SU1201294A1 - Method of reclamating waste of polymeric materials - Google Patents

Abstract

1, METHOD OF UTILIZATION OF POLYMER MATERIAL WASTE, including thermal decomposition at 400980 s with the formation of vapor-gas products and solid carbon residue, cooling them, separation into liquid and vapor phases and solid carbon residue, grinding the carbon residue, granulating it with a wetting liquid drying the granules, characterized in that, in order to reduce harmful emissions into the environment, to increase the yield of carbon granules and their bulk density, the liquid phase is separated by settling on a light hydrocarbons and mixture of heavy hydrocarbons and water, said mixture is used as wetting liquid for the granulation. 2, the method according to claim 1, wherein the carbon granules are dried at 300-450 s.

Description

The invention relates to the thermal processing of solid polymeric wastes and can be applied in petrochemical, chemical and other industrial fields for the regeneration of liquid hydrocarbons, usually used as fuel or raw materials for various processes, as well as solid-phase dispersed carbon filler from polymeric materials and their waste, containing in its composition as hydrocarbon and non-hydrocarbon components that are capable of thermal decomposition to form a liquid emulsified carbon water native and non-hydrocarbon fraction. The purpose of the invention is to reduce harmful emissions into the environment, increasing the yield of carbon granules and their bulk density. The essence of the processes proceeding in the proposed method is reduced to the following. As a result of the thermal decomposition of polymeric wastes containing chloroprene and nitrile rubbers, both light liquid and gaseous hydrocarbon products (fuel, oil), and heavy water-emulsified hydrocarbon, nitrogen sulphate and oxygen compounds and soot resin in suspension are formed. The mixture of these emulsified compounds and water is separated by settling from hydrocarbons that are lighter in specific gravity. The solid carbon residue resulting from the thermal decomposition of waste from the stage of its cooling, grinding and separation is a dispersion of soot-like material. When granulating this product using a heavy mixture of hydrocarbons, water, and a tar resin suspension as a wetting liquid, the active surface products of carbon particles are adsorbed. At the stage of drying carbon granules at 300-450 ° C, these products carbonize into the solid phase, which leads to an increase in the mass and density of the carbon granules. The drawing shows an installation for carrying out the proposed method. The device contains a reactor 1 for thermally decomposing (pyrolysis) polymer waste, a furnace 2 for burning fuel, a cyclone 3 for precipitating soot cooler-condenser 4, a settling tank 5 for liquid products, a screw conveyor 6, a mechanical mill 7, a sieve 8 with a magnetic lattice, a mixer granulator tor 9, dryer 10, precipitation chamber 11, drum cooler 12, furnace 13 of the dryer. The arrows indicate the flow: P polymer waste; G - hydrocarbon pyrolysis gases; P - water vapor; C is ground carbon material; V is a mixture of emulsified heavy hydrocarbons, dispersed carbon and water; O — waste flue gases and water vapor; B - air for burning fuel; M - hydrocarbon fraction (liquid fuel); K - coke and metal residues. Example 1. 100 kg of worn-out cut pieces containing 80% by weight rubber from synthetic rubbers and 20% nylon and viscose cords are fed into the reactor as raw materials. Raw materials in the reactor I is heated. At the beginning, natural gas (15 kg) is burned in the furnace 2, and the flue gases are fed into the reactor at the same time. Dp of temperature control and improvement of heat transfer and stripping of hydrocarbons are fed with 30 kg of water vapor. After 2 hours, the feedstock in the reactor is heated to 450,500 s, and it decomposes into vapor-gas products and solid carbon residue. The vapor-gas products are pumped through a cyclone 3, where they are cleaned of soot, and a cooler 4, where they are cooled to 50 ° C, while the liquid phase is condensed from the vapor-gas products, which flows by gravity into a sump 5. Here, the liquid phase is settled for 4 hours at in this, it is divided due to the difference in specific gravity into two fractions. The first hydrocarbon fraction (lighter) with a specific gravity of less than one is collected in the middle part of the sump 5. The characteristics of this fraction are presented in Table 1. The second (heavy) fraction, which is a mixture of heavy hydrocarbon compounds, water and dispersed carbon, is deposited on the bottom of the sump 5. The composition of this mixture is presented in table. 2. At the end of the separation, the light fraction is pumped out from the average hour of the settling tank 5 in the amount of 44 kg and used as boiler fuel. The heavy mixture of hydrocarbons and water is pumped out from the lower point of the settler 5 in the amount of 35 kg and fed to the mixer-granulator 9, where it is mixed with the crushed carbon residue (soot). The uncondensed gases from the upper point of the settler 5 are pumped out by the blower for burning to the furnace 2 for heating the raw material and partly in the furnace 13 for heating sushki. At the same time, the consumption of natural gas is reduced or completely turned off. The solid residue is discharged from the lower zone of the reactor 1 in an amount of 33 kg and sent to a mechanical mill 7, where it is ground to a pulverized (soot-like) state, then sieved through a sieve S and a magnetic separator. The crushed carbon residue is transferred to the mixer granulator 9, and a mixture of hydrocarbons, dispersed carbon and water in an amount of 35 kg is fed in here, mixed, and formed. the raw granules that are fed by the screw dispenser into the dryer 10. The latter is heated by flue gases supplied from the furnace 13. The granules are dried at 400 C. The water vapor introduced into the drying process and the flue gases and dry granules are sent to the settling chamber 11 where the dry granules settle down and the exhaust gases are vented to the atmosphere. Dry granules in the amount of 35.5 kg after cooling, in the drum 12 are poured as a finished product, intended for use as a filler for rubber and plastics. At the end of the pyrolysis, the products obtained are analyzed and their yield is determined. The yield of carbon granules, their characteristics and the composition of the exhaust gases are presented in Table. 3 and 4 Note 2. Conducted experiments on the pyrolysis of solid polymer waste as in Example 1, but waste rubber rubber products containing chloroprene nitrile rubbish and rubber nylon and viscose cord were taken from the raw material. In additional experiments, the drying temperature of the carbon granules was varied in in; Terval 120–500 ° C. Also conducted 944 control experiments on the method of proto-type. The results of the experiments are presented in table. 1, 2 and 3. The granulated carbon product (filler) obtained by the proposed method was analyzed by standard methods (GOST 7885-77) and tested as a filler in a standard rubber mixture of the following composition, wt.: SKMS Rubber - ZOARK 100.0 Altax3, 0 Sulfur2.0 Stearin1,5 Zinc Oxide5.0 Filler50, O The mixture was vulcanized for 80 minutes and the obtained vulcanizate was tested by standard methods (GOST 270-75) according to the basic strength characteristics. Serial carbon black was used as a control product (base object) arch. PGM-ZZN, which in its main indicators is similar to carbon filler, obtained by the proposed method. The test results are presented in Table. 4. According to the obtained data, it is clear that thermal decomposition of polymeric wastes according to the proposed method achieves an increased yield of carbon granulated filler, 34.6-35.5 kg (experiments 3, 4 and 5 in Table 3) versus 33.0 kg according to the method the prototype (experiments 1 in table. 3). In addition, the granulated product has a higher national density, 388–390 kg / m versus 360 kg / m (the same experiments as tal. H). The waste of the drying process contains significantly less environmental impurities, namely sulfur dioxide. 5.8-6.4 (versus 78.0), hydrogen chloride 6.5-6.8 (versus 35.0) (the same experiments in Table 3). These results have been achieved by using a mixture of emulsified heavy hydrocarbons and water contaminated with reaction products (Table 2) and a waste of the process of thermal decomposition of solid polymer residues. The use of these wastes for the purpose of granulation prevents their discharge into natural water bodies. The filling of carbon granules in the proposed method is provided by the higher temperature of their processing at the drying stage, 300-450s versus 120s (Table 3). The liquid hydrocarbon fractions obtained from polymeric wastes (Table 1) are similar in properties to the corresponding oil fractions used as fuel, and the granular carbon filler is equivalent to the reinforcing properties in rubber to the commercial filler — soot of the PGM-3ZN brand (Table 4) . 9A “The proposed method of thermal processing of polymeric wastes allows for 1y to reduce environmental pollution with waste gases from the process of thermal processing of waste; prevent discharge of contaminated liquid effluents into natural water bodies; to increase the yield and bulk density of the granulated carbon product, as well as to expand the range of binder materials used to granulate dispersed carbon materials.

