that the catalyst further comprises magnesium. 3. The method according to paragraphs. 1 and 2, that is, that the process is carried out at a pressure of 1-100 atm. Sources of information taken into account in the examination 1. For the Germany W 2615150, cl. From 07 to 11/00, published 1976.
    [2]
    2. US patent number 39110, cl. 260-682, published. 1975 (prototype).
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    同族专利:
    公开号 | 公开日
    DE2755229B2|1980-01-10|
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    引用文献:
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    US3529033A|1963-05-20|1970-09-15|Mobil Oil Corp|Catalytic conversion|
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    US4148836A|1977-12-23|1979-04-10|Allied Chemical Corporation|Process for reducing water content of sulfuric acid in hydrocarbon alkylations|DE2928922A1|1979-07-18|1981-02-12|Hoechst Ag|METHOD FOR PRODUCING LOW OLEFINS FROM METHANOL / WATER MIXTURES|
    US4423274A|1980-10-03|1983-12-27|Mobil Oil Corporation|Method for converting alcohols to hydrocarbons|
    DE3008146A1|1980-03-04|1981-09-17|Hoechst Ag|METHOD FOR PRODUCING AN ALUMINUM SILICATE CATALYST FOR CONVERTING WATER-BASED METHANOL AND / OR WATER-BASED DIMETHYL ETHER IN LOWER OLEFINS|
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    NZ199034A|1980-12-05|1984-11-09|Ici Australia Ltd|Production of hydrocarbons from a feed containing methanol,water and a promotor passed over aluminosilicate|
    US4393265A|1981-07-24|1983-07-12|E. I. Du Pont De Nemours & Co.|Light monoolefins from methanol and/or dimethyl ether|
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    US4698452A|1986-10-02|1987-10-06|Institut Nationale De La Recherche Scientifique|Ethylene light olefins from ethanol|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
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