Catalytic method for processing phenolic resin

FIELD: petroleum chemical technology.

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.

EFFECT: improved preparing method.

2 cl, 3 tbl, 6 ex

 

The present invention relates to the field of petrochemical technology, more specifically to a method of processing a phenolic resin, formed during the production of phenol and acetone Kukolnik method (Kruglov D., Golovenko BN. Joint production of phenol and acetone. M, Goskomizdat, 1963, 200 pages).

In the process of producing phenol and acetone from cumene (IPA) along with the target products are formed high-boiling by-products, generally referred to as phenolic resin. The composition of the phenolic resin includes a large number of components: phenol, acetophenone, dimethylphenylcarbinol (DMPC), dimmers α-methylstyrene, para-cumylphenol (FSC), as well as other components contained in small concentrations. The composition of the phenolic resin include mineral components, mainly sodium sulphate (see table 1).

Table 1. The average composition of the phenolic resin
ComponentsContent, wt.%
Phenol10,11
The acetophenone16,35
DMFC8,23
Dimmers α-methylstyrene31,99
Cumylphenol24,13
The amount of unidentified components + heavy residue8,11
Na2SO41,08

To date phenolic resin is not found qualified in full and mostly burned as boiler fuel. However, due to the aggravation of the environmental situation, the use of phenolic resins as boiler fuel is difficult and, as a consequence, she does not find sales.

There is a method of processing a phenolic resin obtained in the production of phenol and acetone Kukolnik method by thermal decomposition at a temperature of 300-340°C. the Process is carried out in the reactor column type with the selection in the distillate desired products, phenol, cumene and alpha-methylstyrene and 50-100% of the input raw materials of acetophenone. Cube reactor serves water vapor in the amount of 1-15% by weight of phenolic resin (patent RF №2120433, publ. 27.05.2001). This method allows to increase the total yield of useful products by 10-50 kg per 1 t of phenolic resin. However, the implementation process without catalyst does not allow you to maximize the potential of raw materials.

A method of refining phenolic resin by dealkylation in the presence of calcium stearate. Phenolic resin is kept in the reactor at 0.1 ATA in the presence of 0.1-4% calcium stearate at 120-130°C. After cooling, the reaction mixture is subjected to distillation PR the temperature 145° In the lower part of the column and at 110-120°at the top at a pressure of 100 mm Hg as distillate receive a mixture of the following composition (wt.%): phenol 42-50; α-methylsterol 21-4; cumene 17-28 (Ed. St. NRB 23087, 1979). A significant drawback of this process is the presence of significant amounts of the mineral component, calcium salts, as product, making its destruction is extremely difficult.

A known method of processing of phenolic resins by its oligomerization in the presence of 1-5% ll3when 60-120°C for 1-3 hours with subsequent decomposition of the aluminum chloride with water and distillation of the organic layer (Ed. St. NRB 33950, 1983). As a result of oligomerization get UPS with the release of 40% and a purity of 98.9 per cent, which is recycled to the stage of oxidation. The output fraction of dimers α-methylstyrene 20-29%, hydrocarbon resin 17%. Translation α-methylstyrene in the dimers simplifies the separation process and reduces the amount of high-boiling tar.

Also known processing techniques phenolic materials by hydrogenation in the presence of high-temperature hydrogenation catalysts (oxides and sulfides of cobalt, Nickel, iron, and other) at 350-450°under hydrogen pressure (Wills-Epstein A.B., Gagarin YEAR of Catalytic conversion of alkyl phenols. - M, Chemistry, 1973). However, these methods have not found use because of the small is on the service life of the catalyst and the complexity of the hardware design process, associated with the use of hydrogen under high pressure at high temperature.

The closest to the technical nature of the present method is a method for dealkylation of phenolic resin at 100-140°in the presence of a strongly acidic cation exchange resin or zeolite NaX at a temperature of approximately 400° (Dimitrov H., Nikolov N. Petrochemicals, 1979, t, No. 5, s, prototype). The proposed method can selectively carry out the decomposition of phenolic resin and its main component - para-cumylphenol) to phenol and α-methylstyrene. The disadvantages of this method of processing phenolic resin should include relatively rapid deactivation of the catalyst. So, after 30 times of regeneration of the catalyst, the content of α-methylstyrene and phenol is reduced by 20-40%. In addition, in the processing of phenolic resins by known catalyst under specified operating temperature is piling system condensation resins, which makes impossible the implementation process. Also among the disadvantages of this method of processing of phenolic resins include short cycle contact, 1 hour, which increases the energy consumption in an industrial environment.

