Catalyst for dealkylation of alkyl aromatic hydrocarbons with steam

专利摘要:
Alkylaromatic hydrocarbons are steam-dealkylated in the presence of a catalyst comprising an alumina carrier and 0.1 to 2% b.w. of a group VIII noble metal selected from Ru, Rh, Pd, Os, Ir and Pt, 0.05 to 2% of a group IB metal (Cu, Ag or Au) and 0.01 to 5% of an alkali metal.
公开号:SU950426A1
申请号:SU792761142
申请日:1979-02-02
公开日:1982-08-15
发明作者:Филипп Курти；Гдаль Носонович Маслянский；Георгий Лазаревич Рабинович
申请人:Всесоюзный научно-исследовательский институт нефтехимических процессов；
IPC主号:

专利说明:

(54) CATALYST FOR DECYLASTING ALKIPAROMATIC HYDROCARBONS WITH WATER STEAM The invention relates to the production of catalysts for dealkylated alkyparomatic hydrocarbons with water vapor. A known catalyst for dealkylation of steam alkylaromatic hydrocarbons containing 0.1-5 wt. % platinum group metal and 0, O1 50 wt. % metal selected from the group H-vanadium, niobium and tantalum, and alumina - the rest is tl3 A catalyst for the dealkylation of steam alkylaromatic hydrocarbons, containing 0.1–5% rhodium, 0.01–2.0% metal IV, is also known D group, for example tin, and alumina or aluminosilicate - the rest 2}. These dealkylation catalysts are sufficiently active, but not sufficiently selective with high conversion of the feedstock. In addition to the target dealkylation reaction on these catalysts, a side reaction of benzene coli cleavage takes place, which reduces the yield of the target dealkylation products. The one closest to the present invention is a catalyst for dealkylation of alkyl aromatic hydrocarbons with water vapor containing 0, O5 2, 0 weight. % Rhodi or Rhodi mixed with a noble metal of group 8 - platinum or palladium, or ruthenium, or iridium, 0.05 - 15 wt. % alkaline or alkaline earth metal and carrier - alumina - the rest NW. However, the known catalyst is characterized by insufficiently high activity and selectivity as a result of a high degree of thawing of the benzene peg, so when converting toluene to 40 7 O%, about 8 to 10% of the benzene rings calculated on the reacted toluene undergoes decomposition. The aim of the invention is to increase the activity and selectivity of the catalyst. This goal is achieved by the fact that. the composition of the catalyst for dealkylation of 395 steam alkylaromatic hydrocarbons containing 0.05-2 weight. % rhodium or rhodium with platinum or palladium, or ruthenium, or iridium, 0.01 - 5% by weight of alkali metal, and additionally contains 0.05 - 2% by weight of copper and / or silver and / or gold, and is - alumina - the rest. As a carrier, any form of alumina with a surface area of 50-400 m vr is used. The catalyst can be prepared by any known method. Active elements are introduced onto the carrier or simultaneously, or separately by impregnation with soluble solutions of soluble active elements with aqueous solutions or solutions in a solvent. The impregnation can be carried out by filling the volume with the carrier with an equal volume of the impregnating solution, followed by drying in air and drying, or contacting the carrier with an excess of solution, the volume of the solution in this case exceeds the pore volume of the specified carrier. At the same time, it is kept for a time sufficient for the metal ions in the solution to be fixed by means of an exchange reaction on the carrier. As soluble salts of these metals, one can use ha, pogene, nitrates, acetates, alkaline carbonates, formates, oxalates, citrates, chlorometalic acids and their ammonium and amine salts, complexes containing at least one of these metals, with oxalic acid and oxalates, citric acid and nitrates, tartaric acid and tartrates, with other polyacids, hydroxy acids, amino alcohols and their salts, acetylacetonates. The catalyst is tested in the process of dealkylation of alkyl aromatic hydrocarbons at 1OO -, pressure 1 20 at, molar ratio hydrogen / feed 3 - 15/1 and volumetric feed rates of 0.5 - 5 h. Example 1. (for comparison). The -jf-alumina carrier is used in the form of extruded cylinders with a diameter of 1.2 mm, a length of 5-7 mm, a specific surface area of 260 m vr, the total pore volume is equal to 58 ml / 100 g, pre-moistened with water vapor to avoid cracking when impregnated. 