KR20160019914A - Fast Catalytic Co-Pyrolysis Process for the High Quality Bio-oil Recovery from the Biomass - Google Patents

Abstract

A large number of technologies regarding a fast pyrolysis method for converting biomass to bio-oil have recently been developed in the world. However, the bio-oil restored by using this method has very different characteristics and quality from the quality of petroleum oil and is not good enough to be used as fuel oil to be practical. The present invention combines the prior art patent applications represented by Patent No. 10-2003-40640 and Patent No. 10-2010-1180580 in order to input molten waste plastic materials which are pretreated in advance (1) into a melting apparatus (3) by using a dual thermal decomposition apparatus (5) continuously while mixing dry biomass powder with a high temperature catalysis of 550-600°C and continually inputting the mixture thereto from a vertical drop thermal decomposition apparatus (18), thereby merging and thermally decomposing the biomass and waste plastic mixture. Accordingly, the present invention can enhance quality by using the synergies of the coupling, re-decomposition, and hydrogenation of the products of the decomposition reactions in order to provide a cost-effective method of restoring the high-quality bio-oil meeting the fuel petroleum quality standards.

Description

[0001] The present invention relates to a rapid catalytic pyrolysis process for recovering high-quality bio-oils from biomass,

TECHNICAL FIELD OF THE INVENTION The present invention relates to a rapid merge pyrolysis method of biomass and mixed synthetic resin. Biomass is a renewable resource collectively referred to as living resources on the earth. Among them, woody biomass with low recycling rate is composed of cellulose, hemicellulose and lignin, and when it is pyrolyzed, it is converted into charcoal, syngas and bio oil. Recently, the rapid pyrolysis method is a method of rapidly heating woody biomass in the vicinity of 500 ° C in a few seconds to increase the yield of bio-oil up to 75%, and is widely used as a fluidized bed method, a rotary cone method, (ABLATIVE) method, and TWIN-AUGER method have been developed, and the power generation facilities employing these have been operated in Gumi with 5 ~ 6 sites and dozens of processes are under development.

Mixed waste plastics in the living system are produced by mixing aliphatic polymer compounds such as vinyl chloride resin (PVC), poly (ethylene terephthalate), and polypropylene (PP) with poly (ethylene terephthalate) A mixture of aromatic polymer compounds such as a styrene-butadiene-styrene (ABS) resin, which is a pyrolysis method, can be decomposed into low-molecular substances by heating them with high heat without contact with air, Is a public law. However, the pyrolysis reaction is a sensitive catalytic reaction in which flammable vapor of high temperature is generated. Also, since the pyrolysis reaction temperature reaches 500 ° C, the pyrolysis point of generated low molecular hydrocarbons is higher than that of the resulting low molecular hydrocarbons, Due to catalyst pollution and loss of activity, it is not practical to use due to excessive production of gas and tar-like carbides, mechanical vulnerability of the apparatus, and difficult operating method. In addition, half-blend plastic waste plastics contain vinyl chloride resin (PVC), which has a relatively low pyrolysis temperature and releases a large amount of corrosive gas, chlorine, when decomposed. , Which is an element that hinders practical use of the recovered fuel oil.

Patent Application No. 10-2003-40640 has developed a method suitable for pyrolysis of biomass and synthetic resin by improving air-flow pyrolysis technology which is known pyrolysis method. The reaction step is divided into a one-stage drop thermal decomposition and a two-stage drop thermal decomposition. In the one-stage drop thermal decomposition step, the thermoplastic resin melted by high heat is first pyrolyzed in the mixed waste synthetic resin, In the dropping thermal decomposition step, a high-temperature catalyst is additionally introduced into the reactor to increase the temperature to pyrolyze the powdery biomass and the thermosetting resin which have not reacted in the previous stage, thereby generating a decomposition gas of a low molecular hydrocarbon, Is effectively continuously pyrolyzed in a single reaction system.

