The way to reduce the impurity content of methylbenzofuran in phenol

 

(57) Abstract:

The invention is intended to reduce the impurity content of methylbenzofuran in the phenol obtained by decomposition of cumonherface. Originally phenol is treated with an amine to reduce the concentration of acerola, then phenol with low levels acetal subjected to contact with the acidic polymer, for example, sulfonic cation exchanger in acid form or solid perechislennim catalyst at a temperature of 70-120oand contact time sufficient to reduce the content of methylbenzofuran by conversion into compounds with a higher boiling point. Phenol was separated by distillation from compounds with a higher boiling point. Processing Amin allows to reduce the concentration of acetal to a value of not more than 200 ppm, and the residual content of methylbenzofuran amounts to less than 10 ppm. 8 C.p. f-crystals, 3 tables.

The invention relates to the production of pure phenol, and in particular to the process associated with lower levels of methylbenzofuran in the phenol to obtain the desired high purity. Phenol can be obtained from cumene by its oxidation to hydroperoxide, followed Ross and recovery in which the acetone is separated from the rest of the product by distillation. After that, the remaining product is subjected to further distillation for separation of cumene. Column recovery of cumene can work, if you want to restore alfamethylstyrene (AMS) with cumene, or product output column recovery of cumene can be entered in the column of raw AMS for AMS Department from the rest of the product. Then the remaining product is introduced into the column recovery of phenol to separate phenol from the rest of the form with a higher boiling point.

Phenolic product obtained by fractional distillation, contains many impurities, including AMS, acetal (hydroxyacetone), acetophenone, cumylphenol and 2 - and 3-methylbenzofuran (jointly or individually MBF). For some applications it is important reduction of the content of such impurities in order to avoid problems with discoloration with aging or by sulfonation or chlorination. Since phenol and MBF have the same volatility, MBF cannot be effectively separated using fractional distillation. Application to reduce the amount of MBF distillation in the presence of water or steam desorption (Stripping) are disclosed in U.S. patent N 5064507 and N 4857151. The use of such desorptive use of large distillation columns to allow the flow of organic vapors and additional water vapor. Therefore, the destruction of MBF using Stripping steam is expensive in operation and volume of investments. In U.S. patent N 3,810,946 disclosed a process for reducing the content of impurities MBF by heating phenol with Hydrobromic or idiscovered acid. However, the processing of halogenated compounds leads to problems of corrosion, which greatly increases the cost of materials cost of the process plant.

In view of the above, there is a need for an effective and economic process of reducing levels of MBF in the phenol to obtain the desired phenol of high purity.

The recovery process impurities methylbenzofuran (MBF) phenol obtained from the product of the decomposition of cumene hydroxyperoxide requires processing of phenol to reduce the levels of acetol, contacting phenol containing low acetol, with acid polymer at this temperature and time sufficient to reduce the level of MBF by conversion into compounds with a higher boiling point, followed by distillation of phenol to separate phenol from compounds with a higher point kippei treatment with the amine. After phenol containing low acetol, enter in contact with concentrated acid polymer to reduce the level of MBF.

Phenolic product which can be purified by the method in accordance with the present invention, obtained by the decomposition of cumonherface with the formation of phenol and acetone as the main products, followed by distillation to remove the acetone, which has a lower boiling point than phenol. We found that 2 - and 3 - methylbenzofuran can be effectively and economically removed from the phenol by treatment with a polymer of aromatic sulfonic acid or solid perechislennim catalytic compound at moderate temperatures, in the absence of acetol (hydroxyacetone), other than a mixture of phenol, or subject to the presence of acetal in phenol at low levels, for example, in quantities of not more than 260 million-1and mostly, not more than 200 million-1and preferably not more than 100 million-1and better yet, no more than 5 million-4. At higher concentrations of acetol effect processing of the polymer decreases and gradually becomes less economically attractive.

Concentrated acidic polymers, COI is but represent granules sulfonated cross-linked polystyrene. Such polymers are aromatic sulfonic acids may be purchased, for example, the firm Rohm and Haas, in the form of granules cation exchange polymer sulfonic acid Amberlyst 15. Additionally, there may be used a solid perechislennye catalytic system. These systems were created as alternatives to liquid acid systems, such as hydrofluoric acid, which is used in the acylation of oil. Some of the systems can be obtained from already existing systems (AlCl3, SbF5, SO42-on the supporting substrate ZrO2or TiO2), by merging existing forming a strong acid to the oxide or salt substrates (substrates) for immobilization of acid activity. Other systems are more new heteroalicyclic made of clusters of metal oxide (tungsten or molybdenum). Representative catalysts are discussed in the publication Makoto Misuno and Toshio of Okuhara "Solid perechislennye catalysts", Chemtech, November 1993, In this description solid perechislennye catalytic compounds referred to these acidic compounds which have an acid concentration greater than 100% H2SO4.

