The method of reducing the concentration of toxic fragrances in a hydrocarbon mixture

 

(57) Abstract:

Describes a method of reducing the concentration of toxic fragrances in a hydrocarbon mixture by processing agent, while the agent is processing carried out by passing the original hydrocarbon mixture together with at least one olefinic hydrocarbon through a reaction zone containing a fixed bed of particles of inert polar material, in the presence as catalyst of a fluorinated sulfonic acids with subsequent diversion of the flow alkyl hydrocarbons from the reaction zone. The technical result - increase in the efficiency of the method. 5 C.p. f-crystals, 1 Il.

The invention relates to the processing of hydrocarbons, and more particularly to a method of reducing the concentration of toxic fragrances in a hydrocarbon mixture.

It is widely known fully or partially isolate the components from a hydrocarbon mixture using thermal or mechanical methods, for example by fractional distillation or extraction (see, for example, F. A. Henglein, Grundrib der this trade Technik, publisher Chemie GmbH, Weinheim, 1963, pp. 90-110).

The known method can also be used to reduce the concentration of toxic aromatic Vesela.

The objective of the invention is to develop a cost-effective way to reduce the concentrations of toxic fragrances in a hydrocarbon mixture.

This task is solved by the proposed method of reducing the concentration of toxic fragrances in a hydrocarbon mixture by processing agent due to the fact that the agent is processing carried out by passing the original hydrocarbon mixture together with at least one olefinic hydrocarbon through a reaction zone containing a fixed bed of particles of inert polar material, in the presence as catalyst of a fluorinated sulfonic acids with subsequent diversion of the flow alkyl hydrocarbons from the reaction zone.

As the catalyst is preferably used performancesarticle with 1 to 5 carbon atoms. The most preferred catalyst is triftoratsetata.

Due to the high efficiency and stability of fluorinated sulfoxylate catalyst during the processing of the initial hydrocarbon mixture, which results in the alkylation of hydrocarbons, acid catalyst should be applied only in a small quantity of inert polar material with the polar material is silicon dioxide 0.1 to 200 ml, preferably 1 to 100 ml, most preferably 5 to 50 ml of acid on 1 cm2the area occupied by the particles of inert polar material in the reaction zone sufficient to provide a high degree of alkylation.

In addition to silicon dioxide in an inert polar material, you can use any polar and ponownie refractory material. The preferred materials are silicon dioxide, aluminum borate, boron phosphate, sulfate, boron, zirconium dioxide, titanium dioxide, niobium oxides, tin oxides, or mixtures thereof.

As a result of interaction of the polar groups of the molecules of inert material and the polar groups of the molecules of the fluorinated sulfonic acid in a precisely defined area firmly adsorbed on the particles of inert material and thus is formed the reaction zone. Band width adsorbed acid, where the reaction takes place alkylation, is determined by the number of used inert polar material.

The source of the hydrocarbon stream can pass through the reaction zone at temperature from - 40 to 100oC and a pressure of 1 to 100 bar abs. depending on the composition of the initial flow and the reaction temperature.

Wasim as agent for alkylation, is 1.5:1 to 30:1.

During the alkylation acid catalyst and thus the reaction zone as a result of interaction with a noise through her reaction mixture is moved to another location closer to the exhaust end of the reactor alkylation.

As a theoretical explanation for this can be said that the removal of the fluorinated sulfonic acids caused by the reaction in the reaction mixture of an acid catalyst with an olefin, with the receipt of ester sulfonic acids, which is less polar than the original acid in the reaction zone less strongly adsorbed on inert material. Ester is moved together with the reaction mixture before splitting with obtaining the free acid and carbonium ion, which reacts with aromas precept of alkyl aromatic hydrocarbons.

The moving speed of the acid catalyst in the reactor together with particles of an inert polar material is much less than the speed of movement of the hydrocarbons in the reaction mixture and the desired product, which leads to more long term removal of acid catalyst in comparison with the period of removal of hydrocarbons.

During the move to the e fluorinated sulfonic acids mainly retained and the acid is still catalytically active, when the reaction zone reaches the outlet end of the reactor.

When the acid exhaust end of the alkylation reactor can be used for further process, without her recovery. Thus Peremena the direction of flow of the reaction mixture fed to the alkylation reactor, and as a result of this interaction with the reaction mixture, the reaction zone moves towards the opposite end of the reactor.

Described by periodic changes of direction of the reaction mixture and moving the reaction zone in the reactor from one end to the other layer of particles of inert polar material is possible even when using a small amount of acid catalyst to provide a large output alkyl flavors without restoring or regenerating the catalyst utilized for a long time.

At change of a direction of flow of the reaction mixture a small part is brought directly before this mixture is not yet in the reaction zone and therefore leaves the reactor in unreacted form.

So that part of the reaction mixture, which is extracted from realtracker.

Instead of recirculation of the reaction mixture during changes of direction of flow of the mixture leaving the reactor immediately after the change of adding the reaction mixture can be submitted in the prescribed from the first reactor, the second alkylation reactor in which a hydrocarbon stream handle such exercised in the first reactor by.

If you carry out the proposed method at least two series-connected reactors, the flow of the original hydrocarbon mixture and olefinic hydrocarbon sequentially pass in one direction through the reactor having a reaction zone containing a catalyst fluorinated sulfonic acids adsorbed on inert polar material placed in the reactor. When this acid catalyst with the reaction mixture sequentially passed through the first and second reactors and recycle it in the first reactor in the case, if he leaves the second reactor without change of direction of the flow of hydrocarbons. The advantage of the circulation of acid catalyst at least between the two reactors is that inert polar material in the reactor can be cleaned after translation sour is in contact with the acid catalyst in the reactor, in which it is present.

