WO2008111750A1 - The method and system for contact catalytic cracking by upward moving bed catalyst - Google Patents

The method and system for contact catalytic cracking by upward moving bed catalyst Download PDF

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Publication number
WO2008111750A1
WO2008111750A1 PCT/KR2008/001201 KR2008001201W WO2008111750A1 WO 2008111750 A1 WO2008111750 A1 WO 2008111750A1 KR 2008001201 W KR2008001201 W KR 2008001201W WO 2008111750 A1 WO2008111750 A1 WO 2008111750A1
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Prior art keywords
catalyst
catalytic cracking
synthetic resin
waste synthetic
regenerator
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PCT/KR2008/001201
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French (fr)
Inventor
Jae Sak Koo
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Jae Sak Koo
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Publication of WO2008111750A1 publication Critical patent/WO2008111750A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/082—Controlling processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/16—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "moving bed" method
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4087—Catalytic distillation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a method and system for contact catalytic cracking by which hydrocarbons can be efficiently decomposed, and, more particularly, to a method and system for contact catalytic cracking using an upward moving-bed catalyst, in which hydrocarbons are decomposed using an upward moving-bed catalyst, and the catalyst is regenerated using an electric heating method, thereby increasing the efficiency of the decomposition of hydrocarbons and the efficiency of the regeneration of the catalyst, and in which catalyst circulation can be accurately controlled, and decomposed hydrocarbon gases cannot be fired, so that methods for treating waste synthetic resin can be widely used.
  • the catalyst that is used in the present invention is a catalyst generally used in the contact catalytic cracking of hydrocarbons, and is a solid acid catalyst including spherical particles the same as those of a zeolite catalyst.
  • the contact catalytic cracking method which is compared to thermal cracking, is a technology for decomposing heavy oil, such as asphalt, into light oil in large quantities in a short period of time using a solid acid catalyst having acidic characteristics and a large porous area of about 200 ⁇ 800 mVg, in which heat necessary for decomposing hydrocarbon polymers is supplied to the process together with a solid acid catalyst having the same form as a zeolite catalyst.
  • the contact catalytic cracking method is a continuous circulation-loop type catalytic cracking method in which a catalyst can be continuously used by regenerating the catalyst by oxidizing carbon remaining in pores of the catalyst, the carbon being produced by the decomposition of hydrocarbons, using air.
  • oil refining companies modify this contact catalytic cracking into fluid catalytic cracking (FCC), and this fluid catalytic cracking (FCC) is used in the process of decomposing asphalt, which is a final residue in vacuum distillation, into light oils, such as gasoline, kerosene, diesel oil, etc., without leaving behind any asphalt.
  • FCC fluid catalytic cracking
  • a fluid bed is made in a fluid catalytic cracking reaction tube (Riser) by shooting powdered catalyst upwards at a speed of 25 m/sec, and when asphalt is injected into the fluid bed, the asphalt is decomposed into gas oil in several seconds by a solid acid catalyst, and then the gas oil is separated from the solid acid catalyst in a cyclone located at the upper portion of the reaction tube, and then the separated gas oil is converted into various kinds of light oils through subsequent condensing, distilling and refining processes and finally recovered.
  • iser fluid catalytic cracking reaction tube
  • a fluid catalytic cracking apparatus includes a reaction tube and a cyclone, the sum of the height of the reaction tube and the height of the cyclone being about 30 ⁇ 50 m, and has a treatment capacity of 30,000 ⁇ 100,000 barrels per day. Therefore, this fluid catalytic cracking apparatus is a large sized apparatus, and it is basically impossible to manufacture a small sized fluid catalytic cracking apparatus, so that it has been limited to develop the fluid catalytic cracking apparatus in other uses. Moreover, in the fluid catalytic cracking apparatus, a catalyst regeneration tower also has a heavy weight of about 600 ⁇ 1,000 tons.
  • gas heated by a burner is blown into a highly-concentrated fluid bed catalyst, flowing downwards, and then from down to up at high pressure, and thus carbon deposited on the fluid bed catalyst or non-vaporized hydrocarbons are fired, and then continuously fired by the blowing air.
  • the fluid bed catalyst in order to uniformly regenerate the fluid bed catalyst, the fluid bed catalyst must maintain the fluid bed structure, and air flow must be of a plug flow type without causing a channeling phenomenon. Therefore, in order to maintain the air flow under high pressure, it is required to manufacture a large-sized fluid catalytic cracking apparatus.
  • gas oil which is a product obtained by decomposing synthetic resins through a catalytic cracking process
  • gas oil is an inflammable gas which can leak easily, unless the gas oil is completely separated from a catalyst regenerator filled with air
  • methods or apparatuses for solving these problems are not proposed.
  • a first object of the present invention is to provide a contact catalytic cracking method, which enables decomposed gases to become easily detached from the catalyst and easily vaporized by preventing the catalyst from continuously lying on a moving bed due to the downward movement of the catalyst, and which can naturally increase thermal efficiency by controlling the flow of the catalyst and the flow of decomposed gas oil.
  • a second object of the present invention is to provide an economical catalyst regeneration technology, which can exhibit a fluid bed effect even in a moving bed catalyst regeneration tower, and in which the heat of combustion of a catalyst is used as an ignition source, and thus a supply of heat is not required.
  • a third object of the present invention is to provide a technology allowing stable circulation of a catalyst.
  • a fourth object of the present invention is to provide a technology of basically preventing the ignition of fluids when the fluids move between apparatuses through pores of a particulate catalyst due to the difference in pressure between the apparatuses.
  • the present invention provides a contact catalytic cracking method, in which a catalyst flows from a down location upwards, contrary to conventional catalytic cracking methods, so that the heat supplied to the catalyst flows from a down location upwards and simultaneously enables the decomposed gas detached from the catalyst to naturally vaporize, and in which the size of a catalyst moving bed is minimized, so that the catalyst is prevented from lying on the catalyst moving bed, with the result that decomposed gas can be easily detached from the catalyst.
  • the present invention provides a contact catalytic cracking apparatus using an upward moving bed catalyst (referred to as a bucket elevating cracker) provided therein with a bucket elevator transferring a catalyst from a down location upwards and an electric heater controlling the temperature in the upward catalytic cracking apparatus.
