CS239572B1 - Method of processing from height of phenol production by cumene method and equipment for carrying out this process - Google Patents

Abstract

The invention relates to the field of chemistry. It solves the method of processing the residue from the production of phenol by cumene and the apparatus for carrying out this method. The acids contained in the residue are neutralized, the fractions are separated by distillation to a boiling point of 85 ° C at 1.3 kPa, the crude cumylphenol is separated by distillation as a mixture of positional isomers containing at least 85 percent by weight to a boiling point of 190 ° C, at 0, 1 kPa ', applicable as product. It is recrystallized from a hydrocarbon having a pofite of carbon atoms in the molecule of 5 to 7 per p-cumylphenol at a concentration of at least 99% by weight. The device, the schematic of which is connected, makes it possible to perform the described method.

Description

239572

BACKGROUND OF THE INVENTION The present invention relates to a process for treating phenol residue from cumene by means of a device for carrying out this process.

The principle of concomitant preparation of phenol and acetone, also called cumene, is the alkylation of benzene with propylene to cumene, oxidation with oxygen to cumene hydroperoxide and subsequent decomposition, catalysed by sulfuric acid to form phenol and acetone, are recovered by distillation. As by-products, acetophenone, dimethylphenylcarbinol, alpha-methylstyrene, dimers of alpha-methylstyrene, cumylphenols, and other materials, including bituminous, are formed. In the distillation residue, with the addition of sulfuric acid and elevated temperature, they release additional pordiel of the desired phenol, and a sour substance of acidic nature is used, which is used as a component in less quality heating oils, which is economically disadvantageous. The growth of the product, which is in the distillation residue, requires its processing. From the distillation residues of the simultaneous preparation of phenol and acetone by cumene, it is possible to extract the high purity glycol by p-methylphenol (Japanese Patent No. 74 28.741). In the Romanian Patent Patent No. 57 169, the distillation residue is separated by distillation into a fraction containing phenol, alpha-methylstrene, acetophenone and dimethylphenylcarbinol and a heavy fraction containing the alpha-methylstyrene dimer and p-cumylphenol, which can be obtained by crystallization. A further fraction of p-cumylphenol is obtained from the 1 ' light fraction after addition of phenol and hydrogen chloride and recycled after separation and separation of the acetophenone.

Another process (U.S. Pat. No. 1,235,415) suggests rectifying the separation of the enriched fraction into cumylphenols and dimers of alpha-methylstyrene, from which cumyl phenol crystallizes, which after centrifugation and washing with solvent is a product of 31% yield.

A similar procedure (Italian patent 722 524) is based on the rectification-separated fraction enriched in p-cumylphenol. From it by recrystallization from n-pentane at 10 ° C and after washing with n-pentane, p-cumylphenol is obtained in a yield of 79.5% with a purity of 98.5% by weight.

A further procedure involves evaporation of the residue in a thin film over a period of 5 seconds with a temperature of 158 ° C and a pressure of 1.3 kPa followed by recrystallization from a propylene tetramer environment (U.S. Pat. No. 1,411,730).

The object of the invention, which alleviates the disadvantages mentioned, is to process the residue from the phenol production by cumene method, the principle of which is the neutralization of the acids contained in the residue with an alkali hydroxide, bicarbonate, carbonate or phenolate. boiling to 85 ° C at 1.3 kPa, followed by distillation under reduced pressure to separate the boiling fraction up to 1900

Celsius at 0.1 kPa with a content of at least 85 percent by weight. the positional isomers of cumyl phenol, wherein the distillation residue does not exceed 20% by weight of the treatment feed, which can be recrystallized from a carbonaceous hydrocarbon having a molecular weight of 5 to 7 to at least 99% by weight . The apparatus according to the invention consists of a reservoir of bulk material connected to a column, into which a reservoir of neutralizing agent, coupled with a reservoir of forestock and vacuum distillation, is connected to a reservoir of diffraction and a reservoir of distillation residue, further with a reservoir of crude ketylphenol which it is coupled to a crystallizer, filter and cumyl phenol reservoir, the filter being coupled to a solvent regenerator associated with the combustible reservoir and the solvent reservoir associated with the recrystallizer.

The apparatus of the present invention operates as follows. The required amount of raw material is metered into the column from the stock container. From the reservoir of neutralizing agent, a calculated amount of neutralizing agent is added to the feedstock to react with the acids present in the feedstock. After heating and vacuum are applied, the forward fractions are rectified into the stock portions. The contents of the column boil are transferred to vacuum distillation, where the intermediate fraction is separated into the intermediate container, the crude cumylphenol is separated into the crude cumylphenol reservoir and the distillation residue is pumped into the distillation container. The crude cumylphenol from the stock of cumylphenol is either removed from the product or transferred to a crystallizer, whereupon solvent is introduced from the solvent reservoir and recrystallization is carried out, followed by separation of the cumene phenol on the filter and transferring the acofinal product to the cumylphenol reservoir. The filtrate is treated in a solvent regenerator to a recirculating solvent which is pumped into a solvent reservoir and combustible waste which is disposed of into a combustible waste reservoir. requirements based on analyzes of the content of the desired products in drop-offs.

