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WO2008026681A1 - Procédé de craquage catalytique fluide - Google Patents

Procédé de craquage catalytique fluide Download PDF

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Publication number
WO2008026681A1
WO2008026681A1 PCT/JP2007/066868 JP2007066868W WO2008026681A1 WO 2008026681 A1 WO2008026681 A1 WO 2008026681A1 JP 2007066868 W JP2007066868 W JP 2007066868W WO 2008026681 A1 WO2008026681 A1 WO 2008026681A1
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WO
WIPO (PCT)
Prior art keywords
catalytic cracking
catalyst
fluid catalytic
zone
cracking method
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/066868
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English (en)
Japanese (ja)
Inventor
Yuichiro Fujiyama
Toshiaki Okuhara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
Nippon Oil Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Oil Corp filed Critical Nippon Oil Corp
Priority to JP2008532109A priority Critical patent/JP5399705B2/ja
Publication of WO2008026681A1 publication Critical patent/WO2008026681A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • 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
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a fluid catalytic cracking method, and more particularly, to a method for fluid catalytic cracking of a liquid product mainly composed of hydrocarbons obtained by Fischer's Tropsch synthesis.
  • FT synthetic oil contains an oxygen-containing compound such as alcohol having a high normal paraffin content. It is difficult to use as it is as a fuel raw material or a petrochemical raw material. More specifically, the synthetic oil has an insufficient octane number for use as automobile gasoline, and low temperature fluidity for use as diesel fuel. In addition, oxygen-containing compounds such as alcohol adversely affect the oxidation stability of the fuel. Therefore, FT synthetic oil is subjected to hydrogenation treatment to convert normal paraffin in the synthetic oil to isoparaffin or oxygenated compounds to other substances, and then to fuel raw materials and petrochemical raw materials. It is generally used as
  • Patent Document 1 Pamphlet of International Patent Publication No. 00/020535
  • Patent Document 2 French Patent Publication No. 2826971 Specification
  • Patent Document 3 International Patent Publication No. 05/118747 Pamphlet
  • a coke yield of 5 to 7% is generally required in order to achieve heat balance.
  • the coke yield is extremely low in the conventional method, and the coke yield is externally reduced. Unless the shortage of heat is compensated, the decomposition reaction cannot be continued.
  • the present invention has been made in view of such circumstances, and even when a synthetic oil obtained by the Fischer-Tropsch synthesis method is processed, it can be stably processed over a long period of time.
  • the object is to provide a possible fluid catalytic cracking process.
  • the present invention is a catalytic cracking method using a fluid catalytic cracking apparatus having a reaction zone, a separation zone, a stripping zone and a regeneration zone, which is obtained by a Fischer-Tropsch synthesis method.
  • the raw material oil containing the above liquid product is used with a catalyst containing 10 to 50% by mass of ultrastable Y-type zeolite, the outlet temperature of the reaction zone is 550 to 650 ° C, and the catalyst / oil ratio is 10 to 40 wt. / wt, reaction pressure;! ⁇ 3 kg / cm 2 G, the contact time between the feedstock and the catalyst in the reaction zone 0;.!
  • the catalyst used in the second step is the temperature of the catalyst rich phase in the regeneration zone 620 to 690 ° C, the regeneration zone pressure 1 to 3 kg / cm 2 G, and the oxygen concentration in the exhaust gas at the exit of the regeneration zone 0 to 3 a fluid catalytic cracking method comprising: a third step of treatment under mol% conditions.
  • the synthesis product obtained by the Fischer-Tropsch synthesis method is divided into a liquid product mainly composed of hydrocarbons, unreacted hydrogen and carbon monoxide, It separates into a gaseous product mixture and the separated liquid product is subjected to fluid catalytic cracking.
  • the fluid catalytic cracking process in the second step and the catalyst regeneration process in the third step result in a shortage of coke, which was a problem when performing the fluid catalytic cracking process of FT synthetic oil by the conventional method.
  • the resulting process instability can be sufficiently suppressed, and the catalyst activity can be maintained at a high level over a long period of time. Therefore, when the hydrocarbon liquid product obtained by the FT synthesis method is subjected to fluid catalytic cracking, it can be stably treated over a long period of time while maintaining the heat balance.
