Method for purifying phenol from hydroxyacetone

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

 

The invention relates to a process of co-production of phenol and acetone produced Kukolnik method. Due to the fact that to obtain plastics (polycarbonates) required phenol of high purity (with a total impurity content of not more than 0.01 wt.%), the problem of obtaining high-purity phenol is extremely relevant. One of the impurities, which significantly reduces the quality of commercial phenol is hydroxyacetone (HA), which, interacting with the phenol in the distillation columns to the stage catalytic treatment, forms a 2-methylbenzofuran (2-MBF), for the Department of phenol are forced to use highly effective extractive distillation with a high consumption of extractant water (up to 4 t/t phenol), which leads to increased costs of steam. The phenol used for plastics, HA must be absent, and the content of 2-ICF should not exceed 15 ppm.

Existing methods of purification of phenol from the HA based on the application of physical and chemical methods, while cleaning are directly decomposition of cumene hydroperoxide (CHP) to the stage of rectification and phenolic stream at the stage of rectification.

The approach of cleaning the decomposition products of the CCP from GA is the most preferred, because in this case it is possible to avoid the formation of 2-MBF at the stage of rectification. In atente USA 6066767, 2000, it is proposed to remove HA from the decomposition products of the CCP at the stage of neutralization of sulfuric acid, i.e. to the stage of selection of commercial products, using the ability of HA to be extracted from the products of decomposition of the CCP water-salt phase and turn it in the presence of alkali in the deep condensation. This method has not received until distribution due to increased capital expenditures, increased consumption of alkali and complexity of the technological scheme.

Most common in the industry received methods of distillation removal of HA from phenolic flow with subsequent catalytic purification of phenol raw, as from residual amounts of HA and carbonyl-containing impurities and unsaturated compounds that affect the quality of commercial phenol.

Depending on the content of cumene and water in the decomposition products of the CCP in the industry implemented a fundamentally three types of allocation patterns of commodity phenol:

Type 1 - the content of the cumene - 1-3 wt.% and the water content is 15 to 17 wt.%;

Type 2 - the content of the cumene - 10-13 wt.% and the water content is 10 to 12 wt.%;

Type 3 - the content of the cumene - 28-30 wt.% and the water content is 5-6 wt.%.

The most effective from the point of view of the purification of phenol stream from HA is the method presented in the application U.S. 0066661, 2002, where the separation of the products of decomposition of the CCP with the content is of cumene 10-13 wt.% and water 10-12 wt.% removal of HA from the phenol stream is held on the first column (the separation of acetone and phenol threads). The content of ha in the phenol stream reaches 8 to 20 ppm in terms of the design load. The efficiency of the distillation HA in this type of technology the selection commodity phenol raw is determined by the presence in the composition of the decomposition products of mass ratio cumene and water meet their azeotropic composition. However, even a slight excess load compared with the project or in violation of the ratio of water and cumene in the power of the column lowers the efficiency of the distillation HA of phenol stream.

When selecting a trademark of phenol decomposition products of CPC containing cumene 28-30 wt.% and water 5-6 wt.% HA can be removed from the phenol stream after azeotropic distillation (U.S. patent 3,405,038, 1968). The disadvantages of this method is the increased content of cumene, for effective distillation of phenol requires the use of large amounts of water. In addition, the use of return water phase from the distillate of the column on the phlegm column azeotropic distillation in the column receives a large number HA, dramatically reduces the degree of purification of phenol stream from HA.

When the separation of the products of decomposition of the CCP, in which the content of cumene is 1-3 wt.% and water 15-17 wt.%, to drive away HA from phenol stream is impossible without large losses of phenol and a huge overload stage definalely (d is stellate column separation of acetone and phenol streams at full distillation of water from the cube column the content of the phenol reaches 10-20 wt.%). The concentration of HA in phenolic threads in this scheme reaches 0.1 to 0.4 wt.%. This leads to the serious problem of purification of phenol raw from HA and 2-ICF and, accordingly, greater problems for phenol a high degree of clearing.

