The method of purification of phenol from the organic impurities

 

(57) Abstract:

The invention relates to a method of purification of phenol obtained in the process of co-production of acetone and phenol Kukolnik method. The purpose of the invention is the presence of active and stable catalyst for the purification of phenol. This goal is achieved by a method for continuous contacting of the phenol obtained after the distillation of light and heavy products joint synthesis and containing an impurity oxide mesityl, -methylstyrene, 2-methylbenzofuran and other carbonyl compounds, industrial synthetic aluminosilicate zeolite catalyst at 120 - 200oC, atmospheric pressure or the pressure corresponding to the state of liquid phenol and space velocities of 0.3 to 3.5 h-1. the invention provides a conversion of the oxide mesityl and alpha-methylstyrene not less than 90% during the lifetime of the catalyst without loss of activity for 3 years. table 4.

The invention relates to a method of purification of phenol obtained in the process of co-production of acetone and phenol Kukolnik method.

Phenol after the distillation of heavy and light products joint synthesis contains impurities of organic substances such as oxide Maisy methods for example, by distillation, which degrades the properties of the commodity phenol.

The industry uses two methods of purification of phenol from the organic trace contaminants - sulfuric acid method, which is in the handling of phenol with concentrated sulfuric acid. The disadvantages are the loss of phenol and low clearance.

Another method is a method based on the transmission of phenol through the cation [2] . The disadvantages of the method are: a narrow temperature interval using cation exchange resin (50-80oC), the limited period of its use due to the irreversible destruction of the granules of the catalyst, and disposal of the treated cation.

In U.S. patent [3] described a method of purification of phenol from impurities (prototype) on silica-alumina catalyst, modified with metals of group VI. The disadvantage of this method is the low activity of the catalyst and hence, greater contact time (4-8 hours).

The aim of the invention is the presence of a catalyst having high activity during the purification of phenol impurities from the possibility of its regeneration and have a long service life.

This goal is achieved by purification of phenol in synthetic realidades the ale without loss of activity, be subjected to regeneration, have high mechanical strength and stability.

Phenol, obtained after distillation of light and heavy products and containing an impurity oxide mesityl, -methylstyrene, 2-methylbenzofuran and other carbonyl compounds in contact with the aluminosilicate zeolite catalyst at temperatures of from 120 to 250oC (preferably 140-200oC) and space velocities of 0.3-3.5 h-1(preferably 0.8-1.2 h-1).

It is established that during the cleaning of the conversion of such impurities as oxides of mesityl and methylsterol not lower than 90%. When cleaning the observed increase in the number of 2-methylbenzofuran, which can successfully be removed from the phenol by distillation. The service life of the catalyst without loss of activity for three years.

Example 1. The sodium silicate solution (1.8 N. the oxide of sodium, the ratio of silica to sodium oxide - 2.9), the solution acidified with aluminum sulfate (1.2 N. the aluminum oxide, 75 g/l of free sulfuric acid) and aqueous suspension of zeolite NaY (82 g/l) was mixed in techstream mixer in a ratio of 1: 0.5:0.3. Got a silica-alumina gel containing zeolite NaY - 15 wt. %. The gel was washed with water, homogenized with a view to ensuring that stereonation sodium ammonium, after processing, the residual sodium was 0.3 wt.%. Then the catalyst is not washed from the ammonium salts were treated with a mixture of nitrates of rare-earth elements (0.03 N. the solution) and ammonium nitrate (0.1 n solution) at 200oC in the autoclave. After treatment, the catalyst was filtered, washed with water from salts, dried and progulivali. In this way there was obtained A catalyst whose properties are given in table. 1. The catalyst B, the properties of which are given in table. 1, was obtained in a similar way, only the ratio of sodium silicate solution, the solution was acidified ammonium sulfate and aqueous suspension of zeolite NaY was 1:0.5:0.1. Catalyst C without rare earth elements have also received, as A catalyst, but without treatment of the catalyst solutions of nitrates of rare-earth elements and ammonium nitrate. The chemical composition and physical properties of the obtained catalysts were determined by the techniques presented in [5].

Example 2. Phenol containing 22 ppm acetone, 217 ppm oxide mesityl (ACM), 1304 ppm-methylstyrene (AMS) and 236 ppm 2-methylbenzofuran (MBF), the pump was fed to the reactor tube length 1500 mm, an inner diameter of 30 mm, filled with 950 ml of catalyst A (physico-chemical properties cialiscanada 0.3 h-1. Phenol after passing the catalyst was analyzed by gas chromatography [4]. Sample for analyses were taken every hour. Time of experiment 5 o'clock Composition of phenol after treatment (mean values) - 5 ppm ACM (the degree of conversion of 98%), 25 ppm AMS (the degree of conversion of 98%), and 269 ppm MBF (plus 13%).

Example 3. The experiment was conducted as in example 1, the volumetric rate equal to 3.5 h-1. The composition of the phenol to clean 5 ppm of acetone, 53 ppm ACM, 1106 ppm AMS and 214 ppm MBF, the composition of phenol after cleaning - 4 ppm ACM (conversion rate - 92%), 21 ppm AMS (conversion rate - 98%) and 256 ppm MBF (plus 20%).

Example 4. The experiment was conducted as in example 1, but the temperature was equal to 200oC. the composition of the phenol to clean 21 ppm acetone, 107 ppm ACM, 230 ppm AMS and 217 ppm MBF, the composition of phenol after cleaning - 8 ppm ACM (conversion rate - 93%), 3 ppm AMS (conversion rate - 99%) and 345 ppm MBF (plus 50%).

