The method of producing olefins and catalyst for olefin production

 

(57) Abstract:

The invention relates to a method for producing olefin vapor-phase dehydration of alcohols in the presence of a catalyst at elevated temperature. As catalyst, use aluminium oxide, which receive additional treatment with an aqueous solution of acetate alkaline earth metal when the metal content of 0.1-1 mol/l and heat treated in air at 380-420oC. In accordance with the invention, a catalyst for olefin production, which is an oxide of aluminum, and further processed as described above and subjected to heat treatment at a specified temperature. Effect: lowering the amount of colored impurities and increase the yield of olefin hydrocarbons. 2 C. p. F.-ly, 3 tables.

The invention relates to the petrochemical industry, in particular to a method for producing olefins by dehydration of alcohols and catalysts for alcohols, and can be used to obtain isobutylene, styrene, divinylbenzene, etc.

Known to produce olefinic hydrocarbons by dehydration of alcohols. As catalysts for the dehydration of use is different is some salt: potassium hydrosulfate, copper sulphate, zinc chloride, etc.

A known method of producing vinylbenzene vapor-phase dehydration of erelcaoloo over molecular sieves 4A at a temperature of 350oC and a flow rate of 1-10 h-1in a flow reactor with a fixed bed of the catalyst (U.S. Pat. RAF 56184, C 07 C 15/10, op. 15.12.1973). However, in this method there is a low yield of the target products.

Known to produce isobutylene (Japan's Bid 41431/88, C 07 C 1/24, op. 22.02.1988) dehydration of tert-butanol in the gas phase at 100-450oWith over a fixed bed of catalyst based on aluminum oxide and silicon dioxide.

A known method of producing styrene (Ed. St. The USSR 775100, C 07 C 15/10, op. 30.10.1980) vapor-phase dehydration of methylphenylcarbinol (IFC) in the presence of aluminum oxide and water vapor at a temperature of 260-300oIn a two-stage adiabatic reactors with intermediate heating of the contact strip.

A known method of producing styrene by a vapor-phase dehydration of the IFC at a temperature of 260-300oIn the presence of water vapor on the catalyst is aluminum oxide, optionally containing molybdenum oxide and iron oxide, in a two-stage adiabatic reactors with intermediate heating of conidential the target product (RF Patent 1216941, 07 With 15/46, op. 1999).

The disadvantage of these methods is the low yield of olefins, is not sufficiently high activity and selectivity of catalysts in the processes of dehydration of alcohol.

The closest in technical essence is a method of dehydration of alkanols of the formula RR'CHCR R'(OH), where RR'R"R"' is hydrogen, alkyl or cycloalkyl C1-s, possibly containing aryl, and aryl is separated from HE group two or more carbon atoms in the presence of zinc aluminate at a temperature of 200-600oC. the Catalyst was prepared by mixing zinc oxide with aluminum oxide in a molar ratio of 1:0.95 to-1.1 and a heat treatment at 700-1400oC for 0.1 to 30 hours (U.S. Patent 4260845, 1/00 C 07 C, op. 07.04.1981).

The disadvantage of this method is the low yield of the target products and the formation of impurities that degrade the color.

Closest to the proposed catalyst is the catalyst for dehydration of monohydroxy alcohols with 2-25 carbon atoms at 200-500o(UK Application 2181070, 01 J 23/06, op. 15.04.1987). The catalyst consists of a carrier - aluminum oxide (III), on the surface of which is coated with the zinc aluminate. The formed aluminum oxide is impregnated with the aqueous solution of zinc salts, sureblade insufficiently high activity and selectivity in the process of dehydration of alcohols, and, therefore, is relatively low yield of the target product.

The task of the invention is to decrease number of colored impurities in the target products, increase the yield of olefinic hydrocarbons.

The problem is solved by a method of producing olefins by a vapor-phase dehydration of alcohols in the presence of water vapor on the catalyst is aluminum oxide is at an elevated temperature, and as a catalyst using alumina, which receive additional treatment with an aqueous solution of acetate alkaline earth metal when the metal content of 0.1-1 mol/l and heat treated in air at a temperature of 380-420oC.

To obtain olefins using a catalyst comprising an oxide of aluminum, optionally treated with an aqueous solution of acetate alkaline earth metal when the metal content of 0.1-1 mol/l and which is subjected to heat treatment in air at a temperature of 380-420oC.

Additional processing of aluminum oxide in an aqueous solution of salts of the alkali earth metal causes a partial inhibition of the catalytic centers that are incidental (non-selective) reaction, which leads to the catalyst and to increase the lifetime of the catalyst.

The dehydration process is carried out in isothermal flow reactor of stainless steel at a temperature of 310-330oC, space velocity of the organic phase 0.9 h-1water 1.1 h-1.

The preparation of the catalyst includes an extract of the source of alumina in a solution of salts of alkaline earth metal at room temperature for 18-48 hours, drying in air at 140-160oWith over 8-12 hours, the heat treatment in air at 380-420oWith over 8-12 hours and heat treated in air in the presence of water vapor at a temperature of 500-550oWith over 8-12 hours.

The invention is illustrated by the following examples.

Example 1. The process is carried out at a temperature of 320oBy using quality raw material methylphenylcarbinol fraction composition, % wt: methylphenylcarbinol 81,917; acetophenone 15,030; ethylbenzene 0; styrene 0; unidentifiable impurities 3,053. The catalyst is aluminum oxide (GOST 8136-85) is heat treated in air in the presence of water vapor at a temperature of 525oC for 8 hours.

