The way to obtain a cation exchange resin

 

(57) Abstract:

Usage: the invention relates to a method for producing ion exchangers method of sulfonation, as well as to methods of disposing of liquid wastes of petrochemical industries, in particular oil sludge wastewater treatment process of joint production of acetylene and ethylene high-temperature homogeneous pyrolysis of light petroleum products and waste sulfuric acid containing organic impurities. The ion exchangers can be used in the petrochemical industry, for example for treatment of alkaline wastewater and as a catalyst of acid type. The inventive method of producing cation involves sulfonation of spent sulphuric acid at 120 - 130C oil sludge wastewater joint production of acetylene and ethylene in the mass ratio of sludge and sulfuric acid equal to 1 : (1 - 0,4). 3 table.

The invention relates to methods for cation method of sulfonation, as well as to methods of disposing of liquid wastes of petrochemical processes, in particular reflexly wastewater treatment process, the joint production of acetylene and ethylene high-temperature homogeneous pyrolysis lung nefteproduktov, can be used in the petrochemical industry, in particular for the purification of alkaline wastewater and acid catalyst type.

Along with the main products of the petrochemical plants, produce large quantities of by-products, which up to the present time are not implemented and is often seen as waste. This problem becomes even more acute due to the growth in recent years, industrial capacity and tendency to further increase. The complexity of finding ways of using industrial wastes is that they usually consist of a mixture of hydrocarbons that differ in composition, structure, and reactivity. Separation of a mixture of individual compounds is often a very difficult technical task, requiring considerable technical and economic costs.

Therefore, the most promising is the use of waste without dividing them into separate components.

Known [2] the method of recycling waste sulfuric acid with the aim of obtaining sulfur by mixing with heated up to 300 to 400aboutWith oil tar with the introduction of additional who take it in the ratio 1: 3-30. The disadvantage of this method is the addition of pure sulphur waste and the allocation of free sulphur, which is not a scarce material, and the large consumption of heat for heating and tar almost burned, releasing a large amount of gases.

Known [1] a method of processing cracking-residue, polymesoda straight race and hard resinous oil and getting this ion exchange material in the form of powder or small granules.

The cation exchangers are statistical exchange capacity (SOY) in NaOH 0.1 N. 2-3,3 mgecw/L.

The disadvantage of this technical solution is that the sulfonic cation obtained with low SOY; they are unstable in alkaline medium, to receive them use 100% sulfuric acid. In addition, it does not solve the problem of disposal of sewage sludge and waste sulfuric acid - waste co-production of acetylene and ethylene by pyrolysis of light oil products.

Currently proposed, and this method of recycling waste sulfuric acid [2] , as recycling waste sulfuric acid by mixing with heated up to 300 to 400aboutWith oil tar. The acid contained in the acid waste is restored to sulfur dioxide. The R properties, as well as the necessity to create an appropriate system for cleaning and preparation for processing. A significant disadvantage is the loss of hydrocarbons contained in the oil tar.

The known method [3] thermal decomposition of sulfuric acid containing hydrocarbon impurities, including evaporation and oxidation of hydrocarbon impurities oxygen when contacting acid at 450-600aboutWith molten persulfate potassium and vanadium pentoxide. This produces a gas containing sulfurous and sulfuric anhydride.

The disadvantages of this method are the high cost of heat and results in a mixture of gases requiring further separation and purification, as well as when there is no recycling of sewage sludge.

Thus there are many different methods of disposal of spent sulphuric acid. But all these methods require additional large material and energy costs. Moreover, in these cases it does not solve the problem of disposal of the second production waste oil sludge.

Closest to the invention to the technical essence and the achieved result way of getting to the La increase the capacity of the cation exchanger and simplify the process as a resinous product of oil refining use godrano-residual products of vacuum distillation of fuel oil and sulfonation spend the spent sulfuric acid alkylation process gasoline direct first race at 95-100aboutC for 2-4 h and the mass ratio of tar and acid equal to 1:(5-15), and then when 250-280aboutC for 1-2 h

The disadvantages of this method are:

1) a large excess of sulfuric acid

- mass ratio, 5-15 sulfuric acid to 1 part tar;

2) small output sulfonic cation of 5.0 to 51,0% by weight is taken of the original substance;

3) large amounts of wastewater generated during the washing of the obtained sulfonic cation exchanger from an excess of sulfuric acid;

4) the need for two-stage heating at temperatures above 250aboutC.

The purpose of the invention to increase the yield of sulfonic cation exchanger, simplifying the process and joint utilization of sewage sludge and waste sulfuric acid waste pyrolysis of light petroleum products in the joint receipt of acetylene and ethylene.

This objective is achieved in that the sewage sludge co-production of acetylene and ethylene is subjected to sulfonation spent sulphuric acid at a temperature of 120-130aboutAnd the mass ratio of sludge and acid 1:(1-0,4).

Thus, in the prototype tar contains mainly paraffin hydrocarbons - mA is aboutAnd a large excess of spent sulphuric acid, which complicates the process.

The proposed method in the sewage sludge contains highly reactive aromatic, bicyclic and polycyclic compounds, which allows the sulfonation at a lower temperature 120-130aboutWith, and the best solution of the cation is achieved at a ratio of 1: 0,4.

