RU2522615C2 - Method of combined refinery of oil fractions and polymer wastes - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to the field of chemistry and can be used in oil processing in order to utilise the most widely spread polymer wastes and to obtain valuable oil refinery products. A method includes a combination of polymer wastes and oil fractions, introduction of the obtained mixture directly into a reactor and realisation of cracking at a higher temperature and atmospheric pressure, as oil fractions used is a vacuum distillate, and as the reactor - a catalytic cracking reactor, the said combination is realised by dissolution of polymer wastes, taken in a quantity of 1-7 wt % relative to the initial raw material, in oil fractions at a temperature, ensuring complete dissolution in them of polymer wastes, cracking is performed at a temperature of 475-525°C with the weight rate of the raw material supply 1.8-7.0 h^-1 in the presence of a zeolite-containing catalyst of Y type, containing rare earth metals as exchange cations.

EFFECT: invention makes it possible to increase the output of a petrol fraction of distillates to 53 wt % and light gas oil to 24 wt % and obtain an additional amount of motor fuels and raw material for oil chemistry - lower hydrocarbon gases of C2-C4 composition, use operating installations, which are available in the domestic industry, reduce environment pollution with polymer wastes, obtain the petrol fraction with the high octane number (not lower than 91,0).

2 cl, 2 tbl, 12 ex

Description

The invention relates to the field of chemistry, namely to the chemical processing of polymer waste, and can be used in oil refining with the aim of disposing of the most widespread polymer waste and to obtain valuable oil refining products from them.

The relevance and importance of the task of developing a modern method for the disposal of polymer wastes is determined both by their widest distribution and resistance to environmental conditions, as a result of which they can remain almost unchanged for many years, polluting the environment.

Existing methods for the disposal of polymer waste, such as recycling, incineration, photo and biodegradation of polymers, have their drawbacks and for a number of reasons are not widespread, and the problem of recycling polymer waste is currently far from being resolved.

An alternative to these methods are the methods of catalytic and thermal processing of polymer waste using industrially produced heterogeneous acidic and bifunctional catalysts.

One of the possible approaches, from the point of view of the need for careful spending of hydrocarbon resources and protecting the environment from pollution, is the joint processing of oil fractions used for the production of fuels, oils, coke, bitumen, etc., and polymer waste using catalytic depolymerization. This method of disposal is characterized by:

- the possibility of large-scale processing of polymeric, and in the future, all carbon-containing, wastes in raw materials for oil refining and petrochemical industries;

- the maximum return of hydrocarbons to industrial circulation in order to minimize the consumption of natural hydrocarbon resources;

- minimum capital and operating costs.

The technical solution described in JP 2002-294251 is known. According to it, polymers, including waste polypropylene, polyethylene and polystyrene, are dissolved in a hydrocarbon solvent - alkane C5-C8. Then, in the mixer at 250-320 ° C, the polymer component is mixed in an amount of 0.5-30 wt.% With hydrocarbon oils, including light cracking gas oil, heavy cracking gas oil, cracking residue, desulfurization residue - oil oils. After separating the hydrocarbon solvent using a vapor / liquid separation column, the resulting mixture is introduced into a catalytic cracking reactor with a permutite-containing catalyst at 0.4-3 MPa and 100-300 ° C. The amount of polymer is 0.1-20% wt. (after removal of solvent). The reaction proceeds at a pressure of 0.02-0.5 MPa and a temperature of 480-550 ° C. Reach the yield of gasoline fraction - 47.8-49.2% wt. and propane-propylene fraction - 3.6-5.3% wt.

However, this method is multi-stage, including before cracking the initial dissolution of the polymer, mixing it with oil fractions and removing the solvent. The implementation of this method requires special equipment for dissolving the polymer in alkane and for separating the solvent, which is associated with high capital costs and does not allow the effective use of this method in existing catalytic cracking units. The processing cost increases due to the consumption of solvent, as well as the need to maintain high pressure at the inlet to the reactor. The waste solvent is waste that must be disposed of, which dramatically reduces the environmental effect of the disposal of polymer waste in this way.