Raw materials and produce analyzed by gas chromatography on the content of methylphenylcarbinol, acetophenone, ethyl benzene, styrene. Dopolnitelnymi region of the spectrum with the optical filter 400 nm. Solution comparison - water; cuvette thickness of 0.5 cm For raw optical density of 0.05.

Data on the composition and optical density catalyzate are given in table.1.

Example 2. The process is conducted according to example 1, using a catalyst, optionally treated with an aqueous solution of calcium acetate with calcium 1 mol/liter of Catalyst is maintained in an impregnating solution for 24 hours, dried in air at 150oC for 8 hours, heat-treated in air at 400oC for 8 hours and then in air in the presence of water vapor at 525oC for 8 hours. Data on the composition and optical density catalyzate are given in table.1.

Example 3. The process is conducted according to example 1, using a catalyst, optionally treated with an aqueous solution of calcium acetate with calcium content of 0.2 mol/L. Data on the composition and optical density catalyzate are given in table.1.

Example 4. The process is conducted according to example 1, using a catalyst, optionally treated with an aqueous solution of calcium acetate with calcium content of 0.1 mol/L. Data on the composition and optical density catalyzate are given in table.1.

Example 5. The process is conducted within three hours the th mixture composition, % wt.: alcohol tributyl 85,338, water 14,525, unidentifiable impurities 0,137. The volume flow of the organic phase 0.9 h-1. Additionally, the reactor is fed with water volumetric rate of 1.3 h-1. The catalyst is aluminum oxide (GOST 8136-85) is heat-treated in air in the presence of water vapor at a temperature of 525oC for 8 hours. Conversion of alcohol calculated on the results of chromatographic analysis of the aqueous phase catalyzate. After completion of the experiment, the spent catalyst is transferred into the apparatus Cocklet and washed for three hours, ethyl ester acetic acid for extraction of resinous products. After cooling the extract to room temperature by measuring optical density "And" on the photocolorimeter ck-2 in the visible region of the spectrum with the optical filter 400 nm. Solution comparison - water; cuvette thickness 3,0 see the Obtained absorbance value "A" is directly proportional to the amount of tar formed during the experiment. Data on the content of tertbutanol in the aqueous phase catalyzate, conversion tertbutanol and optical density are given in table.2.

Example 6. The process is conducted according to example 5, using a catalyst that will complement the butanol in the aqueous phase of catalyzate conversion tertbutanol and optical density are given in table.2.

At the same conversion tertbutanol in the conditions of example 5 and 6, the optical density of the product obtained according to example 6, more satisfactory.

Example 7. The process is conducted for three hours at a catalyst loading of 100 cm3, a temperature of 330oBy using quality raw material dimethylphenylcarbinol fraction containing, % wt.: dimethylphenylcarbinol (DMPC) 78,057, acetophenone 9,897-methylsterol 10,252, unidentifiable impurities 1,794. The volume flow of the organic phase 0.9 h-1. Additionally, the reactor is fed with water volumetric rate of 1.3 h-1. The catalyst is aluminum oxide (GOST 8136-85) is heat-treated in air in the presence of water vapor at a temperature of 525oC for 8 hours.

Raw materials and produce analyzed by gas chromatography, optionally measured optical density "And" raw materials and the organic phase catalyzate.

Data on the content of dimethylphenylcarbinol in the organic phase catalyzate, conversion dimethylphenylcarbinol and optical density are given in table. 3.

Example 8. The process is conducted according to example 7, using the catalyst, updat what about the content of dimethylphenylcarbinol in the organic phase catalyzate, conversion dimethylcarbinol and optical density are given in table.3.

Example 9. The process is conducted according to example 7, using a catalyst, optionally treated with an aqueous solution of magnesium acetate magnesium content of 0.3 mol/L.

Data on the content of dimethylphenylcarbinol in the organic phase catalyzate, conversion dimethylphenylcarbinol and optical density are given in table. 3.

Example 10. The process is conducted according to example 7, using a catalyst, optionally treated with an aqueous solution of barium acetate with a content of barium 0.3 mol/L.

Data on the content of dimethylphenylcarbinol in the organic phase catalyzate, conversion dimethylphenylcarbinol and optical density are given in table. 3.

Example 11. The process is conducted according to example 7, using a catalyst, optionally treated with an aqueous solution of strontium acetate content of strontium of 0.3 mol/L.

Data on the content of dimethylphenylcarbinol in the organic phase catalyzate, conversion dimethylphenylcarbinol and optical density are given in table. 3.

As seen from the above examples, obtaining the olefin vapor-phase dehydration of alcohols in the presence of water vapor on to the ri, the metal content of 0.1-1 mol/l, allows you to reduce the amount of colored impurities and to improve performance on the color of the products obtained with a simultaneous increase of the yield of the desired olefin hydrocarbons.

1. The method of producing olefins by a vapor-phase dehydration of alcohols in the presence of water vapor on the catalyst is aluminum oxide at elevated temperature, characterized in that the catalyst used aluminum oxide, which receive additional treatment with an aqueous solution of acetate alkaline-earth metal in the metal content of 0.1-1 mol/l and heat treated in air at 380-420oC.

2. The catalyst for olefin production on the basis of aluminum oxide, wherein the catalyst is an oxide of aluminum, optionally treated with an aqueous solution of acetate alkaline-earth metal in the metal content of 0.1-1 mol/l and subjected to heat treatment in air at 380-420oC.

 

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