Now the example, in the range from 70 to 120oC, and mainly in the range from 80 to 110oC. Greater contact time (long duration of contact) also leads to increased efficiency, but increases the processing cost. Contact with acidic phenol polymer can be obtained in a known manner, for example, by mixing pellets of the polymer with phenol, or by passing phenol through a layer of acidic polymer, which may be a predominant commercial alternative. The effectiveness of increasing the temperature and contact time are demonstrated in the following examples. Cm. example 1 to determine the units of the layer volumes/hour, which is in accordance with the present invention preferably lie in the range from 1 to 10, and more preferably, from 2 to 6 layer volumes/hour. In these examples, the analysis of 2-MBF was carried out using conventional gas chromatography, if there was a concentration of approximately 1 million-1or more. At lower concentrations was carried out by liquid chromatography using the polar octadecylsilane column and UV detector configured to wavelength of 254 nm. A solution of methanol/water was used as eluent at a temperature okrujayushevo peaks from the calibration standards.

Example 1

Phenol containing less than 1 million-1acetal and quantity MBF specified in table I in the column "inlet", was passed through a layer of acidic polymer (Amberlyst 15) at the tabulated flow rates and temperatures. Layer volume represents the volume of the phenol corresponding to the size of the used polymer layer. Unit volume of the layer/h is inversely proportional to the contact time. The results of the analysis of sample output show that the processing proceeds more efficiently at higher temperatures and at lower values of the layer volumes/hour (at high contact times). The results also show that the levels MBF can be reduced to values less than 0.1 million-1.

Example 2

Phenol, containing the number of acetol and MBF listed in table II in the column "inlet", was passed through a layer of acidic polymer (Amberlyst 15) at a flow rate of 4.0 volume layer/hour. After that, samples were taken after the polymer layer and produced their analysis. The results show that although acetal during processing and is removed to levels less than 1 million-1but the content MBF cannot be reduced to less than 4 million-1.

Example 3

Phenol, containing 20 million-1MBF and the number of acetol appropriate to the HH/h and at different temperatures, listed in table III. After that, samples were taken after the polymer layer and produced their analysis.

The results show that acetol prevents the destruction of MBF during processing, and at higher temperatures it is to a greater extent. When the content of acerola 500 million-1and at a temperature of 110oC remove MBF no.

1. The way to reduce the impurity content of methylbenzofuran (MBF) phenol obtained from a decomposition product of cumonherface, characterized in that it provides for the processing of phenol to reduce the content of acetal to a value of not more than 260 million-1put into contact phenol containing low acetal, with the polymer of aromatic sulfonic acid or solid perechislennim catalytic compound, at a temperature and time sufficient to reduce the level of MBF by conversion into compounds with a higher boiling point, and then distillation of phenol to separate him from compounds with a higher boiling point.

2. The method according to p. 1, characterized in that the phenol is treated to reduce the level of acetol to a value not more than 200 million-1then entering into contact with the acidic polymer or polymer is about level MBF reduce to less than 10 million-1.

4. The method according to p. 3, characterized in that the level of MBF reduce to less than 1 million-1.

5. The method according to p. 1, characterized in that the phenol is treated with an amine to reduce the level of acetol to a value not more than 200 million-1then entering in contact with the polymer of aromatic sulfonic acid in the polymer layer at a temperature of from 70 to 120oC and at a flow rate from 1 to 10 volumes of a layer in an hour.

6. The method according to p. 5, characterized in that the level of MBF reduce to less than 10 million-1.

7. The method according to p. 6, characterized in that the level of MBF reduce to less than 1 million-1.

8. The method according to p. 1, characterized in that the phenol is treated with an amine to reduce the level of acetol to a value of not more than 10 million-1then entering in contact with the polymer of aromatic sulfonic acid in the polymer layer at a temperature of from 70 to 120oC and at a flow rate from 1 to 10 volumes of layers per hour, resulting in a level of MBF reduce to less than 1 million-1.

9. The method according to p. 1, characterized in that the phenol is treated with an amine to reduce the level of acetol to a value of not more than 5 million-1then entering in contact with the polymer of aromatic sulfonic key is E. what is the level of MBF was reduced to less than 1 million-1.

 

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SUBSTANCE: invention relates to utilization of phenolic resin and preparing additional amounts of cumene, phenol and α-methylstyrene. For this aim phenolic resin containing less 0.2 wt.-% of salts is subjected for thermocatalytic decomposition in the range of temperatures 420-550oC in the presence of steam on catalyst comprising the following components, wt.-%: aluminum, oxide, 5.0-30.0; iron oxide, 0.4-1.0; magnesium oxide, 0.4-1.0; calcium oxide, 5.2-7.0; sodium oxide, 1.0-3.0; potassium oxide, 1.0-3.0; titanium (IV) oxide, 0.4-1.0; silicon (IV) oxide, 0.4-1.0, the balance, up to 100%. The proposed method provides preparing 61.5 wt.-% of useful products - cumene, phenol and α-methylstyrene for a single run. Invention can be used in the process for combined preparing phenol and acetone by cumene method.

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