The closest in technical essence is the technical solution described in patent RU 2047645, according to which by thermal cracking of heavy and residual crude oil in the presence of an initiating additive - 10-20% of any kind of polyethylene, including waste, at 360-460 ° С and atmospheric pressure get gasoline-kerosene distillates boiling in the temperature range 100-300 ° C in the amount of 22-36% of the feedstock, oil distillates boiling in the temperature range 300-440 ° C in the amount of 60-72% of the feedstock. In this case, first, the heavy and residual oil feedstocks (oil residue of direct distillation of oil, heating oil) are mixed with polyethylene, then the resulting mixture is subjected to thermal cracking in a reactor.

This solution excludes the stages of dissolution of polymer wastes before they are mixed with oil fractions and solvent removed. The disadvantage of the described technical solution is the need for complex hardware design and insufficiently high yield of gasoline-kerosene fraction of distillates.

The objective of the proposed technical solution is to develop a simple method for the joint processing of oil fractions and polymer waste, which can be carried out on catalytic cracking units already available in the domestic industry, without significant capital expenditures, and which allows to increase the yield of high-quality gasoline-kerosene fraction of distillates and propane propylene and butane-butylene fractions - a valuable raw material for petrochemicals.

The problem is solved in that a method is proposed for the joint processing of oil fractions and polymer waste, including combining polymer waste and oil fractions, introducing the resulting mixture directly into the reactor and cracking at elevated temperature and atmospheric pressure, characterized in that vacuum fractions are used as oil fractions distillate, as a reactor - a catalytic cracking reactor, the specified combination is carried out by dissolving polymer waste taken in an amount of 1-7% m ss. in relation to the feedstock, in oil fractions at a temperature that ensures complete dissolution of polymer waste in them, and cracking at a temperature of 475-525 ° C with a mass feed rate of 1.8-7.0 h ^-1 in the presence of a zeolite-containing catalyst of the type Y containing rare earth elements as exchange cations.

Preferably, polyethylene or polypropylene, or polyethylene terephthalate, or a mixture thereof, is used as polymer waste.

The proposed technical solution allows you to:

1) increase the yield of gasoline fraction of distillates to 53% wt. and light gas oil up to 24% of the mass. and get an additional amount of motor fuels and raw materials for petrochemistry - lower hydrocarbon gases of the composition C2-C4;

2) use existing facilities available in domestic industry;

3) reduce environmental pollution with polymer waste;

4) to obtain a gasoline fraction with a high octane number (not lower than 91.0).

The following examples illustrate the proposed technical solution, but in no way limit it.

In all examples, the cracking of the oil fraction and polymer waste was carried out in a vacuum distillate obtained at the Moscow refinery. Its properties are given in table 1.

Table 1. Characteristics of the used oil fraction - vacuum distillate Density, g / cm ³ The temperature range of boiling, ° C Group composition, wt.%: paraffin - naphthenes aroma light (monocyclic) aromatic medium (bicyclic) aromatics heavy (polycyclic) neutral resins acidic resins asphaltenes 0.889 166..533 57.9 20.5 8.5 10.8 1.0 1.3 1.3

In all examples, the cracking of the oil fraction and polymer waste was carried out in the presence of a typical industrial microspherical zeolite-containing catalyst type Y containing rare earth elements (REDUXION DMS РНО) of BASF company (Germany) as exchange cations. The main characteristics of the catalyst:

1) an average particle size of 88 microns;

2) the residual coke content of 0.08%;

3) specific surface area 175 m ² / g, incl. zeolite 113 m ² / g and a matrix of 65 m ² / g.

The composition of the catalyst:

Al ₂ O ₃ - 40.8% of the mass., SiO ₂ - 54.8% of the mass. REO (CeO ₂ ; LaO ₂ ; Sm ₂ O ₃ ) 0.93% wt., The rest is impurities.

Example 1

The syringe dispenser is loaded with raw materials - a vacuum distillate, in which 3% of the mass is pre-dissolved. waste polyethylene at a temperature of 130 ° C and inject it directly into the catalytic cracking reactor at a mass feed rate of 1.8 h ^-1 . Carry out the catalytic cracking of the resulting mixture in the presence of a zeolite-containing catalyst composition at a temperature of 500 ° C and atmospheric pressure. The results are shown in table.2.