  • This bucket elevator includes a bucket filled with the catalyst, a conveyor link forming a transfer pathway while moving up and down and rotating, and a sprocket gear transmitting power to the conveyor link from the outside or supporting the movement of the conveyor link.
  • the bucket may have a volume of below 50 L, and the outer wall of the bucket is formed of meshed screen, so that decomposed gas oil formed in the catalyst can be easily detached therefrom.
  • the size and number of the bucket elevators is very important to determine reaction time. It is preferred that the reaction time in the catalytic cracking apparatus be 3 ⁇ 10 minutes. In consideration of the reaction time, the size and number of the buckets and the length of the conveyor link are to be determined.
  • a temperature control unit provided in the contact catalytic cracking apparatus serves to maintain reaction temperature. In order to prevent the ignition of the decomposed gas oil due to the introduction of oxygen, a heater emitting radiant heat is used as the temperature control unit. It is preferred that the reaction temperature be controlled in a range of 450 ° C ⁇ 550 ° C .
  • the present invention provides an apparatus for sucking decomposed gas oil produced in the contact catalytic cracking apparatus and then rapidly discharging the decomposed gas oil to the outside.
  • This apparatus includes a pressure transmitter measuring the pressure of the decomposed gas oil and a suction blower discharging the decomposed gas oil, and serves to collect the decomposed gas oil without causing the difference in pressure between a contact catalytic cracking reactor and a catalyst regenerator.
  • a moving-bed catalyst regeneration tower is manufactured in a vertical fashion such that the combustion heat flowing upward from the catalyst regeneration tower can easily burn carbon in the catalyst lying on the upper portion of the catalyst regeneration tower, and a multi-stage air supply unit is vertically provided in the catalyst regeneration tower such that the flow of air on a moving bed is the same as the flow of air on a fluid bed, and further, electric heaters having the same number as the air distributors are provided in the catalyst regeneration tower.
  • the present invention provides a vertical catalyst regeneration tower, the inner diameter and capacity of which is designed such that it takes 3 ⁇ 10 minutes to regenerate a catalyst, and the inner wall of which is provided with a castable refractory material in order to prevent it from being overheated by combustion heat .
  • the present invention provides multi-stage air distributors and electric heaters, which are vertically provided in the catalyst regeneration tower.
  • the multi ⁇ stage air distributors are uniformly distributed in the catalyst regeneration tower, and enable air to uniformly flow in a catalyst moving bed as well as in a catalyst fluid bed, and are provided in the catalyst regeneration tower together with the electric heaters such that the air distributor and electric heater make a pair.
  • the electric heaters are provided right over the respective air distributors in order to efficiently supply heat and to prevent the electric heaters from being damaged by the air becoming overheated owing to the accumulation of air.
  • the amount of the catalyst loaded in a catalyst regenerator and catalyst storage units are accurately measured in real time, and thus the catalyst regenerator and catalyst storage units are operated such that these measured data are combined with the control speed of a catalyst transfer unit.
  • the present invention provides a load cell unit measuring the weight of two catalyst storage units (referred to as "catalyst hoppers" ) located between a catalyst reactor and a catalyst regenerator.
  • the load cell unit In order for the load cell unit not to be influenced by the change in weight of the two catalyst storage units, the change in weight thereof being caused by pipes connected to the catalyst storage units, the catalyst storage units are connected to each other using flexible pipes.
  • the present invention provides an apparatus for measuring the level of a catalyst in the upper portion of a catalyst generator.
  • This apparatus measures the height of a catalyst in the upper portion of a catalyst regenerator using a laser, and is provided with an additional measuring tube to compensate for the measuring error caused by dusts and flame generated from a combustion furnace in the upper portion of the catalyst generator.
  • the present invention provides screw feeders provided at the lower ends of the catalyst storage units and the catalyst regenerator and the above mentioned bucket elevator in the catalytic cracking reactor. These screw feeders and bucket elevator are operated by a reduction motor controlled by a frequency control unit, and their speeds are controlled by the weight of the load cell and the values measured by a laser sensor.
  • a catalytic cracking reactor may not be controlled by measuring and controlling the amounts of the catalysts charged in the catalyst regenerator and the catalyst storage units.
  • the present invention provides the above mentioned catalyst storage unit, which is a physical device serving to compensate for the ununiform flow of a catalyst and to basically prevent the phenomenon in which decomposed gas oil charged in the contact catalytic cracking reactor is brought into contact with air charged in the catalyst regenerator, and thus the decomposed gas oil is fired.
  • the height of the catalyst stored in this apparatus must be determined by pressure loss design.
  • the present invention provides a heat exchanger, which is provided at the rear end of a combustion gas outlet in order to remove excess positive pressure caused by the thermal expansion of combustion gas in the upper portion of the catalyst regenerator, and which serves to enable the combustion gas to be easily discharged by greatly decreasing the volume of the combustion gas, and provides a pressure balancing pipe which serves to transfer the high-pressure air coming out of the lower end of the catalyst regenerator in the direction in which discharged gases flow without applying any pressure load to the catalyst storage unit.
  • the contact catalytic cracking system using a upward moving bed catalyst according to the present invention is advantageous in that it can overcome the problems of a decrease in decomposition efficiency, ununiform catalyst generation, uneconomical thermal efficiency, an unreliable catalyst circulation control method, and the ignition of decomposed gases in the contact catalytic cracking system, and further in that it can maintain the rapid decomposition of raw materials and the uniform regeneration performance of the catalyst, and in that it can be variously designed in small size.
  • FIG. 1 is a schematic view showing a contact catalytic cracking system according to an embodiment of the present invention.
  • the system for catalytic cracking using a moving bed catalyst includes a mixer for mixing a molten polymer, which is a raw material used for cracking, with a catalyst; a catalytic cracking apparatus using an upward moving bed catalyst (referred to as a bucket elevating cracker); a vertical catalyst regenerator; two catalyst storage units (referred to as catalyst hoppers); three catalyst transfer units (referred to as screw feeders); and the like.
  • the mixer 1 serves to mix a molten hydrocarbon polymer, which is a raw material used for cracking, with a regenerated catalyst. Since the catalyst introduced into the mixer 1 from a catalyst transfer unit 12 supplies most of heat necessary for cracking, the catalyst is referred to as a contact catalyst.