The aim of the present invention is to reduce kokoulina in the processing of the entire phenolic resins, and also liquidation of the driving system condensing contact ha is A.

This goal is achieved by catalytic decomposition of phenolic resin containing less than 0.2 wt.% mineral salts, at a temperature of 420-550°in the presence of water vapor, preferably with a ratio of phenolic resin : steam 1:3, respectively. The ratio may be different and depends on the hardware design process. The process is performed on the catalyst containing (wt.%):

Aluminum oxide 5,0-30,0

The oxide of iron of 0.4 to 1.0

Magnesium oxide 0,4-1,0

Calcium oxide 5,2-7,0

The sodium oxide 1,0-3,0

The potassium oxide 1,0-3,0

The titanium oxide (IV 0,4-1,0

The silicon oxide IV rest

Received contact gas condense and catalyzate method of rectification produce useful products: phenol, α-methylsterol and ISP.

Using the catalyst obtained by the known method described in the patent RAF No. 88186, CL B01j 27/8, SS 3/58, 1983, or others, ensure receipt of the catalyst of this team. Before use, the catalyst is calcined.

The proposed catalyst is used for splitting the high-boiling by-products and/or paranavai fraction of the synthesis of isoprene from isobutylene and formaldehyde (RF Patent No. 2167710, publ. 27.05.2001, BIPM No. 15).

The use of such catalyst for the decomposition of phenolic resins authors are not known, which allows to draw a conclusion about the novelty and non-obviousness his use of the Finance for another purpose.

The application of the proposed catalyst for the processing of phenolic resins allows to process all of the tar formed during the production of phenol and acetone Kukolnik method, not only the easy part. The catalyst was stable during operation and condensation system is not clogged.

In addition, the total yield of useful products (phenol, α-methylstyrene and cumene) in a single pass amounts to about 60 wt.%, and kokoulina does not exceed 20 kg per 1 ton of raw materials.

In the proposed conditions, the technical effect is achieved by using a phenolic resin containing less than 0.2 wt.% mineral salts. Phenolic resin, resulting in the production of phenol and acetone Kukolnik method may contain a different amount of salt depending on the technology option Kumanovo method. When using non-demineralized phenolic resin containing more than 0.2% of salts, there is an accumulation of mineral components of the resin in the catalyst layer, which leads to the decrease of its activity, to increase the flow resistance in the catalyst layer, increase the time of regeneration. In this case, you want desalting phenolic resin before processing to the specified value of the salt content.

In the processing of desalted phenolic resin of the proposed structure on a non-calcined what Ohm the proposed catalyst is rapid decontamination, a sharp reduction mezhregionalnogo period, which reduces the efficiency of the proposed method of processing a phenolic resin.

Industrial applicability the present invention is illustrated by the following examples.

Example 1.

30 cm3solid pellets of a catalyst containing (wt.%):

Aluminum oxide 22,4

The oxide of iron of 0.4

Magnesium oxide 0,4

Calcium oxide 6,7

Oxide sodium 1,2

The oxide of potassium 2,4

The titanium oxide (IV 0,47

The silicon oxide IV rest

calcined before use for 2 hours at 700°loaded in a quartz reactor, which is placed in the furnace. In the reactor for 2 hours serves a mixture of water vapor and phenolic resins. Phenolic resin pre-absoluut to the salt content of <0.2 wt.%. The composition of the phenolic resin, in which the research was conducted, are shown in table. 2. The ratio of phenolic resin : steam = 1:3,0 (wt.); the temperature in the reactor 500°C. After 2 hours of contacting the catalyst was rinsed with water vapor for 10 minutes at a temperature of the experience.

The resulting contact the gas condense and get 2 layers of water and oil, which analyze chromatographic content of phenol, α-methylstyrene, cumene, DMPK etc. On the basis of data analysis make up the balance of the processing of phenolic resins. Individually the e components of the resulting condensate allocate rectification.

After 2 hours of contact regenerate the catalyst by burning coke deposited vapor-air mixture at 550°within 2 hours.

