The method and catalyst of obtaining parameningeal

C07C37/48 - by exchange of hydrocarbon groups which may be substituted, from other compounds, e.g. transalkylation

 

(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 purpose of the present invention to increase the activity, selectivity and simplification of the process of obtaining parameningeal.

This goal is achieved by alkylation of phenol, alpha-methylstyrene using heterogeneous acid aljumotsinkovanija catalyst at a temperature of 80-110oC and space velocity of the feedstock 1-3 h-1.

The catalyst is a mixture of aluminum oxide and zirconium oxide promoted sulfate, when the total content of sulfates of aluminum and zirconium, equal to from 5 to 15 wt.% (in terms of ion SO4), the total content of the oxide and aluminium sulphate 5-30 wt.% (in terms of A12O3).

Typically, alumina carriers of catalysts are prepared by precipitation of aluminum hydroxide from sodium aluminate solution with concentrated nitric acid at a pH of 8.7-8.9 in two streams: cold deposition at 18-20oAnd "hot" at 100-120oC. Mixing of these flows in different proportions allows you to adjust the quality of the product. The resulting mass of aluminum hydroxide is washed from sodium ions, plastificator, peptizer and molded in screw-presses into granules of a given R is ishemia for various syntheses, prepare by the method of deposition of circinelloides (ZnOCl28H2O) aqueous solution of ammonia, followed by drying of the resulting sludge and treatment 1 N. sulfuric acid. For forming into pellets sulfonated powder of zirconium oxide is mixed with aluminum hydroxide, used as a binder (J. Catal. 153, 218-233 (1955)).

For example, there is a method of cooking aljumotsinkovanija catalyst for the isomerization of paraffin hydrocarbons (U.S. patent 6326328, 2001 - prototype). At the specified method take a mixture of powders of hydroxides of zirconium and aluminium with the addition of sulfurous agent is a salt of ammonium sulfate, stirred, ekstragiruyut and the obtained granules were calcined at 600oC. aluminum Hydroxide or hydrated aluminum oxide is used as a binder. However, the catalyst prepared according to the method prototype is not suitable for obtaining FSC, because it has insufficient activity.

The method of preparation of the proposed composition of the catalyst synthesis parameningeal by alkylation of phenol, alpha-methylstyrene includes the stage of precipitation of zirconium hydroxide, a mixture of hydroxides of zirconium and aluminum, sulfation hydroxides, peptization RA is of aluminum using aluminum hydroxide, consisting of boehmite and pseudoboehmite at mass ratio of 1:3-3:1 (in terms of A12ABOUT3). As sulfatides agent and patinator uses sulfuric acid.

Salient features of the proposed method of preparation of the catalyst are the use of a mixture of boehmite and pseudoboehmite in the ratio indicated on the stage of the preparation of aluminum hydroxide and an aqueous solution of sulfuric acid at the stage of sulfation and peptization catalyst mass. Received the proposed method, the catalyst based on sulfated oxides of aluminum and zirconium can be regenerated by treatment of the heated gas (nitrogen) or by washing with a solvent, for example, phenol.

This catalyst is much cheaper ion-exchange resins and has, as will be shown below in the examples, a high activity and selectivity in the proposed process. Methods of cooking alumiinium catalysts proposed composition unknown to us.

Industrial applicability of the proposed catalyst for the synthesis of parameningeal alkylation of phenol, alpha-methylstyrene and the method of its preparation are confirmed by the trace of the/SUB>8H2O dissolved in 5.2 l of distilled water. To the resulting solution was poured dropwise within 20 minutes 332 ml NH4HE with a concentration of about 25%. The precipitate is filtered off and washed with a Buechner funnel water from the ammonium chloride. Received the washed precipitate is dried in a drying Cabinet at 110oWith in 24 hours. Dried sludge grind at the mill, and the obtained fine powder sieved through sieve 180 μm. The mass of powder is 190 g or 147 g in terms of ZrO2.

Powder process for the sulfation of 1.14 l of 1 n sulfuric acid solution for 1 hour. Then the mixture is filtered from the excess solution, the product is dried at 110o(10 h) and then used for forming.

To obtain pseudoboehmite take 3 liters of sodium aluminate solution with a concentration of 100 g/l, the Deposition is carried out by the simultaneous discharge of a specified aluminate solution and a 60% aqueous solution of nitric acid (flow rate of 1.8 l) at a temperature of 20-25oWith pH in the range from 9.1 to 9.5 for 2 hours. After draining of fluids suspension is subjected to operation stabilization by boiling (102-105o(C) at a constant pH in the range from 9.1 to 9.3 by the addition of a solution of alumina is

To obtain boehmite take 1 l of sodium aluminate solution with a concentration of 100 g/l, the Deposition is carried out by the simultaneous discharge of a specified aluminate solution and a 60% aqueous solution of nitric acid (flow rate 0.7 l) at a temperature of 102-105oWith (at boiling), pH in the range from 8.5 to 8.9 for 2 hours. Get the suspension chalky sediment boehmite containing 100 g of Al2O3.

The resulting suspension of pseudoboehmite and boehmite are mixed and subjected to washing with a Buechner funnel from the impurity salt of sodium nitrate. The washed precipitate is dried for 10 hours at 110oWith and grind into fine powder passing entirely through a sieve with the hole diameter of 0.25 mm Loss on ignition (SPT) at 850oWith the obtained dried mixed powder of aluminum hydroxide make up 24.6 wt.%. The ratio of boehmite : pseudoboehmite powder of aluminum hydroxide in terms of Al2ABOUT3is 1:3.

Next, the powder sulfated zirconium hydroxide is mixed with of 83.6 g of powder of aluminum hydroxide in the mixer of the Werner with Z-shaped blades, peptizer solution of sulfuric acid (3.8 ml of a 60% aqueous solution), add in small portions of about 250 ml of water, bringing humidity (SRR) weights to 55 wt. %. Poluchenie 8 hours at a temperature of 110oC, and then calcined in a flow of dry air for 4 hours at 630oC.

The gross composition of the finished catalyst, wt. %: ZrO266,2; -Al2O330; S 5,0. The total content of sulfates of aluminum and zirconium in the catalyst in terms of SO4made up 15.0%, the total content of the oxide and sulphate of aluminium in terms of Al2ABOUT330 wt.%.

b) the catalyst Test

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.

 

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