The most common in the industry by the catalytic method is a method of purification of phenol raw from impurities on heterogeneous acid catalysts, which are used most commonly sulfonic cation. However, the use of sulfonic cation as catalysts for purification is not without flaws. These catalysts are polymeric materials having a low mechanical strength and thermal stability and are prone to swelling and cracking during operation. Selfactivity the catalysts for purification of phenol have a limited lifespan, not regenerated and after unloading processed by incineration in special furnaces, but the biggest drawback is that HA sulfonic cation is transformed into a 2-MBF (conversion of HA is 20 mol.%). In the patent of the Russian Federation 2004111561, 2004 proposed a method of two-stage catalytic purification of phenol raw, where the first step uses catalytic oxidation of HA, as the first stage of purification, and the second the formation of 2-ICF does not occur. This method effectively allows ESAT problems ultrapure phenol for the decomposition products of CPC 2 and 3 types in the case of decomposition products type 1, where the HA content in phenolic stream reaches 0.25 to 0.4 wt.%, capital costs for catalytic cleaning, including the volume of the reactors and the cost of the catalyst becomes extremely high. The problem of removal of HA from phenolic flow in the flow charts of type 1 and the production of phenol highly purified (carbonate purity) for this type of allocation patterns of commercial products most relevant.

In the patent of the Russian Federation 2004105639, 2005 (prototype) describes the process of removal of HA from phenol raw, obtained after distillation of the acetone, water, basic quantities of hydrocarbons, cumene and α-methylstyrene (AMS) and heavy products, forming the so-called phenolic resin, by reconstructing the column azeotropic distillation (the name of the author, but this column is rather operates in the mode of extractive distillation, as for Stripping 2-MBF use a huge surplus of water - extracting agent)used for purification of phenol stream from hydrocarbons and 2-MBF. It is proposed to take liquid side stream (BP) phenol raw with half-deaf plates extractive distillation column located in a remote section of the column where there is no water. To remove HA from phenol raw add the cumene in the number corresponding to the azeotropic composition of a mixture of HA - cumene (of 39.8 wt.% HA), napravlyayut flow on nutrition additional Stripping column (efficiency 15 TT), which method of azeotropic distillation the distillate is collected fraction azeotropic mixture of HA and cumene, and CC the flow of the Stripping column return to discomania cumene and HA under half-deaf plate column extractive distillation. The purified phenol-raw cube extractive distillation column is directed to the catalytic cleaning of traces of other carbonyl-containing and unsaturated compounds. However, to carry out the purification of phenol stream from HA by the method of azeotropic distillation of a mixture of phenol-HA-cumene impossible because of the presence is not revealed by the author of a number of azeotropic properties of the investigated system and the features of phase equilibria of the system the cumene-phenol.

In the patent of the Russian Federation 2004105639, 2005 it is assumed that the purification of phenol from GA is carried out by distillation of ternary mixtures of phenol-cumene-HA, as special points in which according to the author there are two azeotrope with a minimum boiling point (cumene-phenol 149°and cumene-HA 139,8°C at 760 mm Hg). It should be noted that if really in HA-phenol-cumene was above a particular point, then hypothetically in this case, when the continuous distillation column with the actual number of plates with finite reflux ratio can be obtained CBM product containing purified from HA phenol and of the input in which the system of cumene and the distillate would contain the entire HA and part of the cumene and phenol. The amount of cumene in Cuba and phenol in the distillate was determined by the efficiency of the column, the reflux ratio and the mass ratio of the cumene-HA.

However, our study showed that the azeotropic properties of the system the cumene-phenol-HA not correspond to those shown in the patent of the Russian Federation 2004105639, 2005. In the system of the cumene-phenol-HA have the following azeotropic point azeotrope with a minimum boiling point (cumene-HA), the azeotrope with a maximum boiling point (phenol-HA)and the cumene-phenol not azeotrope. In this case, the original point of the line rectification is the azeotrope of the cumene-HA, and the end point of the azeotrope of phenol-HA. Continuous rectification as the distillate and bottoms distillation product will contain all three components (phenol, cumene, HA) and effectively clean the phenol from GA is not possible. In this case, the phenol stream leaving the Stripping column, the concentration of HA will decrease very slightly, but this thread will contain cumene, to drive away which is on the column extractive distillation zone to the lack of water and low efficiency is not possible.

The purpose of this invention is to develop technologies for maximum purification of phenol stream from HA method azeotrope-extractive distillation using kombinirov the aqueous separating agent. Using the ability of HA to effectively extracted water from the organic phase in the presence of huge quantities of cumene and/or α-methylstyrene (AMS), and the presence of azeotropes with a minimum temperature of boiling water-cumene and water-AMS, apply to azeotrope-extractive distillation as a combined separating agent hydrocarbons (cumene and/or the AMC) and water, allows to increase the selectivity of the distillate HA by increasing its relative volatility, and use as phlegmy in the column azeotropic-extractive distillation only organic phase, the number of HECTARES in which 5-10 times lower than in the aqueous phase, allows the main number of HECTARES to withdraw from the column with a water stream.