10O g of the carrier is impregnated by immersing in 12O ml of a solution containing 0.61 g of rhodium in the form of trichloride 64 rhodium and 4 ml of pure hydrochloric acid (ofiot 1.19). After depletion of the solution (rhodium is not detected when tin chloride is added to the solution: the presence of rhodium gives a characteristic red color), the catalyst is filtered off, existing for 2 hours at 100 ° C; 2 hours at, then activated in air at 4OO ° C for 2 hours. Next, the carrier is impregnated with 1.1 g of potassium as an aqueous solution of potassium nitrite with a volume of 55 ml, then dried for 2 hours at 1OO ° C, then 1 hour at 200 ° C and vos1 2h at. Set aside The catalyst contains, in weight. %: RVi 0.6; K 1; the carrier is the rest. The catalyst is tested in the demethylation reaction of toluene at a pressure of 7 atm, the bulk flow rate of the raw material is the molar ratio water / toluene 6. The process temperature at which the conversion of toluene to 7O% is equal. Under these conditions, the yield per 1OO mol of the skipped raw material is mol: benzene 61.6; xylenes 1; 7.4 moles of toluene were decomposed. PRI mme R 2. 100 g of the carrier used in Example 1 are contacted with 120 ml of a solution containing 0.41 g of copper as copper chloride and 0.5 ml of hydrochloric acid (1 | 19). After 3 hours, the copper is completely exchanged for the carrier, then the latter is filtered off, dried for 1 hour at, then 2 hours at and salted in air for 5 hours at. Then the catalyst is impregnated with 55 ml of a solution containing 0.61 g, rhodium in the form of trichloride, 1.1 g of potassium in the form of nitrate, 1.5 g of monohydrated citric acid and 2 ml of pure hydrochloric acid (1.19). After 4 hours of aging at 20 ° C, the catalyst is dried at 10 ° C at 12 ° C, then calcined in air flow at 40 ° C for 1 hour, reduced at 35 ° C for 2 hours in the presence of a gas containing 0.8 volumes of nitrogen and 0 , 2 volumes of hydrogen. The resulting catalyst contains, in weight. %: Cu 0.4; Rtt 0.6; K 1; the carrier is the rest. Under the conditions and feedstock of Example 1, the temperature for the conversion of toluene is 7%, 45 ° C. The yield per 100 ml of the feedstock is mol: benzene 66.5; xylenes 1.5; 2 moles of toluene were decomposed. Example 3. The catalyst was prepared as in example 1, adding to the aqueous solution of potassium nitrate 0.61 g of silver nitrate, the resulting catalyst contains, wt%: Rti 0.6; Ac 0.6; K 1; the carrier is the rest. Under the conditions and feedstock of example 1, conversion of 70% on this catalyst reached chickpeas at 448 ° C. The output per 100 ml of dried toluene, mol: benzene 65,8; xylenes 1.2, decomposed 3. Example 4. The catalyst is prepared analogously to example 1, adding to the solution of aqueous potassium nitrite 0.92 g of gold in the form of hydrochloric acid, a total volume of 55 ml. The impregnated catalyst is dried, then activated by calcining in air at 43 Ot for 2 h and reduced at 5OO ° C in the presence of a nitrogen-hydrogen mixture (8O% N 2 2: - 20% H) for 1 h. The resulting catalyst contains, wt%: I-LOB; b; Au 0.9; K 1; Mr. Media - the rest. o Under the conditions and feedstock of Example 1, a conversion of 70% was achieved on this catalyst at 475 ° C. The yield per 100 mol of missed toluene, mol: benzene 63,7 xylenes 1,5; 4.8 broke up. EXAMPLE 5 An industrial carrier — alumina in the form of balls with a diameter of 0.8–1.5 mm, with a specific surface area of 240 and a total volume of 55 ml / 100 g, previously jfe splashed with saturated water vapor — is used. at 60 ° C. 1OO g of carrier is impregnated by immersing it in 10O ml of a solution containing 0.32 g of rhodium (as trichloride), 0.42 g of palladium (as chloride) and 4 ml of pure hydrochloric acid (. 