CS259263B1 - Process for processing bituminous compounds from the production of cyclohexanone - Google Patents

Abstract

Processing of resinous compounds discharged in alkaline wastewater from the cyclohexane oxidation process in the production of cyclohexanone by cyclohexane oxidation and accumulating during the storage of alkaline wastewater in a manner that allows their disposal by the known process - incineration. Resinous compounds are dissolved in a mixture of organic waste products from the production of cyclohexanone by cyclohexane oxidation, in an amount of 0.2 to 10 parts by weight per 1 part by weight of resinous products, in a defined ratio, at a temperature of 30 to 130 °C for a period of 0.5 to 12 hours.

Description

259263

The present invention provides a process for treating bituminous compounds removed in alkaline wastes from the cyclohexane oxidation process in the production of cyclohexanone which accumulate when storing alkaline wastewater.

The process of oxidizing cyclohexane in liquid phase with oxygen-containing gases is usually carried out at temperatures of 130 to 180 ° C under a pressure of 0.8 to 2 MPa. The desired process products are cyclohexanone and cyclohexanol. Higher yields of these products are achieved by conducting the oxidation process at a low end! cyclohexane. The crude oxidation reagent usually contains 85 to 95% by weight of cyclohexane and the remainder consists of cyclohexanol, cyclohexanone, as well as undesirable byproducts such as alcohols, aldehydes, esters, acids and the like, but also compounds of a bituminous nature. The bituminous compounds formed directly in the oxidation process are substantially directly incorporated in the oxidation reactor, or the cyclohexane oxidation node, together with the oxidation mixture, is incorporated into other parts of the machinery, some of which are usually deposited on heat exchange surfaces, thereby impairing heat transfer. but also on trays of rectification columns and the like.

The source of bituminous products xn may also be the process of acidic but especially alkaline hydrolysis of the esters, coupled with the distillation of cyclohexanone and cyclohexanol by aqueous water, from mono- and dicarboxylic acids, sodium salts of monocarboxylic acids, their derivatives, as well as other undesirable side compounds, including bituminous. From the above processes, these compounds are removed in the form of distillation products, waste products destined for disposal (most often by combustion), possibly for further use. During the separation of cyclohexanone acyclohexanol from the oxidation mixture, the bituminous products are concentrated mainly into the so-called alkaline effluents discharged by the alkaline hydrolysis process. Following their subsequent storage prior to disposal, these products precipitate and accumulate on the surface.

The most commonly used method of disposal of alkaline waste by incineration in a multilayer burner together with the fuel - organic waste and ground gas while soda production - is not due to their specific properties (viscosity, strong tack and other bitter compounds) processable.

The experiments carried out have shown that it is not possible to convert a mixture of bituminous compounds into a processable form by known methods, e.g. The commonly used method of dissolving and disrupting the vitreous compounds from the oxidation reactor and the other triple-technology plant also did not know any effect in the Polish patent no. Although bituminous compounds dissolve in some organic solvents, e.g. toluene, this form of disposal is economically unacceptably expensive.

In these circumstances, the disposal of these waste products has been directed to a particularly demanding mechanical cleaning of the containers, especially for physical work, since the technique is virtually impossible due to the nature of the waste. Waste handling is very demanding, and its disposal with solid waste in landfills has a very negative impact on the environment. However, it has surprisingly been found in the course of the experiments that the bituminous compounds can be converted into a processable form by further waste products from the cyclohexanone production by oxidation of cyclohexane according to the invention.

SUMMARY OF THE INVENTION The present invention relates to a process for the treatment of nutrient compounds accumulating the depositing of alkaline effluents by a process for the oxidation of cyclohexane in the production of cyclohexanone. In accordance with the present invention, these bituminous compounds are converted by the organic waste products into the process for 0.5 to 12 hours, with a temperature of 30 DEG to 130 DEG C., with continuous homogenization into a processable form by a known process.

