RU2451696C2 - Catalyst, method of recycling polymer wastes using said catalyst and method of producing engine fuel and oil - Google Patents

Abstract

FIELD: chemistry. ^ SUBSTANCE: invention relates to methods of recycling polymer wastes and specifically catalytic decomposition of said wastes to obtain engine fuel and/or components thereof. The method involves conversion of polymer wastes, such as polyethylene, polypropylene, polystyrene or any mixtures thereof, into a mixture of hydrocarbons. The process is carried out in the presence of a catalyst at temperature 350-550C and pressure not higher than 1.5 MPa. The catalyst used is a zeolite with aluminosilicate composition with molar ratio SiO2/AlO3 not higher than 450 and a structure of the type: ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or gallosilicate or galloaluminosilicate or ferrosilicate or ferroaluminosilicate or chromosilicate or chromoaluminosilicate with a ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA structure, or aluminophosphate with a structure of the type A1PO-5, A1PO-11, A1PO-31, A1PO-36, A1PO-37, A1PO-40, A1PO-41, with introduction of an element into the structure of any of said types of catalysts, said element being selected from: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium or any mixture thereof. The obtained mixture of hydrocarbons undergoes further processing to obtain high-quality engine fuel and oil. Use of the catalyst reduces reaction temperature and increases output of liquid hydrocarbons to 85 wt %. Change in the amount of the obtained gasoline, diesel and liquefied gas can be controlled in a wide range by altering process conditions. ^ EFFECT: efficient method of recycling polymer wastes. ^ 11 cl, 17 ex, 3 tbl

Description

The invention relates to methods for the disposal of polymer wastes, namely, the catalytic destruction of these wastes to produce motor fuels and / or their components.

There is a steady tendency in the world community to increase the proportion of polymers in municipal solid waste (MSW). According to the US Environmental Protection Agency, more than half of the polymer wastes in the MSW are from products with a useful life of less than one year (packaging, containers, disposable tableware, medical syringes, etc.). About 80% of such products are made from polyethylene and polypropylene. In 2007, the amount of such waste in the USA amounted to 14 million tons. Approximately 10% of the polymer waste is recycled.

The patent and scientific literature describe many ways to recycle polyethylene. Most of these methods offer various methods and devices for fractionation and molding of products from polyethylene waste. The main disadvantage of these methods is the formation of centers of initiation of degradation processes, as a result of which the mechanical properties of products from recycled polyethylene deteriorate by 15-20% compared to the original products [F. La Mantiy European Polymer Journal 1984, v.20, p.993].

A known method of processing secondary polyethylene [RU 2106365, C08J 11/04, C10M 171/04, 03/10/1998]. According to this method, crushed polyethylene is subjected to fractionation in a boiling solvent into soluble sol and insoluble gel fractions with separation and washing of fractionation products, after which low-temperature pyrolysis in vacuum is carried out separately for each fraction. The main disadvantages of this method are the complex multi-stage process technology, the need to use vacuum equipment, the use of toxic solvents.

The closest in its technical essence and the achieved effect is a method of processing polymer waste [US 6172275, C10B 57/00, 01/09/2001]. According to this method, the polymer waste is heated at a temperature of from 270 to 350 ° C, then the resulting gaseous products are sent to a separator heated to a temperature of 300 ° C, after which the heavy hydrocarbons are returned to the reactor, and the light products are sent to the refrigerator to separate hydrogen chloride. Then, the dechlorinated polymer is subjected to pyrolysis at a temperature of 450 ° C or higher and a pressure of up to 1.5 MPa with further isolation of the pyrolysis products. The separator may be filled with a catalyst to improve the quality of the resulting pyrolysis products.

The main disadvantage of this method is the relatively small yield of liquid hydrocarbons (not more than 80 wt.%), As well as the low quality of the resulting products. The use of plastics such as polyvinyl chloride and polyphthalates as raw materials leads to a significant increase in the content of aromatic compounds in the pyrolysis products. Also, the resulting products contain a large amount of olefins, which complicates their use as motor fuels without additional processing. The presence of hydrogen chloride in the products leads to a significant complication of the polymer processing plant. Use a large amount of catalyst in the separator, from 10 to 200 wt.% Relative to the loaded polymer.

The present invention solves the problem of creating an improved method for processing polymer wastes into a mixture of hydrocarbons, from which it is possible to obtain gasoline with an octane rating of at least 83 points by the motor method, diesel fuel with a pour point of no higher than -35 ° C, as well as liquefied gas and engine oil components .