Conventional known air flow transport pyrolysis processes are a process in which a liquid or powder waste synthetic resin is continuously fed into a vertical tubular air flow transport pyrolysis reactor in which regenerated high temperature regenerated catalyst is circulated together with decomposition gas or inert gas to produce a high temperature regenerated catalyst and a raw resin In the case of the air flow transport thermal cracking reactor, there are two methods of ascending and descending. However, the reaction time is very short as a few seconds, so that the thermal decomposition temperature and conditions are varied It is difficult to completely pyrolyze the mixed synthetic resin as a single reaction step. U.S. Patent No. 6,534,689 attempts to complete the reaction by performing pyrolysis of the fluidized bed again in the lower part of the falling-type air flow pyrolyzer. However, in order to form a fluidized bed, it is necessary to blow a decomposition gas or an inert gas to the bottom of the fluidized bed, which hinders the recovery of the produced hydrocarbons and the removal of the hydrogen chloride gas.

Patent Registration No. 10-2010-1180580 is a high efficiency pyrolysis method of mixed synthetic resin. Pyrolysis is a method of heating a polymer compound with high heat without contact with air and decomposing it into small molecules by the action of a catalyst, Aromatic monomers. However, mixed mixed waste plastics contain vinyl chloride resin (PVC), which has a relatively low pyrolysis temperature and releases a large amount of corrosive gas, chlorine, during the pyrolysis process, resulting in contamination of the generated fuel oil, . In order to prevent the contamination of recycled fuel oil, this method first decomposes resin streams having a low decomposition temperature such as vinyl chloride resin and polystyrene resin as one step, and rapidly recovers the product hydrogen chloride and low boiling point oil, The petroleum plastics are continuously withdrawn from the kerosene liquefied hydrocarbons from which contamination of chlorine has been removed by continuously feeding the petroleum plastics into the two-phase fluidized bed binary auger catalytic pyrolyzer. At this time, the high boiling point waxes descending to the bottom of the distillation column are pyrolyzed It is a selective multi-stage catalytic pyrolysis method which is recovered by kerosene flow.

The characteristics of the bio-oil produced by the rapid pyrolysis of biomass are unstable due to the high moisture content of about 30%, the high oxygen content of about 40%, the low heat of combustion (HHV) of about 20 MJ, and low PH and foreign substances, Deposits are formed, and it is difficult to use the storage and general combustor, which is low practicality.

Bio-oil can be upgraded to fuel for transportation such as gasoline and diesel oil due to hydrogenation process and catalytic cracking, but it is not practical because it requires facility investment and cost of expensive equipment. However, in high temperature catalyst hopper (6) The high temperature catalyst is dropped in a vertical dropping thermal cracker 18 and the dried powder biomass is supplied to the vertical dropping thermal cracking unit 18 in the biomass hopper 4 in a quantitative manner, The biomass and the high temperature catalyst are rapidly thermally decomposed by heating to 500 ° C. within a few seconds in direct contact with the turbulent flow and are continuously introduced into the fluidized bed paired auger thermal cracker 5 and the mixed waste plastics melted from the melter 3 are paired The biodegradation steam is continuously introduced into the auger pyrolyzer 5 and pyrolyzed to produce a synergistic effect of a chain reaction such as a series of binding, decomposition and hydrogenation between decomposition products in the biodegradable vapor and the biodegradable vaporizer 5 The Catalyst regeneration circulation rapidly merge catalytic pyrolysis process to be nitrided it can be recovered with high quality bio-oil economically.

1) The woody biomass that has been simply incinerated is made into high quality bio-oil with less than 5% moisture, less than 10% oxygen and more than 40MJ of combustion heat (HHV).

2) The total annual amount of biomass in Korea is about 80 million tons, which is equivalent to about 30 million TOE of energy equivalent, which opens up the possibility of supplying renewable energy to replace the light oil for transportation by developing economical high quality technology of bio oil. .

 FIG. 1 is a process diagram of a rapid-merge catalytic pyrolysis process for recovering bio-oil from biomass and mixed synthetic resin.

