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  . 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  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 .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 . 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. SOSThe 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%$
FIELD: medicine, pharmaceutics.
SUBSTANCE: invention refers to an improved method for carbonylation of at least one carbonylating reagent specified in a group consisting of dimethyl ester and methanol, carbon monoxide in the presence of a catalyst to prepare at least one carbonylation product specified in a group consisting of methyl acetate and acetic acid, and the above catalyst is prepared by combining modernite comprising one of: silver and copper with an inorganic oxide binding agent.
EFFECT: improved method for carbonylation.
14 cl, 2 dwg, 2 tbl, 4 ex
FIELD: organic chemistry, medicine, pharmacy.
SUBSTANCE: invention relates to new derivatives of glucopyranosyloxybenzylbenzene represented by the formula (I): wherein R1 represents hydrogen atom or hydroxy(lower)alkyl; R2 represents lower alkyl group, lower alkoxy-group and lower alkylthio-group being each group is substituted optionally with hydroxy- or (lower)alkoxy-group, or to its pharmaceutically acceptable salts. Also, invention relates to pharmaceutical composition eliciting hypoglycemic activity and to a method for treatment and prophylaxis of hyperglycemia-associated diseases, such as diabetes mellitus, obesity and others, and to their intermediate compounds. Invention provides preparing new derivatives of glucopyranosyloxybenzylbenzene that elicit the excellent inhibitory activity with respect to human SGLT2.
EFFECT: valuable medicinal properties of compounds.
13 cl, 2 tbl, 2 ex
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to production of phenol via acid catalytic decomposition of cumene hydroperoxide followed by isolation of phenol from decomposition products and purification of phenol to remove trace impurities including acetol. Purification of phenol is accomplished through hetero-azeotropic rectification with water. Acetol is isolated as a part of liquid-phase side stream from semiblind plate located within exhausting section of hetero-azeotropic rectification column. Side stream is supplemented by cumene and used to supply stripping column, from which fraction of acetol/cumene azeotropic mixture is taken as distillate and residue is returned under semiblind plate of hetero-azeotropic rectification column to be further exhausted. From the bottom of the latter, crude phenol is withdrawn and passed to final purification from the rest of reactive trace impurities. Acetol/cumene azeotropic mixture is subjected to heat treatment at 310-350°C, which may be performed in mixtures with high-boiling production waste or in mixtures with bottom product of rectification column for thermal degradation of high-boiling synthesis by-products, which bottom product is recycled via tubular furnace. Above-mentioned semiblind plate, from which side stream is tapped, is disposed in column zone, wherein content of water is minimal and below which contact devices are positioned with efficiency at least 7.5 theoretical plates. Side stream with cumene added to it is passed to the vat of stripping column with efficiency at least 15 theoretical plates.
EFFECT: minimized content of acetol in purified phenol and reduced power consumption.
5 cl, 3 dwg, 6 tbl, 4 ex
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to joint phenol-acetone production via selective decomposition of cumene hydroperoxide. Process is conducted in several in series connected reactors constructed in the form of shell-and-tube heat-exchangers, wherein part of decomposition product is recycled into reaction zone and mixed with feed stream to be decomposed, weight ratio of recycled stream to feed stream being less than 10. Reactors with tubular hydrodynamic characteristic have volumetric heat-exchange surface equal to or larger than 500 m2/m3. Preferably, residual concentration of cumene hydroperoxide is 0.1-0.3 wt % and its residence time in decomposition zone ranges from 0.5 to 10 min.
EFFECT: increased selectivity of decomposition at lesser recycle apparatus volume and reduced investment expenses.
11 cl, 1 dwg, 9 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to manufacturing phenol by cumene method, in particular, to a step for treatment of final product and preparing phenol of high purity degree. Method for treatment of crude phenol is carried out for two steps. At the first step method involves oxidation of acetol, aldehydes and α-methylstyrene with air oxygen in phenol medium by using a heterogeneous catalyst comprising metals with transient valence. At the second step method involves condensation of oxidation products and non-oxidized products by using a heterogeneous acid catalyst. Separation of compounds in the process of phenol treatment is carried out on the final step of isolation of the commercial product by distillation method. At the first stage metal compounds of by-side subgroups 1 and 6 and metals of 8 group of Periodic system on neutral or acid carrier are used as a catalyst preferably. At the second step alumosilicate contacts based on zeolites of type "X" or "Y", or other zeolites comprising or not comprising promoting and modifying additives are used as a catalyst. Invention provides the high degree of purification of phenol from impurities and the improvement of economy indices of the process.
EFFECT: improved method for phenol treatment.
12 cl, 5 ex
FIELD: chemical industry; methods of production of phenol and acetone.
SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the industrial process of production of phenol and acetone by the cumene method. The method is realized by decomposition of the technological cumene hydroperoxide in the in series connected reactors in two stages with formation on the first stage of the dicumylperoxide at the temperature of 40-65°С at presence as the catalytic agent of 0.003-0.015 mass % of the sulfuric acid with its subsequent decomposition on the second stage in the reaction medium at the temperature of 90-140°С. The process is conducted at the excess of phenol in the reaction mixture at the molar ratio of phenol : acetone exceeding 1, preferentially - from 1.01 up to 5. Excess of phenol is formed either by distillation (blowing) of acetone or addition of phenol in the reaction medium. The technical result of the invention is reduction of formation of hydroxyacetone, which one worsens the quality of the commercial phenol.
EFFECT: the invention ensures reduction of formation of hydroxyacetone, which one worsens the quality of the commercial phenol.
5 cl, 4 ex, 8 tbl
FIELD: industrial organic synthesis.