  • the mixing ratio of the catalyst to the raw material is determined in consideration of total decomposition heat and evaporation heat. In the present invention, it is preferred that the mixing ratio of the catalyst to the raw material be 3 ⁇ 10: 1.
  • the temperature of the catalyst is in a range of 450 ° C ⁇ 550 ° C
  • the temperature of the raw material is in a range of 300 ° C ⁇ 350 ° C .
  • the mixer 1, having a cylindrical shape, is provided therein with a zigzag multi-stage slope way such that a catalyst curtain is formed when a catalyst flows through the multi-stage slope way and falls down.
  • the raw material is introduce into the middle portion of the mixer 1, and then mixed with the catalyst.
  • wax materials which are formed into azeotropes and vaporized by low molecular weight gas, are instantaneously produced. These wax materials move toward the top of the mixer 1, and simultaneously come into contact with the catalyst on the catalyst curtain, so that they are decomposed again.
  • a discharge line is connected to the upper portion of the mixer 1 such that decomposed gases are discharged therethrough.
  • the contact catalytic cracking apparatus 2 is provided therein with electric heaters in order to compensate for thermal loss. These electric heaters emit radiant heat to prevent the ignition of decomposed gas oil.
  • the temperature of the contact catalytic cracking apparatus 2 is in a range of 350°C ⁇ 450°C .
  • a suction blower 14 is provided over the contact catalytic cracking apparatus 2.
  • the suction blower 14 serves to forcibly discharge excess decomposed gas oil produced in the catalytic cracking apparatus 2 to maintain the temperature of the catalytic cracking apparatus 2 constant. Due to this action of the suction blower 14, reaction yield can be increased without performing a steam stripping process and an oil separation process in fluid catalytic cracking.
  • the catalytic cracking apparatus 2 is completely sealed such that decomposed gas oil is not brought into contact with external air. After the decomposition reaction, the catalyst is transferred to a regenerative catalyst storage unit 3 (referred to as a catalyst hopper).
  • Regenerative catalyst storage unit (catalyst hopper) ⁇ 62> After the decomposition reaction, the catalyst is transferred to a regenerative catalyst storage unit 3 from the contact catalytic cracking apparatus 2 along a sloping path.
  • the regenerative catalyst storage unit 3 is provided in consideration of being placed at a sufficient height such that it can prevent the movement of fluid due to the difference in pressure between the catalytic cracking apparatus 2 and a catalyst regenerator 4.
  • the regenerative catalyst storage unit 3 has a function of measuring the change in weight of the catalyst. In order to accurately measure the change in weight of the catalyst, the regenerative catalyst storage unit 3 is connected to outer apparatuses using a flexible pipe. Further, the regenerative catalyst storage unit 3 has another function of refilling a new catalyst corresponding to the loss of the circulated catalyst.
  • a horizontal screw feeder 10 serves to control the total amount of the catalyst.
  • the catalyst discharged from the catalyst storage unit is introduced into a catalyst regenerator 4 by the catalyst transfer unit 10, and the carbon deposited in the pores of the catalyst is burned.
  • Electric heaters 7 are used as the ignition source.
  • the electric heaters 7 are disposed in the catalyst generator 4 at regular intervals to uniformly regenerate the catalyst.
  • Air distributors 8 are disposed right under the respective electric heaters 7, and serve to uniformly diffuse the heat generated from the electric heater 7 and to supply air into the catalyst generator 4.
  • the carbon deposited on the catalyst can be continuously burned by the heat generated from the electric heaters 7 and the air supplied from the air distributors 8.
  • the normal operating temperature of the catalyst regenerator 4 is 650°C ⁇ 750°C .
  • the catalyst regenerator 4 Since the catalyst regenerator 4 is provided with a heat exchanger for cooling air at the rear end thereof, combustion air is easily discharged due to the pressure difference, so that back pressure does not occur, thereby decreasing the load of the entire process.
  • a laser reflection type level measuring device 13 is provided in the top portion of the catalyst regenerator 4. This level measuring device 13 is particularly fabricated using an air-purging type laser in order to remove the measurement error caused by dust and flame.
  • the time taken to regenerate the catalyst in the catalyst regenerator 4 is determined by a horizontal screw feeder 11 provided under the catalyst regenerator 4. It is preferred that the time taken to regenerate the catalyst be in a range of 3 ⁇ 10 minutes.
  • the catalyst regenerated in the catalyst regenerator 4 is transferred to a reactive catalyst storage unit 5 by a catalyst transfer unit 11.
  • this reactive catalyst storage unit 5 serves to prevent the air in the catalyst regenerator 4 from being brought into contact with the decomposed gas in the catalyst cracking apparatus 2, and serves to solve the excessive heat and pressure in the catalyst. Therefore, unlike the regenerative catalyst storage unit 3, the reactive catalyst storage unit 5 is provided therein with a heat exchanger for cooling a catalyst, so that the catalyst is made to have a temperature necessary for reaction, thereby preventing the introduction of overheated catalyst. Further, the reactive catalyst storage unit 5 is configured to be pressure- balanced with a flue gas line such that the positive-pressure air introduced into the reactive catalyst storage unit 5 from the catalyst regenerator 4 does not flow into the catalytic cracking apparatus 2 and can be safely discharged.
  • the catalyst in the reactive catalyst storage unit 5 is introduced into the mixer 1 by a catalyst transfer unit 12 at a predetermined flow rate, while the weight of the catalyst being maintained constant.
  • waste synthetic resins are difficult to collect in large quantities in one place, considering transportation expenses, collection routes, and the like, they are actually treated in small quantities at every place from which the waste synthetic resins are collected. Further, since waste synthetic resins are difficult to select because they are mixed with other waste materials or foreign materials, the ratio of recycled synthetic resins is very limited. These waste synthetic resins which cannot be recycled incur environmental pollution and increase treatment expenses.
  • the contact catalytic cracking apparatus using a upward moving bed catalyst according to the present invention is designed such that waste synthetic resins, which are collected in small quantities and have low recycle ratio, are more efficiently decomposed and treated. Since this contact catalytic cracking apparatus functions to prevent the deterioration of catalytic performance by separating undecomposed inorganic materials from a catalyst in a catalytic cracking process, it can be very usefully used to decompose and treat waste vinyl products which are very difficult to treat in agricultural villages.