The results of the experiment are given in table 2 (experiment 1).

Example 2.

The processing of phenolic resins carried out as described in example 1, except that the process temperature is 420°C.

The results of the experiment are given in table 2 (experiment 2).

Example 3.

The processing of phenolic resins carried out as described in example 1, except that the process temperature is 550°C.

The results of the experiment are given in table 2 (experiment 3).

Example 4.

The processing of phenolic resins carried out as described in example 1, except that as the catalyst used lumosity contact that contains (wt.%):

Aluminum oxide 5,0

Iron oxide 0,5

Magnesium oxide 0,5

Calcium oxide 5,3

The oxide of sodium 1,1

The potassium oxide 2,1

The titanium oxide (IV 0,57

The silicon oxide IV rest

The results of the experiment are given in table. 2 (experiment 4).

Example 5.

The processing of phenolic resins carried out as described in example 1, except that as the catalyst used lumosity contact that contains (wt.%):

Aluminum oxide 30,0

Iron oxide 0,6

Magnesium oxide 0,7

The oxide is Alicia 5,5

The sodium oxide 3,0

The potassium oxide 3,0

The titanium oxide (IV 0,4

The silicon oxide IV rest

The results of the experiment are given in table 2 (experiment 5).

Example 6 (for comparison, without calcination of the catalyst).

The processing of phenolic resins carried out as described in example 1, except that the catalyst before use, not calcined.

Coke kg/t raw materials28,6
Conversion, % 
The amount of dimers α-methylstyrene95,4
The amount of cumylphenol87,5
Heavy residue62,6
The output of useful products, wt.% 
IPA4,89
α-Methylsterol34,55
Phenol20,37
Total59,71

Thus, the proposed method for the processing of phenolic resins enables the catalytic thermal decomposition of the entire phenolic resin and receive at the same time for one pass to 61.5 wt.% useful products (phenol, α-methylstyrene and cumene). It should be noted that the yield of useful products with the proposed method of disposal, phenolic resins depends on the content of dimers α-is ethylstyrene and cumylphenol in the original resin. Therefore, in the processing of phenolic resins with a high content of dimers and cumylphenol yield of useful products will be more than a 61.5 wt.%.

The final product is quite small and is at the level of 15 kg per 1 ton of raw materials.

1. Catalytic method for processing of phenolic resins, resulting in the production of phenol and acetone Kukolnik method by decomposition at elevated temperatures in the presence of a catalyst followed by condensation and separation of the resulting catalyzate by distillation, characterized in that the process is carried out with the use of resins containing less than 0.2 wt.% salt, as a catalyst using alumina solid contact, contains, wt%:

Aluminum oxide 5,0-30,0

The oxide of iron of 0.4 to 1.0

Magnesium oxide 0,4-1,0

Calcium oxide 5,2-7,0

The sodium oxide 1,0-3,0

The potassium oxide 1,0-3,0

The titanium oxide (IV 0,4-1,0

The silicon oxide IV rest

and the process is carried out at a temperature of 420-550°in the presence of water vapor.

2. Catalytic method for processing phenolic resin according to claim 1, characterized in that the process is carried out at a mass ratio of phenolic resin and water vapour 1:3,0.



 

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FIELD: petroleum chemical technology.

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.

EFFECT: improved preparing method.

2 cl, 3 tbl, 6 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 a method for preparing phenol and acetone by acid-catalyzed cleavage of cumyl hydroperoxide. Method involves preliminary heating the reaction mixture to temperature above 100°C and then for thermal treatment of product heat in exothermic reaction is used, mainly the cleavage reaction of cumyl hydroperoxide that presents in the concentration from 5 to 10 wt.-%. The preferable residual content of dicumyl hydroxide in thermally treated product is 0.01-0.05 wt.-%. Stages in cleavage of cumyl hydroperoxide and the following thermal treatment can be carried out in a single reactor with two zones among that one zone is fitted with a device for heat removing and another zone has a feature of the flow-type pipe. Reactor is equipped by a device for circulation of part of product from thermal treatment zone to a feeding line for decomposition of product. Method provides improving energetic indices of process due to optimal consumption of heat energy in maintaining high selectivity of the decomposition process.

EFFECT: improved preparing method.

15 cl, 3 dwg

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

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