SUBSTANCE: isopropyl alcohol production process comprises hydrogenation of starting acetone including from 0.01 to 10000 ppm benzene in presence of hydrogen and catalyst to give isopropyl alcohol and benzene hydrogenation products, acetone and benzene contained in feedstock being hydrogenated simultaneously. In its second embodiment, isopropyl alcohol production process comprises product separation stage. Process of producing phenol and isopropyl alcohol containing benzene hydrogenation products comprises stages: alkylation of benzene with isopropyl alcohol and/or propylene to form cumene, oxidation of resulting cumene into cumene hydroperoxide, acid cleavage of cumene hydroperoxide to produce phenol and acetone including from 0.01 to 10000 ppm benzene, preferably concentration of produced benzene-polluted acetone, and catalytic hydrogenation of benzene-polluted acetone into isopropyl alcohol containing benzene hydrogenation products, hydrogenation of benzene and acetone proceeding simultaneously.
EFFECT: enhanced process efficiency.
3 cl, 1 dwg, 1 tbl
FIELD: chemical industry; methods of extraction of phenol and biphenols from the homogeneous reactionary mixtures.
SUBSTANCE: the invention is pertaining to the method of extraction of phenol and biphenols from the homogeneous reactionary mixtures of the direct oxidation of benzene by hydrogen peroxide. The method includes delivery of the reactionary mixture containing benzene, water, phenol, the sulfolane and the reaction by-products (biphenols) in еру distillation plant consisting of two or more columns for production of one or more products basically consisting of the azeotropic mixture of benzene with water and phenol, and also the product consisting of sulfolane, phenol and the reaction by-products. The stream including sulfolane is mixed with the water solution of the base and benzene for formation of the salts of the phenols and the subsequent stratification of the mixture, extraction by benzene and separation in the flow column containing benzene and sulfolane, which is returned in the reactor. From the same column separate the stream including sodium phenolates in the water solution, which is treated with the sulfuric acid for extraction of the phenols from their salts. At the stage of the extraction separate the extracting solvent, after distillation of which in the tailings bottom product receive the biphenols water solution. The separated organic solvent recirculates in the system. The technical result of the invention is improvement of the process of separation of phenols and biphenols from the complex azeotropic mixtures containing sulfolane.
EFFECT: the invention ensures the improved process of separation of phenols and biphenols from the complex azeotropic mixtures containing sulfolane.
9 cl, 1 ex, 1 dwg, 1 tbl
FIELD: chemical industry; methods of production of the phenols by the catalytic decomposition of the cumene hydroperoxide into phenol and acetone.
SUBSTANCE: the invention is pertaining to production of phenols by the catalytic decomposition of the cumene hydroperoxide into phenol and acetone. The method provides for oxidization of the cumene into the cumene hydroperoxide, catalyzed by the acid decomposition of the cumene hydroperoxide, neutralization of the produced product of the decomposition, maintaining the product in the homogeneous phase before neutralization, which is conducted by means of the aqueous base. The phenol is separated by fractionation of the neutralized product. The aqueous base represents the water solution of the sodium hydroxide or phenoxide. In particular use the regenerated phenoxide, at least, on one phase of the treatment at production of the phenol. It is preferential to add the sodium hydroxide water solution to the reaction product in such a concentration and such amount, that to receive the concentration of sodium phenolate in the homogeneous phase from 0.2 up to 2.5 mass %. The temperature of the homogeneous phase after the add-on of the aqueous base is set within the range of 20°С-150°С, the preferable temperature is within the range of 60°С-120°С. It is preferential, that the reaction product is saturated with the oxygen-containing gas. The technical result of the invention is the decreased quantity of the undesirable impurities in the products of the acid decomposition of the cumene hydroperoxide.
EFFECT: the invention ensures the decreased quantity of the undesirable impurities in the products of the acid decomposition of the cumene hydroperoxide.
13 cl, 4 ex
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for purifying phenolic flow prepared after distillation of raw acetone in separating decomposition products of cumene hydroperoxide from hydroxyacetone by rectification method. For removal of hydroxyacetone from phenolic flow methods of azeotropic-extractive rectification is used with using a combined separating agent wherein hydrocarbon (cumene and/or α-methylstyrene) is used as one components, and water is used as another component. Method involves feeding a separating agent in common with feeding a column, maintaining the mass ratio of hydrocarbon and water that equal or above the mass ratio of concentrations of hydrocarbon and water in the corresponding azeotropic mixtures, removing hydroxyacetone from column with distillate aqueous flow and feeding organic phase to phlegm wherein this organic phase is depleted with hydroxyacetone. Use of this method provides enhancing selectivity and complete distillation of hydroxyacetone.
EFFECT: improved purifying method.
17 cl, 2 dwg, 13 ex
SUBSTANCE: invention relates to the method of obtaining phenol and acetone by acid-catalysable decomposition of hydro-peroxide of cumene in the environment of the reaction products at elevated temperatures in one stage. In this case the process is carried out in the presence of a catalyst, prepared immediately before its introduction into the reactor for the decomposition of hydro-peroxide of cumene by mixing sulfuric acid with phenol at the ratio of from 2:1 till 1:1000 and the waiting time from mixing till putting into the reactor for the decomposition of hydro-peroxide of cumene from 1 to 600 minutes at a temperature from 20 to 80°C. As a rule, sulfuric acid has a concentration of higher than 75% or oleum is used.
EFFECT: it makes it possible to decrease the output of the by-product hydroxyacetone, improves the quality of market-grade phenol and decreases the consumption of sulfuric acid.
2 cl, 4 tbl, 4 ex