The development of the proposed technology has carried out detailed studies of the phase equilibria and the azeotropic properties of the binary and ternary systems, including the basic components Kumanovo process and HA.

It was experimentally found:

- HA does not form water azeotropic mixture (similar results are given in the work / Vuerstaek and other "study of the process of rectification and phase equilibrium liquid-vapor systems phenol-water-HA and phenol-water - α-methyl-styrene". Russian journal of applied chemistry, volume 76, issue 2, 2003);

- HA forms an azeotropic mixture of cumene and AMS with a minimum temperature of Kipen is I (to 121.0 and 141° C at a pressure of 1013 HPa and content - ha, respectively 65,8 and 73,8 mol.%);

- phenol forms an azeotropic mixture with HA with a maximum boiling point (184,8°and HA content of 6.8 mol.%);

- phenol does not form azeotropic mixtures with cumene (in the literature, there is incorrect information about the existence of azeotropic mixtures / Scholarone.com, Timishev, Vbegin. Azeotropic mixtures. The Handbook. - M. - L.: Chemistry, 1971. - 848 S.);

- phenol forms an azeotropic mixture with AMC with a minimum boiling point (165°C at 1013 HPa and a phenol content of 15.1 mol.%), our study confirmed the presence of an azeotrope, but it azeotropic characteristics differ from those found in the literature / Scholarone.com, Timishev, Vbegin. Azeotropic mixtures. The Handbook. - M. - L.: Chemistry, 1971.-848 C./;

- AMS forms an azeotropic mixture with water with a minimum boiling point (96,2°C at 1013 HPa and content α-methylstyrene to 9.3 mol.%);

in ternary mixtures of phenol-cumene-water and phenol-AMS-water is not detected by the formation of triple azeotropes.

Based on studies of the phase equilibria and the azeotropic properties of mixtures of phenol-cumene (AMC)-water-HA received the chart lines distillation and areas rectification (figure 1).

Analysis of the graphs shows that because of the complex pattern of phase equilibria and the existence of azeotropic mixtures of phenol-HA with a maximum boiling point of the floor is awn clear phenol from GA impossible, but it is possible to determine the basic conditions of rectification for maximum removal of HA from phenol. These conditions are:

maintaining the mass ratio of the concentrations of cumene (and/or the AMC) and water in the composition of the partial mixtures (power columns)equal to or greater than their mass ratio in azeotropic mixtures (mass azeotropic ratio of cumene and water at atmospheric pressure is equal to 0.77, and the mass azeotropic ratio AMC and water is equal to 0.67);

- lack of water (<0.01%)as product - phenol;

- presence in the VAT product hydrocarbon in an amount not less than 0.1 (0,005) wt.%.

Experimental studies based on identified topological patterns made it possible to find optimal conditions for purification of phenol stream from HA method azeotrope-extractive distillation using a combined separating agent whose schema is presented in figure 2.