Example 2

The syringe dispenser is loaded with raw materials - a vacuum distillate, in which 3% of the mass is pre-dissolved. waste polyethylene at a temperature of 130 ° C and inject it directly into the catalytic cracking reactor at a mass feed rate of 2.0 h ^-1 . Carry out the catalytic cracking of the resulting mixture in the presence of a zeolite-containing catalyst composition at a temperature of 500 ° C and atmospheric pressure. The results are shown in table.2.

Example 3

The syringe dispenser is loaded with raw materials - a vacuum distillate, in which 5% of the mass is pre-dissolved. waste polyethylene at a temperature of 130 ° C and inject it directly into the catalytic cracking reactor at a mass feed rate of 2.0 h ^-1 . Carry out the catalytic cracking of the resulting mixture in the presence of a zeolite-containing catalyst composition at a temperature of 500 ° C and atmospheric pressure. The results are shown in table.2.

Example 4

The syringe dispenser is loaded with raw materials - a vacuum distillate, in which 7% of the mass is pre-dissolved. waste polyethylene at a temperature of 130 ° C and inject it directly into the catalytic cracking reactor at a mass feed rate of 2.0 h ^-1 . Carry out the catalytic cracking of the resulting mixture in the presence of a zeolite-containing catalyst composition at a temperature of 500 ° C and atmospheric pressure. The results are shown in table.2.

Example 5

The syringe dispenser is loaded with raw materials - a vacuum distillate, in which 1% of the mass is pre-dissolved. waste polypropylene at a temperature of 170 ° C and inject it directly into the catalytic cracking reactor at a mass feed rate of 2.0 h ^-1 . Carry out the catalytic cracking of the resulting mixture in the presence of a zeolite-containing catalyst composition at a temperature of 500 ° C and atmospheric pressure. The results are shown in table.2.

Example 6

The syringe dispenser is loaded with raw materials - a vacuum distillate, in which 3% of the mass is pre-dissolved. polyethylene waste and 1% of the mass. waste polypropylene at a temperature of 170 ° C and inject it directly into the catalytic cracking reactor at a mass feed rate of 2.0 h ^-1 . Carry out the catalytic cracking of the resulting mixture in the presence of a zeolite-containing catalyst composition at a temperature of 500 ° C and atmospheric pressure. The results are shown in table.2.

Example 7

The syringe dispenser is loaded with raw materials - a vacuum distillate, in which 1% of the mass is pre-dissolved. waste polyethylene terephthalate at a temperature of 250 ° C and inject it directly into the catalytic cracking reactor at a mass feed rate of 2.0 h ^-1 . Carry out the catalytic cracking of the resulting mixture in the presence of a zeolite-containing catalyst composition at a temperature of 500 ° C and atmospheric pressure. The results are shown in table.2.

Example 8

The syringe dispenser is loaded with raw materials - a vacuum distillate, in which 3% of the mass is pre-dissolved. polyethylene waste, 1% of the mass. polypropylene waste and 1% of the mass. waste polyethylene terephthalate at a temperature of 250 ° C and inject it directly into the catalytic cracking reactor at a mass feed rate of 2.0 h ^-1 . Carry out the catalytic cracking of the resulting mixture in the presence of a zeolite-containing catalyst composition at a temperature of 500 ° C and atmospheric pressure. The results are shown in table.2.

Example 9

The syringe dispenser is loaded with raw materials - a vacuum distillate, in which 3% of the mass is pre-dissolved. waste polyethylene at a temperature of 130 ° C and inject it directly into the catalytic cracking reactor at a mass feed rate of 3.5 h ^-1 . Carry out the catalytic cracking of the resulting mixture in the presence of a zeolite-containing catalyst composition at a temperature of 500 ° C and atmospheric pressure. The results are shown in table.2.

Example 10

The syringe dispenser is loaded with raw materials - a vacuum distillate, in which 3% of the mass is pre-dissolved. waste polyethylene at a temperature of 130 ° C and inject it directly into the catalytic cracking reactor at a mass feed rate of 7.0 h ^-1 . Carry out the catalytic cracking of the resulting mixture in the presence of a zeolite-containing catalyst composition at a temperature of 500 ° C and atmospheric pressure. The results are shown in table.2.