  • the reaction zone is preferably a downward flow reactor.
  • the difference between the temperature of the catalyst rich phase in the regeneration zone and the outlet temperature of the reaction zone is preferably within 150 ° C.
  • the delta coke on the catalyst is 0.2 to;
  • Owt% is preferred! /.
  • the Si / Al ratio of the ultrastable Y-type zeolite is preferably 3 to 20 in atomic ratio! /.
  • the crystal lattice constant of the ultrastable Y-type zeolite of the catalyst is preferably 24.35% or less, and the crystallinity of the ultrastable Y-type zeolite is preferably 90% or more.
  • an alkali rare earth metal is introduced into the ion exchange site of the ultra-stable cage-type zeolite.
  • the active matrix of the catalyst preferably further contains silica alumina.
  • the present invention provides a fuel for a fuel cell, characterized by containing hydrogen obtained by the fluid catalytic cracking method of the present invention.
  • the present invention provides a gasoline characterized by containing a part or all of a fraction having a boiling point of 25 to 220 ° C obtained by the fluid catalytic cracking method of the present invention or a hydride thereof. Provide.
  • the present invention provides a boiling point of 170 to 370 obtained by the fluid catalytic cracking method of the present invention.
  • diesel fuel characterized by containing a part or all of a fraction at ° C.
  • the present invention provides a liquefied petroleum gas characterized by containing a hydrocarbon having 3 or 4 carbon atoms obtained by the fluid catalytic cracking method of the present invention.
  • the present invention also provides a synthetic resin comprising propylene obtained by the fluid catalytic cracking method of the present invention as a constituent monomer.
  • the present invention also provides a gasoline characterized by containing an ether obtained by reacting isoprene obtained by the fluid catalytic cracking method of the present invention with methanol or ethanol.
  • the present invention provides a gasoline characterized by containing a reaction product obtained by reacting butylene obtained by the fluid catalytic cracking method of the present invention with isobutane using an alkylation device. To do.
  • the present invention also provides a gasoline characterized by containing a dimer of butylene obtained by the fluid catalytic cracking method of the present invention.
  • a fluid catalytic cracking method capable of stably treating a synthetic oil obtained by the FT synthesis method over a long period of time.
  • a synthesis product obtained by a Fischer-Tropsch synthesis method using a synthetic gas mainly composed of hydrogen and carbon monoxide as a raw material is converted into a hydrocarbon as a main component.
  • first step Into a mixture of unreacted hydrogen and carbon monoxide and gaseous product (first step).
  • gaseous product refers to a hydrocarbon and hydrogen corresponding to 2 or less carbon atoms
  • liquid product refers to a product other than the above gaseous product.
  • Separation of liquid and gaseous products is generally done by distillation from the viewpoint of industry. Therefore, the liquid and gaseous products are completely separated from each other, for example, one of them is mixed with the other. Although it is difficult, the liquid product thus separated can be used without problems in the present invention.
  • synthesis gas mainly composed of hydrogen and carbon monoxide is known as a reaction process of FT synthesis, that is, fixed bed, supercritical fixed bed, slurry bed, fluidized bed, etc.
  • a process can be used.
  • the reaction conditions can be selected according to a conventional method, for example, the molar ratio of hydrogen / carbon monoxide from 1.5 to 2.5, the reaction temperature is 200 to 280 ° C, the gas space velocity is lOOO SOOOlT 1.
  • a known catalyst can be used as the catalyst.
  • An example is a catalyst in which an active metal such as iron or cobalt is supported on silica / alumina.
  • a method of separating the synthesis product obtained by the FT synthesis method into a liquid product mainly composed of hydrocarbons and a mixture of unreacted hydrogen and carbon monoxide and a gas product As a method of separating the synthesis product obtained by the FT synthesis method into a liquid product mainly composed of hydrocarbons and a mixture of unreacted hydrogen and carbon monoxide and a gas product.
  • a distillation apparatus generally used in petroleum refining can be used.
  • the boiling range of the liquid product is preferably 150 ° C or higher, more preferably 30 ° C or higher.