The composition of the liquid

Worn tires made of synthetic rubbers (styrene butadiene, butyl rubber, isoprene, etc.), textile and metal cord

Rubber waste from chloroprene and nitrile rubbers

Waste kapronog and viscose rubberized cord

50 0.963 165 218 310 430

50 0,980 180 230 340 450

50 0.976 190 235 328 440 polymeric wastes, conditions of their pyrolysis, conditions of phase separation and characteristics of the obtained light hydrocarbon fractions (liquid fuel T a b i c a 1

Worn pockets of synthetic rubbers: butadiene styrene, isoprene butyl rubber, etc., J textile and metal cord

2 Rubber chloroprene waste

and nitrile rubbers

3Washes of the kapron and viscose rubberized cord

The composition of the feedstock (polymer waste) and the characteristics of the resulting heavy mixture of hydrocarbon compounds and water

Worn pokryshki

Rubber waste from chloroprene and nitrile rubbers

Waste rubberized kapron and viscose cord

Continuation of table 1

2.7

S, 5 0,8

86.0

10.2 0.6

3.0

86.2

10.0 0.5

87.0

2.5

Table 2

430

13600

50

410

8100

50

. 180

50

15200

120129D

The conditions for drying the granules, their yield, density and composition of the exhaust gases of the drying process

Worn tires on prototype method

Worn tires by

Also

Rubber chloroprene rubber

10 Continued table. 2

T a b. l and c a 3

120

33.0

360

Worn pokryshki

78.0 prototype methods

Worn pokryshki on the proposed method

3 4 5

Same II

- -

Rubber waste from chloroprene and nitrile rubbers

Waste rubber nylon and viscose cord

Physico-chemical properties of carbon granules and strength properties of a filled vulcanizate of standard composition

Continuation of table 3

56.0 13.0 33.0 54.0

35.0

12.5 15.0 16.0 30.0 54.0

18.5 15.0 31.0: 54.0

Spreadsheets

Carbon granules according to the proposed method 12.0

Series carbon black PGM-ZZN 0.4

Continuation of table 4

154

31 30

660 590 152

Claims (2)

.one. METHOD FOR DISPOSAL OF POLYMERIC MATERIAL WASTE, including their thermal decomposition at 400980 ° C with the formation of vapor-gas products and a solid carbon residue, their cooling, liquid separation the vapor and vapor phases and the solid carbon residue, grinding the carbon residue, granulating it with a wetting liquid, drying the granules, characterized in that, in order to reduce harmful emissions into the environment, * increase the yield of carbon granules and their bulk density, the liquid phase is separated by settling on light hydrocarbons and a mixture of heavy hydrocarbons and water, this mixture is used as a wetting liquid for granulation. 2. The method according to p. ^ Characterized in that the carbon granules are dried at 300-450 ° C.