  • the present invention provides an apparatus for converting waste synthetic resins, which are difficult to recycle, into higher value-added fuel oils. Since this apparatus does not produce decomposed residues, like fluid catalytic cracking apparatuses, it contributes to environmental conservation.

Abstract

The present invention relates to a method of producing light oils by decomposing hydrocarbon polymers through a contact catalytic cracking process, and, particularly, to a method of decomposing heavy oils into light oils through conventional fluid catalytic cracking (FCC) or moving bed catalytic cracking (MBCC), which can be designed in a small size. The present invention provides a method of continuously decomposing and treating a waste synthetic resin, the method having a catalyst circulation structure including: contact catalytic-cracking a waste synthetic resin using an upward moving bed catalyst by a bucket elevator; regenerating the catalyst using an electric heating type vertical catalyst regenerator, wherein catalyst storage units are provided for each of the processes.

Description

[DESCRIPTION] [Invention Title]
THE METHOD AND SYSTEM FOR CONTACT CATALYTIC CRACKING BY UPWARD MOVING BED CATALYST [Technical Field]
<i> The present invention relates to a method and system for contact catalytic cracking by which hydrocarbons can be efficiently decomposed, and, more particularly, to a method and system for contact catalytic cracking using an upward moving-bed catalyst, in which hydrocarbons are decomposed using an upward moving-bed catalyst, and the catalyst is regenerated using an electric heating method, thereby increasing the efficiency of the decomposition of hydrocarbons and the efficiency of the regeneration of the catalyst, and in which catalyst circulation can be accurately controlled, and decomposed hydrocarbon gases cannot be fired, so that methods for treating waste synthetic resin can be widely used.
<2> For reference, the catalyst that is used in the present invention is a catalyst generally used in the contact catalytic cracking of hydrocarbons, and is a solid acid catalyst including spherical particles the same as those of a zeolite catalyst. [Background Art]
<3> In the reference book "Fluid Catalytic Cracking Handbook" , the contact catalytic cracking method, which is compared to thermal cracking, is a technology for decomposing heavy oil, such as asphalt, into light oil in large quantities in a short period of time using a solid acid catalyst having acidic characteristics and a large porous area of about 200 ~ 800 mVg, in which heat necessary for decomposing hydrocarbon polymers is supplied to the process together with a solid acid catalyst having the same form as a zeolite catalyst. Further, the contact catalytic cracking method is a continuous circulation-loop type catalytic cracking method in which a catalyst can be continuously used by regenerating the catalyst by oxidizing carbon remaining in pores of the catalyst, the carbon being produced by the decomposition of hydrocarbons, using air. In particular, oil refining companies modify this contact catalytic cracking into fluid catalytic cracking (FCC), and this fluid catalytic cracking (FCC) is used in the process of decomposing asphalt, which is a final residue in vacuum distillation, into light oils, such as gasoline, kerosene, diesel oil, etc., without leaving behind any asphalt. In this fluid catalytic cracking (FCC) method, a fluid bed is made in a fluid catalytic cracking reaction tube (Riser) by shooting powdered catalyst upwards at a speed of 25 m/sec, and when asphalt is injected into the fluid bed, the asphalt is decomposed into gas oil in several seconds by a solid acid catalyst, and then the gas oil is separated from the solid acid catalyst in a cyclone located at the upper portion of the reaction tube, and then the separated gas oil is converted into various kinds of light oils through subsequent condensing, distilling and refining processes and finally recovered. For this reason, a fluid catalytic cracking apparatus includes a reaction tube and a cyclone, the sum of the height of the reaction tube and the height of the cyclone being about 30 ~ 50 m, and has a treatment capacity of 30,000 ~ 100,000 barrels per day. Therefore, this fluid catalytic cracking apparatus is a large sized apparatus, and it is basically impossible to manufacture a small sized fluid catalytic cracking apparatus, so that it has been limited to develop the fluid catalytic cracking apparatus in other uses. Moreover, in the fluid catalytic cracking apparatus, a catalyst regeneration tower also has a heavy weight of about 600 ~ 1,000 tons. Furthermore, in the fluid catalytic cracking apparatus, gas heated by a burner is blown into a highly-concentrated fluid bed catalyst, flowing downwards, and then from down to up at high pressure, and thus carbon deposited on the fluid bed catalyst or non-vaporized hydrocarbons are fired, and then continuously fired by the blowing air. Here, in order to uniformly regenerate the fluid bed catalyst, the fluid bed catalyst must maintain the fluid bed structure, and air flow must be of a plug flow type without causing a channeling phenomenon. Therefore, in order to maintain the air flow under high pressure, it is required to manufacture a large-sized fluid catalytic cracking apparatus.
<4> Considering all the factors, in the fluid catalytic cracking (FCC) process, only when a fluid catalytic cracking apparatus having a size larger than predetermined size is used, process troubles attributable to the ununiformity of the fluid bed of the catalyst can be prevented. Accordingly, in order to overcome the above problem of miniaturization of the fluid catalytic cracking apparatus, technologies of performing the fluid catalytic cracking (FCC) process using modified fluid beds have been proposed several times.
<5> In particular, since most of synthetic resins are saturated hydrocarbons, liquid light oils, obtained by decomposing the synthetic resins through a contact catalytic cracking process, have better quality then those obtained by decomposing asphalt through the catalytic cracking process. Therefore, various attempts to produce light oil by decomposing waste synthetic resins have been made. In these attempts, for the purpose of improving the quality of the produced light oils and allowing for the continuity of the operations, the catalytic cracking process has been frequently used in addition to an external heating type thermal cracking process.
<6> Conventional technologies related to the present invention are as follows.