The main effect of the invention is that it allows a higher value of the raw material used predominantly for energy recovery. From the point of view of the main product obtained, it is possible to obtain a mixture of semi-solid cumylphenol isomers with a content of 85% by weight, a p-cumylphenol with a purity of at least 99% by weight. The first product can be used for less demanding purposes, such as the preparation of phenol-formaldehyde resins of the base component, the preparation of synthetic chips, CSSR AO210 966, and in those cases where the impurities, predominantly saturated and unsaturated alkylaromatic hydrocarbons , do not interfere with further processing or can be separated from the resulting product. The second product is intended for more sophisticated syntheses, such as some types of antioxidants, possibly disinfectants, as well as pure synthetic powders (J. syntheses). which could not be disposed of by burning, preferably as an additive to oil for pre-energetic purposes, which has also been done by post-dispatch, in addition to the unpleasant co-properties of the raw material as well as the products, which has so far caused the inconvenience of their energy It makes it possible to recover from the raw material over 90% by weight of the present positional isomers of cumylphenol or p-cumylphenol in the reuse, the yield of the desired products can be increased mainly by recycling the inter-fractions and the solvent used, while simple the technology of the process is not complicated, and the solvent used can be n in alkane, aroyl MAT Cyclanes, alkylaromatics alkylcyklán, chemically individual Animal drawn mixture thereof, also všaktechnická fraction, which is decided by diametral These aspects, availability and economy. By not neutralizing the sulfuric acid, the coated alkyl or aryl sulfuric acids, the corrosivity of the materials to be treated is reduced to a minimum, and the undesired side reactions are suppressed, and the thermal decomposition of the treated distillation residue is also suppressed to a certain temperature. The neutralizing agent is preferably used in an excess of, for example, 20 mol%, with particular needs being selected within the scope of the claims.

The fraction obtained by rectification containing mainly phenol, acetophenone, alpha-methylstyrene and dimethylphenylcarbinol need to be returned to the separation process prior to processing the distillation residue, where it is separated into individual components and further processed. Excess or withdrawn fractions, coating residues, can be used to dilute the residue from the vacuum distillation for combustion. Requirements for rectification. not large, a column typically having a plurality of trays up to a maximum of 5 is sufficient, the reflux ratio may be close to 1. The symptom of the end of vacuum distillation is the development of fumes, the dyeing of the distillate, and the score dependent at a temperature of about 220 to 240 ° C, such as the distillation pressure used, which is preferably maintained at 0.1 kPa, while the use of a different pressure is not excluded. It is important to note that, in these cases, more precisely, the end pressure of the non-condensed gases and the vapors measured as a rule after freezing and before the vacuum aggregate of the vacuum aggregate used. It is preferable to use an efficient droplet separating device, preferably one which is capable of preventing the distillation of the distilled substance into the condenser. It is advantageous to keep the substances at a temperature such that they do not crystallize, which is also true of the vacuum distillation cooler. -tilácie. It is also possible to increase the purity of the products by repeating operations such as distillation, coating recrystallization. An example of the device according to the invention is shown in Fig. 1 in the form of a circuit diagram of the individual apparatuses.

The device for processing the phenol residue by cumene means consists of a raw material container 1 connected to the wheel 2, into which the neutralizing agent reservoir 3, connected to the reservoir reservoir 4 and the vacuum distillation, is connected to the reservoir 6 of the distillation reservoir 7 followed by a reservoir 8 of crude cumylphenol which is connected to the crystallizer 9, the filter 10a by the accumulator 11, the filter 10 being connected to the solvent regenerator 12 connected to the combustible reservoir 14 and the reservoir 13 connected to the crystallizer 9. Example

A sample of cumene phenol residues weighing 2745.80 g of the composition of Table 1 in a third column containing 1.21% by weight of sulfuric acid was neutralized by the addition of 37.00 g of sodium carbonate.

The thus prepared sample was rectified on a Vigreaux column of 100 cm in length, 3 cm in diameter at a pressure of 1.3 kPa and reflux ratio of 5. 210 g of distillate as described in Table 1 in the fourth column were obtained. The reboiler residue was subjected to a vacuum distillation of 0.1 kPa and the three fractions described in Table 1, fifth, sixth and seventh columns were obtained; the remainder shown in the eighth splice-linking Fraction! in the sixth and seventh and their recrystallization from benzene, 1310 g of p-cumylphenol with a purity of 99% by weight were obtained, representing 87% by weight of p-cumylphenol present in the feed.