The problem is solved by a catalyst, a method for processing polymer wastes into a mixture of hydrocarbons and methods for producing motor fuels and oils from products from the processing of polymer wastes.

As a catalyst, an aluminosilicate zeolite with a molar ratio of SiO ₂ / Al ₂ O _{3 of} not more than 450 is used, selected from the series: ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or gallosilicate, either galloaluminosilicate, or iron silicate, or iron aluminosilicate, or chromosilicate, or chromal aluminosilicate with a structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or aluminophosphate with a structure like AlPO-5, AlPO-11 , AlPO-31, AlPO-36, AlPO-37, AlPO-40, AlPO-41 with an element selected in the structure of any of the indicated types of catalyst at the stage of synthesis selected from the series: magnesium, zinc, gallium, manganese, iron, cre mnium, cobalt, cadmium or any mixture thereof.

The catalyst may additionally contain a modifying additive of at least one of a number of metals: zinc, gallium, nickel, cobalt, molybdenum, tungsten, rhenium, rare earth elements, platinum group metals in an amount of not more than 10 wt.%.

The modifying additive is introduced into the catalyst by impregnation, or by activated impregnation in an autoclave, or by ion exchange at a temperature of at least 20 ° C, or by application from the gas phase or by mechanical mixing with the starting material, followed by drying and calcination.

A method for producing hydrocarbon raw materials from polymer wastes with a yield of liquid products of at least 85% is proposed, which consists in the catalytic conversion of these wastes into a mixture of hydrocarbons at a temperature of 350-500 ° C and a pressure of not more than 1.5 MPa, the process is carried out in the presence of a porous catalyst selected from the series : either a zeolite of aluminosilicate composition with a molar ratio of SiO ₂ / Al ₂ O _{3 of} not more than 450 and a structure of the type: ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or gallosilicate, or galloaluminosilicate, either iron silicate or iron aluminum silicate or chrome msilicate or chromaluminosilicate with the structure: ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or aluminophosphate with the structure of the type: AlPO-5, AlPO-11, AlPO-31, AlPO-36 , AlPO-37, AlPO-40, AlPO-41 with an element introduced into the structure of any of these types of catalyst at the stage of synthesis, selected from the series: magnesium, zinc, manganese, iron, silicon, cobalt, cadmium, or any mixture thereof with further processing of the obtained hydrocarbon feedstock to gasoline with an octane rating of at least 83 points by the motor method, diesel fuel with a pour point not higher than -35 ° C and liquefied gas or component motor oils.

Polymer waste may contain, for example, polyethylene, polypropylene, polystyrene, polybutylene or any mixtures thereof and similar homopolymers, copolymers of ethylene, propylene, butylene, butadiene, styrene with other copolymerizable hydrocarbon monomers.

The main distinguishing feature of the proposed method is that when disposing of these wastes, a catalyst of the above composition is used, which allows achieving a yield of liquid hydrocarbon products of at least 85 wt.%,

- The second distinguishing feature is that the resulting mixture of hydrocarbons is subjected to further processing to produce high-quality motor fuels.

The resulting hydrocarbon feed from polymer wastes is divided into a nk-370 ° C fraction (nk is the beginning of boiling) and a 370 ° C-kk fraction (kk is the end of boiling).

The nk-370 ° C fraction is converted to gasoline with an octane rating of at least 83 points by the motor method, diesel fuel with a pour point of no higher than -35 ° C, and also to liquefied gas in the presence of a catalyst at a temperature of 250-500 ° C, pressure not more than 2.5 MPa, mass consumption of raw materials not more than 10 h ^-1 . As a catalyst, a zeolite with a molar ratio of SiO ₂ / Al ₂ O _{3 of} not more than 450 is used, selected from the series: ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or gallosilicate, galloaluminosilicate, iron silicate, iron aluminum silicate, chromosilicate, chromium aluminum silicate with the structure: ZSM-5, ZSM-11, ZSM-38, ZSM-48, BETA, or aluminophosphate with the structure of the type AlPO-5, AlPO-11, AlPO-31, AlPO-36, AlPO -37, AlPO-40, AlPO-41 with an element selected from the series: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium, or any mixture thereof, introduced into the structure of any of these types of catalyst at the stage of synthesis.

The catalyst may additionally contain a modifying additive of at least one of a number of metals: zinc, gallium, nickel, cobalt, molybdenum, tungsten, rhenium, rare earth elements, platinum group metals in an amount of not more than 10 wt.%.