As will be described in detail with reference to the accompanying drawings,

[1] is a rapid merging catalyst pyrolysis process for recovering high-quality bio-oils from biomass and mixed waste plastics. The pretreated (1) plastic is put into the melting vessel 3 through the automatic injector 2 under nitrogen sealing , The molten plastic is continuously introduced into the fluidized bed biolizer (5) and pyrolyzed. The high temperature catalyst at 550 to 600 ° C is dropped into the falling thermal decomposer 18 in the high temperature catalyst hopper 6 and the dry powder biomass is introduced into the falling thermal decomposer 18 through the outlet of the biomass hopper 4 in a fixed amount, The biomass and the high-temperature catalyst are directly contacted with each other in the falling pyrolyzer 18 in direct turbulence, heated to 500 ° C within a few seconds, and then rapidly introduced into the biodegradable pyrolyzer 5, And is then introduced into the distillation column 8 through the steam pipe to obtain a high-quality bio-oil which is fractionally distilled from the distillation column 5, And is stored in the bio oil tank 13 through the cooler 10. The catalyst is mixed with the pyrolysis charcoal and discharged to the lower part of the pyrolysis pyrolyzer 5 and introduced into the catalyst regeneration furnace 7 by the air flow conveyor circulated by the circulating blower 20 to generate a gas The pyrolysis-producing charcoal mixed with the catalyst is burned by the combustor, and the catalyst is regenerated and calcined at 650 to 750 ° C., transferred to the high-temperature catalyst hopper 6, and then dropped to the vertical drop pyrolyzer 18 and circulated. The wax separated from the distillation column 8 and falling down is re-decomposed at the catalyst fixed bed 9 and is raised again to be fractionally distilled. The low boiling point steam rising at the column top is liquefied in the condenser 11 and flows into the reflux tank 11 And the noncondensed gas is neutralized in the washing tower 14 and collected in the gas tank 16 and then pressurized and stored in the liquefied gas tank 19 so that the liquefied gas Is used to heat the biodegradable pyrolyzer 5 or to be used as a catalytic regeneration fuel in a gas burner of the catalyst regeneration furnace 7 and the excess gas is incinerated in the gas combustion furnace 15.

The symbols of the respective apparatuses in the process diagram of Fig. 1 are as follows;
(1) Pretreatment (11) Reflux tank
(2) Automatic dispenser (12) Condenser
(3) Melting machine (13) Bio-oil tank
(4) Biomass Hopper (14) Cleaning Tower
(5) Pair auger pyrolyzer (15) Gas burner
(6) High temperature catalyst hopper (16) Gas tank
(7) Catalyst regeneration furnace (17)
(8) Distillation tower (18) Vertical drop pyrolyzer
(9) Catalytic stationary phase (19) Liquefied gas tank
(10) Coolers (20) Circulating blowers

Claims (1)

In recovering high quality bio-oils from biomass;
1) The high-temperature catalyst at 550 to 600 ° C is dropped in the high-temperature catalyst hopper 6 by the vertical dropping thermal cracker 18 and the dried powder biomass is quantitatively measured by the vertical dropping thermal cracker 18 in the biomass hopper 4 The biomass and the high-temperature catalyst are directly thermally decomposed in a few seconds by direct contact with the biomass and the high temperature catalyst in the vertical drop pyrolyzer 18, heated to 500 ° C. and continuously introduced into the fluidized bed pair auger decomposer 5, The mixed waste plastics melted from the reactor 3 are continuously introduced into the two-auger pyrolyzer 5 and pyrolyzed so that the biomass liquefied steam is mixed with the plastics decomposed vapor in the biplane pyrolyzer 5 to form a series of decomposition products The bio-oil, which has been upgraded by chain reaction such as binding, regeneration and hydrogenation, is fractionally distilled from the distillation column 8 and recovered.
2) Characteristics of recovered high-quality bio-oil satisfies 5% or less moisture, 10% or less oxygen, 40H or more in heat of combustion (HHV)
3) The input ratio of biomass to plastic is 1: 3 to 3: 1, usually 1: 1,
4) The feed rate of biomass and high temperature catalyst is between 1:20 and 1: 2, usually 1:10, the biomass temperature of the vertical drop pyrolysis outlet is automatically controlled by adjusting to 500 to 600 ° C,
5) catalyst is mixed with the pyrolysis-producing charcoal and discharged to the lower portion of the pyrolyzer 5, introduced into the catalyst regeneration furnace 7 by the air flow conveyor circulated to the circulating blower 20, The catalyst is burned and regenerated at a temperature of 650 to 750 占 폚, the catalyst is transferred to the hot catalyst hopper 6, and the catalyst is discharged again to the falling pyrolyzer 18 by burning the pyrolysis-
Characterized in that, through the above-described continuous circulation process, high-quality biomass that can be practically used economically is recovered by the synergistic effect of the biomass and the mixed waste plastic by the thermal decomposition of the combined waste plastics, Catalytic pyrolysis method

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