1.19). After the solution has matured, it is established that the palladium and rhodium are evenly distributed in the carrier beads. After dripping, the impregnated carrier is dried for 4 hours, then reduced directly in the presence of hydrogen. Then the reduced catalyst is impregnated with 50 ml of an aqueous solution containing 0.61 g of copper as chloride, 1 g of hydrated citric acid and 1.6 g of potassium as nitrate. After 3 hours of aging and 2 hours at 15 ° C, the catalyst is activated at 400 ° C for 2 hours. Get the catalyst, which contains, wt%: Rfi 0,3; Pd 0.4; Co 0.6 K 1.55; carrier- the rest; When tested for raw materials and under the conditions of example 1, a conversion of 70% on this catalyst was achieved at, the yield of missed toluene, mol: toluene 30; 9,266 benzene 66.4; xylenes 1,3; decay of ring 2. Example 6 (comparative). The catalyst was prepared as in Example 5, removing the copper. Get the catalyst, which contains, wt%: Rti 0.3; PdO, 4; K 1.55; the carrier is the rest. When this catalyst was tested under the conditions of example 1, conversion of 7O% was achieved at 525 ° C. The output per 100 mol of missed toluene, mol: beschol 60,2; xylenes 1.7; decay 8.1. Example 7. The carrier described in example 5 is used. 10 O g of carrier, previously dried at BO-C, is impregnated, immersing it in 120 ml of a solution containing 0.42 g of rhodium (in Trichloride), 0.42 g of platinum (in chloroplatinic acid) and 5 ml of pure hydrochloric acid (d # 2 (} OQ 1.19). After the solution has matured, it is established that platinum and rhodium are evenly distributed in carrier media. Then the catalyst is dried at 1 h, 2 h at 2OO ° С , then calcined for 2 hours at 40 ° C. Next, the catalyst is impregnated with 50 ml of a solution containing, g: copper 0.53; silver O, 11; potassium in de nitrates 1.6. After 3 hours of aging in air, 2 hours of drying at 15 ° C, the catalyst is calcined in air for 2 hours at, then reduced with hydrogen at 350 ° C for 2 hours. A catalyst is obtained which contains, in wt.%:, 4; Pt 0.4; Cu flqjO ;; 1.55; carrier — the rest. When testing the catalyst under the conditions of example 1, the conversion of 7O% was reached at. The yield of 100 mol of passed toluene, mol: benzene 66.8; xylenes 1, 2; decomposition 2. Example 8; The carrier described in example 5 is used. The South-East carrier, previously dried at 70 ° C, is impregnated with 54.6 ml of a solution containing 0.31 g Rti (RliCea), 0.41 G RO (Rute) 0.52 g Cu () 1.60 gK (kNOj,), 4 ml of it (d 1.19), 5 g of monohydrate tyrant of citric acid. After aging for 4 h, substances with 20 O for 3 h in air flow (volumetric rate of 20 OU volumes of air per volume of catalyst per hour) calcination at 2 hours and reduction at 4OO ° C for 1 h () gives a catalyst which contains, Bec. 0.3; Ru 0.4; CU 0.5; K 1.55; the carrier is the rest.
Under the conditions and raw materials of example 1, toluene conversion of 70% was achieved at 528 C. The yield per 100 mol of the passed toluene, mol: benzene, 65.8; xylenes 1,2; decay 3.0.0
Example 9. A carrier of y-aluminum oxide in the form of balls with a diameter of 0.8-1.5 mm with a specific surface area of 260 m / g and a total pore volume of 80 ml / 10.0 oh, previously removed from the surface by treatment with water vapor at 70 ° C, is impregnated with the following method.
100 g of carrier are contacted with a 160 ml solution containing 0.83 g of ruthenium and 0.26 g of rhodium (in the form of trichlorides), 4 ml is