The modifying additive is introduced into the catalyst by impregnation, activated impregnation in an autoclave, ion exchange at a temperature of at least 20 ° C, applying from the gas phase or by mechanical mixing with the starting material, followed by drying and calcination.

At the outlet of the reactor, the products are divided in a separator into a mixture of motor fuels and a gas phase, from which a C ₃₊ fraction is isolated, followed by mixing the latter with a stream of hydrocarbon feed at the reactor inlet.

The 370-cc ° C fraction is hydroisomerized to produce a motor oil component in the presence of a porous catalyst at a temperature not exceeding 400 ° C, a pressure of not more than 10 MPa, a mass feed rate of not more than 10 h ^-1 , a molar ratio of hydrogen / hydrocarbons of not more than 50 , aluminophosphate with a structure of the AlPO-31 type with an element selected from the series: magnesium, zinc, silicon, cobalt, manganese, nickel, cadmium, is introduced into the structure at the stage of synthesis.

The catalyst may additionally contain a modifying additive of at least one of the metals of the series: nickel, cobalt, molybdenum, tungsten, rhenium, platinum group metals in an amount of not more than 10 wt.%.

The modifying additive is introduced into the catalyst by impregnation, activated impregnation in an autoclave, ion exchange at a temperature of at least 20 ° C, applying from the gas phase or by mechanical mixing with the starting material, followed by drying and calcination.

The gases formed during the reactions after separation from liquid products can be processed together with the NK-370 ° C fraction.

The technical effect of the invention consists of the following components:

1. The use of the catalyst directly in the pyrolysis reactor leads to a decrease in the reaction temperature, as well as to an increase in the yield of liquid hydrocarbons to 85 wt.%;

2. The change in the amount of gasoline, diesel fuel and liquefied gas produced can be regulated within wide limits by changing the process conditions;

3. As a catalyst for the catalytic destruction of polymers can be used waste catalyst production.

In General, in the claimed invention, the average yield of motor fuels (total liquefied gas, gasoline, diesel fuel and engine oil components) exceeds 98 wt.%.

The method is as follows.

As a starting material for the preparation of a polymer waste disposal catalyst, this method uses one of the materials selected from the series: either zeolite ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA with a molar ratio SiO ₂ / Al ₂ O ₃ not more than 450, or gallosilicate, galloaluminosilicate, or iron silicate, or iron aluminosilicate, or chromosilicate, or chromoaluminosilicate with a structure of ZSM-5, ZSM-11, ZSM-48, BETA, or aluminophosphate with a structure of the type: AlPO -5, AlPO-11, AlPO-31, AlPO-36, AlPO-37, AlPO-40, AlPO-41, with any of these types of catalyst introduced into the structure at the stage of synthesis by elements selected from the range: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium, or any mixture thereof.

Further, the starting material, if necessary, is modified by introducing into its composition compounds of at least one of the metals of the series: zinc, gallium, nickel, cobalt, molybdenum, tungsten, rhenium, rare earth elements, platinum group metals in an amount of not more than 10 wt.%.

Zeolite modification is carried out by the method of impregnation, activated impregnation in an autoclave, deposition from the gas phase, ion exchange, mechanical mixing of the components. After the introduction of the modifying additive, the catalyst is dried and calcined at temperatures up to 600 ° C.

The resulting catalyst is placed in a batch reactor (autoclave) in an amount of not more than 5 wt.% Of the polymer feed, after which the polymer feed is loaded into the autoclave. The process is carried out at a temperature of 350-500 ° C and a pressure of not more than 1.5 MPa. After exiting the autoclave, the products after cooling in the refrigerator are fed to a separator, where the separation into gas and liquid hydrocarbon components takes place. Next, the liquid fraction is divided into fractions nk-370 ° C and 370 ° C-kk, which are subjected to further processing.

As the starting material for the preparation of the catalyst for the conversion of the nk-370 ° C fraction, one of the materials selected from the series is used: either zeolite with the structure: ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA with the molar ratio of SiO ₂ / Al ₂ O _{3 is} not more than 450, or gallosilicate, galloaluminosilicate, iron silicate, ferroaluminosilicate, chromosilicate, chromosilicate with a structure of ZSM-5, ZSM-11, ZSM-38, ZSM-48, BETA, or aluminophosphate with a structure of type AlPO-5, AlPO-11, AlPO-31, AlPO-36, AlPO-37, AlPO-40, AlPO-41 with an element introduced into the structure of any of these types of catalyst at the synthesis stage, selected from the group of magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium, or any mixture thereof.