<7> [Document 1] Reza Sadeghbeigi . Fluid Catalytic Cracking Handbook, Houston Texas, 1995, page 1-36 (Process Flow Description)
<8> [Document 2] Korean Examined Patent Application Publication No. 10- 0241543
<9> PCT/JP94/001302 (Kuroki Takeshi) 1994.08.05 <io> [Document 3] Korean Unexamined Patent Application Publication No. 2002-
0052168
<ii> PCT/CN2000/00196 (Chow Jip) 2000.07.13
<12> [Document 4] Japanese Unexamined Patent Application Publication No. Heisei09-310075 (Furukawa Electric co., Ltd et al. 11) 1997.12.0. <13> The conventional technologies disclosed in the above documents are aimed at obtaining light oils by decomposing waste synthetic resins using a catalyst generation principle in a fluid catalytic cracking process. These conventional technologies are commonly characterized in that a catalyst is used in the form of a moving bed, rather than fluid bed, a catalyst flows downward, rather than upward, and, in a catalyst regeneration apparatus, a catalyst is regenerated by continuously applying hot air or a flame to the catalyst using an ignition source, rather than by igniting the catalyst using combustion heat generated from a vertical regeneration tower.
<14> However, these catalytic cracking processes for decomposing waste synthetic resins using a moving bed catalyst, disclosed in the above documents, have the following disadvantages.
<i5> First, since a mixture of a catalyst and a raw material continuously flows downward and then lies on a moving bed, as the mixture moves downward, decomposed gases formed in pores of the catalyst are difficult to detach therefrom and to vaporize upward through a catalyst layer, thereby decreasing yield. Therefore, in order to solve this problem, a heater is additionally required. However, this heater also causes the passage of the catalyst in the moving bed to be complicated, so that the rapid detachment of the decomposed gases from the catalyst, which is the best advantage of the fluid catalytic cracking (FCC) process, cannot be suitably realized.
<i6> Second, in methods of regenerating a catalyst in a fluid catalytic cracking reactor, such as which is generally used in oil refining companies, once a catalyst starts to ignite and be regenerated by supplying heated gas to the catalyst from the bottom of a vertical regeneration tower using the principle that heat naturally flows from low to high, the heat can be continuously used as an ignition source, so that, thereafter, only air need be uniformly supplied. Further, in these methods, a large sized vertical tower provided with catalyst fluid beds is required in order to allow air to easily flow. In contrast, in the conventional methods of regenerating a catalyst, disclosed in the above documents, whether or not catalyst fluid beds are formed or the detailed explanation of a vertical regeneration tower is not specifically proposed, and the vertical regeneration tower is proposed to be designed in the form of a horizontal kiln. Further, in the conventional methods of regenerating a catalyst, it is required to continuously use heated gas, a flame or the like, so that these conventional methods of regenerating a catalyst are uneconomical in the aspect of energy efficiency.
<i7> Third, since the amount of the used catalyst is decreased as apparatuses are designed smaller in size, each of the apparatuses must accurately control the amount of the catalyst and thus control the entire circulation of the catalyst. However, in the conventional methods of regenerating a catalyst, disclosed in the above documents, devices for precisely measuring the amount of the catalyst at 450°C ~ 750°C in each of the apparatuses are not specifically proposed, and devices and methods for uniformly transferring the catalyst are also not specifically proposed.
<18> Fourth, since catalytic cracking reactors are operated under positive pressure in order to forcibly detach and discharge decomposed gases from a catalyst, transfer the catalyst upward using a high-pressure blower, and blow heated high-pressure gases into the catalyst in order to regenerate the catalyst, when the difference in pressure between apparatuses occurs, it is very probable that fluids move between small sized apparatuses through pores of a particulate catalyst. That is, since gas oil, which is a product obtained by decomposing synthetic resins through a catalytic cracking process, is an inflammable gas which can leak easily, unless the gas oil is completely separated from a catalyst regenerator filled with air, there are problems in that the danger of a fire is increased due to the ignition of the gas oil, the yield of the gas oil is decreased due to the ignition thereof, and the quality of the gas oil is deteriorated by incompletely combusted carbon. However, methods or apparatuses for solving these problems are not proposed. [Disclosure] [Technical Problem] <i9> Accordingly, in order to develop a method of producing light oils by decomposing hydrocarbon polymers through a moving bed contact catalytic cracking process, which can overcome the problems of the conventional technologies and is commercially available, objects of the present invention are as follows.
<20> A first object of the present invention is to provide a contact catalytic cracking method, which enables decomposed gases to become easily detached from the catalyst and easily vaporized by preventing the catalyst from continuously lying on a moving bed due to the downward movement of the catalyst, and which can naturally increase thermal efficiency by controlling the flow of the catalyst and the flow of decomposed gas oil.
<2i> A second object of the present invention is to provide an economical catalyst regeneration technology, which can exhibit a fluid bed effect even in a moving bed catalyst regeneration tower, and in which the heat of combustion of a catalyst is used as an ignition source, and thus a supply of heat is not required.
<22> A third object of the present invention is to provide a technology allowing stable circulation of a catalyst.
<23> A fourth object of the present invention is to provide a technology of basically preventing the ignition of fluids when the fluids move between apparatuses through pores of a particulate catalyst due to the difference in pressure between the apparatuses. [Technical Solution]
<24> In order to accomplish the first object of the present invention, the present invention provides a contact catalytic cracking method, in which a catalyst flows from a down location upwards, contrary to conventional catalytic cracking methods, so that the heat supplied to the catalyst flows from a down location upwards and simultaneously enables the decomposed gas detached from the catalyst to naturally vaporize, and in which the size of a catalyst moving bed is minimized, so that the catalyst is prevented from lying on the catalyst moving bed, with the result that decomposed gas can be easily detached from the catalyst.
<25> In order to accomplish the first object of the present invention, the present invention provides a contact catalytic cracking apparatus using an upward moving bed catalyst (referred to as a bucket elevating cracker) provided therein with a bucket elevator transferring a catalyst from a down location upwards and an electric heater controlling the temperature in the upward catalytic cracking apparatus. This bucket elevator includes a bucket filled with the catalyst, a conveyor link forming a transfer pathway while moving up and down and rotating, and a sprocket gear transmitting power to the conveyor link from the outside or supporting the movement of the conveyor link. These parts, the bucket, conveyor link and sprocket gear, are entirely sealed to prevent the inflow or leakage of gases.
<26> The bucket may have a volume of below 50 L, and the outer wall of the bucket is formed of meshed screen, so that decomposed gas oil formed in the catalyst can be easily detached therefrom. The size and number of the bucket elevators is very important to determine reaction time. It is preferred that the reaction time in the catalytic cracking apparatus be 3 ~ 10 minutes. In consideration of the reaction time, the size and number of the buckets and the length of the conveyor link are to be determined. A temperature control unit provided in the contact catalytic cracking apparatus serves to maintain reaction temperature. In order to prevent the ignition of the decomposed gas oil due to the introduction of oxygen, a heater emitting radiant heat is used as the temperature control unit. It is preferred that the reaction temperature be controlled in a range of 450°C ~ 550°C .