Phenol stream (stream 1), obtained after distillation of the acetone raw from the decomposition products of the CCP (1, 2 or 3 types) with HA content from 0.01 to 0.4 wt.% comes either in an additional column (I) azeotrope-extractive distillation, either in an existing column azeotropic distillation (I) changes its operation mode azeotrope-extractive distillation. The column must have at least 17-20 theoretical triloki can operate at atmospheric pressure (760 mm Hg), and when the vacuum (150 mm Hg). In the power of the column depending on the content in the feedstock hydrocarbons (cumene and AMS) and water served an additional amount of recycle cumene (and/or the AMC) (stream 2) and an additional amount of fresh water - flow 3 (steam condensate), so that the mass ratio of the concentrations of hydrocarbons and water was responsible or was beyond their mass ratio in azeotropic mixtures. The quantity of hydrocarbons in the power of the column azeotropic-extractive distillation must exceed the number of hydroxyacetone in the original phenolic flow of not less than 25 times. Power is supplied to the upper part of the column (3-4 theoretical plates above). Steam flow - air flow 4 - the top of the column containing hydrocarbons, water, and virtually the entire HA, coming from the power of the column, and a small amount of phenol is condensed in the fridge (II) and directed into the Florentin (III) to separate the oil and water layers. The aqueous layer stream 6 containing the phenol of not more than 3 wt.% and GA is not more than 3.5 wt.% (87 Rel.% from the received power), is continuously withdrawn from Florentina on alkaline treatment to remove HA. The organic layer thread 5 (cumene and/or AMS, phenol - no more than 9 wt.%, HA - not more than 0.5 wt.% (13 Rel.% from the received power) is divided into two streams, one stream 5 is directed to the irrigation quantity is NY with a reflux ratio of at least 2 (preferably 2.5 to 3), and the other thread 5B - cleaning from GA. Purification of the organic layer from HA is a water solution of alkali in a specially installed capacity (IY) with a residence time of at least 30 minutes and a temperature of not lower than 50°C. Purified from HA hydrocarbon stream from the cleaning tank is returned to the recycling on the power of the column. CBM product columns - flow 7 - azeotrope-extractive distillation, which represents a phenol stream, in which the HA content was reduced from 0.02 to 0.4 wt.% to 0.0005-0.01 wt.%, the concentration of hydrocarbon is 0.005 to 2%, the water content should not exceed 0.01 wt.%, sent in a scheme to obtain phenol raw with subsequent catalytic purification, and isolation of highly pure commodity phenol.

The advantages and differences of the developed technology are demonstrated by examples 1-13. The examples do not limit the scope of this invention.

Example 1

In a laboratory distillation column continuous efficiency 30 TT 5 TT served raw with a flow rate of 200 ml/hour composition (wt.%): HA - 0,4; cumene - 0,1; AMS - 0,1; water - 3,0; heavy (the components that make up the so-called phenolic resin) - 6; phenol - rest. Raw material is phenolic stream obtained after distillation of the acetone raw for decomposition products CPC 1 type. In the power of the column dopolnitelnogo washed from HA hydrocarbon fraction with a flow rate of 22 ml/h composition (wt.%): the cumene - 35,0; AMS - 65,0 and water with a flow rate of 18 ml/hour. The content of hydrocarbons (cumene and AMS) and water in a food column respectively equal to 8 and 11.4 wt.%, what is their azeotropic ratio of 0.7.

Top of the column at a temperature of 140°With a selected mixture of hydrocarbons, water and phenol, which after cooling to room temperature, divided in Florentine into two streams: organic and water. Water flow (25,0 ml/HR)containing 3.5 wt.% HA and 2.5 wt.% phenol, was taken to an alkaline treatment to remove HA. Organic stream representing a mixture of hydrocarbons with 0.5 wt.% HA and 6.0 wt.% phenol, partially directed for irrigation columns (supported reflux number - 2.5), the rest (18.8 ml/h) after the alkali treatment, where they removed HECTARES, was returned for recycling in the power of the column. Cube column at a temperature of 183°With a flow rate of 180 ml/hour was selected phenol stream containing 0,0100 wt.% HA; 1 wt.% AMC; 6.3 wt.% heavy. The degree of purification of phenol stream from HA amounted to 97.5%.

Example 2

The process is carried out analogously to example 1, but is used as raw material phenol stream obtained after distillation of the acetone raw for the decomposition products of CPC 2 type and composition (wt.%): HA - 0,025; cumene - 0,1; AMS - 2,5; water - 0,01; heavy - 4; phenol - rest. In the power of the column was additionally supplied water with a flow rate of 5.2 ml/hour. The content of hydrocarbons (cumene and AM is) and water in a food column, respectively, equal to 2.6 and 2.6 wt.%. (Close) above the azeotropic ratio of 0.7.

Top of the column at a temperature of 146°With a selected mixture of hydrocarbons, water and phenol, which was sent in Florentin to separate the organic and aqueous layers. Water flow (5,4 ml/h), containing 2 wt.% HA and 3 wt.% phenol, was taken to an alkaline treatment to remove HA. Organic stream representing a mixture of hydrocarbons with 0.2 wt.% HA and 9.0 wt.% phenol, partially directed for irrigation columns (supported reflux number - 2.5), the rest were sent to the alkaline treatment, where they removed HA. Cube column at a temperature of 183°With consumption 196,1 ml/hour was selected phenol stream containing 0,0006 wt.% HA, 0,008 wt.% AMC; 4.1 wt.% heavy. The degree of purification of phenol stream from HA amounted to 97.5%.

