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INVENTION
Russian Federation Patent RU2142494

METHOD FOR PRODUCING GASOLINE, DIESEL FUEL AND WASTE FROM CARBON BLACK RUBBER
AND / OR WASTE PLASTIC MATERIAL

Name of the inventor: Xing Li (CN)
The name of the patentee: Xing Li (CN)
Address for correspondence: 121087, Moscow, p / 33, Kurysheva VV
Starting date of the patent: 1995.11.07

Use: chemical industries.

SUMMARY: waste pyrolyzed, desulfurization and / or denitration and / or catalytic cracking and dechlorinated. Describes processes for obtaining the catalysts used for desulfurization and / or denitration and / or dechlorination and catalytic cracking. Technical result: an increase in diesel fuel and soot output.

DESCRIPTION OF THE INVENTION

The present invention relates to a method for processing waste rubber and / or plastics waste and generally to a method of using a pyrolysis and catalytic cracking waste rubber and / or waste plastics for the production of gasoline, diesel and carbon black.

Already many reported methods for the production of gasoline and diesel fuel from waste rubber and waste plastics, including those described in US5,414,169, US4,851,601 and EP-A-060 786 2, and the like. US 5,414,169 describes a method in which the first reaction is carried out a pyrolysis of waste rubber or plastics waste, the product obtained is then liquefied and finally catalytic cracking using catalyst in the liquid phase. US4,851,601 discloses a method in which the catalytic cracking of waste plastic pyrolysis product is carried out in the gas phase with the catalyst ZSM-5. This method can not be used for processing a polyolefin containing halogen, which inactivates the catalyst. EP-A-0607862 discloses a method in which materials after pyrolysis subjected to catalytic cracking reaction with an acidic solid catalyst to get the primary product of the catalytic pyrolysis, which is separated by cooling, then the resulting components in the gaseous phase treated catalyst such as H 3 PO 4 to give secondary hydrocarbon oil.

The invention provides a method of producing gasoline, diesel and carbon black using the waste plastic and / or rubber waste. According to the invention, plastics waste and / or waste rubber materials, previously treated properly charged to the pyrolysis reactor with a screw feeder or feeder chute with reciprocating. The pyrolysis reactor is a screw mixer is used to mix the contents, after the reagent is loaded. After completion of the pyrolysis reaction, the resulting carbon black is removed from the helical stirrer pyrolysis reaction vessel. Other resulting substances of gaseous phase having lower molecular weight, the tank is subjected to desulfurization and / or denitration and / or dechlorinated to desulfurize and / or denitrirovat and / or dechlorinates. Remaining sulfur, nitrogen and chlorine are removed during the passage through the fixed catalyst bed, at the same time held primary catalytic pyrolysis. gas phase materials are placed in a catalytic cracking unit to expose there the catalytic cracking reaction. Substances obtained by catalytic cracking is separated to yield the desired products. A spiral stirrer located in the pyrolysis reactor according to the invention reduces the coking and reactants increases heat conductivity. Furthermore, the agitator rotates clockwise during the pyrolysis reaction, but removes soot when rotated counterclockwise. The invention uses a special catalyst, and an apparatus for desulfurization and / or denitration and / or dechlorination catalyst makes a longer life and limits wider processed materials. This solves the problem, known in the art.

Schematic representation of the reaction apparatus for producing gasoline and diesel fuel from waste rubber and plastics

The drawing schematically shows a reaction apparatus according to the invention, which shows the following elements:
27 - screw feeder Feeder with or reciprocating;
1 - a heating furnace;
5 - pyrolysis reactor;
2 - screw mixer;
8 - the first device for the desulfurization and / or denitration and / or dechlorination;
9 - a second apparatus for desulfurization and / or denitration and / or dechlorination while carrying the primary catalytic cracking reaction;
10 - the device for catalytic cracking;
25 - fractionator.