<27> In order to accomplish the first object of the present invention, the present invention provides an apparatus for sucking decomposed gas oil produced in the contact catalytic cracking apparatus and then rapidly discharging the decomposed gas oil to the outside. This apparatus includes a pressure transmitter measuring the pressure of the decomposed gas oil and a suction blower discharging the decomposed gas oil, and serves to collect the decomposed gas oil without causing the difference in pressure between a contact catalytic cracking reactor and a catalyst regenerator.
<28> In order to accomplish the second object of the present invention, a moving-bed catalyst regeneration tower is manufactured in a vertical fashion such that the combustion heat flowing upward from the catalyst regeneration tower can easily burn carbon in the catalyst lying on the upper portion of the catalyst regeneration tower, and a multi-stage air supply unit is vertically provided in the catalyst regeneration tower such that the flow of air on a moving bed is the same as the flow of air on a fluid bed, and further, electric heaters having the same number as the air distributors are provided in the catalyst regeneration tower.
<29> In order to accomplish the second object of the present invention, the present invention provides a vertical catalyst regeneration tower, the inner diameter and capacity of which is designed such that it takes 3 ~ 10 minutes to regenerate a catalyst, and the inner wall of which is provided with a castable refractory material in order to prevent it from being overheated by combustion heat .
<30> In order to accomplish the second object of the present invention, the present invention provides multi-stage air distributors and electric heaters, which are vertically provided in the catalyst regeneration tower. The multi¬ stage air distributors are uniformly distributed in the catalyst regeneration tower, and enable air to uniformly flow in a catalyst moving bed as well as in a catalyst fluid bed, and are provided in the catalyst regeneration tower together with the electric heaters such that the air distributor and electric heater make a pair. In this case, the electric heaters are provided right over the respective air distributors in order to efficiently supply heat and to prevent the electric heaters from being damaged by the air becoming overheated owing to the accumulation of air.
<3i> In order to accomplish the third object of the present invention, the amount of the catalyst loaded in a catalyst regenerator and catalyst storage units are accurately measured in real time, and thus the catalyst regenerator and catalyst storage units are operated such that these measured data are combined with the control speed of a catalyst transfer unit.
<32> In order to accomplish the third object of the present invention, the present invention provides a load cell unit measuring the weight of two catalyst storage units (referred to as "catalyst hoppers" ) located between a catalyst reactor and a catalyst regenerator. In order for the load cell unit not to be influenced by the change in weight of the two catalyst storage units, the change in weight thereof being caused by pipes connected to the catalyst storage units, the catalyst storage units are connected to each other using flexible pipes.
<33> In order to accomplish the third object of the present invention, the present invention provides an apparatus for measuring the level of a catalyst in the upper portion of a catalyst generator. This apparatus measures the height of a catalyst in the upper portion of a catalyst regenerator using a laser, and is provided with an additional measuring tube to compensate for the measuring error caused by dusts and flame generated from a combustion furnace in the upper portion of the catalyst generator.
<34> In order to accomplish the third object of the present invention, the present invention provides screw feeders provided at the lower ends of the catalyst storage units and the catalyst regenerator and the above mentioned bucket elevator in the catalytic cracking reactor. These screw feeders and bucket elevator are operated by a reduction motor controlled by a frequency control unit, and their speeds are controlled by the weight of the load cell and the values measured by a laser sensor. In the present invention, a catalytic cracking reactor may not be controlled by measuring and controlling the amounts of the catalysts charged in the catalyst regenerator and the catalyst storage units.
<35> In order to accomplish the fourth object of the present invention, principled design must be performed such that the difference in pressure between apparatuses does not occur, and a fluid blocking layer using a catalyst is provided between the contact catalytic cracking reactor and the catalyst regenerator such that the fluid cannot move even by minute pressure difference.
<36> In order to accomplish the fourth object of the present invention, the present invention provides the above mentioned catalyst storage unit, which is a physical device serving to compensate for the ununiform flow of a catalyst and to basically prevent the phenomenon in which decomposed gas oil charged in the contact catalytic cracking reactor is brought into contact with air charged in the catalyst regenerator, and thus the decomposed gas oil is fired. In order to efficiently operate this apparatus, the height of the catalyst stored in this apparatus must be determined by pressure loss design.
<37> In order to accomplish the fourth object of the present invention, the present invention provides a heat exchanger, which is provided at the rear end of a combustion gas outlet in order to remove excess positive pressure caused by the thermal expansion of combustion gas in the upper portion of the catalyst regenerator, and which serves to enable the combustion gas to be easily discharged by greatly decreasing the volume of the combustion gas, and provides a pressure balancing pipe which serves to transfer the high-pressure air coming out of the lower end of the catalyst regenerator in the direction in which discharged gases flow without applying any pressure load to the catalyst storage unit.
[Advantageous Effects]
<39> The contact catalytic cracking system using a upward moving bed catalyst according to the present invention is advantageous in that it can overcome the problems of a decrease in decomposition efficiency, ununiform catalyst generation, uneconomical thermal efficiency, an unreliable catalyst circulation control method, and the ignition of decomposed gases in the contact catalytic cracking system, and further in that it can maintain the rapid decomposition of raw materials and the uniform regeneration performance of the catalyst, and in that it can be variously designed in small size. [Description of Drawings]
<40> FIG. 1 is a schematic view showing a contact catalytic cracking system according to an embodiment of the present invention.