The invention is illustrated in the attached drawing which is a flow chart of the preferred forms of embodiment of the invention.

The stream containing fragrances hydrocarbon mixture and at least one olefinic hydrocarbon is served by lines 1 through the four-way valve 2 in the reactor 3, loaded porous layer of particles of inert polar material 4. In this reactor creates a reaction zone 5 by the feed material 4 to line 6 fluorinated sulfonic acids. As shown in the drawing, in the beginning of the process according to the invention the reaction zone 5 is placed near the end 7 of the reactor 3. The flow of material into the reactor at the end of the 7 line 8 due to the fact that the valve 2 opens the passage from line 1 to line 8.

During the implementation of the process according to the invention the flow of raw material is passed through a reaction zone 5 in the direction of the end 9 of the reactor 3. In the reaction zone 5 hydrocarbons react with olefinic alkylation agent, which is catalyzed by fluorinated acid adsorbed on polar inert material 4. Containing alkylated products flow away along the line 10 at the end 9 of the reactor 3. According paysannes process and serves either not shown in the drawing, the capacity for storage, or for processing.

During the initial stage of the process flow of the reaction zone 5 is moved from the end 7 to the end 9 of the reactor 3 in the above-described interaction of hydrocarbons from the alkylation agent. Upon reaching a position near the end of 9 the direction of flow of the reaction mixture in the reactor 3 peremeshautsa by switching valve 2, which is intended to link lines 1 and 11. In this position of the valve 2 stream in line 11 is fed into the reactor 3 at the end of the 9th and the reaction zone is moved in the direction of the end 7 of the reactor 3. In this case, the flow of the target product away from the end 7 of the reactor 3 through line 8, which communicates with the line 11 through the valve 2. At the beginning of each stage of the process the portion of the feedstock that is fed into the reactor 3 immediately before the change of direction of flow and which has not passed through the reaction zone 5, will be discharged from the reactor 3 in unreacted form. This unreacted portion of the raw material recycle from line 11 through line 13 to line 1 at the initial stage of each cycle of the proposed method.

The proposed method is illustrated by the following examples.

Example 1. The process is carried out in stainless is El particle size of 0.2 to 0.5 mm, which serves as an inert polar material (produced under the name Merck 100 Merck, DE). At the inlet end of the tubular reactor on silica gel serves 6 ml of catalyst, triftoratsetata. During the alkylation temperature of the reactor is maintained at the 40oWith by immersing it in a temperature-controlled water bath. In this tubular reactor subjected to alkylation mixture consisting of 10 wt.% benzene, 5 wt.% of propene and 85 wt.% isobutane.

As the target product from the reactor discharge mixture of alkyl aliphatic and aromatic compounds. When this fraction of the fragrance consists of 34 wt.% benzene, 27 wt.% monoalkylphenol, 20 wt.% dialkylphenols and 19 wt.% trialkylborane.

Example 2. Repeat example 1 with the only difference that in the reactor serves the reaction mixture consisting of 20 wt.% benzene, 4 wt.% 2-butene and 76 wt. % isobutane. Get a mixture of alkyl aliphatic and aromatic hydrocarbons, a fraction of fragrances which consists of 69 wt.% benzene, 23 wt. % butylbenzene, 7 wt.% debutante and 1 wt.% tributyrate.

Example 3. Repeat example 1 with the only difference that in the reactor serves the reaction mixture and the new aliphatic aromatic compounds, aromatic fraction which consists of 17 wt.% benzene, 12 wt.% of cumene, 12 wt.% butylbenzene, 31 wt.% dialkylphenols and 28 wt.% trialkylborane, including 1.8 wt.% tributyrate.

Example 4. Repeat example 1 with the only difference that in the reactor serves the reaction mixture consisting of 70 wt.% obtained by reforming fraction containing 63,2% of Lipatov C5and C6, 33.5% benzene, 3,3% toluene and 30 wt.% of propene. The feed rate is 3.2 g/min, and recycling - about 14 g/min gives a blend of aliphatic alkyl aromatic compounds, aromatic fraction which consists of 20 wt.% benzene, 13 wt.% of cumene, 11 wt. % butylbenzene, 16 wt.% dialkylphenols, 35 wt.% trialkylborane and 5 wt.% tetraalkylammonium benzene.

1. The method of reducing the concentration of toxic fragrances in a hydrocarbon mixture by processing agent, wherein the agent is processing carried out by passing the original hydrocarbon mixture together with at least one olefinic hydrocarbon through a reaction zone containing a fixed bed of particles of inert polar material, in the presence as catalyst of a fluorinated sulfonic acids with subsequent is the fact that as fluorinated sulfoxylate catalyst used perflorocarboxylic with 1 or 2 carbon atoms.

3. The method according to p. 1, characterized in that as fluorinated sulfoxylate catalyst used triftormetilfullerenov.

4. The method according to p. 1, characterized in that an inert polar material from the group comprising silicon dioxide, aluminum borate, boron phosphate, sulfate, boron, alumina, titanium dioxide, zirconium dioxide, oxides of niobium, tin oxides, and mixtures thereof.

5. The method according to p. 1, characterized in that an inert polar material used is silicon dioxide.

6. The method according to p. 1, characterized in that the use of olefinic hydrocarbons with 2 to 20 carbon atoms.

 

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