Further, the starting material, if necessary, is modified by introducing into its composition compounds of at least one of the metals of the series: zinc, gallium, nickel, cobalt, molybdenum, tungsten, rhenium, rare earth elements, platinum group metals in an amount of not more than 10 wt.%.

Modification of the zeolite is carried out by impregnation, or activated impregnation in an autoclave, or applying from the gas phase, or ion exchange, or mechanical mixing of the components. After the introduction of the modifying additive, the catalyst is dried and calcined at temperatures up to 600 ° C.

The resulting catalyst is placed in a flow reactor, purged with either nitrogen or an inert gas, or a mixture thereof at temperatures up to 600 ° C, after which liquid hydrocarbon feed is supplied at mass flow rates up to 10 h ^-1 , temperatures 250-500 ° C, pressure no more 2.5 MPa.

After leaving the reactor, the products are cooled in the refrigerator, and then they are fed to a separator, where the separation into gas and liquid components takes place. Further, liquid products by distillation are separated into gasoline and diesel fuel.

A part of the obtained hydrocarbon gases can be directed to the reactor inlet, where it is mixed with liquid hydrocarbon feed so that the gas mass flow through the reactor is in the range of 0.1-5 h ^-1 .

Aluminophosphate with an AlPO-31 structure with an element introduced at the stage of synthesis selected from the range of magnesium, zinc, silicon, cobalt, manganese, nickel, and cadmium is used as the starting material for the preparation of the hydroisomerization catalyst for the 370 ° C-cc fraction. Further, the catalyst is modified by introducing into its composition compounds of at least one of a series of metals: nickel, cobalt, molybdenum, tungsten, rhenium, platinum group metals in an amount of not more than 10 wt.%.

Modification of the catalyst is carried out by the method of impregnation, or activated impregnation in an autoclave, or deposition from the gas phase, or ion exchange, or mechanical mixing of the components. Next, the resulting catalyst is dried and calcined at temperatures up to 700 ° C.

The resulting catalyst is placed in a flow reactor, purged with either nitrogen or an inert gas, or a mixture thereof at a temperature of up to 600 ° C, after which a 370 ° C-kk fraction is fed at a mass velocity of up to 10 h ^-1 , at a temperature not exceeding 400 ° C, a pressure of not more than 10 MPa and a molar ratio of hydrogen / hydrocarbons of not more than 50.

In the examples below, the present invention is described in detail and its implementation is illustrated.

Examples 1-6 show methods for producing hydrocarbon feed from polymer waste. The yield of the obtained products, as well as the composition of the NK-370 ° C fraction, are shown in Table 1.

Examples 7-12 describe methods for producing motor fuels from the obtained nk-370 ° C fraction. The yields of motor fuels and their quality are shown in table 2.

Examples 13-17 describe methods for producing a motor oil component from a previously obtained fraction of 370 ° C-kk. The results are shown in table 3.

Example 1

A 0.2-0.8 mm fraction is prepared from a BETA type zeolite powder with a molar ratio of SiO ₂ / Al ₂ O ₃ = 30. 5 g of the obtained catalyst and 300 g of low-pressure polyethylene are placed in an autoclave, heated to a temperature of 440 ° C and incubated for 2 hours at a pressure of 0.6 MPa with a constant removal of the resulting products. The products obtained, after cooling in the refrigerator to a temperature of 15 ° C, are separated in the separator into gas and liquid components. Then, the liquid phase is separated by distillation into fractions nk-370 ° С and 370 ° С-кк.

Example 2

A mechanical mixture of 20 g of iron silicate with the structure of ZSM-38 and 2 g of WO _{3 is} prepared. The obtained sample is calcined at 550 ° C for 4 h, after which a 0.2-0.8 mm fraction is prepared. 4 g of the obtained catalyst and 310 g of high-pressure polyethylene are placed in an autoclave, heated to a temperature of 420 ° C and incubated for 3 hours at a pressure of 1.0 MPa with a constant removal of the resulting products. The separation of the obtained products is carried out analogously to example 1.

Example 3

30 g of zeolite powder ZSM-5 with a molar ratio of SiO ₂ / Al ₂ O ₃ = 80 is poured into 1 liter of an aqueous solution containing 15 g of Ga (NO ₃ ) ₃ · 8H ₂ O. The resulting suspension is refluxed for 4 hours, after which the powder is separated on the filter, washed repeatedly with distilled water and dried. The resulting sample is calcined at 550 ° C, after which a 0.2-0.8 mm fraction is prepared. The catalyst contains 0.7 wt.% Gallium.