<4i> description of the elements in the drawings>
<42> 1 : Mixer
<43> 2 : Upward Catalytic Cracking Apparatus (Bucket Elevating Cracker)
<44> 3 : Regenerative catalyst Storage Unit (Catalyst Hopper)
<45> 4 : Catalyst Regenerator
<46> 5 : Reactive Catalyst Storage Unit (Catalyst Hopper)
<47> 6 : Radiation Heater (Aero Fin Heater)
<48> 7 : Electric Heater
<49> 8 : Air Distributor
<50> 9 : Bucket Elevator
<5i> 10, 11, 12 : Catalyst Transfer Unit (Screw Feeder)
<52> 13 : Level Sensor
<53> 14 : Suction Blower [Best Mode]
<54> The system for catalytic cracking using a moving bed catalyst according to the present invention includes a mixer for mixing a molten polymer, which is a raw material used for cracking, with a catalyst; a catalytic cracking apparatus using an upward moving bed catalyst (referred to as a bucket elevating cracker); a vertical catalyst regenerator; two catalyst storage units (referred to as catalyst hoppers); three catalyst transfer units (referred to as screw feeders); and the like.
<55> Hereinafter, the above apparatuses constituting the system for contact catalytic cracking using a upward moving bed catalyst according to the present invention will be described in detail with reference to the attached drawing (FIG. 1).
<56> 1. Mixer
<57> The mixer 1 serves to mix a molten hydrocarbon polymer, which is a raw material used for cracking, with a regenerated catalyst. Since the catalyst introduced into the mixer 1 from a catalyst transfer unit 12 supplies most of heat necessary for cracking, the catalyst is referred to as a contact catalyst. The mixing ratio of the catalyst to the raw material is determined in consideration of total decomposition heat and evaporation heat. In the present invention, it is preferred that the mixing ratio of the catalyst to the raw material be 3~10: 1. In this case, the temperature of the catalyst is in a range of 450°C ~ 550°C, and the temperature of the raw material is in a range of 300°C ~ 350°C .
<58> The mixer 1, having a cylindrical shape, is provided therein with a zigzag multi-stage slope way such that a catalyst curtain is formed when a catalyst flows through the multi-stage slope way and falls down. The raw material is introduce into the middle portion of the mixer 1, and then mixed with the catalyst. When an initial decomposition reaction violently occurs, wax materials, which are formed into azeotropes and vaporized by low molecular weight gas, are instantaneously produced. These wax materials move toward the top of the mixer 1, and simultaneously come into contact with the catalyst on the catalyst curtain, so that they are decomposed again. In order to accelerate the decomposition of the wax materials, a discharge line is connected to the upper portion of the mixer 1 such that decomposed gases are discharged therethrough.
<59> 2. Contact Catalytic Cracking apparatus using an upward moving bed catalyst (bucket elevating cracker) <6o> The decomposition reaction of the raw material is partially conducted in the mixer 2, and the catalyst mixed with the raw material is immediately introduced into a contact catalytic cracking apparatus 2 using an upward moving bed catalyst. The contact catalytic cracking apparatus 2 is provided therein with a bucket elevator 9 serving to transfer the catalyst introduced into the lower portion of the catalytic apparatus 2 to the upper portion thereof. The bucket elevator 9 transfers the catalyst to the upper portion of the contact catalytic cracking apparatus 2 in the form of a moving bed, and simultaneously imparts decomposition reaction time. Further, the bucket elevator 9 functions to control the circulation speed of the catalyst together with catalyst transfer units 10, 11 and 12 (referred to as screw feeders). Since the outer walls of buckets in which the decomposition reaction is conducted are formed of meshed screens, the decomposed gas oils produced in the buckets are easily detached from the catalyst, and are also easily vaporized because the moving bed catalyst moving to the upper portion of the catalytic cracking apparatus supplies heat to the decomposed gas oils. Further, the contact catalytic cracking apparatus 2 is provided therein with electric heaters in order to compensate for thermal loss. These electric heaters emit radiant heat to prevent the ignition of decomposed gas oil. The temperature of the contact catalytic cracking apparatus 2 is in a range of 350°C ~ 450°C . A suction blower 14 is provided over the contact catalytic cracking apparatus 2. The suction blower 14 serves to forcibly discharge excess decomposed gas oil produced in the catalytic cracking apparatus 2 to maintain the temperature of the catalytic cracking apparatus 2 constant. Due to this action of the suction blower 14, reaction yield can be increased without performing a steam stripping process and an oil separation process in fluid catalytic cracking. The catalytic cracking apparatus 2 is completely sealed such that decomposed gas oil is not brought into contact with external air. After the decomposition reaction, the catalyst is transferred to a regenerative catalyst storage unit 3 (referred to as a catalyst hopper).
<6i> 3. Regenerative catalyst storage unit (catalyst hopper) <62> After the decomposition reaction, the catalyst is transferred to a regenerative catalyst storage unit 3 from the contact catalytic cracking apparatus 2 along a sloping path.
<63> In this procedure, inorganic materials, such as soil, remaining in catalyst particles without being decomposed, and catalyst powders produced by the abrasion of particulate catalyst are separately removed through a screen provided in the sloping path.
<64> The regenerative catalyst storage unit 3 is provided in consideration of being placed at a sufficient height such that it can prevent the movement of fluid due to the difference in pressure between the catalytic cracking apparatus 2 and a catalyst regenerator 4. The regenerative catalyst storage unit 3 has a function of measuring the change in weight of the catalyst. In order to accurately measure the change in weight of the catalyst, the regenerative catalyst storage unit 3 is connected to outer apparatuses using a flexible pipe. Further, the regenerative catalyst storage unit 3 has another function of refilling a new catalyst corresponding to the loss of the circulated catalyst. In the regenerative catalyst storage unit 3, a horizontal screw feeder 10 serves to control the total amount of the catalyst.
<65> 4. Catalyst Regenerator
<66> The catalyst discharged from the catalyst storage unit is introduced into a catalyst regenerator 4 by the catalyst transfer unit 10, and the carbon deposited in the pores of the catalyst is burned. In this procedure, it is important to provide an ignition source for burning the carbon remaining in the catalyst. Electric heaters 7 are used as the ignition source. The electric heaters 7 are disposed in the catalyst generator 4 at regular intervals to uniformly regenerate the catalyst. Air distributors 8 are disposed right under the respective electric heaters 7, and serve to uniformly diffuse the heat generated from the electric heater 7 and to supply air into the catalyst generator 4. The carbon deposited on the catalyst can be continuously burned by the heat generated from the electric heaters 7 and the air supplied from the air distributors 8. In this case, the normal operating temperature of the catalyst regenerator 4 is 650°C ~ 750°C .