  • the liquid product mainly composed of hydrocarbons separated from the synthesis product may be used alone as a feed oil for fluid catalytic cracking.
  • the fluid catalytic cracking feedstock oil may further contain a heavy oil obtained by distilling crude oil.
  • heavy oil include atmospheric residual oil, vacuum gas oil obtained by further distillation of atmospheric residue, vacuum residual oil, hydrotreated oil, or pyrolysis oil, and mixed oil thereof.
  • Etc. The mixing ratio of the heavy oil is arbitrary, but is preferably 10 to 90% by mass, more preferably 30 to 50% by mass, based on the total amount of the raw material oil.
  • fluid catalytic cracking means that a heavy hydrocarbon is brought into contact with a catalyst that is maintained in a fluid state to form a light hydrocarbon mainly composed of gasoline or light olefin. It means to break down.
  • the fluid catalytic cracking apparatus used in the present invention is not particularly limited as long as it has a reaction zone, a separation zone, a stripping zone and a regeneration zone.
  • the reaction zone includes either a downward flow reactor in which both catalyst particles and raw material oil flow downward in the pipe, and an upward flow reactor in which both catalyst particles and raw oil flow upward in the pipe.
  • a downward flow type reactor is preferably used in the present invention.
  • the catalytic cracking catalyst used in the present invention contains 10 to 50% by mass, preferably 15 to 40% by mass of ultrastable Y-type zeolite.
  • the ultrastable Y-type zeolite those having an Si / Al atomic ratio of 3 to 20 are preferably used.
  • the atomic ratio of Si / Al is more preferably 5 to 20, and further preferably 7 to 15; If the Si / Al atomic ratio is less than 3, the catalyst activity becomes excessively large, and the amount of gas and LPG generated increases. Also, if the Si / Al atomic ratio exceeds 20, the cost of the zeolite increases, which is preferable in terms of economy! /.
  • the ultrastable Y-type zeolite has a crystal lattice constant of 24.35A or less and a crystallinity of
  • ultrastable Y-type zeolite those obtained by introducing an alkali rare earth metal at the ion exchange site are preferably used.
  • the catalyst used in the present invention is preferred! /
  • an ultrastable Y-type zeolite is added as a matrix, kaolin or the like, which is a secondary active ingredient and can decompose large molecules of heavy oil. What was shape
  • molded into the particle form with the binder with the agent is mentioned.
  • Silica alumina is preferably used as the matrix component used in the catalyst of the present invention.
  • the catalyst further includes a pore size smaller than that of the Y-type zeolite! /, Crystalline aluminosilicate zeolite, silicoaluminophosphate (SAPO), and the like. You may have.
  • SAPO silicoaluminophosphate
  • Such zeolites include ZSM-5, and SAPOs include SAPO-5, SAPO-11, and SAPO-34. These zeolites or SAPOs may be contained in the same catalyst particles as the catalyst particles containing ultrastable Y-type zeolite, or may be contained as separate catalyst particles.
  • the outlet temperature of the reaction zone in the present invention is 550 to 650 ° C as described above, preferably (or 560 to 640 ° C, more preferably (or 590 to 630 ° C). If the outlet temperature of the reaction zone is less than 550 ° C, the target product gasoline and light olefins cannot be obtained in high yields, and sufficient coke yield cannot be obtained. Thermal decomposition becomes prominent and the amount of dry gas generated increases when it exceeds C.
  • the “reaction zone outlet temperature” as used in the present invention is the outlet temperature of the reactor, and the decomposition product is cooled rapidly or the catalyst. This is the temperature before separation.
  • the catalyst / oil ratio in the present invention is 10 to 40 wt / wt, preferably 15 to 35 wt / wt, and more preferably 20 to 30 wt / wt.
  • the catalyst / oil ratio is less than lOwt / wt, a sufficient decomposition rate and coke yield cannot be obtained, and when the catalyst / oil ratio exceeds 40 wt / wt, the catalyst circulation rate increases and the regeneration zone In this case, the catalyst residence time necessary for catalyst regeneration cannot be secured, and the regeneration of the catalyst becomes insufficient.