5 g of the obtained catalyst, 290 g of ultra-high molecular weight polyethylene and 50 g of polystyrene are placed in an autoclave, heated to a temperature of 440 ° C and incubated for 3 hours at atmospheric pressure with a constant removal of the resulting products. The separation of the obtained products is carried out analogously to example 1.

Example 4

20 g of aluminophosphate with an AlPO-5 structure containing 2 wt.% Si introduced into the structure during hydrothermal synthesis are impregnated with a solution of nickel nitrate based on 1.7 wt.% Ni in the final catalyst, then the catalyst is calcined for 2 hours at a temperature of 600 ° C, then a 0.2-0.8 mm fraction is prepared.

8 g of the obtained catalyst and 280 g of ultra-high molecular weight polyethylene are placed in an autoclave, heated to a temperature of 450 ° C and incubated for 2 hours at a pressure of 1.3 MPa with a constant removal of the resulting products. The separation of products is carried out analogously to example 1.

Example 5

A mechanical mixture is prepared from 15 g of iron aluminum silicate and 15 g of chromosilicate.

The obtained sample is calcined at 600 ° C for 4 h, after which a 0.2-0.8 mm fraction is prepared. 4 g of catalyst and 300 g of a mixture of polyethylene of various grades (100 g of low-pressure polyethylene, 100 g of high-pressure polyethylene and 100 g of ultra-high molecular weight polyethylene) are placed in an autoclave, heated to a temperature of 430 ° C and incubated for 3 hours at a pressure of 0.5 MPa s the constant withdrawal of the resulting products. Further, the products are separated analogously to example 1.

Example 6

5 g of the catalyst from example 5 and 300 g of polymer raw materials consisting of 270 g of a mixture of polyethylene from example 5 and 30 g of polypropylene are placed in an autoclave, heated to a temperature of 450 ° C and incubated for 2 hours at a pressure of 1.0 MPa with a constant discharge of the resulting products. The separation of products is carried out analogously to example 1.

Table 1 Example No. Yield, wt.% The composition of the fraction nk-370 ° C, wt.% gas nk-370 ° C 370-kk ° C petrol DT * one 8.5 82.3 9.2 43.8 56.2 2 15.0 81.1 3.9 59.2 40.8 3 3.9 71.4 24.7 33.7 66.3 four 18.1 79.1 2.8 63.5 36.5 5 7.4 81.3 11.3 42.3 57.7 6 12.9 82.4 4.7 55.1 44.9 * - diesel fuel.

Example 7

A fraction of 0.2-0.8 mm is prepared from zeolite powder of the ZSM-5 type with a molar ratio of SiO ₂ / Al ₂ O ₃ = 90. 5 g of the obtained catalyst are placed in a flow reactor, purged with nitrogen (5 l / h) at a temperature of 500 ° C for 2 hours, after which the temperature is lowered to 350 ° C and the flow of nitrogen is stopped. Then, at this temperature and pressure of 1.3 MPa, the feed of the NK-370 fraction obtained in Example 1 begins with a mass velocity of 1.8 h ⁻¹ . At the outlet of the reactor, the products are cooled to a temperature of 15 ° C and separated into gas and liquid phases. The liquid phase is collected for 8 hours, then it is accelerated to gasoline and diesel fuel.

Example 8

The preparation of the catalyst, the process conditions and the separation of the products is carried out analogously to example 7. The resulting gas is sent to a second separator cooled to -50 ° C, where a C ₃₊ fraction is isolated from it, which is then returned to the reactor inlet.

Example 9

20 g of an aluminosilicate with a ZSM-38 structure is purged with nitrogen containing molybdenum acetylacetonate vapors at a temperature of 250 ° C. After the amount of molybdenum acetylacetonate passed through the sample corresponds to the molybdenum content in the sample equal to 5 wt.%, The nitrogen supply is stopped, the sample is purged with air at a temperature of 550 ° С for 3 hours. Then, a 0.2-0.8 mm fraction is prepared.

4 g of the obtained catalyst are placed in a flow reactor, purged with nitrogen (5 l / h) at a temperature of 550 ° C for 3 hours, after which the temperature is reduced to 370 ° C and the flow of nitrogen is stopped. Then, at this temperature and atmospheric pressure, the feed of the NK-370 ° C fraction obtained in Example 4 begins with a mass rate of 1.3 h-1. The separation of products is carried out analogously to example 7.