In the sulphonation of sludge is destructive oxidation of the side alkyl substituents of aromatic and polycyclic fragments with the formation of carboxyl and phenolic groups, which results in further condensation of alphaproducts and obtaining sulfonic cation.

One of the original substances in the sewage sludge has a chemical composition of the hydrocarbon moiety, are presented in table. 1.

The slime is a viscous black substance with a characteristic petroleum odor, non-flammable. For thermal processing requires an additional amount of fuel.

Thermo-deactivation impractical, both from an economic and environmental point of view, because it leads to pollution of the atmosphere by the combustion products.

As the sludge is lsout natural gas.

As the second educt used waste sulfuric acid liquid black that is waste flushing gases of pyrolysis gasoline and having the following composition, wt.%:

Monohydrate sulfuric acid 84-86

Organic compounds 6-8

Water the Rest

The reaction of sulfonation is carried out in cityregion reactor, equipped with a mechanical stirrer, addition funnel, reflux condenser and thermometer.

As the sewage sludge contains a large amount of water, first it is separated from the aqueous phase. In a glass put the sludge and allow to settle for 10 h is divided into two phases: the bottom of the hydrocarbon layer, top - water, slightly contaminated with oil. Water degenerous, and the hydrocarbon layer is used for the reaction of sulfonation.

Charged to the reactor the sludge is pre-separated from the water, and addition funnel - waste sulfuric acid (USC). Heating of the reactor is produced using a glycerin bath. The temperature of the heating support 120-130aboutWith the reactor. Sulfonation at a given temperature should be performed within 6 hours After the end of the process in the reactor, there are two layers: the upper-dcou phase - unreacted USC, water is poured into a beaker and weighed. Plastic sulfones hot unloaded from the reactor in a glass of cold distilled water. As cooling sulfopropyl harden and then place it on a Buechner funnel and washed with several portions of distilled water until acid reaction and dried. After drying, weigh and determine the yield of the mass of the initial reagents. Dried sulfopropyl transferred to N+the form and determine the static exchange capacity (SOY).

P R I m e R 1. The reactor is placed a portion 57 g of sludge, and addition funnel download 57g spent sulphuric acid concentration of 84.5%, at mass ratio of 1:1. Under vigorous stirring dose of sulphuric acid and the reaction mass is heated to 120-130aboutUsing the glycerin bath. Sulfonylamine carried out under stirring and heated for 6 h In the reactor is observed the presence of two phases - liquid mobile phase and a viscous - plastic mass. After the reaction sulfones hot unloaded from the reactor. As it cools down it hardens. The liquid phase is poured into a beaker and weighed. Get 54,0 g (47.4% of the mass of the original substance). Solid fazem dried. After drying, weighed and receive of 57.5 g (50.4 percent by weight of the original products) dry soloproject. Dried sulfopropyl transferred to the H-shape and define SOY cation exchanger. The determination is carried out by the method GOST 20255.1-74. SOY 0.1 N. the NaOH solution is equal to 6.0 mgecw/L.

P R I m m e R 2. According to the above method sulferous is 49.0 g of sludge is 39.2 g of spent sulphuric acid at a mass ratio (1:0.8) is at 120-130aboutC for 6 h Output sulfopropyl to 53.0 g (60,0 wt.%).

SOY 0.1 N. the NaOH solution of 6.4 mg EQ/l

P R I m e R s 3-7. Sulfonation get analogously to example 1.

In table. 2 shows the results obtained by sulfonation of waste sludge with sulfuric acid.

As can be seen from the table. 2, the maximum yield of cation exchanger obtained in example 6, and the optimal are the results of examples 4 and 5, where the resulting product yield 68,4 and 81.5%, respectively, and SOY greatest. When the mass ratio of 1: 0.3 to sharply decreases, SOY, because, apparently, insufficient concentration of sulfuric acid.

To increase the mass ratio of sludge and sulfuric acid to 1:5 leads to a sharp decrease in the output of sulfonic cation exchanger and reduce the SOY to 4.5 mgecw/L. Their, bicyclic and polycyclic compounds, which reduces the number of active sulfo-and the result is reduced SOY.

Comparative data on preparation of sulfonic cation in a variety of ways conducted table. 3.

Thus, the possibility of the application of sewage sludge and spent sulphuric acid in the production of sulfonic cation than is achieved by the utilization of two waste co-production of acetylene and ethylene. The sulfonic cation exchanger is increased to 87.8%, and SOY is at the level of the known method of the prototype and is 6.8-8,04 mgecw/L.

In the production of equivalent annually produce 4000 tons of the sludge processing which will allow you to get 4800 t sulfonic cation exchanger. When calculating the total cost of 1 ton of sulfonic cation exchanger according to the existing methods obtained wholesale price sulfonic cation exchanger of about 100 rubles

The WAY to OBTAIN a CATION exchange resin by sulfonation of the hydrocarbon waste waste sulfuric acid by heating, characterized in that as hydrocarbon waste use of sewage sludge co-production of acetylene and ethylene, and the sulfonation is carried out at 120 - 130oWhen the mass ratio is not the Sabbath.

 

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