HCE (CC 1.19), 30 ml of ethanol and 5 g of monohydrated citric acid. After the solution has matured, it is observed that rhodium and ruthenium are evenly distributed in the carrier beads. After decanting the solution, the catalyst is dried for 1 hour, then at 2OO ° C for 3 hours. Then the catalyst is impregnated with 55 ml of a solution containing 0.9 g of silver and 1.6 g of potassium as nitrates. The catalyst is dried as indicated. Then it is calcined for 2 hours at 380 ° C and reduced for 5 hours in the presence of nitrogen containing 2O% Hq.
A catalyst is obtained which contains, in wt.%: Ru 0.8, R 0.25; 0.9-, K 1.55; the carrier is the rest. Under the conditions of Example 1, toluene conversion is 70%; reached at 506 ° C. Outputs to 100 mop of the passed toluene, mol: benzene 66.1; h5 xylenes 1,3; decay 2.6.
Example 1O. The catalyst was prepared, analogously to example 9, replacing 0.92 g of silver and 1.6 Og of potassium in the input of nitrates for 0.62 g of copper and 1.6 Og of potassium in the form of chlorides. The rest of the preparation, drying conditions and thermal activator remain identical.
Get the catalyst containing, wt.%: RU O, b; RhO, 25; Co 0.6; 45 K 1.55; the carrier is the rest.
Under the conditions of Example 1, toluene conversion of 7O% was achieved at. Outputs to 1OO mol of missed toluene, mol: benzene 65.9; xylenes 1.6; 2.5 decay. Jq
Example 11. Example media is used. 100 g of the carrier is impregnated with 1OO ml of a solution containing 0.6 g of rhodium in the form of tri-chloride, 0.3 g of copper as bilord and 5 ml of hydrochloric acid (). The catalyst is dried at 3 hours and at 15 ° C for 3 hours. The catalyst obtained is impregnated with 60 ml of an aqueous solution containing, g: sodium 0.5; rubidium 0.15;
lithium in the form of nitrates is 0.15. The catalyst is dried as indicated, and calcined in air at 400 ° C for 2 h, then reduced in a stream of hydrogen for 1 h at 5OOt A catalyst is obtained containing, in wt.% RhO, 6; tu O, 3; No 0.5; Rb 0.15; Ui 0.15; the carrier is the rest.
Under the conditions of example 1, conversion of luol to 70% was achieved at 460 ° C. The outputs per 100 mol of missed toluene, mol: benzene 65,8; xylenes 1,8; decay 2.4.
Example 12. Using the carrier of example 5. UOg of the carrier is impregnated with 80 ml of solution, sod. 0.05 g of rhodium (as trichloride), 0.01 g of cesium (as nitrite), 0.05 g of silver (as nitrite) and 2% nitric acid. The catalyst is dried at 150 ° C for 3 hours and 3aTebf is calcined in air at 400 ° C for 2 hours and reduced with hydrogen at 40 ° C for 2 hours. The catalyst contains, by weight. %: Pb 0.05; ts 0.01; Aq; 0, O5; carrier
Under the conditions of Example 1, a tochopal conversion of 70% is achieved at 59 ° C. The outputs per 100 mol of missed toluene, mol: benzene 65,9; xylenes 1.0; decay 3.1.
Example 13. The carrier of example 5 is used. The UOg of the carrier is impregnated with 110 ml of a solution containing 0.8 g of rhodium (as trichloride), 0.8 g of platinum {as chloroplatinic acid) 0.4 g of iridium as chloriridic acid and 4 ml of hydrochloric acid (, 19).
The catalyst is dried in air for 24 hours with stirring first, then for 5 hours at 15 ° C, after which it is impregnated with 60 ml of a solution containing 5.2 g of potassium, 42.1 g of silver in the form of nitrates. The drying operation is repeated and then the catalyst is calcined in a stream of air at 2 hours and reduced with hydrogen at 5OO ° C for 2 hours. The catalyst contains, wt%: Aq; 2; Rh 0.8; Pt 0.8 g 0.4; K 5; the carrier is the rest.
Under the conditions of Example 1, toluene conversion of 7O% was achieved at. The outputs per 100 mol of missed toluene, mol: benzene 64,9; xylenes 2.1; decay 3.0.
The test results of the catalysts in examples 1 to 13 are presented in table. 1 The addition of metals of group 1b - copper and / or silver and / or gold allows to obtain more selective catalysts, i.e. giving a lower degree of decomposition of aromatic for a given conversion