Example 3

The process is carried out analogously to example 1, but is used as raw material phenol stream obtained after distillation of the acetone raw for decomposition products CPC 3 type and composition (wt.%): HA - 0,25; cumene - 42,5; AMS - 2,5; water - 7; heavy - 4; phenol - rest. The ratio of hydrocarbons (cumene and AMS) and water in the power of the column is much higher than the azeotrope. Therefore, in the power of the column additionally nothing was filed. Top of the column at a temperature of 146°With a selected mixture of hydrocarbons, water and phenol, which was sent in Florentin to separate the organic and aqueous with the OEB. A stream of water (17 ml/HR)containing 1.6 wt.% HA and 2 wt.% phenol, was taken to an alkaline treatment to remove HA. Organic stream representing a mixture of hydrocarbons with 0.16 wt.% HA and 8.0 wt.% phenol, partially directed for irrigation columns (supported reflux number - 2), the rest were sent to the alkaline treatment, where they removed HA. Cube column at a temperature of 183°With a flow rate of 82 ml/hour was selected phenol stream containing 0.004 wt.% HA, 0.5 wt.% AMC; 9 wt.% heavy. The degree of purification of phenol stream from HA was 98.4%.

Example 4

The process is carried out analogously to example 1, but maintain reflux a number equal to 4.0. As phenolic stream the HA content was 0,0070 wt.%. The degree of purification of phenol stream from HA was 98,3%.

Example 5

The process is carried out analogously to example 4, but maintain the concentration of hydrocarbons in the VAT phenolic thread 2 wt.%. The concentration of HA in phenolic thread was 0,0050 wt.%. The degree of purification of phenol stream from HA was 98,8%.

Example 6

The process is carried out analogously to example 1, but the flow of the hydrocarbon fraction is increased 3 times (54 ml/hour). The concentration of HA in the VAT phenolic flow amounted to 0.001 wt.%. The degree of purification of phenol stream from HA was 99.5%.

Example 7

The process is carried out analogously to example 1, but water consumption was reduced in 2 times - 9 ml/hour. oncentrate HA in the waste water flow of the distillate amounted to 5.2 wt.%, organic is 0.55 wt.%. The concentration of HA in the VAT phenolic thread was 0,560 wt.%. The degree of purification of phenol stream from HA was 86%.

Example 8

The process is carried out analogously to example 7, but the flow of the hydrocarbon fraction was reduced in 4 times 5 ml/hour. The concentration of HA in the outgoing single-phase flow of the distillate amounted to 0.6 wt.%. The concentration of HA in the VAT phenolic thread was 0,740 wt.%. The degree of purification of phenol stream from HA amounted to 81.5%.

Example 9

The process is carried out analogously to example 1, but with the HA content in the raw material is 0.2 wt.% and 0.05 wt.%. As phenolic stream the HA content was 10 and <1 ppm, respectively. The degree of purification of 99.5 and 99.8 per cent, respectively.

Example 10

The process is carried out analogously to example 1, but for irrigation of the column serves not organic layer and the mixture of organic and aqueous layers. The concentration of HA in the VAT phenolic thread was 0,0560 wt.%. The degree of purification of phenol stream from HA was 86%.

Example 11

The process is carried out analogously to example 1, but for irrigation of the column serves not organic layer and an aqueous layer. The concentration of HA in the VAT phenolic thread was 0,415 wt.%. The degree of purification of phenol stream from HA amounted to 0%.

Example 12

The process is carried out analogously to example 1, but used the column efficiency 18 TT the Concentration of HA in the phenol stream is put also 0,0100 wt.%. The degree of purification of phenol stream from HA amounted to 97.5%.

