TW517078B - A process of producing gasoline, diesel and carbonblack from waste rubbers - Google Patents

Abstract

This invention relates to a process of producing gasoline, diesel and carbonblack from waste rubbers, which consists of the steps of thermal cracking, desulphurizing, catalytic cracking, impurity removal by inorganic acid, and fractionating. This invention also discloses the catalyst(s) used in the process as well as the way of making the catalyst(s).

Description

517078 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (The present invention relates to a method for producing gasoline, diesel and black from waste rubber, especially a method for thermal cracking and catalytic cracking Chu Wangli waste rubber is used to produce gasoline, diesel and carbon black. Recently, due to the rising awareness of environmental protection and energy conservation, more and more people have been involved in the production of gasoline and diesel using waste rubber as raw materials. First, in the PCT / US 92/10800 patent case, a method for producing light oil and slave black from waste rubber was disclosed, but the reaction must be carried out under the condition of maintaining a negative pressure with a vacuum pump, which is harsh. And the method used to control the temperature is less than 438 ° c, it can not vaporize a large amount of sulfur in rubber, and there is no practical and effective desulfurization step in the industry, which makes the sulfur content of its light oil high, and Stable (approximately 0.4-L5% by weight). Sulfur in light oil products will corrode equipment and generate a large amount of S02 when used, polluting the environment. Moreover, its reaction temperature cannot be lower than 438X: As a result, the conversion of its reactants is not complete, the light oil production rate is low (only about 47%), the content of residues is large (about 43%), and a considerable amount of raw materials have not been converted into light oil and carbon black In addition, in US Pat. No. 3,990,922, a method of reacting a rubber and an acid halide in a molten state has been disclosed. This method is only suitable for use in a laboratory. In the industrial production process, the method Chloride ions will seriously rot equipment at high temperatures, so its actual production cannot be carried out, and the residual carbon black is often mixed with a large amount of unrefined halides, resulting in its carbon black being of no commercial value. In US5208404, there was also Disclose a method for reacting by mixing rubber and catalyst in a reaction kettle. The catalyst is composed of a large number of inorganic compounds. The paper size is applicable to Chinese National Standard (Cps) A4 specification (2 丨 〇> 2297 mm) (Please read first (Notes on the back then fill out this page)

517078 A7 --------___ B7__ 5. Description of the invention (>) ~ The materials such as limestone, oxidized dance and precious metals (Ni, Nb # 〇Ti), the catalyst is not volatile in the reaction, and It will be mixed in the residue and carbon black after the reaction, so that the stone anti-black is difficult to be purified and purified in the industry without commercial value. And the reaction process is carried out under the pressure of 2kg / cm2, the equipment material and strength are not high, the investment is large, the environment is harsh, and the conversion rate of rubber to oil is also low, only about 37%. In addition, US4108730 discloses a method for performing a catalytic reaction using a technically complicated fluidized catalytic bed. Rubber needs to be mixed with a large amount of heavy oil (heavy oil), followed by catalytic cracking, which limits its production plant to be built near oil refinery. Moreover, the sulfur content of the product light oil is high)) and the production of fine process towels will produce SOC and environmental pollution that are several times higher than the environmental protection allowable standards. The secret method 4175211 and the leg 18281 also use a similar method, requiring large heavy oil as a melting agent. In Japanese Unexamined Patent Publication No. 6-2 and No. 8, it is disclosed that a method of adding hydrogen treatment has complicated procedures and no desulfurization steps. The purpose of the present invention is to provide a method for producing gasoline, diesel, and carbon black from waste rubber (including tires). The steps include: first performing a thermal cracking reaction, then performing desulfurization, denitrification, and finally performing a catalytic cracking reaction. According to the present invention, after the waste rubber raw material has been appropriately processed in advance, it is fed into the pyrolysis reactor via a screw feeder or to a reinjection-based feeder. At the same time as the materials enter, start the spiral stirrer in the thermal cracking reactor to stir. The stone anti-black generated after the thermal cracking reaction is discharged out of the kettle under the driving of a spiral mixer, and the smaller molecular hydrocarbon gaseous phase produced by the cracking enters a desulfurization and / or denitrification tank, and then enters a fixed bed. Further remove the remaining sulfur and nitrogen, and carry out the primary catalytic cracking simultaneously. The Chinese and National Standards (CyS) A * specifications (2 丨 〇 &^; 297 mm) are applicable. (Please read the (Please fill in this page again)