Mixture of organic wastes in the mutual mass. a ratio of 1: 0 to 0.4: 0 to 0.5: distillation residues from the process of acid hydrolysis of esters with simultaneous distillation of cyclohexanol from cyclohexanone and other compounds with water vapor pressure of 140 to 2 ° 0 ° C and a pressure of 0.5 to 1.4 MPa, adjusted to a water content of 3 to 20% by weight, distillation residues removed from the process of cyclohexanone-cyclohexanol mixture recrystallization at a temperature of 130 to 170 ° C and a pressure of 4 to 50 kPa and a front alcohol fraction removed as distillate from the process the rectification of the cyclohexanone-cyclohexanol mixture at atmospheric pressure at 120 to 150 ° C, wherein 0.2 to 10 parts by weight of said mixture is used to dissolve 1 part by weight of the bituminous compounds. An advantage of the process of the present invention is the elimination of the strenuous physical work at the disposal of these wastes, the protection and improvement of the environment, as well as the increased operational security and safety of storage of alkali waste water from cyclohexanone production by oxidation of cyclohexane. Example 1

55,000 kg of organic waste products are introduced into a container equipped with a circulation pump, of which 44,600 kilograms of distillation residues from process hydrolysis in the production of cyclohexanone containing 8.3 wt. water, 5,950 kg of the fifth alcohol fraction from the rectification

Claims (1)

259263 5 6 refining of cyclohexanone-cyclohexanol mixture and 4,450 kg of distillation residue from the same refining. The weight ratio of the components in the mixture used is 1: 0.13: 0.09. 30,000 kg of bituminous compounds are pumped through the gear pump and the circulation pump is homogenized over a period of 5 hours at 70 ° C to give a mixture which is dispensed as an organic waste with additional natural gas. and thickened alkaline effluents to a dry weight of 52% by weight. into a multilayer burner for disposal of alkali wastewater from cyclohexanone production. The combustion takes place at a temperature of 960 ° C, whereby the resulting aqueous sodium bicarbonate solution is treated with crystalline soda or used to neutralize the acid wastewater from the cyclohexanone production prior to its biological purification. Example 2 55,000 kg of organic waste products are introduced into a container equipped with a circulating pump consisting of a distillation residue from the acid hydrolysis process in the production of cyclohexanone containing 8.3% by weight. water. The weight ratio of the components in the mixture used is 1: 0: 0. To this amount, 30,000 kg of resinous compounds are pumped through the gear pump and, after homogenization with the circulating pump, for 8 hours, a mixture is obtained at 70 ° C. which is treated analogously to Example 1. EXAMPLE 3 49,500 kg of distillation residues from the acid hydrolysis process with a content of 7.8% by weight are introduced into a container equipped with a circulating pump. water and 5,500 kg of the pre-alcohol fraction from the rectification refining of the cyclohexanone-cyclohexanol mixture. The weight ratio of the components in the mixture used is 1: 0.11: 0. The homogenization with 30% is carried out under analogous quantitative and qualitative conditions as in Example 1. 000 kilograms of bituminous compounds and subsequent disposal. EXAMPLE 4 49,500 kg of distillation residues from the acid hydrolysis process with a content of 7.8% by weight are introduced into a container equipped with a circulating pump. water and 5,500 kg of distillation residue from the rectification refining of the cyclohexanone-cyclohexanol mixture. The weight ratio of the components in the mixture used is 1: 0: 0.11. 30,000 kg of the resinous compounds are pumped into the above-mentioned amount by a gas pump and, after homogenization for 4 hours at 70 DEG C., a mixture is obtained which is destroyed by the procedure of Example 1. SUBSTITUTE A method for treating bituminous compounds decomposed in alkaline effluents from a process for the oxidation of cyclohexane to produce water, characterized by the fact that, at constant temperature of 30 to 12 hours, the bituminous compounds are kept at 30 ° C. from about 130 DEG C. to about 130 DEG C., with the organic waste products of this production, a mixture of distillation residues from the acid hydrolysis process of esters taking place simultaneously with the distillation of cyclohexanol, cyclohexanone and other water vapor-flowing compounds at 140 DEG -200 DEG C. and a pressure of 0.5 to 1.4 MPa, adjusted to a water content of 3 to 20% by weight, of distillation residues removed from the process of refining the cyclohexanone cyclohexanol mixture at a temperature of 130 to 170 ° C and pressures 4 to 50 kPa and the front alcohol fraction removed as distillate from the process of refining the cyclohexanone-cyclohexanol mixture under atmospheric pressure a lacquer varnish of 120 to 150 ° C, with a weight ratio of 1: 0 to 0.4: 0 to 0.5 to one another, with 1 to 10 parts by weight of a mixture of organic waste being added per 1 part by weight of bituminous products; products.