JPS5812260B2 - Method for producing monophenyl alkylates - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing monophenyl alkylates as raw materials for cleaning agents.

More specifically, the present invention is intended to treat mainly dialkylbenzenes and diphenylalkanes, which are by-products when alkylating benzene with a range of n-paraffins or mixtures thereof, for use in partially chlorinated detergents. The present invention relates to a method for producing monophenyl alkylates from high boiling point compounds contained therein.

As a method for producing cleaning agent raw material monophenyl alkylate, a linear paraffin having a carbon number of about 10 to 16 or a mixture thereof is partially chlorinated, and the partially chlorinated paraffin is heated in the presence of an aluminum chloride catalyst. A method for producing monophenyl alkylate, a raw material for cleaning agents, by alkylating benzene with the partially chlorinated paraffin is known.

It is also well known that in this process, several percent of high boiling point compounds containing dialkylbenzenes and diphenylalkanes are produced as by-products.

The formation mechanism of this high-boiling byproduct is that diphenylalkanes are mainly formed from dichloroalkanes produced when n-paraffin is partially chlorinated, and dialkylbenzenes are formed from the molar ratio of chloroparaffin and benzene used in the alkylation reaction. It is assumed that the generation depends on the ratio.

Conventionally, in an attempt to effectively utilize the by-products, the polyphenyl alkanes present in the high-boiling by-products were converted into monophenyl alkylates for cleaning agent raw materials by reacting the high-boiling by-products with aluminum chloride. A method (Japanese Patent Publication No. 41-966) has been proposed.

However, according to this method, diphenyl alkanes in high-boiling by-products are advantageously converted to chamonophenyl alkylates, but dialkylbenzenes are converted to monophenyl alkylates. It is about 0.3 to 0.4 position compared to that of alkanes, indicating that the recovery of monophenyl alkylates from dialkylbenzenes by this method is not a very effective means.

In addition, as a method of suppressing the by-production of diphenylalkanes in the high-boiling by-products, a method of recycling diphenylalkanes in the high-boiling by-products to the alkylation process (Japanese Patent Publication No. 44-1999-1)
No. 6261) has been proposed.

However, although it is taught that this method suppresses the by-product of diphenylalkane, it does not teach anything about the behavior of dialkylbenzene.

On the other hand, in the process of producing monophenyl alkylate, a raw material for cleaning agents, by alkylating benzene with an olefin such as propylene tetramer in the presence of an aluminum chloride catalyst, high-boiling byproducts produced as by-products are recycled to the alkylation process. Method of suppressing the amount of living organisms CI industry
al and engineering Chemises
try (Industrial and Engineering Chemistry) Vol. 46 No. 225 (
1954)) and a method of producing monoalkylbenzene by reacting the high-boiling by-product with benzene in the presence of an aluminum chloride catalyst (Japanese Patent Publication No. 1982-2053) is also known.

However, since both methods use propylene tetramer olefin as a raw material, lephenyl alkanes are essentially not contained in the by-products, and the behavior of diphenyl alkanes is completely unknown. Not taught.

A method for efficiently recovering monophenyl alkylates from both dialkylbenzenes and diphenylalkanes in the by-products produced during the production of monophenyl alkylates using partially chlorinated paraffins, which is the object of the present invention, is disclosed. It has not been done.

The purpose of the present invention is to convert both dialkylbenzenes and diphenyl alkanes in high-boiling by-products into monophenyl alkylates at a high rate during the production of monophenyl alkylates using partially chlorinated paraffins. This is to provide a way to do so.

That is, the present invention mainly deals with the by-products mainly produced when benzene is alkylated with chlorinated paraffins containing 0.1 to 0.8 gram atom of chlorine per molecule of n-paraffins having 10 to 16 carbon atoms. 100 parts by weight of high-boiling byproducts containing alkylbenzenes and diphenylalkanes are brought into contact with 40 to 500 parts by weight of benzene in the presence of aluminum chloride and hydrogen chloride as catalysts to remove dialkylbenzenes and diphenylbenzenes in the high-boiling byproducts. The present invention provides a method for producing monophenyl alkylates from high-boiling by-products, which comprises transalkylating and transphenylating enyl alkanes, respectively.

