CS259263B1 - Method of bituminous compounds treatment from cyclohexanone production - Google Patents

Abstract

Treatment of bituminous compounds removed in alkaline waste water from the process oxidation of cyclohexane in the production of cyclohexanone by oxidizing cyclohexane and cumulating to store alkaline waste waters in a way that will enable them disposal by a known process - by combustion. Bituminous compounds are dissolved in the mixture production of organic waste products cyclohexanone by oxidation of cyclohexane, in an amount of 0.2 to 10 parts by weight per 1 part by weight of bituminous products in a defined ratio, at a temperature of 30 to 130 ° C for 0.5 to 12 hours.

Description

The invention provides a process for the treatment of bituminous compounds discharged in alkaline waste water from the cyclohexane oxidation process to produce cyclohexanone, which accumulate in the storage of alkaline waste water.

The process of oxidizing cyclohexane in the liquid phase with oxygen-containing gases is usually carried out at temperatures of 130 to 180 ^° C at a pressure of 0.8 to 2 MPa. Desired products of the process are cyclohexanone and cyclohexanol. Higher yields of these products are achieved by conducting the oxidation process at low conversion! cyclohexane. The crude oxidation product usually contains 85 to 95 wt. cyclohexane and the remainder being cyclohexanol, cyclohexanone, as well as unwanted by-products such as alcohols, aldehydes, esters, acids and the like, but also compounds of the bituminous nature.

The bituminous compounds formed directly in the oxidation process are largely deposited directly in the oxidation reactor, or, together with the oxidation mixture, are fed into other parts of the machinery of the cyclohexane oxidation node, where they are most often deposited on heat exchange surfaces. on the levels of rectification columns and the like.

The source of the bituminous products xn may also be a process of acidic but mainly alkaline ester hydrolysis associated with the steam distillation of cyclohexanone and cyclohexanol from mono- and dicarboxylic acids, sodium monocarboxylic acids, derivatives thereof, as well as other undesirable by-products, including bituminous. From these processes, these compounds are discharged in the form of distillation residues, and the products to be disposed of (most often by incineration) or for further recovery are discarded.

During the separation of cyclohexanone and cyclohexanol from the oxidation mixture, the bituminous products are concentrated to a so-called " alkaline waste water removed from the alkaline hydrolysis process. When stored for storage prior to disposal, these products precipitate and accumulate on the surface.

Due to their specific properties (viscosity, strong tackiness and other bituminous compounds), the most commonly used method of disposal of alkaline waste conduits, by burning in a multi-layer burner together with auxiliary fuel - organic waste and natural gas while producing soda, is not workable.

The experiments carried out have shown that, by known methods, the mixture of bituminous compounds can be converted into a processable form, e.g. on a multi-layer burner cannot. A commonly used process for dissolving and disrupting bituminous compounds from an oxidation reactor and other three-process equipment according to Polish patent no. 79 347 also produced no effect.

While the bituminous compounds dissolve in some organic solvents, e.g. toluene, but this form of disposal is economically unacceptable.

In these circumstances, the disposal of these waste products was directed to a very demanding mechanical cleaning of the cartridges, especially to physical work, since the deployment of the technique is virtually impossible due to the nature of the waste. Waste handling is very demanding and its exports of solid waste to landfills have a very negative impact on the environment.

However, it has surprisingly been found during the experiments that the bituminous compounds can be converted into a workable form by treatment with other waste products from cyclohexanone production by oxidation of cyclohexane according to the process of the invention.

SUMMARY OF THE INVENTION The present invention provides a process for the treatment of bituminous compounds accumulating in the storage of alkaline waste water from the cyclohexane oxidation process to produce cyclohexanone. According to the process according to the invention, these bituminous compounds are converted into a workable form by a known process by treatment with organic waste products from this production for 0.5-12 hours, at a temperature of 30-130 [deg.] C., while homogenizing.