1T ΦΑΎ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 517078 A7 B7 V. Description of the invention (>) ~ '(please read the precautions on the back before filling this page) Solution; then the gas phase materials enter catalytic cracking The device performs catalytic cracking, and the product after catalytic cracking is separated to obtain the desired product after condensation. The spiral mixer provided in the thermal cracking reaction kettle of the present invention can reduce coking of materials and improve heat transfer efficiency. When the screw mixer rotates in the forward direction, it can stir the raw materials, and in the reverse direction, it can send the generated carbon black to the outside of the fleas. The invention selects a unique catalyst and adds a desulfurization and / or denitrification device before the catalytic cracking, which ensures that the catalyst is not contaminated by sulfur, prolongs the service life, expands the scope of processing raw materials, and overcomes Problems with the prior art.

The main chemical cracking reactions of the present invention are as follows: nCH2 = C—CH = CH2 catalyst, 350—500 ° CX atmospheric pressure or slightly higher than normal pressure n [C + H2 + C2H4 + C2H6 + C3H8 + C3H6 + C4H8 + C4Hl0 + C5Hl0 C5H12 + C6H6 + C7H8 + ... + C12H24 + C12H26 + ... + C20H40 + C20H42 + ... + C25H52] where X is CH3 (or SR, SBR, BR 'IR, IIR , CR, NBR, EPM); C6Hh ~ CL] are gasoline components, C12H26-C2QH42 are diesel components, and CH4-QHio are combustible gases. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Please refer to Figure 1, which is a reaction flowchart of the present invention. As shown in Figure 1, 27 is a screw feeder or reciprocating plug-type feeder, 1 is a heating kettle, 5 is a thermal cracking reaction kettle, 2 is a spiral stirrer, 8 is a desulfurization and / or denitrification device 9 is a continuous desulfurization and / or denitrification device, which is also a primary catalytic cracking device, 10 is a catalytic cracking device, and 25 is a fractionation column. According to the present invention, the waste rubber (NR 'SR' SBR, BR, IR, CR, and this paper size are applicable to the Chinese national standard (cps) A4 specification (210'4297 mm) '517078 A7 B7 V. Description of the invention (p) (Please read the precautions on the back before filling out this page) NBR, EPM, IIR, etc.) Pre-treatment to remove impurities. The heating source 1 provides a heat source to heat the pyrolysis reactor 5 and the temperature in the kettle is controlled at 350 ~ 500 ° C. The treated waste rubber is added to the reaction dad 5 through the feeding hole 3. At the same time as the materials entered, the spiral stirrer 2 in the thermal cracking reactor 5 was started for stirring. Within this temperature range, the rubber raw material undergoes a thermal cracking reaction, and is decomposed into smaller molecular hydrocarbon gaseous substances in the reaction vessel 5. The residue after the waste rubber is completely decomposed in the reactor 5 is carbon black, and under the action of the spiral stirrer 2, the carbon black is discharged out of the reaction valve 5 through the valve 6 and can be sold as industrial carbon black. The gas phase hydrocarbons with smaller molecules enter the desulfurization and / or denitrification device 8 from the top of the reactor 5, and the device 8 is provided with alkaline substances [such as NaOH, K0Η]. NaOH has a melting point of 318 ° C and a boiling point of 1182 ° C. It is in a molten state in the temperature range of 350 -450 ° C. Gas phase hydrocarbons pass through a molten base in a molten state, which has low fluid resistance and does not cause gas phase material obstruction. After that, most of the acid gases generated by thermal cracking such as S02, S03, IfeS, etc. are absorbed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the desulfurization and / or denitrification device. The gas phase material produced by the system 8 enters the fixed bed 9 and continues to absorb the acid gases and other odorous gases that are not completely absorbed in the device 8 and simultaneously performs the primary catalytic cracking reaction. The catalyst used in the fixed bed 9 is a DL-type catalyst made by the inventors. The gaseous material extracted through the fixed bed 9 enters the catalytic cracking device 10. The catalytic cracking device 10 uses a fixed bed device, and the catalyst is based on The inventor made the XL type catalyst. After the catalytic cracking of the gas-phase material in the fixed bed 9 primary catalytic cracking in the catalytic cracking 10, a series of superimposition reactions, hydrogen transfer reactions, aromatization reactions and other reactions are carried out to generate gasoline, diesel components and other Combustion gases such as gas and other mixtures, the reaction temperature in the fixed bed 9 and the catalytic cracking unit 10 is 250-40 (TC, the pressure is normal pressure or slightly smaller than the paper size applicable to the Chinese National Standard (CNS) A4 specification (210 > ^ 297) Meal) 517078 A7 B7 V. Description of the invention (f) is higher than normal pressure, and the space velocity is 1-2000M3 / h.-The cracked products from the catalytic cracking unit 10 enter the condenser 19 to cool to room temperature, and the mixed liquid is Gas and diesel. It enters the buffer tank 21 through the separator 20, and the gas enters the job slot n through the top of the separator. The flammable gas in this job concept can be returned to Kadapa 1 for combustion. Gas storage tank; ^ The excess gas in the can also be discharged into the atmosphere for combustion and evacuation through the water-tight tank 12. The mixed liquid in the tartar tank 21 / is processed by inorganic acids (such as sulfuric acid, phosphonic acid, etc.) and separates impurities After that, use the oil pump 23 to pump the mixed oil into the Dad 24, heated to 300-40 (TC after entering the sub-guiding tower 25, depending on the gasoline and diesel, depending on the process, is separated in the fractionation tower π 'Gasoline from the top of the tower into the condenser 14, through the oil-water separator into the gasoline storage Device 18. The diesel enters the stripping column 26 through the middle of the fractionation column 25. After the action of superheated steam, its diesel enters the condenser 13, passes through the oil-water separator 15, and finally enters the diesel storage 17. The DL catalyst in the fixed bed 9 It is composed of 30-60% kaolin or activated white clay, 20-50% oxidized zinc (ZnO) or copper oxide (CuO) as active components, and an appropriate amount of aluminum silicate adhesive such as water glass. Dry and calcined at 60 ° C for 3-5 hours. DL catalyst:

Appearance p3x 4 —10mm Bulk density 1 · 0—1 · lkg / L Crushing strength N / cm (pieces) > 40 The working pressure (MPa) is normal pressure-0.5 working temperature. C100 — 450 with airspeed of l-2000M3 / h

The catalyst can be removed to the total sulfur (H2S + C0S) content < 0.05PPM of the XL catalyst in the catalytic cracking unit 10, which is made of HZSM-5 zeolite through the size of this paper to Chinese National Standard (C ^ S) A4 specifications ( 21〇xg97mm) (Please read the notes on the back before filling this page)

1T • 4 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 517078 A7 B7 V. Description of the invention (<) The modified ZnNiHZSM-5 and the synthetic carrier are blocked. The ZnNiHZSM-5 Buddha stone is obtained by impregnating a HZSM-5 Buddha stone with a nitrate solution of a metal such as zinc (Zn), nickel hafnium) or gallium (Ga). In the metal-modified ZnNiHZSM-5 catalyst, Zinc content 丨 5% (preferably 3%), nickel content 0.5-5% (preferably 1.5%) QfiZSM-5 zeolite is a spherical argon type that has been prepared, and the ratio of silicon to aluminum is 38. Sodium 16.5PPM is a commonly used cracking catalyst. The presence of nickel in the ZnNiHZSM-5 catalyst improves the performance of dehydrogenation and cracking, and the content of benzene and toluene is significantly increased.