The method of the present invention will be explained in detail below.

First, the high-boiling by-products mainly containing dialkylbenzenes and diphenylalkanes that are treated in the method of the present invention will be described.

The raw material n-paraffin used in the method of the present invention is C
Straight chain paraffins having a length of 10 to C16 carbon atoms are used.

A mixture of these paraffins can be easily separated from petroleum fractions such as kerosene and gas oil by the well-known molecular sieving method or urea derivatization method.

As a mixture of n-paraffins, the reaction after alkylation uses a mixture in which the difference in carbon atom chain length between the paraffin with the lowest molecular weight and the paraffin with the highest molecular weight does not exceed 4 carbon atoms. When separating each fraction from the product by distillation, the boiling temperature range of higher n-paraffins and the boiling temperature range of the alkylate produced by lower n-paraffins can be separated without overlapping, and as a result, The resulting detergent raw material alkylbenzene is desirable because it can be recovered from the alkylation reaction mixture in a relatively pure state.

The raw n-paraffin is then partially chlorinated.

As the chlorination method, ordinary liquid phase chlorination or vapor phase chlorination can be adopted.

The amount of chlorine reacted with the paraffin ranges from 0.1 to 0.8 gram atoms per molecule of paraffin present, preferably 0.
．． A range of 15 to 0.4 gram atoms is used.

When carrying out liquid phase chlorination, the applicable temperature range is approximately room temperature to 200°C, preferably about 100 to 150°C.

For vapor phase processes, chlorination temperatures of about 200-400°C, preferably 220-360°C are generally used.

The partially chlorinated chlorinated paraffins are then reacted with benzene in the presence of a 7-Riedel-Crafts catalyst in an alkylation step.

In the alkylation reaction, the molar ratio of benzene to chlorinated baraffin can be used within a wide range, but is generally about 1:1 to 1:30, preferably about 1:5 to 1:2.
0 is used.

Although Friedel-Crafts catalysts are used to facilitate the alkylation of benzene with chlorinated paraffins, aluminum chloride is preferred because it provides rapid alkylation rates.

The amount of aluminum chloride used is about 1 to 10 weight percent based on the alkylation reaction mixture.

A known method can be used to supply aluminum chloride to the reaction system.

The alkylation reaction is generally carried out at temperatures from room temperature to 120°C, with the preferred temperature range being about 60-100°C.

The exact amount of time required to carry out the alkylation reaction will, of course, be governed by a number of factors, including the amount of catalyst used, the ratio of chlorinated paraffin to benzene used, temperature, etc., but in general The reaction may be carried out for about 1 to 60 minutes.

The alkylation reaction product is then directed to a catalyst separator,
The catalyst and sludge products are then removed.

The effluent thus obtained is then subjected to acidic removal treatment, generally by treatment with a caustic wash.

The alkylation reaction effluent, treated as appropriate, is then treated with recycled benzene, recycled n-paraffins, monophenyl alkylate, and other polycyclic alkylates within the monophenyl alkylate boiling range. It is separated into alkylate-forming substances and high-boiling fractions consisting mainly of dialkylbenzenes and diphenylalkanes.

The high-boiling components separated here, mainly consisting of dialkylbenzenes and diphenylalkanes, are the high-boiling byproducts to be treated in the method of the present invention.

The high boiling by-products generally have a content of dialkylbenzenes and diphenylalkanes of about 50% by weight or more, with the remainder consisting of monophenyl alkylates and other high boilers.

In particular, high-boiling by-products containing 65% by weight or more of dialkylbenzenes and diphenylalkanes are preferably used.