Example 5. The experiment was conducted as in example 3, but the volumetric rate equal to 3.5 h-1. The composition of the phenol prior to cleaning 23 ppm acetone, 63 ppm ACM, 5 ppm AMS and 178 ppm 2-MBF, the composition of phenol after cleaning - 6 ppm ACM (the degree of conversion of 90%), 2 ppm AMS (conversion rate - 96%) and 201 ppm MBF (plus 13%).

Example 6. The example illustrates the effect of water in phenol raw and to the pre-Catalyst was calcined in a stream of nitrogen at 250oC. the results of the experiment are presented in table. 2.

Example 7. The example illustrates the lifetime of the catalyst without loss of activity.

The experiment was conducted as in example 1. Install continuously worked for 1043 hours, the Temperature of the experiment ranged from 115 to 190oC, space velocity of 0.4 to 3.75 h-1. The atmospheric pressure or the appropriate state of liquid phenol. The main results are presented in table. 3.

Example 8. The example illustrates the possibility of catalyst without regeneration for three years.

The experiment was conducted as in example 6, but the time of the experiment was 24000 hours Volumetric rate ranged from 0.6 to 3.5 h-1temperatures from 140 to 190oC, atmospheric pressure or the appropriate state of liquid phenol. The average composition of impurities in the phenol-raw - 50 ppm ACM, 346 ppm AMS and 208 ppm MBF. The average conversion ACM was 95% AMS - 98%, and the increase MBF - 78%.

Example 9. (comparative prototype). The experiment was conducted as in example 1, but used a silica-alumina catalyst (oxide silicon 83-89%, alumina - 9-15%, specific surface area of 250-300 m2/g, pore volume of 0.5 - 0.55 cm3/g). The temperature of the experience is and, 32 ppm ACM, 540 ppm AMS, 273 ppm MBT and 38 ppm other carbonyl compounds. After cleaning, the phenol contained 19 ppm ACM (conversion rate - 41%), 83 ppm AMS (conversion rate - 85%), 102 ppm MBF (conversion rate - 63%) and 35 ppm other carbonyl compounds (conversion rate - 8%)

Example 10. (comparative prototype). The experiment was conducted as in example 8, but the catalyst contained 0.3% of chromium. After cleaning the phenol found 20 ppm ACM (conversion rate of 37%), 85 ppm AMS (conversion rate of 84%), 73 ppm MBF (conversion rate - 73%) and 34 ppm other carbonyl compounds (conversion rate - 11%)

Example 11. (for comparison, the upper limit on temperature). The experiment was conducted as in examples 1 and 2, but the temperature was equal to 250oC. the composition of the phenol to clean 21 ppm acetone, 46 ppm ACM, 142 ppm AMS and 218 ppm MBF.

Phenol after cleaning included:

a) the volumetric rate of 0.3 h-1< / BR>
5 ppm ACM (conversion rate - 89%)

4 ppm AMS (conversion rate - 97%)

343 ppm MBF (plus 57%)

b) the volumetric rate of - 3.5 h-1< / BR>
4 ppm ACM (conversion rate - 91%)

5 ppm AMS (conversion rate - 96%)

391 ppm MBF (plus 79%)

Gas chromatographic analysis showed the presence of high condensation products in the amount of 2000 ppm at 140-200o-1. Composition to clean the 3 ppm of acetone, 30 ppm ACM, 1396 ppm AMS and 82 ppm MBF.

Phenol after cleaning included:

a) temperature 140oC

16 ppm ACM (conversion rate - 47%)

17 ppm AMS (conversion rate - 99%)

196 ppm MBF (plus 139%)

b) temperature 200oC

15 ppm ACM (the degree of conversion of 50%)

21 ppm AMS (conversion rate - 98%)

231 ppm MBF (an increase of 182%)

Example 13 (for comparison, the catalyst does not contain rare earth elements). The experiment was conducted as in examples 1-4, but was used for catalyst C. the composition of the phenol to clean 5 ppm of acetone, 39 ppm ACM, 1200 ppm AMS and 201 ppm MBF. The cleaning results are presented in table. 4.

Similar results were obtained when using catalyst B. (examples 14-16)

Example 14. The experiment is carried out as in example 1. The composition of phenol after cleaning - 8 ppm ACM (conversion rate - 96%), 30 ppm AMS (conversion rate - 98%), 250 ppm 2-MBF (plus 6%).

Example 15. The experiment was conducted as in example 2. The composition of phenol after cleaning - 4 ppm ACM (conversion rate 92%), 25 ppm AMS (conversion rate - 98%), 26 ppm MBF (plus 22%).

Example 16. The experiment was conducted as in example 3. SOS

The method of purification of phenol from the organic impurities by passing phenol at elevated temperature and atmospheric pressure or the pressure corresponding to the state of liquid phenol, through the layer of synthetic aluminosilicate zeolite catalyst, characterized in that the processing is carried out at 120 - 220oC and a space velocity of phenol 0.3 to 3.5 h-1when using a catalyst containing zeolite type Y 5 - 15% by weight of the binder and the binder is a silicate of the following composition, wt.%:

Aluminum oxide - 5 - 30

The sodium oxide - 0,05 - 0,3

Iron oxide - 0,05 - 0,2

Oxides riskseeking elements - 0,5 - 2,5

Silica - the Rest is up to 100%$

 

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