Mixture of organic wastes. the ratio of 1: 0 to 0.4: 0 to 0.5 consists of: distillation residues from the acid hydrolysis process of the esters while distilling off cyclohexanol from cyclohexanone and other compounds vapor-volatile at. at a temperature of 140 to 20 ° 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 the rectifying cyclohexanone-cyclohexanol mixture at a temperature of 130 to 170 ° C and a pressure of 4 to 50 kPa and the front alcohol fraction removed as a distillate from the rectification refining process of the cyclohexanone-cyclohexanol mixture at atmospheric pressure at 120-150 ° C, using 0.2-10 parts by weight of said mixture to dissolve 1 part by weight of the bituminous compounds.

The advantage of the process according to the invention is the elimination of strenuous physical work in the disposal of these wastes, protection and improvement of the environment, as well as increasing the operational safety and security in the storage and disposal of alkaline waste water from cyclohexanone production by oxidation of cyclohexane.

Example 1

55,000 kg of organic waste products are placed in a tank equipped with a circulation pump, of which 44,600 kilograms of distillation residues from the acid hydrolysis process in the manufacture of cyclohexanone containing 8.3 wt. water, 5 950 kg of the front alcohol fraction from the rectification refining of the cyclohexanone-cyclohexanol mixture and 4 450 kg of the 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 to the said mass by means of a gear pump and after homogenization by a circulation pump for 5 hours at 70 ° C a mixture is obtained which is dosed as organic waste with additional natural gas and concentrated alkaline waste water to 52% wt. to a multilayer burner of an incineration plant for the disposal of alkaline waste water from cyclohexanone production.

The incineration takes place at a temperature of 960 ° C, the resulting aqueous solution of sodium carbonate and bicarbonate being treated to crystalline soda or used to neutralize the acidic waste water from cyclohexanone production prior to biological treatment.

Example 2

55,000 kg of organic waste products, consisting solely of the distillation residue from the acid hydrolysis process in the production of cyclohexanone, containing 8.3% by weight, are introduced into a container equipped with a circulation pump. water. The weight ratio of the components in the mixture used is 1: 0: 0. To this amount, 30,000 kg of bituminous compounds are pumped through the gear pump and after homogenization by a circulation pump for 8 hours at 70 ° C, a mixture is obtained. Example 1.

Example 3

49,500 kg of distillation residues from the acid hydrolysis process containing 7.8 wt. water and 5 500 kg of the front 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. Under analogous quantitative and qualitative conditions as in Example 1, homogenization with 30,000 kilograms of bituminous compounds and subsequent disposal is carried out.

Example 4

49,500 kg of distillation residues from the acid hydrolysis process containing 7.8 wt. 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. The said amount was pumped with a gear pump of 30 000 kg of resin compound and the homogenization for 4 hours at 70 ^C to give a mixture which was discarded In accordance with one method of Example

Claims (1)

Processing method. of bituminous compounds discharged in alkaline waste water from the cyclohexene oxidation process in the production of waters prior to their combustion characterized in that the bituminous compounds are impregnated with organic waste products for a period of 0.5 to 12 hours at 30 to 130 [deg.] C. from this preparation, by a mixture of the following: distillation residues from the process of acid hydrolysis of esters, carried out by distillation of cyclohexanol, cyclohexanone and other compounds volatile with water vapor at a temperature of 140 to 200 ° C and a pressure of 0,5 to 1,4 MPa, treated YNELEZ for a water content of 3 to 20% by weight, the distillation residues removed from the rectification refining process of the cyclohexanone-cyclohexanol mixture at a temperature of 130 to 170 ° C and a pressure of 4 to 50 kPa and the front alcohol fraction removed as distillate from the at a temperature of from 120 to 150 ° C, in a weight ratio of 1: 0 to 0.4: 0 to 0.5 relative to each other, with 0.2 to 10 parts by weight of a mixture of organic waste products being impregnated per 1 part by weight of bituminous products.