DETAILED DESCRIPTION OF THE INVENTION

In preferred embodiments of the invention the waste rubber materials (natural rubber, synthetic rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, butadiene rubber, low-temperature polymerization, butadiene rubber, ethylene propylene rubber, double ethylene-propylene copolymer and isobutylene isoprene rubber) and / or waste plastics (polyethylene, polypropylene, polystyrene, PVC, ABS, etc.) are pre-treated in a known manner to remove impurities. The heating furnace 1 provides heat to a pyrolysis reactor 5, to maintain a temperature therein in the range 350-500 o C. Treated waste rubber and / or waste plastics is charged into the reactor 5 through the inlet 3. The feeder spiral stirrer 2 in the reactor is used for mixing materials after loading reaction. The waste rubber and / or plastics waste to pyrolysis reaction within this temperature. In the reactor 5, they decompose to give gaseous hydrocarbons in the form of substances having a lower molecular weight. If the waste materials are rubber, they are completely decomposed, and the residual soot is discharged from the reactor through valve 6, with a helical stirrer and step 2 may be used for tires. Through the top of the pyrolysis reactor 5 substances of gaseous phase having lower molecular weight, are sent to the device 8 for desulfurization and / or denitration and / or dechlorination, to which is added, in addition, a base such as granular NaOH or KOH or molten form. Most of the acid gases such as HCl, SO 2, SO 3, H 2 S and others. Evolved during pyrolysis are absorbed in the device 8. The gaseous substance coming from the device 8 in the fixed catalyst bed 9, in which acidic gases are removed and unabsorbed other odorous gases while simultaneously flowing the primary catalytic cracking reaction. Specific catalyst DL, prepared by the inventor, is used in a fixed bed 9. The gaseous substances from the fixed catalyst bed 9 placed in an apparatus 10 having a fixed catalyst bed, which is then used for catalytic cracking. Catalyst XL, used in the apparatus 10 and received by the inventor. Final reaction of catalytic cracking of gaseous substances from the device 9 is thus carried, along with a series of other reactions such as a reaction to minimize hydrogen transfer reaction and the reaction of aromatization. Gasoline, diesel fuel and other flammable gases mixed components are obtained from these reactions. Reaction in fixed beds 9 and 10 is carried out at a temperature of 200-400 o C, pressure 0.02-0.08 MPa and at an air velocity of 1-2000 m / h.

Products of catalytic cracking unit 10 is placed into the condenser 19 wherein they are cooled to room temperature. The resulting liquid is a mixture of gasoline and diesel fuel. Substances from the apparatus 19 received in the buffer reservoir 21 through a separator 20. Gases are loaded into the storage tank 11 from the top of separator 20 from which the combustion gas is returned to the heating furnace for combustion. The remaining gas in the tank 11 is discharged to the atmosphere through the combustion tank with a roof 12. The liquid flooded oil mixture in the buffer tank 21 is treated with an inorganic acid such as sulfuric acid, to remove impurities. The oil mixture is pumped to the heat exchanger 24, a pump 23 to be heated to a temperature of 250-350 o C, and then placed into a fractionator 25, in which petrol and diesel oil are divided into various distillation fractions. Gas is introduced into the condenser 14 from the top of the column 25 and enters the storage tank 18 via a fuel separator device 16 for separating oil and water. Diesel fuel is supplied to the stripper column 26 of the middle section of fractionator 25. Diesel fuel is introduced into the condenser 13 after the treatment with superheated steam, and then enters the storage tank 17 through the diesel fuel separator device 15 for separating oil and water.

The catalyst DL in the fixed bed 9 consists of a mixture of materials A and B, wherein the material A comprises 40-70% kaolin or activated clay, 10-30% aqueous solution of KOH or NaOH (10-20% solids content -s) 10 15% ZnO or a soluble zinc salt, 3-5% CuO or a soluble copper salt and the necessary amount of silicon or aluminum coupling agents, such as conventional binders used in the art, for example, sodium silicate. These materials are mixed, washed, dried and calcined at a temperature of 500-700 o C, thereby obtaining a material A. Material B comprises 40-80% kaolin or activated clay, 10-30% aqueous solution of KOH or NaOH (10-20% - tion solid content), 10-20% CaO or CaCO 3 and the necessary amount of silicon or aluminum coupling agents, such as conventional binders used in the art, such as sodium silicate. These materials are mixed, shaped, washed, dried and calcined at a temperature of 500-700 o C, thereby obtaining a material B.

The ratio of materials A and B in the mixture can vary by experts working in this art, if desired. Preferably, it is prepared as in the recipe.