<67> In order to normally operate the catalyst regenerator 4, the uniform burning of carbon and the uniform flow of air must be maintained by efficiently disposing the electric heaters 7 and the air distributors 8.
<68> Since the catalyst regenerator 4 is provided with a heat exchanger for cooling air at the rear end thereof, combustion air is easily discharged due to the pressure difference, so that back pressure does not occur, thereby decreasing the load of the entire process. In order to measure the amount of the catalyst in the catalyst regenerator 4, a laser reflection type level measuring device 13 is provided in the top portion of the catalyst regenerator 4. This level measuring device 13 is particularly fabricated using an air-purging type laser in order to remove the measurement error caused by dust and flame. The time taken to regenerate the catalyst in the catalyst regenerator 4 is determined by a horizontal screw feeder 11 provided under the catalyst regenerator 4. It is preferred that the time taken to regenerate the catalyst be in a range of 3 ~ 10 minutes.
<69> 5. Reactive Catalyst storage unit (Catalyst Hopper)
<70> The catalyst regenerated in the catalyst regenerator 4 is transferred to a reactive catalyst storage unit 5 by a catalyst transfer unit 11. Like the regenerative catalyst storage unit 3, this reactive catalyst storage unit 5 serves to prevent the air in the catalyst regenerator 4 from being brought into contact with the decomposed gas in the catalyst cracking apparatus 2, and serves to solve the excessive heat and pressure in the catalyst. Therefore, unlike the regenerative catalyst storage unit 3, the reactive catalyst storage unit 5 is provided therein with a heat exchanger for cooling a catalyst, so that the catalyst is made to have a temperature necessary for reaction, thereby preventing the introduction of overheated catalyst. Further, the reactive catalyst storage unit 5 is configured to be pressure- balanced with a flue gas line such that the positive-pressure air introduced into the reactive catalyst storage unit 5 from the catalyst regenerator 4 does not flow into the catalytic cracking apparatus 2 and can be safely discharged.
<7i> The catalyst in the reactive catalyst storage unit 5 is introduced into the mixer 1 by a catalyst transfer unit 12 at a predetermined flow rate, while the weight of the catalyst being maintained constant. [Industrial Applicability]
<72> Since waste synthetic resins are difficult to collect in large quantities in one place, considering transportation expenses, collection routes, and the like, they are actually treated in small quantities at every place from which the waste synthetic resins are collected. Further, since waste synthetic resins are difficult to select because they are mixed with other waste materials or foreign materials, the ratio of recycled synthetic resins is very limited. These waste synthetic resins which cannot be recycled incur environmental pollution and increase treatment expenses.
<73> The contact catalytic cracking apparatus using a upward moving bed catalyst according to the present invention is designed such that waste synthetic resins, which are collected in small quantities and have low recycle ratio, are more efficiently decomposed and treated. Since this contact catalytic cracking apparatus functions to prevent the deterioration of catalytic performance by separating undecomposed inorganic materials from a catalyst in a catalytic cracking process, it can be very usefully used to decompose and treat waste vinyl products which are very difficult to treat in agricultural villages.
<74> In the catalytic cracking apparatus using a moving bed catalyst according to the present invention, since a solid acid catalyst is used as in a conventional fluid catalytic cracking apparatus, high grade fuel oils, such as gasoline, kerosene, diesel oil, and the like, can be produced by distilling and refining the resulting decomposed gas oil.
<75> The present invention provides an apparatus for converting waste synthetic resins, which are difficult to recycle, into higher value-added fuel oils. Since this apparatus does not produce decomposed residues, like fluid catalytic cracking apparatuses, it contributes to environmental conservation.

Claims

[CLAIMS] [Claim 1]
<77> A method of continuously decomposing and treating a waste synthetic resin, the method having a catalyst circulation structure comprising•'
<78> contact catalytic-cracking the waste synthetic resin using an upward moving bed catalyst by a bucket elevator;
<79> regenerating the catalyst using an electric heating type vertical catalyst regenerator,
<80> wherein catalyst storage units are provided for each of the processes. [Claim 2]
<8i> The method of continuously decomposing and treating the waste synthetic resin according to claim 1, wherein, in the contact catalytic-cracking of the waste synthetic resin, a catalyst carriage bucket having an outer wall formed of a mesh screen is used, and a temperature of the catalyst is controlled by a radiation heater, and a discharge pressure of a decomposed gas is controlled by a pressure sensor and a suction blower. [Claim 3]
<82> The method of continuously decomposing and treating the waste synthetic resin according to claim 1, wherein, in the regenerating of the catalyst, the catalyst regenerator is provided therein with electric heaters and air distributors in multiple stages, in which one electric heater and one air distributor make a pair. [Claim 4]
<83> The method of continuously decomposing and treating the waste synthetic resin according to claim 1, wherein the catalyst storage units function to block a flow of fluid due to a difference in pressure between the contact catalytic-cracking of the waste synthetic resin and the regenerating of the catalyst . [Claim 5]
<84> The method of continuously decomposing and treating the waste synthetic resin according to claim 1, wherein, in the catalyst circulation structure, an amount of the catalyst is measured using a laser reflection type level measuring device of the catalyst regenerator and a load cell unit of the catalyst storage units, and thus an amount of the circulated catalyst is controlled using a screw feeder. [Claim 6]
<85> A system for continuously decomposing and treating a waste synthetic resin, comprising:
<86> a contact catalytic cracking apparatus in which an upward moving bed catalyst carried by a bucket elevator formed of a mesh screen is used, a temperature of the catalyst is controlled by a radiation heater, and a discharge pressure of a decomposed gas is controlled by a pressure sensor and a suction blower;
<87> a vertical catalyst generator provided therein with electric heaters and air distributors in multiple stages, in which one electric heater and one air distributor make a pair; and
<88> catalyst storage units functioning to block the flow of fluid due to the difference in pressure between the catalytic cracking apparatus and the catalyst regenerator,
<89> wherein a level of the catalyst is measured using a laser reflection type level measuring device of the catalyst regenerator, a weight of the catalyst is measured using a load cell unit of the catalyst storage units, and thus the circulation of the catalyst is controlled using a screw feeder.
PCT/KR2008/001201 2007-03-15 2008-03-03 The method and system for contact catalytic cracking by upward moving bed catalyst WO2008111750A1 (en)

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