Example 10

A 0.2-0.8 mm fraction is prepared from a chromosilicate powder with a ZSM-11 structure. 7 g of the obtained catalyst are placed in a flow reactor, purged with nitrogen (5 l / h) at a temperature of 450 ° C for 2 hours, after which they reduce the temperature to 350 ° C and stop the flow of nitrogen. Then, at this temperature and pressure of 0.5 MPa, the feed of the NK-370 ° C fraction obtained in Example 3 begins with a mass speed of 2.4 h ^-1 . The separation of products is carried out analogously to example 7.

Example 11

40 g of a zeolite powder with a BETA type structure with a molar ratio of SiO ₂ / Al ₂ O ₃ = 40 are impregnated with a solution of zinc nitrate based on the content of 0.7 wt.% Zn in the final catalyst. After drying, the obtained catalyst is calcined for 3 hours at a temperature of 600 ° С, then a 0.2-0.8 mm fraction is prepared.

4 g of the obtained catalyst are placed in a flow reactor, purged with nitrogen (5 l / h) at a temperature of 450 ° C for 2 hours, after which they reduce the temperature to 340 ° C and stop the flow of nitrogen. Further, at this temperature and pressure of 2.0 MPa, the feed of the NK-370 ° C fraction obtained in Example 5 begins with a mass speed of 1.5 h ^-1 . Next, the separation of products is carried out analogously to example 7.

Example 12

30 g of aluminophosphate with an AlPO-31 structure containing 0.9 wt.% Zn introduced into the structure at the stage of synthesis are impregnated with a solution of cobalt nitrate based on the content of 2.0 wt.% Co in the final catalyst. After drying, the resulting catalyst is calcined at a temperature of 630 ° C, then a 0.2-0.8 mm fraction is prepared.

5 g of the obtained catalyst are placed in a flow reactor, purged with nitrogen (5 l / h) at a temperature of 450 ° C for 4 hours, after which they reduce the temperature to 360 ° C and stop the flow of nitrogen. Then, at this temperature and pressure of 1.0 MPa, the feed of the NK-370 ° C fraction obtained in Example 6 begins with a mass speed of 1.9 h ^-1 . The separation of products is carried out analogously to example 7.

table 2 Example No. Yield, wt.% OHMM * gasoline Cetane number diz. fuel T _stasis. diz. fuel, ° С Gas Petrol Diz. fuel 7 21.3 45.2 33.5 83.1 45 -51 8 17.5 49.1 33.4 85.4 46 -49 9 25.2 60.9 13.9 83.2 44 -52 10 15.1 29.6 55.3 83.9 46 -51 eleven 20.2 44.1 35.7 83.0 45 -fifty 12 21.1 56.9 22.0 83.2 46 -53 * - octane number, measured by the motor method.

Example 13

30 g of aluminophosphate with an AlPO-31 structure containing 2 wt.% Si, introduced into the structure at the synthesis stage, is impregnated with a solution of tetrammine palladium (II) based on the content of 0.8 wt.% Pd in the composition of the final material. Next, the catalyst is dried and calcined at a temperature of 530 ° C for 3 h, then a 0.2-0.8 mm fraction is prepared.

5 g of the obtained catalyst are placed in a flow reactor, purged with hydrogen for 2 hours at a temperature of 400 ° C, and then the temperature is reduced to 340 ° C. Then, at this temperature and pressure of 2.5 MPa, the 370 ° C-kk fraction obtained in Example 3 is started to flow at a mass rate of 2.0 h ⁻¹ and a hydrogen / hydrocarbon molar ratio of 20.

Example 14

40 g of aluminophosphate with an AlPO-31 structure containing 0.9 wt.% Mg introduced into the structure at the stage of synthesis are impregnated with a solution of tetrammine platinum (II) based on the content of 0.6 wt.% Pt in the composition of the final material. Next, the catalyst is dried and calcined at a temperature of 540 ° C for 3 h, then a 0.2-0.8 mm fraction is prepared.

4 g of the obtained catalyst are placed in a flow reactor, purged with hydrogen for 2 hours at a temperature of 400 ° C, and then the temperature is reduced to 330 ° C. Then, at this temperature and pressure of 2.0 MPa, the 370 ° C-kk fraction obtained in Example 1 is started to flow at a mass rate of 3.0 h ⁻¹ and a hydrogen / hydrocarbon molar ratio of 15.