In carrying out the method of the present invention, the high-boiling by-products mainly consisting of dialkylbenzenes and diphenylalkanes are brought into contact with benzene in the presence of aluminum chloride and hydrogen chloride as catalysts, and the dialkylbenzenes in the high-boiling by-products are brought into contact with benzene in the presence of aluminum chloride and hydrogen chloride as catalysts. and diphenyl alkanes, respectively, transalkylation and transphenylation (hereinafter referred to as conversion reaction)
and convert it to monophenyl alkylates at a high rate.

The proportion of benzene used in the high-boiling by-products needs to be approximately 40 to 500 parts by weight per 100 parts by weight of the high-boiling by-products. It is undesirable because the conversion rate of monophenyl alkylates to monophenyl alkylates becomes low, the recovery rate of monophenyl alkylates from high-boiling byproducts decreases, and the quality of the monophenyl alkylates produced deteriorates. If the amount increases, the conversion rate of diphenylalkane will decrease, so generally high boiling point by-products 100%
The reaction is carried out in about 40 to 500 parts by weight, preferably about 60 to 300 parts by weight of benzene.

Aluminum chloride and hydrogen chloride are used as catalysts to facilitate the conversion reaction between high boiling byproducts and benzene.

The amount of aluminum chloride used is approximately 1 part per high boiling point by-product.
~20% by weight.

Aluminum chloride catalyst is the catalyst slurry from the alkylation process,
Catalysts regenerated by adding aluminum metal to the catalyst slurry from the alkylation process, catalysts newly synthesized from aluminum metal, hydrogen chloride, and aromatic hydrocarbons, catalysts synthesized from the above catalysts in the main conversion reactor, etc. are applicable. .

Additionally, hydrogen chloride is used as a catalyst to increase the conversion rate of high boiling byproducts and benzene.

The amount of hydrogen chloride present is 1% by weight or more, preferably 2 to 20% by weight, based on the high-boiling byproduct.

If the amount of hydrogen chloride present is less than 1% by weight, the conversion rate of monophenyl alkylates from high boiling point by-products is low and it is not suitable for engineering.On the other hand, if it is present in a large amount, there is no particular problem, but if it is present in large quantities, However, it is often added in an amount of less than 20% by weight, so that a proportional effect cannot be expected.

It was also unexpectedly found that when hydrogen chloride is present in this range, the quality of the monophenyl alkylate produced is improved compared to when it is not present.

The conversion reaction is generally carried out at 40-150°C, preferably 60-150°C.
A temperature range of 20°C applies.

The contact time depends on the amount of catalyst used, high boiling point byproduct/benzene ratio,
Although it varies depending on the temperature etc., it is generally sufficient to react for 1 minute to 5 hours.

The conversion reaction product is then directed to a separator where it is separated into catalyst mud and oily fraction.

The catalyst mud can be reused as it is or after being regenerated for conversion reactions and alkylation reactions.

After purification, the oily component is fractionated and separated into benzene, paraffin, monophenyl alkylate, and high boiling point components.

Benzene, paraffin, and high boiling point components are recycled and used as appropriate.

Further, the conversion reaction product may be supplied as it is to the catalyst separation step, or the oily component separated from the catalyst mud may be supplied to the refining step of the previous alkylate production step and treated at the same time.

According to the method of the present invention described in detail above, during the production of monophenyl alkylate from partially chlorinated halafine, both dialkylbenzenes and diphenyl alkanes in the high-boiling by-products produced are converted into monophenyl alkylate. It can be converted to a similar compound at a high rate, and is extremely useful industrially.

Furthermore, the method of the present invention has the advantage that higher quality monophenyl alkylate can be recovered compared to conventional methods.

The method of the present invention will be explained in more detail with reference to Examples below, but the method of the present invention is not limited thereto.