权利要求:
Claims (1)
[1]
SUMMARY OF THE INVENTION Catalyst for dealkylation of alkyl aromatic hydrocarbons with steam containing rhodium or rhodium with platinum or palladium or ruthenium or iridium, an alkali metal and an alumina support, characterized in that, in order to increase the activity and selectivity of the catalyst, it further comprises copper and / or silver and / or gold in the following: nii components, wt.%: Rhodium or rhodium with platinum or palla-
in the afternoon, or ruthenium, or iridium ’ 0.05-2 Alkali metal 0.01-5 Copper and / or Silver and / or gold 0.05> -2 Alumina Rest

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同族专利:

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公开号 | 公开日

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IT1109900B|1985-12-23|

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BE873818A|1979-07-31|

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NL7900829A|1979-08-07|

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GB2016510A|1979-09-26|

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DE2903420A1|1979-08-09|

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FR2416210B1|1981-01-09|

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FR2416210A1|1979-08-31|

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JPS54115325A|1979-09-07|

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IT7919840D0|1979-02-02|

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JPS6147811B2|1986-10-21|

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GB2016510B|1982-06-09|

引用文献:

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GB1355344A|1970-08-06|1974-06-05|Ici Ltd|Dealkylation of aromatic hydrocarbons|

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US3812196A|1970-11-30|1974-05-21|Mitsubishi Petrochemical Co|Catalytic steam dealkylation|

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FR2254542B1|1973-12-13|1976-05-14|Inst Francais Du Petrole|

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US3992468A|1974-03-01|1976-11-16|Institut Francais Du Petrole, Des Carburants Et Lubrifiants Et Entreprise De Recherches Et D'activities Petrolieres Elf|Process for the catalytic hydrodealkylation of alkylaromatic hydrocarbons|FR2469204B1|1979-11-12|1983-09-23|Inst Francais Du Petrole|

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IT1254909B|1992-04-23|1995-10-11|PROCEDURE FOR THE PREPARATION OF A METAL CATALYST SUPPORTED FOR THE SELECTIVE HYDROGENATION OF HYDROCARBONS, CATALYST OBTAINED THROUGH THIS PROCEDURE AND PROCEDURE OF THE SELECTIVE HYDROGENATION OF HYDROCARBONS THAT USES SUCH CATALYST.|

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US5475173A|1994-07-19|1995-12-12|Phillips Petroleum Company|Hydrogenation process and catalyst therefor|

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GB2408956A|2003-12-11|2005-06-15|Johnson Matthey Plc|Reforming catalyst|

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DE102005053232A1|2005-11-06|2007-05-10|Basf Ag|Process for dealkylation of alkyl-substituted aromatic hydrocarbons with water vapor|

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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FR7803307A|FR2416210B1|1978-02-03|1978-02-03|

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