The method and catalyst of obtaining parameningeal
(57) Abstract:The invention relates to the production of parameningeal by alkylation of phenol, alpha-methylstyrene and the catalyst for this process. The reaction is carried out at a temperature of 80-110oC and space velocity of the feedstock 1-3 h-1on alumiinium catalyst consisting of a mixture of aluminum oxide and Zirconia and sulfated oxides of aluminum and zirconium. The catalyst contains sulfates in the amount of 5-15 wt. % (in terms of SO4), oxides of 5-30% (in terms of Al2O3). For the preparation of the catalyst as aluminum hydroxide, a mixture of boehmite and pseudoboehmite (ratio of from 1: 3 to 3: 1 by weight). Carry out the precipitation of the hydroxides of zirconium, and the above-mentioned mixture of hydroxides of aluminum, mixing the obtained aluminum hydroxide and zirconium, sulfation aqueous solution of sulfuric acid, peptizer also using an aqueous solution of sulfuric acid, after which produce a screw extrusion obtained catalyst mass and heat treatment of the extrudates. The technical result is an increase in the activity of the process while simplifying technology, creating a highly active catalyst. 3 S. and 2 C. p. F.-ly. This is ay catalytic alkylation of phenol, alpha-methylstyrene (AMS).Parameningeal finds wide application in obtaining effective stabilizers for fuels, oils, polymers and rubbers.Known methods for producing parameningeal using homogeneous acid catalysts, such as strong mineral acids such as sulfuric, oxalic, phosphoric, etc., (Kumok, Gurvich, Stiskin, Greenberg J. of Uses. Chem. Society for them. Mendeleev, 1972, T. 17, 4, 460-462; U.S. patent 2441408, 1948; U.S. patent 2751437, 1950). The disadvantages of this method typical use of homogeneous catalysts. This low selectivity of the process, the difficulty of separating the catalyst from the reaction products, the environmental problems associated with the use of strong acids.These shortcomings deprived way to get parameningeal using heterogeneous catalysts, for example, on the basis of synthetic zeolites of type dealuminated mordenite or zeolite of the ZSM family, which is prepared with a binder or without and with additives of metal promoters or without additives (U.S. patent 4409412, 1982). The disadvantage of the use of catalysts of this type is their lack of activity and increased formation of by-products, for example, in the case of obtaining FSC-is SUP> the content of the target PCF in catalyzate is using as a catalyst dealuminated mordenite 12-13 wt.%, the content of dimers of more than 4%, and the content of orthotolidine (TFR) - 0,5-0,7% (the sum of the two last more than 4.5%). On the sample of zeolite DCM (representative of the family of ZSM-5) these values are respectively 11-12%, and 0.6-0.7% and about 2.2% (more than 2.8%).Closest to the proposed method according to the essential characteristics and the achieved result is a method of obtaining FSC using as a heterogeneous catalyst ion-exchange resin type Am-berlyst in the hydrogen form (U.S. patent With 185475, 1993 - prototype).At a temperature of 80-110oC, atmospheric pressure and space velocity of the raw materials 1,0 h-1the content of the PCF in catalyzate is 16.2 to 16.5%, the content of dimers of about 0.3-0.5%, and the content of the TFR of 4.4% (the sum of the last two more than 4.6%). The disadvantage proposed in the prototype method for the synthesis of PCF using ion-exchange resins as catalyst are:
- high content of by-products (FSC and dimers);
- not enough high activity of the catalyst;
- low thermal stability of the catalyst, reducing its service life;
The process of alkylation of phenol AMC on the resulting catalyst is carried out at a temperature of 80oC and space velocity of the raw material 1 h-1.As a raw material, a mixture of phenol, cumene and AMS composition, wt.%: the cumene 45; phenol 45; AMS 10.The resultant catalysate was 99.89 per cent, its composition is the following, wt%: the cumene of 46.68; AMC 0.05; phenol 34,57; FSC 16,61; TFR 1,19; dimers 0,9.After selecting parameningeal by distillation, the product has the following composition, wt.%: PKF level 98.2; TFR of 1.4; dimers 0,16; AMC and other 0,24.The composition catalyzate was determined by gas chromatography on the chromatograph "Crystal 2000M with capillary column 25 m long and stationary phase OV-1.Example 2.a) Preparation of catalyst
The catalyst is prepared as in example 1, the I is 3: 1. For sulfation precipitate of zirconium hydroxide take 380 ml solution of sulfuric acid. The number of mixed powder of aluminum hydroxide obtained for the mixing of powder sulfated zirconium hydroxide, equal to 13.9, Other parameters are the same as those in example 1.The total content of sulfates of aluminum and zirconium in the obtained sample calcined (ready) catalyst in terms of SO4amounted to 5.0 wt.%, the total content of the oxide and sulphate of aluminium in terms of Al2ABOUT35 wt. %.b) the catalyst Test