Example 13

The process is carried out analogously to example 1, but is used as raw material phenol stream composition (wt.%): HA - 0,4; cumene - 0,1; AMS - 0,1; water - 15,0; heavy - 6; phenol - rest. In the power of the column was additionally submitted washed from HA hydrocarbon fraction with a flow rate of 24 ml/h composition (wt.%): the cumene - 35,0; AMS - 65,0. The content of hydrocarbons (cumene and AMS) and water in a food column, respectively, equal to 9.5 and 13.6 what is the azeotropic ratio of 0.7. Top of the column at a temperature of 140°With a selected mixture of hydrocarbons, water and phenol, which after cooling to room temperature, divided in Florentine into two streams: organic and water. Water flow (31,0 ml/HR)containing 3.0 wt.% HA and 2.5 wt.% phenol, was taken to an alkaline treatment to remove HA. Organic stream representing a mixture of hydrocarbons with 0.4 wt.% HA and 6.0 wt.% phenol, partially directed for irrigation columns (supported reflux number - 2.5), the rest (24 ml/h) after the alkali treatment, where they removed HECTARES, was returned for recycling in the power of the column. Cube column at a temperature of 183°With a flow rate of 169 ml/hour was selected phenol stream containing 0,0100 wt.% HA; 1 wt.% AMC; about 6.5 wt.% heavy. The degree of purification of phenol stream from HA amounted to 97.5%.

1. The method of purification of phenol stream, ochomogo after distillation of the acetone raw when the separation of the products of the decomposition of cumene hydroperoxide, from hydroxyacetone by rectification method, characterized in that the removal of hydroxyacetone phenolic flow method azeotrope-extractive distillation with a combined separating agent, as one of the components which is used hydrocarbon (cumene and/or α-methylsterol), and as another component is water, the flow separating agent together with the power of the column, maintaining the mass ratio of the hydrocarbon and water, equal to or greater than the mass ratio of the concentrations of hydrocarbon and water in the respective azeotropic mixtures, the output hydroxyacetone from the column with a water flow of distillate and feed on the phlegm organic phase depleted in hydroxyacetone.

2. The method according to claim 1, characterized in that the content of cumene and/or α-methylstyrene in the phenol stream is from 0.2 to 45,0 wt.%.

3. The method according to claim 1, characterized in that the water content of the phenol stream is from 0.01 to 15 wt.%.

4. The method according to claim 1, characterized in that the content of hydroxyacetone in phenol stream is from 0.01 to 0.4 wt.%.

5. The method according to claim 2, characterized in that as the hydrocarbon in the composite separating agent can be used cumene, α-methylsterol or a mixture of cumene and α-methylstyrene.

6. The method according to claim 1, characterized in that the amount is entered in the combined hydrocarbon separating agent must exceed the number of hydroxyacetone in the original phenolic flow of not less than 25 times.

7. The method according to claim 1, characterized in that the mass ratio of hydrocarbon and water in the composite separating agent is supported such that the power of the column it was equal to or above the mass ratio of the concentrations of hydrocarbon and water in the azeotropic mixture.

8. The method according to claim 7, characterized in that in the case of use as a hydrocarbon hydroperoxide mass ratio of the cumene-water in the combined separating agent should not be less than 0,77, and in the case of α-methylstyrene should not be less than 0,67.

9. The method according to claim 1, characterized in that the concentration of hydroxyacetone in the waste water flow of the distillate of the column azeotropic-extractive distillation should not exceed 3.5 wt.%, and the concentration of hydroxyacetone in the organic flow of the distillate should not exceed 0.5 wt.%.

10. The method according to claim 1, characterized in that the concentration of phenol in the waste water flow of the distillate of the column azeotropic-extractive distillation should not exceed 3 wt.%, and the concentration of phenol in the organic flow of the distillate should not exceed 9 wt.%.

11. The method according to claim 1, characterized in that the columns in the cube azeotrope-extractive distillation of the hydrocarbon content is 0.005 to 2 wt.%.

12. The method according to claim 1, characterized in that the columns in the cube azeotrope-extractive distillation sod is neigh water should not exceed 0.01 wt.%.

13. The method according to claim 1, characterized in that the efficiency of the column azeotropic-extractive distillation must be at least 17 TT

14. The method according to claim 1, characterized in that the feeding is preferable to apply in the upper part of the column azeotropic-extractive distillation.

15. The method according to claim 1, characterized in that column azeotropic-extractive distillation supported reflux number not less than 2, preferably 2.5 to 3.

16. The method according to claim 1, characterized in that the composite separating agent is injected with a power of the column.

17. The method according to claim 1, characterized in that the pressure in the column azeotropic-extractive distillation preferably should be from 760 mm to 150 mm Hg



 

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5 cl, 4 ex, 8 tbl

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: 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: 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: 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

The invention relates to petrochemistry and can be used in the production of phenol and acetone Kukolnik method

The invention relates to analytical chemistry of organic compounds and can be used for concentration of phenol in analytical control of natural water, drinking water and treated wastewater

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 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: 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

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

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