Example 15

30 g of aluminophosphate with an AlPO-31 structure containing 2 wt.% Si and 0.7 wt.% Ni introduced into the structure at the stage of synthesis are impregnated with a solution of tetrammine palladium (II) based on the content of 0.7 wt.% Pd in the composition of the final material. Next, the catalyst is dried and calcined at a temperature of 530 ° C for 3 h, then a 0.2-0.8 mm fraction is prepared.

5 g of the obtained catalyst are placed in a flow reactor, purged with hydrogen for 2 hours at a temperature of 400 ° C, and then the temperature is reduced to 320 ° C. Then, at this temperature and pressure of 3.5 MPa, the 370 ° C-kk fraction obtained in Example 5 is started to flow at a mass rate of 3.5 h ⁻¹ and a hydrogen / hydrocarbon molar ratio of 30.

Example 16

20 g of aluminophosphate with an AlPO-31 structure containing 0.6 wt.% Zn introduced into the structure at the synthesis stage are impregnated with a solution of tetrammine platinum (II) based on the content of 0.8 wt.% Pt in the composition of the final material. Next, the catalyst is dried and calcined at a temperature of 530 ° C for 3 h, then a 0.2-0.8 mm fraction is prepared.

5 g of the obtained catalyst are placed in a flow reactor, purged with hydrogen for 2 hours at a temperature of 400 ° C, and then the temperature is reduced to 340 ° C. Then, at this temperature and pressure of 2.0 MPa, the 370 ° C-kk fraction obtained in Example 3 is started to flow at a mass rate of 1.5 h ⁻¹ and a hydrogen / hydrocarbon molar ratio of 25.

Example 17

30 g of aluminophosphate with an AlPO-31 structure containing 1.1 wt.% Si and 0.7 wt.% Cd introduced into the structure at the synthesis stage are impregnated with a solution of tetrammine platinum (II) based on the content of 0.6 wt.% Pt in the composition of the final material. Next, the catalyst is dried and calcined at a temperature of 520 ° C for 3 h, then a 0.2-0.8 mm fraction is prepared.

4 g of the obtained catalyst are placed in a flow reactor, purged with hydrogen for 2 hours at a temperature of 400 ° C, and then the temperature is reduced to 350 ° C. Then, at this temperature and pressure of 3.5 MPa, the 370 ° C-kk fraction obtained in Example 1 is started to flow at a mass rate of 4.5 h ⁻¹ and a hydrogen / hydrocarbon molar ratio of 15.

Table 3 Example No. The output of the oil fraction, wt.% The content of n-alkanes in the oil fraction, wt.% 13 95.2 7.0 fourteen 96.0 6.3 fifteen 94.3 6.9 16 93.9 7.1 17 94.8 5.9

Thus, as can be seen from the above examples and tables, the proposed method allows to obtain high-quality motor fuels and a component of motor oils with a yield of more than 90% from waste polymer products.

Claims (11)