The resulting catalyst was tested under the conditions of example 1 at a temperature of 110oC and space velocity of the raw materials 3 h-1. It can produce the following composition, wt.%: the cumene 46,13; AMC 0,04; phenol 34,6; FSC 17,17; TFR 1,10; dimers of 0.5.Thus, the proposed Aluminiy the catalyst obtained by the proposed method allows the synthesis of parameningeal alkylation of phenol, alpha-methylstyrene at a temperature of 80-110oC and space velocity of the feedstock 1-3 h-1with very high efficiency: the content of the target PCF in catalyzate is more than 17 wt.% if you have a low education pobochnymi and selectivity. 1. The method of producing parameningeal by alkylation of phenol, alpha-methylstyrene in the presence of acid aljumotsinkovanija catalyst at elevated temperature, followed by separation of parameningeal of catalyzate by distillation, characterized in that as alumoxane catalyst, a mixture of oxides and sulfates of aluminum and zirconium, with a total content of sulfates of aluminum and zirconium from 5 to 15 wt.% (in terms of ion SO4and the total content of the oxide and aluminium sulphate 5-30 wt.% (in terms of Al2O3and the process is carried out at 80-110S and space velocity of the feedstock 1-3 h-1.2. Catalyst to obtain parameningeal alkylation of phenol, alpha-methylstyrene, comprising a mixture of aluminum oxide and zirconium oxide promoted sulfate, when the total content of sulfates of aluminum and zirconium from 5 to 15 wt.% (in terms of ion SO4and the total content of the oxide and aluminium sulphate 5-3 wt.% (in terms of Al2O3).3. The method of preparation aljumotsinkovanija catalyst to obtain parameningeal alkylation of phenol, alpha-methylstyrene by precipitation of zirconium hydroxide, mixing hydroxycholesterol mass and heat treatment, characterized in that as aluminum hydroxide, a mixture of boehmite and pseudoboehmite mass ratio of from 1:3 to 3:1 in terms of Al2O3.4. The method according to p. 3, characterized in that as patinator use an aqueous solution of sulfuric acid.5. The method according to PP.3 and 4, characterized in that the sulfuric acid solution is introduced into the catalyst mass in two steps: in the precipitate of zirconium hydroxide at the stage of sulfation and on stage peptization in the mixture of powders selfaddressed zirconium hydroxide and aluminum hydroxide prior to moulding.
< / BR>where R' is hydrogen, or alkyl WITH1or benzyl; R 'and R" are identical or different and represent CH3WITH4H9by parallelomania mixture of alkyl phenols, which are used or waste 2,6-di-tert-butylphenol obtained by alkylation of phenol with isobutylene, from the stage of rectification, or waste 2,6-di-tert-butyl-4-METHYLPHENOL (BHT) from the stage of regeneration of the methanol
FIELD: chemical industry, in particular method for production of value products from lower alkanes.
SUBSTANCE: claimed method includes passing of gaseous reaction mixture containing at least one lower alkane and elementary chlorine through catalytic layer. Used catalyst represents geometrically structured system comprising microfiber with diameter of 5-20 mum. Catalyst has active centers having in IR-spectra of adsorbed ammonia absorption band with wave numbers in region of ν = 1410-1440 cm-1, and contains one platinum group metal as active component, and glass-fiber carrier. Carrier has in NMR29Si-specrum lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio Q3/Q4 from 0.7 to 1.2; in IR-specrum it has absorption band of hydroxyls with wave number of ν = 3620-3650 cm-1 and half-width of 65-75 cm-1, and has density, measured by BET-method using argon thermal desorption, SAr = 0.5-30 m2/g, and specific surface, measured by alkali titration, SNa = 10-250 m2/g in ratio of SAr/SNa = 5-30.
EFFECT: method of increased yield.
3 cl, 4 ex
FIELD: chemical industry, in particular method for production of value monomer such as vinylchloride.
SUBSTANCE: claimed method includes passing of reaction mixture containing dichloroethane vapor trough catalytic layer providing dehydrochlorination of dichloroethane to vinylchloride. Catalyst has active centers having in IR-spectra of adsorbed ammonia absorption band with wave numbers in region of ν = 1410-1440 cm-1, and contains one platinum group metal as active component, and glass-fiber carrier. Carrier has in NMR29Si-specrum lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio Q3/Q4 from 0.7 to 1.2; in IR-specrum it has absorption band of hydroxyls with wave number of ν = 3620-3650 cm-1 and half-width of 65-75 cm-1, and has density, measured by BET-method using argon thermal desorption, SAr = 0.5-30 m2/g, and specific surface, measured by alkali titration, SNa = 10-250 m2/g in ratio of SAr/SNa = 5-30.
EFFECT: method with high conversion ratio and selectivity.
3 cl, 2 ex
FIELD: chemical technology, in particular method for vinylchloride production.
SUBSTANCE: claimed method includes fast gas cooling in quenching column followed by separation of pyrolysis products. Quenching and separation are carried out by barbotage through the layer of liquid concentrated by-products of these gases in quenching column cube. Then steam/gas mixture is brought into contact with returning condensate in regular filling layer of rectification tower with simultaneous purification of steam/gas mixture in rectification zone upstream. Liquid concentrated by-products are additionally rectified in vacuum with isolating and recovery of products having boiling point higher than the same for dichloroethane and distillate recycling. Method of present invention also makes it possible to produce perchloroethylene and tricloroethylene.
EFFECT: vinylchloride of high quality; reduced effort and energy consumption.
2 tbl, 4 dwg, 2 ex
FIELD: industrial organic synthesis.
SUBSTANCE: gas-phase thermal dehydrochlorination of 1,2-dichloroethane is conducted in presence of hydrogen chloride as promoter dissolved in feed in concentration between 50 and 10000 ppm.
EFFECT: increased conversion of raw material and reduced yield of by-products.
4 cl, 1 tbl, 8 ex