Example 11

The syringe dispenser is loaded with raw materials - a vacuum distillate, in which 5% of the mass is pre-dissolved. waste polyethylene at a temperature of 130 ° C and inject it directly into the catalytic cracking reactor at a mass feed rate of 2.0 h ^-1 . Carry out the catalytic cracking of the resulting mixture in the presence of a zeolite-containing catalyst composition at a temperature of 475 ° C and atmospheric pressure. The results are shown in table.2.

Example 12

The syringe dispenser is loaded with raw materials - a vacuum distillate, in which 5% of the mass is pre-dissolved. waste polyethylene at a temperature of 130 ° C and inject it directly into the catalytic cracking reactor at a mass feed rate of 2.0 h ^-1 . Catalytic cracking of the resulting mixture is carried out in the presence of a zeolite-containing catalyst composition at a temperature of 525 ° C and atmospheric pressure. The results are shown in table.2.

The results of the joint processing of polymer waste with oil fractions are given in Table 2, where: PE - polyethylene, PP - polypropylene, PET - polyethylene terephthalate, PPF - propane-propylene fraction, BBP-butane-butylene fraction.

The parameters of gasoline and light gas oil were also checked according to examples 5 and 6. The octane number for the gasoline fraction obtained in example 5 is 91.0, in example 6-91.4. The iodine number of light gas oils obtained according to examples 5 and 6, respectively, is 6, 0 and 2, 3, that is, does not exceed that stipulated by the requirements of GOST.

Thus, the proposed technical solution provides a cost-effective disposal of the most widespread polymeric wastes with the return of hydrocarbon raw materials into economic circulation and obtaining valuable oil products from it with a corresponding increase in the hydrocarbon resource base and can be implemented on existing catalytic cracking units of oil refineries, which will not require excessive capital costs.

The application of the developed technology will solve the problem of recycling polymer waste in oil fractions to produce valuable petrochemical products, including high-quality motor fuels, successfully and at the lowest cost, while improving the environmental situation.

Table 2. Results of co-processing of polymer waste and vacuum distillate by catalytic cracking No.
etc. Polymer type The concentration of polymer in the mixture,
wt.% Temperature
^o C Mass feed rate, h ^-1 The degree of conversion, wt.% Gaseous output,
wt.% Gasoline fraction output,
wt.% Light gas oil outlet,
wt.% PE PP PAT PE PP PAT Amount Dry gas PPF BBF one. + - - 3 - - 500 1.8 90 22 four 7 eleven 51 17 2. + - - 3 - - 500 2.0 89 21 four 6 eleven fifty eighteen 3. + - - 5 - - 500 2.0 89 twenty four 6 10 fifty 19 four. + - - 7 - - 500 2.0 90 22 four 7 eleven fifty eighteen 5. - + - - one - 500 2.0 89 17 3 5 9 53 19 6. + + - 3 one - 500 2.0 87 eighteen 2 5 eleven fifty 19 7. - - + - - one 500 2.0 90 22 four 6 12 fifty eighteen 8. + + + 3 one one 500 2.0 90 21 7 5 9 49 twenty 9. + - - 3 - - 500 3,5 86 twenty 3 6 eleven 48 eighteen 10. + - - 3 - - 500 7.0 76 10 one 3 6 42 24 eleven. + - - 5 - - 475 2.0 87 eleven 2 3 6 53 23 12. + - - 5 - - 525 2.0 89 22 5 7 10 48 19 * - gasoline fraction with a boiling point up to 200 ° C; ** - light gas oil with a boiling point of 200-320 ° C.

Claims (2)

1. A method for the joint processing of petroleum fractions and polymer wastes, including combining polymeric wastes and petroleum fractions, introducing the resulting mixture directly into the reactor and cracking at elevated temperature and atmospheric pressure, characterized in that vacuum distillate is used as petroleum fractions as a reactor - a catalytic cracking reactor, the specified combination is carried out by dissolving polymer waste taken in an amount of 1-7% wt. relative to the feedstock, in oil fractions at a temperature that ensures complete dissolution of the polymer waste in them, cracking is carried out at a temperature of 475-525 ° C with a mass feed rate of 1.8-7.0 h ^-1 in the presence of a zeolite-containing catalyst of type Y containing rare earth elements as exchange cations. 2. The method according to claim 1, characterized in that the waste polyethylene, or polypropylene, or polyethylene terephthalate, or a mixture thereof, is used as polymer waste.