1. The catalyst for the production of hydrocarbon feedstocks from waste polymers such as polyethylene, polypropylene, polystyrene or any mixtures thereof with a yield of liquid products of at least 85%, which is either an aluminosilicate zeolite with a molar ratio of SiO ₂ / Al ₂ O _{3 of} not more than 450 and structure of the type: ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or gallosilicate, or galloaluminosilicate, or iron silicate, or iron aluminosilicate, or chromosilicate, or chromosilicate with the structure: ZSM-5, ZSM -11, ZSM-35, ZSM-38, ZSM-48, BETA, or aluminum phosphate with a structure of the type: AlRO-5, AlRO-11, AlRO-31, lRO-36, AlRO-37, AlRO-40, AlRO-41 with an element selected from the series: magnesium, zinc, manganese, iron, silicon, cobalt, cadmium or any mixture thereof introduced into the structure of any of these types of catalyst at the stage of synthesis . 2. The catalyst according to claim 1, characterized in that the catalyst may further comprise a modifying additive of at least one of a number of metals: zinc, gallium, nickel, cobalt, molybdenum, tungsten, rhenium, rare earth elements, platinum group metals in an amount no more than 10 wt.%. 3. The catalyst according to claim 2, characterized in that the modifying additive is introduced into the catalyst by impregnation, or by activated impregnation in an autoclave, or by ion exchange at a temperature of at least 20 ° C, or by applying from the gas phase or by mechanical mixing with the starting material with subsequent drying and calcination. 4. A method for producing hydrocarbon feedstocks from waste polymers such as polyethylene, polypropylene, polystyrene or any mixtures thereof with a yield of liquid products of at least 85%, which consists in the catalytic conversion of these wastes into a mixture of hydrocarbons at a temperature of 350-500 ° C and a pressure of more than 1.5 MPa, characterized in that the process is carried out in the presence of a catalyst selected from the series: either an aluminosilicate zeolite with a molar ratio of SiO ₂ / AlO _{3 of} not more than 450 and a structure of the type: ZSM-5, ZSM-11, ZSM-35, ZSM -38, ZSM-48, BETA, either gallosilicate or gallo aluminosilicate, or iron silicate, or iron aluminosilicate, or chromosilicate, or chromium aluminosilicate with the structure: ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or aluminophosphate with a structure of the type: AlRO-5, AlRO- 11, AlRO-31, AlRO-36, AlRO-37, AlRO-40, AlRO-41 with an element selected from the series: magnesium, zinc, manganese, iron, silicon, cobalt introduced into the structure of any of these types of catalyst at the stage of synthesis , cadmium or any mixture thereof, with a further separation of the resulting mixture of hydrocarbons into fractions nk-370 ° C, where: nk denotes the beginning of boiling, and 370 ° C-kk, where: kk means end of boil. 5. A method for the simultaneous production of gasoline with an octane rating of at least 83 points by the motor method and diesel fuel with a pour point of no higher than -35 ° C and liquefied gas, which consists in converting a mixture of hydrocarbons in the presence of a catalyst at a temperature of 250-500 ° C, not more than 2.5 MPa, the mass flow of raw materials not more than 10 h ^-1 , while the catalyst is used zeolite aluminosilicate composition with a molar ratio of SiO ₂ / AlO ₃ not more than 450, selected from the series: ZSM-5, ZSM-11, ZSM -35, ZSM-38, ZSM-48, BETA, either gallosilicate or galloaluminosilicon at, or iron silicate, or iron aluminosilicate, or chromosilicate, or chromium silicate with a structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or aluminophosphate with a structure of the type AlRO-5, AlRO-11, AlRO-31, AlRO-36, AlRO-37, AlRO-40, AlRO-41 with an element selected from the series: magnesium, zinc, manganese, iron, silicon, cobalt, cadmium, introduced into the structure of any of these types of catalyst at the synthesis stage or any mixture thereof, characterized in that the nk-370 ° C fraction obtained from polymer wastes according to claim 4 is used as a mixture of hydrocarbons. 6. The method according to claim 5, characterized in that the catalyst may further comprise a modifying additive of at least one of a number of metals: zinc, gallium, nickel, cobalt, molybdenum, tungsten, rhenium, rare earth elements, platinum group metals in an amount no more than 10 wt.%. 7. The method according to claim 6, characterized in that the modifying additive is introduced into the catalyst by impregnation, or by activated impregnation in an autoclave, or by ion exchange at a temperature of at least 20 ° C, or by applying from the gas phase or by mechanical mixing with the starting material with subsequent drying and calcination. 8. The method according to claim 5, characterized in that at the outlet of the reactor the products are divided in a separator into a mixture of gasoline with an octane rating of at least 83 points according to the motor method and diesel fuel with a pour point not higher than -35 ° C and liquefied gas, s subsequent mixing of the latter with a stream of hydrocarbon feed at the inlet to the reactor. 9. A method of producing a component of motor oils, which consists in the conversion of hydrocarbon materials in the presence of a catalyst at a temperature not exceeding 400 ° C, a mass feed rate of not more than 10 h ^-1 , a pressure of not more than 10 MPa, a molar ratio of hydrogen / hydrocarbons not more than 50, in this case, aluminophosphate with an AlRO-31 structure with an element selected at the stage of synthesis selected from the series: magnesium, zinc, silicon, cobalt, manganese, nickel, cadmium, characterized in that the fraction is used as a hydrocarbon feed, is used as a catalyst 370 ° C-kk obtained by the method according to claim 4. 10. The method according to claim 9, characterized in that the catalyst may further comprise a modifying additive of at least one of a number of metals: nickel, cobalt, molybdenum, tungsten, rhenium, platinum group metals in an amount of not more than 10 wt.%. 11. The method according to claim 10, characterized in that the modifying additive is introduced into the catalyst by impregnation, or by activated impregnation in an autoclave, or by ion exchange at a temperature of at least 20 ° C, or by application from the gas phase or by mechanical mixing with the starting material with subsequent drying and calcination.