ZnN i HZSM-5 zeolite improves the aromatization capacity by 20-30% compared with HZSM-5 zeolite. The removed hydrogen causes the double bond (0C) in the raw olefin to be added to a saturated alkane, the gasoline has a high octane number, good stability, and a high exhaustion period. The catalytic conversion reaction of the modified ZnNiHZSM-5 zeolite includes desulfurization polymerization, cyclization, and dehydrogenation, etc., so that a considerable part of the Cs-Cs gas is converted into aromatics and hydrocarbon oils, which improves the conversion rate of the raw materials. . After metal modification, the strength, stability and life of zeolite-5 are 30-50% higher than those of a metal modification such as ZnHZSM-5 or _ZSM-5. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the aforementioned synthetic carrier, which is composed of kaolin and a certain proportion of silica-alumina sol or silica sol, etc .: 1374 kg of 20% sulfuric acid (leg 〇4) solution Added to 〇 79M3 (including

Al2O3 is 46g / L) of Al2 (S04) solution, stir well and cool to room temperature, and then add water glass (12Og / L containing SiO2, with a modulus of 3.2) while stirring. 3 · 3) 4 · 9M3 and 1700kg of kaolin, and stir to obtain a synthetic carrier slurry. The method for preparing XL catalyst is to take 40-60% gold by weight.

517078 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (^) The modified ZnN i HZSM-5 catalyst and 60-40% of the synthetic carrier slurry are mixed and dried in a dry process. 〇Qc calcined for 3 hours. In order to allow your review committee to have further recognition and understanding of the features and effects of the present invention, an example is described as follows: 1) The rubber (tire) is pulverized into 3-5cm pieces after removing mechanical impurities such as sand, wood chips and the like. Shape, then magnetize and remove iron filings, and then use a screw feeder to feed into the thermal cracking reaction father 5 through the feeding hole 3, close the reaction father's feeding cover, and burn coal or heavy oil in the heating furnace 1 to thermal cracking The reaction kettle 5 is heated to make the temperature of the materials in the kettle 5 reach 400-450 ° C. At the same time, the mixer in the father 5 is electrically driven to stir, and the pressure in the cracking reactor 5 is controlled to 0.05 to 〇. · IMPa. Under this condition, the rubber undergoes a thermal cracking reaction, which decomposes into solid carbon black and small-molecular gas phase hydrocarbons. The gas phase hydrocarbons are continuously discharged from the kettle 5 and enter the alkali absorption device 8. The acid gases * H2s, s〇3, s〇2, No, ship 2 and the like come into contact with the molten NaOH in the device 8 to cause a neutralization reaction and are removed. The gas phase hydrocarbons drawn from the device 8 enter the fixed bed 9 again, and the fixed bed 9 The rhenium catalyst is contacted to further remove the remaining sulfur and nitrogen. At the same time, a preliminary catalytic cracking reaction is performed. The gas-phase hydrocarbons drawn out from the fixed bed 9 enter the catalytic cracking device 10 again, and the catalytic cracking reaction occurs when the XL catalyst comes into contact with the device. Both the temperature in the fixed bed 9 and the catalytic cracking unit 10 were maintained at-. c. The pressure is 0.05-G.lMPa. The catalyzed gas phase hydrocarbons are condensed into a liquid mixture. Add sulfuric acid to the liquid mixture and mix well to remove impurities. The liquid mixture after impurities removal is defensed, condensed, and oil-water separated. Finally, various oil products are obtained. Among them, gasoline i38Kg, octane number ⑽) is 93.5, diesel 432Kg, sixteen burning value 59. The heavy oil at the bottom of the branch tower returns to the thermal cracking reaction

(Please read the notes on the back before filling this page} Order ίφψ 0 I- I II. A7