XL catalyst unit 10 in the catalytic cracking comprises 10-70% synthetic carrier or semi-synthetic carrier, 10-50% HZSM-5 zeolite, 10-20% aqueous solution of NaOH or KOH (10-20% solids content -s) 3 -5% ZnO or a compound selected from the group consisting of Zn, Pt, Fe, Cu and Ni, and a suitable amount of silicon or aluminum coupling agents, such as conventional binders used in the art, such as sodium silicate. These materials are mixed, shaped, washed, dried and calcined or not calcined at a temperature of 500-700 o C, thereby obtaining a catalyst XL. Said synthetic medium or produced by the method sozhelatinirovaniya deposition, it contains 20-80% SiO 2 in the form of amorphous Si-Al and Si-Mg, etc. The required amount of clay can be added to the carrier to increase the size of the catalyst. Said semisynthetic medium contains kaolin, polyhydrate kaolin or activated clay, which are used as carriers for this cracking catalyst in the art, and a binder selected from the group consisting of Al 2 O 3, Na 2 SiO 3 and SiO 2 · Al 2 O 3. Preferably the catalyst is prepared as in the recipe.

example 1
1000 kg of waste plastics comminuted after removal of impurities. These materials are then charged to the reactor 5 for the pyrolysis via input feeder 3. Pyrolysis apparatus 5 is heated by the heating furnace 1 to maintain the temperature of materials in the apparatus of 350-500 o C, this time in the pyrolysis reaction is carried out, and the materials decompose to gaseous hydrocarbons of low molecular weight . Gas from apparatus 5 is loaded into the unit 8 for removal of acid gases. The gaseous substances from the device 8 further processed to remove residual sulfur, chlorine and nitrogen through the catalyst DL in the fixed bed in unit 9, where the primary reaction took place catalytic cracking. Substances from the device 9, sent to the apparatus 10 to conduct a catalytic cracking reaction. The temperature in the devices 9 and 10 was 200-400 o C, and the pressure is in the range 0.02-0.08 MPa. Materials from the device 10 and fractionated separated, giving 370 kg gasoline and 370 kg of diesel fuel. Road octane number of the product was 90-93, dried point 205. Cetane diesel fuel characteristic of the product was 45-60. 95% boiling range of the diesel fuel product fractions were less than 360 o C (freezing point -20 O C).

example 2
In the same manner as in Example 1, using 1000 kg of waste rubber to give gasoline 320 kg, 309 kg of diesel fuel and 280 kg of carbon black. BP soot absorption level was 47 7 cm 2/100 g, an ash content 0.3% and decrease by heating 1.0%.

Industrial Applicability.

According to the method of the invention gasoline, diesel and carbon black can be produced with a high yield when used as plastics waste material and / or waste rubber. This method can be used to ensure consistent production industry.

CLAIM

  1. The process for producing gasoline, diesel and carbon black from waste plastic and / or rubber materials comprising feeding materials to the pyrolysis unit through a hopper, discharge of carbon black from the pyrolysis unit, loading the resulting materials in gaseous phase into a device for catalytic cracking, characterized in that the reaction materials mixed screw stirrer in the pyrolysis device and fed to the apparatus for desulfurization and / or denitration and / or dechlorination before entering the device for catalytic cracking, said apparatus for desulfurization and / or denitration and / or dechlorination includes absorber comprising a base and an absorption device with a fixed bed catalyst, said catalyst is used in an apparatus for catalytic cracking is prepared as follows: 10 - 70% synthetic carrier or semi-synthetic media, 10 - 50% HZSM-5 zeolite, 10 - 20% aqueous NaOH solution or KOH (10 - 20% solid content), 3 - 5% ZnO or a compound selected from the group consisting of Zn, Pt, Fe, Cu and Ni, and a suitable amount of silicon or aluminum binder mixed, shaped, dried and calcined, or not calcined to give the desired catalyst, said catalyst is used in a fixed bed are obtained from a and B, in which a is obtained by mixing 40 - 70% kaolin or activated clay, 10 - 30% aqueous solution of NaOH or KOH (10 - 20% content solids), 10 - 15% ZnO or a soluble zinc salt, 3 - 5% CuO or a soluble copper salt and the necessary amount of silicon or aluminum coupling agent, washing, drying and calcining, B is obtained by mixing 40 - 80% kaolin or activated clay 10 - 30% aqueous solution of NaOH or KOH (10 - 20% solid content), 10 - 20% CaO or CaCO 3, with the necessary amount of silicon or aluminum binder, molding, drying and calcination and fractionated the resulting products by fractionating column.
  2. A method according to claim 1, characterized in that said absorption device with a fixed bed catalyst and the catalytic cracking unit.
  3. The method of claim 1, wherein the reaction temperature in the absorption device with a fixed bed or in the catalytic cracking unit is within the range of 200 - 400 o C and the pressure is in the range of 0.02 - 0.08 MPa.

print version
Publication date 31.10.2006gg