The method of thermal processing of waste plastics based on polyolefins hydrocarbons

 

The invention relates to chemical technology, namely the utilization technology of synthetic polymeric materials, and can be used to produce chemicals and motor fuels from waste plastics. Object of the invention is the development of environmentally sound method of waste plastics on the basis of polyolefin hydrocarbons boiling up to 200oWith hydrocarbon products by the method of thermal decomposition without oxygen. In the method of recycling synthetic polymers, comprising preparing a mixture of recycled polymers and substances initiator of free radicals , heating the mixture without oxygen, followed by separation of the liquid products according to the invention as an initiator of free radicals using lignin taken more than 10-15% of the weight of recycled polymers and the process is carried out to the maximum output fraction boiling hydrocarbons. table 1.

The invention relates to chemical technology, namely the utilization technology of synthetic polymeric materials, and can be used for production of the plastics by thermal decomposition at 250-450oWith the environment waxy hydrocarbon compounds with subsequent disposal of the resulting products of combustion. Some of these products are in liquid state, can be used as a solvent, extracting agent or means for cleaning (SU 511837 And 11.08.1976).

However, in the case of recycling of polyolefin hydrocarbons in this method the output boiling fractions, greatest interest for use as motor fuel components and chemicals that are not high. Other disadvantages of this method are the long duration of the process, the necessity of using auxiliary environment - natural or artificial wax carbon compound that assumes technological scheme of the process stage of its production or separation.

Known methods of recycling synthetic polymer materials in a liquid hydrocarbon mixture using them pyrolysis without oxygen, in which to increase the speed of the process of thermal degradation of plastics and exit boiling hydrocarbon products using additive catalysts. As such substances proposed organic acid is mi these methods are the need to use specially synthesized catalysts, regeneration of which is difficult, and a high yield of gaseous products.

Closest to the present invention is a process for the recycling of synthetic polymeric materials to obtain a wide distillate fractions of hydrocarbon products, which consists in the fact that the mixture of shredded plastics are mixed with the solvent, is heated to a temperature of 325-375oIn the presence of additives is 0.5-10 wt.% substances initiator radicals. The role of solvent perform engine oil or their mixture with the high-boiling products of the process. As the initiators of the radicals proposed to use the PVC skin or polyurethane (WO 94/20590, 15.09.1994). The presence of radical initiators in the reaction medium allows for relatively low gas to obtain an increased output of boiling products that are intended to be used as raw materials for the production of motor fuels or chemical products, which are usually derived from petroleum.

The disadvantages of this method is the use of auxiliary protection motor oils, as well as education in the process of pyrolysis of plastics corrosive and environmentally hazardous substances, such as chloride is the circumstance necessitates the manufacture of the main equipment of corosion-resistant materials, as well as the technological scheme of the process difficult stages of purification products and gaseous emissions.

The present invention is the development of environmentally sound method of waste plastics on the basis of polyolefin hydrocarbons boiling up to 200o(C) hydrocarbon products.

The choice of raw materials due to the fact that about 80 wt.% from currently produced plastics are polyolefins hydrocarbons, which determines their predominant content in waste generated synthetic polymeric materials.

The problem is solved in that in the proposed method of thermal processing of waste plastics based on polyolefins hydrocarbons, comprising preparing a mixture of recycled polymers and substances initiator of free radicals, and heating the mixture without oxygen, followed by separation of the liquid products according to the invention as an initiator of free radicals using lignin, taken in an amount greater than 10% to 15% by weight of recycled polymers and the process is carried out to the maximum output of boiling hydrocarbons.

It is known that rading and utilization, Elsevier applied science, London, 1990, p.377]. The maximum rate of its decomposition is achieved at lower temperatures than required for effective thermolysis of polyolefins, which allows the use of lignin as initiators of radical depolymerization of polymers of this type.

Lignin is a large waste of wood processing, processing in which industry is still not fully implemented. The use of lignin as initiators of radical degradation of synthetic polymers will partially solve the problem of its utilization.

The invention is illustrated with specific examples.

Before carrying out thermal degradation of polymers in the presence of additives lignin were determined outputs liquid products from the pyrolysis of individual samples of polymers and lignin.

Example 1.

6 g of polyethylene (GOST 16337-70) is placed in a rotating steel autoclave with a volume of 0.25 liter Autoclave is closed, remove the air by washing 10-fold volume of nitrogen, and then heated under continuous stirring until 375-380oC and maintained at this temperature for 60 minutes. Then the autoclave is cooled. The products are divided into gas the AI using chromatograph Agilent 6890 (column Optima I 726839.50, 50 m*0.2 mm OV-1). Other products subjected to extraction by the Griff petroleum ether. From the extract is distilled petroleum ether at atmospheric pressure, then under vacuum, and determine its output, denoted hereinafter as the output fractions boiling above 200oC. the Yield of liquid products is defined as the sum of the outputs of fractions, wikipaedia 200oC and above 200oC.

The yield of liquid products was 98 wt.%, which included in its membership hydrocarbons: With4-C10- 16 wt.%, With11-C28- 84 wt.%.

Example 2.

Analogously to example 1, but carry out thermal decomposition of atactic polypropylene (MRTU 6-05-1105-67). The yield of liquid products was 98 wt.%: With4-C10- 17 wt.%, With11-C28- 83 wt.%.