Relysis was performed in 5. When the thermal cracking reversed 5 MW, Wen Lai began to fall, the two 400 ~ 450 (: dropped to 300. (: when the time or table beauty fell to ()) Chiri \ = brother Ming difficult to resolve the reaction 15 _ rubber is completely decomposed At the end of the myelolysis reaction, only solids remain in Cang 5 and black, use a spiral mixer inside Dad 5 to drain out of hole 6 from hole 6. Finally, 57% of oil, 32% of carbon black, and volatile gas are obtained. 11%.…, Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Moderate rule paper-quasi | Α4 V- / S Ν / I cm

Claims (1)

517078 (Revised Patent Application Scope No. 08-2007 for Re-examination of the Patent Scope) 1. A method for producing gasoline diesel and carbon black from waste rubber, including crushing the waste rubber into small pieces and adding In the thermal cracking reaction, the waste rubber undergoes a thermal cracking reaction at 400 600C under the condition of 0.02-0.1Mpa to generate gas phase hydrocarbons and solid carbon black. The gas phase hydrocarbons are discharged out of the kettle and passed through desulfurization and / Or denitrified alkali absorption device, then pass through the fixed bed of DL catalyst for the first-stage catalytic reaction, and then pass through the fixed bed of XL catalyst for the second-stage catalytic reaction, and generate mainly gasoline Gas phase hydrocarbons of diesel molecular structure, which become liquid mixtures after condensing. Add inorganic acids to the liquid mixture to remove impurities, and separate brown or black precipitates, and then divide and condense the liquid mixture. , Oil and water separation or oil refining and other conventional treatments, and finally get gasoline and diesel; the solid carbon black in the reactor is discharged out of the kettle through the stirring device in the kettle, and the aforementioned DL-type catalyst uses the following method Preparation ··· 3,60% by weight of kaolin clay or activated white clay as a carrier, 20-50% by weight of ZnO or copper oxide CuO as an active component, and a weight percentage of 10 -20 ° /. A binder containing silicon or aluminum, such as a sodium silicate solution, is formed by mixing, drying, and burning at 600 ° C for 3-5 hours. In addition, the XL catalyst is prepared by the following method: the weight percentage is 60%. _40% synthetic carrier and ZnNiHZSM-5 with a weight percentage of 40-60% are uniformly mixed, shaped, and dried at 600. (: Combustion for 3-5 hours, the aforementioned synthetic carrier is obtained by adding 1374KG of 20% sulfuric acid to a 0.79M3 sulfuric acid solution with an oxidation content of 46 g / L, stirring and cooling to room temperature, then Add 4.9M3 water glass with 120 g / L SiO2 and 1700KG kaolin, stir (please read the precautions on the back before filling this page) Order ---- Consumer Consumption Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs Printed 517078 A8 B8 C8 _ D8 6. The patent application range is mixed evenly; the ZnNiHZSM-5 catalyst is prepared by first soaking the commercial HZSM-5 zeolite with a zinc, nickel or gallium nitrate solution Or ion-exchange, followed by drying; among them, the weight percentage of zinc is 1-5%; the weight percentage of nickel is 0.5-5%, the silicon-aluminum ratio is 20-200, and the grain size is 0.8-1.6cm 2. The method for producing gasoline diesel and carbon black from waste rubber as described in item 1 of the scope of the patent application, wherein the alkali in the alkali absorption device is inorganic, selected from NaOH, KOH, etc., the alkali absorption device or fixed The temperature of the bed or catalytic reaction is 350-400 ° C, and the pressure is 0.02-0.1Mpa 3. The method for producing gasoline diesel and carbon black from waste rubber as described in item 1 of the scope of the patent application, wherein the weight percentage of the binder containing silicon or aluminum used in the preparation of the DL catalyst is 15%. The method for producing gasoline, diesel, and carbon black using waste rubber as described in the scope of the patent application (1), wherein the weight percentage of zinc is 3%, and the weight percentage of nickel is 1.5%. ------------ -------- Order -------- (Please read the note on the back? Matters before filling out this page) The paper printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies this national paper standard (CNS A4 Regulation