Example I 70-16 n-paraffin mixture of CIO-14
Chlorinated paraffins with 17 mol % chlorination were prepared by chlorination in the liquid phase at a temperature of 0° C. for 5 minutes.

Using a molar ratio of chlorinated paraffin to benzene of 1:10 in the presence of 4% by weight of aluminum chloride, based on the chlorinated paraffin content in the chlorination reaction product, at 80° C. under stirring for 30 minutes. Benzene was alkylated.

The alkylation reaction product is then allowed to stand, the catalyst components are separated, and the effluent is washed with a 5% by weight aqueous sodium hydroxide solution and then distilled to remove unreacted benzene, unreacted paraffin, monophenyl alkylates and high boiling point Separated into minutes.

Dialkylbenzenes and diphenylalkanes in the high-boiling by-products were 67.8% by weight and 28.2% by weight, respectively.

To 100 parts by weight of this high boiling point by-product were added benzene in the amount shown in Table 1, 10 parts by weight of an alkylation catalyst containing 27% by weight of aluminum chloride, and 3 parts by weight of hydrogen chloride, and the mixture was stirred for 10 minutes.
The conversion reaction was carried out at 0°C for 4 hours.

After washing the conversion reaction product with water, it was analyzed by gas chromatography.

The results are shown in Table 1.

*Produced as a by-product due to conversion reaction.

※※ Quality evaluation method: Monophenyl alkylate recovered by distillation is purified by sulfuric acid treatment and clay treatment.

The purified monophenyl alkylate 15 ml and 15 ml of concentrated sulfuric acid in a test tube. shake for 1 minute, then 30 minutes. Gardner color of concentrated sulfuric acid after standing for a while Applicable compared to color scale Check quality using Gardner number Ru.

Gardner number 17 or more × 16 △ 15 or less ○ From Table 1, by adding benzene in the range of 40 to 500 parts by weight to 100 parts by weight of high-boiling by-products, dialkylbenzenes and diphenyl in high-boiling by-products can be reduced. It is clear that alkanes can be effectively converted to monophenyl alkylates.

Furthermore, when looking at the quality of the produced monophenyl alkylate, it was found that the quality was good when benzene was added in the range of 40 to 500 parts by weight to 100 parts by weight of the high-boiling byproduct.

Example 2 100 parts by weight of the same high-boiling byproduct as described in Example 1, 87 parts by weight of benzene and an alkylation catalyst containing 27% by weight of aluminum chloride in the amount shown in Table 2 and hydrogen chloride were added and stirred. The conversion reaction was carried out at 80° C. for 4 hours.

After washing the conversion reaction product with water, it was analyzed by gas chromatography.

The results are shown in Table 2.

It is clear from Table 2 that by adding hydrogen chloride to the conversion reaction system, diphenylalkanes and dialkylbenzenes in the high-boiling by-products can be effectively converted to monophenyl alkylates.

Claims (1)

[Scope of Claims] 1 A by-product when benzene is alkylated with a chlorinated paraffin containing 0.1 to 0.8 gram atom of chlorine per molecule of n-halafins having 10 to 16 carbon atoms. 100 parts by weight of high boiling point by-products mainly containing dialkylbenzenes and diphenylalkanes and 40 to 5 parts by weight of benzene.
00 parts by weight in the presence of aluminum chloride and hydrogen chloride as catalysts to transalkylate and transphenylate dialkylbenzenes and diphenylalkanes in the high-boiling by-products, respectively. A method for producing monophenyl alkylates from by-products. 2 Transalkylation and transphenylation to 40
The method for producing monophenyl alkylates according to claim 1, which is carried out in a temperature range of -150°C. 3. The method for producing monophenyl alkylates according to claim 1, wherein the amount of aluminum chloride used is 1 to 20% by weight based on the high boiling point range organism. 4 The amount of hydrogen chloride present is 2 to 20% relative to the high boiling point byproduct.
% by weight, the method for producing monophenyl alkylates according to claim 1.