Example 3.

Analogously to example 1 but conducting thermal degradation of isotactic polypropylene (GOST 26996-86). The yield of liquid products was 98 wt.%: With4-C10- 16 wt.%, With11-C28- 84 wt.%.

Example 4.

Analogously to example 1, but carry out thermal decomposition of hydrolytic lignin. The yield of organic liquid products amounted to 8 wt.%, the content of hydrocarbons: With4-C10- 7 wt.%, The rest 93 wt.%.

Example 5.

6 g of polyethylene and 0.3 g su is the process similar to example 1. The yield of liquid products from polyethylene amounted to 98 wt. %, the content of hydrocarbons: With4-C10- 23 wt.%
With11-C28- 77 wt.%.

Example 6.

Analogously to example 5, but the lignin amount of 10 wt.% by weight of polyethylene. The yield of liquid products from polyethylene amounted to 98 wt.%, the hydrocarbon content:
With4-C10- 34 wt.%
With11-C28- 66 wt.%.

Example 7.

Analogously to example 5, but the amount of lignin 15 wt.% by weight of polyethylene. The yield of liquid products from polyethylene amounted to 97 wt.%, the hydrocarbon content:
With4-C10- 44 wt.%
With11-C28- 56 wt.%.

Example 8.

Analogously to example 5, but the number of added lignin 20 wt.% by weight of polyethylene. The yield of liquid products from polyethylene amounted to 96 wt.%, the hydrocarbon content:
With4-C10- 45 wt.%,
With11-C28- 55 wt.%.

Thus, in the process of thermal degradation of polyethylene without oxygen with increasing amounts of added lignin from 5 to 15 wt.% the output of boiling hydrocarbons from polyethylene increases from 24 to 44 wt.%. With further increase of additives lignin yield of this fraction varies little. Therefore, the use of additives is becoming used atactic polypropylene. The yield of liquid products terupravleniya atactic polypropylene amounted to 97 wt.%, the hydrocarbon content:
With4-C10- 40 wt.%,
With11-C28- 60 wt.%.

Example 10.

Analogously to example 5, but the destruction was subjected to isotactic polypropylene. Lignin was added in the amount of 15% by weight of the polymer. The yield of liquid products terupravleniya isotactic polypropylene amounted to 97 wt.%, the hydrocarbon content:
With4-C10- 41 wt.%
With11-C28- 59 wt.%.

Example 11 (implementation of the method on the prototype).

6 g of polyethylene with a particle size of less than 0.5 mm are mixed with 18 g of motor oil and 0.6 g of the PVC skin. The mixture is placed in a steel rotating autoclave with a volume of 0.25 liter Autoclave is closed, remove the air by washing 10-fold volume of nitrogen, after which it is heated with continuous stirring to a temperature of 375oC and maintained at this temperature for 60 minutes. Then the autoclave is cooled, the products are separated into gaseous and liquid products and determine their output. The yield of liquid products was 27 wt.% based on the polyethylene. The remaining products are removed from the autoclave and subjected to extraction on the filter by the Griff petrocelli amounted to 91 wt.%, based on the weight of the mixture of polyethylene, motor oil, PVC skin. To determine the amount of produced hydrogen chloride was conducted a parallel experiment in which the number loaded into the autoclave polyethylene, motor oil and PVC skin, as well as the conditions of the experiment were similar to the foregoing.

After the end of the experiment, gaseous products were passed through the absorption flask with a fixed amount of 0.1 n solution of sodium hydroxide, the autoclave was opened and washed with a known amount of 0.1 n solution of sodium hydroxide, then washed with distilled water until neutral. The amount of released hydrogen chloride was determined after titrovaniya solutions of sodium hydroxide of 0.1 N. the solution of sulfuric acid. The amount of hydrogen chloride generated as a result of thermal degradation of polyethylene in the presence of PVC skin, amounted to 0.4 g or about 6% by weight of a mixture of polyethylene/PVC skin.

Thus, the proposed method for the processing of plastics based on polyolefins hydrocarbons can be almost fully on 97-98 wt.% turn them into a mixture of liquid hydrocarbons, the concentration of the polymer used, in 1.9-2.0 times higher than in the implementation of the method on the prototype. In addition, the proposed method eliminates the formation of thermolysis plastics corrosive and environmentally hazardous substances.

The results are presented in the table.

The advantage of the proposed method of disposal of polyolefin hydrocarbons is high content in liquid products boiling hydrocarbons, which allows us to consider these fractions as a promising raw material for the production of gasoline and solvents, surfactants, etc. [N. N. Lebedev. "Chemistry and technology of basic organic and petrochemical synthesis", M: "Chemistry", 1988, s.].

An additional advantage of this method is to simplify the process by eliminating from its technological scheme of the stages of cleaning products from environmentally hazardous substances and its implementation without the use of solvent.


Claims

The method of thermal processing of waste plastics based on polyolefins hydrocarbons, comprising preparing a mixture of recycled polymers and substances initiator of free radicals, heated floor is the fact that as initiator of free radicals using lignin, taken in an amount greater than 10% to 15% by weight of recycled polymers and the process is carried out to the maximum output fractions up to 200oWith boiling hydrocarbons.

 

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