The analyzes were carried out by the method. gas chromatography on a Hew-lett-Packard 5830 A apparatus with a flame ionization detector, on all-glass columns filled with 5% Carbowax 20 M on Chromium M AW DME with a grain size of 0.1 to 0.125 mm, column length 60 cm, diameter ko -lon 0.3 cm. Temperature program: working temperature 100 to 200 ° C; temperature gradient 10 ° Gmin -1. The carrier gas, nitrogen flow rate was 28 cm 3 min -1. 239572

The invention can be used to process residues from the production of phenol by cumene, especially to obtain technical cumylphenol with a content of isomers of cymylphenol of at least 85% by weight, coated with 99% by weight of p-cumylphenol.

Table 1

Balance distillation of phenol residue from cumene by batch

Phenol

Acetophenone α-methyl-styreneDimethyl-isopropyl-indene + + trimethyl-iso-propylindene

Dimethylphenylcarboline 1,1,3-triethyl-3-phenylenedienoxy 2,4-diphenyl-4-methyl-2-pentene 2,4-diphenyl-4- methyl-1-pentene o-cumylphenol m-cumylphenol p-cumylphenol

Unidentified substances

Non-distillable residue S 2 [° / o wt] g] [% wt] Hg] [° / o wt] 'f Kl [° / o wt] [g]' [° / o weight [g] [% w / w] [g] [% w / w] i [g] [% w / w] [g] [% w / w] - [g] [° / w wt. [g] [% w / w] [g] [% w / w] [g] [% w / w] [g] [% wt. ][G]

+ at 0.1 kPa and 210 ° C ++ at 0.1 kPa and 190 ° C 1.42 38.984.11 112.82 0.80 21.96 0.40 10.98 0.40 10.98 0.40 10 , 98 10.90 299.21 3.45 94.70 0.25 6.86 5.40 148.23 54.80 1504.26 1.67 45.84 16.00 + 440.00 + 100.00 2745 , 80 I. II. III. IV. Fraction Fraction Fraction Fraction. Temperature Temperature Temperature Temperature Remainder Sum of the head of the head of the head 60 to 85 35 to 130 130 to 163 163 to 190 degrees C degrees G degrees C degrees C Temperature Temperature Temperature Boiler reboiler reboiler temperature 90 to 110 70 to 160 160 to 175 185 to 220 degrees C degrees C degrees C degrees C Pressure Pressure Pressure 1.3 kPa 0.1 kPa 0.1 kPa 0.1 kPa 4 5 6 7 8 9 13.30 0.50 0 2.00 27.93 2.25 0 8.80 38.98 53.75 0 0 0.02 112.87 0 0 0.09 112.91 10.20 0.04 0 0 21.42 0.18 0 0 21.60. 5.30 0 0 0 11.13 0 0 0 11.13 5.10 0.40 0 0.01 10.71 1.80 0 0.04 12.55 1.50 1.70 0 0 3.15 7 , 65 0 0 10.80 2.60 41.20 8.00 2.70 5.46 185.40 96.40 11.88 299.14 0.40 11.00 3.50 0.50 0.84 49 , 50 42.18 2.20 94.72 0 0.70 0 0.80 0 3.15 0 3.52 6.67 1.20 18.40 4.50 2.00 2.52 82.80 54, 22 8.80 148.34 0 24.20 84.00 87.00 0 108.90 1012.9 382.80 1503.90 6.65 1.86 0 4.97 13.97 8.37 0 21.87 44.21 0 0 0 0 100.00+ + 0 0 0 0 440.00+ + 440.00 100.00 100.00 100.00 100.00 210.00 450.00 1205.0 440.00 2744, 95

Claims (2)

IQ P R E D Μ E T 1. A process for treating a phenol residue from cumene by characterized in that it is not alkalinized in lion-containing acid with alkali hydroxide, bicarbonate, carbonate or phenolate; distillation by distillation separates the fraction boiling to 85 DEG C. at 1.3 kPa, followed by distillation. under reduced pressure, a fraction up to 190 ° C is separated at 0.1 kPa with a minimum content of 85% by weight of the isomers of cumylphenol, wherein the distillation residue does not exceed 20% by weight of the processing feed; from carbon monoxide, the carbon numbers in the molecule are equal to 5 to 7 to a p-cumylphenol concentration of at least 99% by weight. THE INVENTION 2. The apparatus according to claim 1, characterized in that it comprises a raw material reservoir (1) connected by a skeleton (2) to which a reservoir (3) of a neutralizing agent is connected, connected to a reservoir (4). ) the forward portions and vacuum distillation (5) connected to the intermediate container (6) and the reservoir (7) of the distillation residue, further with the raw cumylphenol reservoir (8) connected to the crystallizer (9) , a filter (10) and a reservoir (11) of cumylphenol, wherein the filter (10) is connected to a solvent regenerator (12) associated with a combustible reservoir (14) and a solvent reservoir (13) associated with the crystallizer. (9) 1 sheet of drawings