  • the “catalyst / oil ratio” means the ratio between the catalyst circulation rate (ton / h) and the feedstock feed rate (ton / h).
  • the reaction pressure in the present invention as described above;! A ⁇ 3kg / cm 2 G, preferably 1 2 ⁇ 2kg / cm 2 G.. If the reaction pressure force is less than kg / cm 2 G, the difference from the atmospheric pressure becomes excessively small, making it difficult to adjust the pressure with the control valve. In addition, when the reaction pressure is less than 1 kg / cm 2 G, the pressure in the regeneration zone decreases accordingly, and the container must be enlarged to ensure the residence time of the gas necessary for regeneration. Is not preferable. On the other hand, when the reaction pressure exceeds 3 kg / cm 2 G, the ratio of the bimolecular reaction such as the hydrogen transfer reaction to the decomposition reaction, which is a unimolecular reaction, increases.
  • reaction pressure in the present invention means the total pressure of the fluidized bed reactor.
  • the “hydrogen transfer reaction” is a reaction in which olefins receive hydrogen from naphthene or the like and are converted to paraffin. It is a reaction that causes a decrease in olefin and a decrease in the octane number of gasoline.
  • the contact time of the raw material oil and the catalyst in the present invention is from 0.3;! To 1.0 seconds as described above, and preferably from 0.3 to 0.9 seconds. If the contact time is less than 0.1 seconds, sufficient decomposition will not occur, while if it exceeds 1.0 seconds, target organisms such as propylene and gasoline will decrease due to excessive decomposition and hydrogen transfer.
  • the “contact time between the feedstock and the catalyst” in the present invention refers to the period from when the feedstock and the catalyst are brought into contact with each other at the inlet of the fluidized bed reactor until the reaction product and the catalyst are separated at the reactor outlet. Means time.
  • the amount of steam at this time is preferably 2 to 8% by mass relative to the raw material oil. If the amount of steam is less than 2% by mass relative to the feedstock, the droplet size during spraying will not be sufficiently small! /, So the droplets will not contact the catalyst sufficiently and the reaction efficiency will be reduced. Tend to. On the other hand, if it exceeds 8% by mass, the amount of water recovered in the product recovery zone, which will be described later, increases, which is economically undesirable.
  • the mixture of the decomposition product, the unreacted material, and the catalyst that have been subjected to the catalytic cracking treatment in the reaction zone is sent to the separation zone, and the catalyst is separated from the mixture in the separation zone.
  • a gas-solid separation device using a centrifugal force such as a cyclone is preferably used.
  • the catalyst separated in the separation zone is sent to the stripping zone, and most of hydrocarbons such as products and unreacted substances are removed from the catalyst particles in the stripping zone.
  • a part of the raw material becomes heavier carbonaceous (coke) and adheres to the catalyst, and the catalyst with coke or heavier hydrocarbons attached to the regeneration zone (regeneration zone) from the stripping zone.
  • the regeneration zone regeneration zone
  • the catalyst from the stripping zone is converted into a catalyst rich phase temperature of 620 to 740 ° C, a regeneration zone pressure of 1 to 3 kg / cm 2 G, and an oxygen concentration in the exhaust gas at the regeneration zone outlet. Treat under conditions of 0-3 mol%.
  • a part or all of the mixture of unreacted hydrogen and carbon monoxide and gas product separated in the first step is supplied to the regeneration zone as a heat source.
  • Such a heat source can be obtained by separating hydrogen from a mixture of unreacted hydrogen and carbon monoxide and gas products separated from the synthesis product obtained by the FT synthesis method, and then reusing the mixture of carbon monoxide and gas products. Supplying to the raw zone is more preferable because hydrothermal deterioration of the catalyst can be further suppressed.
  • the temperature of the catalyst rich phase in the regeneration zone is 620 to 740 ° C, preferably 650 to 720 ° C, more preferably 660 to 710 ° C. If the regeneration zone liquid temperature is less than 620 ° C, coke combustion will be insufficient. If the temperature exceeds 740 ° C, the deterioration of the catalyst is promoted, and more expensive materials for withstanding the temperature of the catalyst rich phase in the regeneration zone must be used as the material in the regeneration zone, which is economically undesirable.
  • the difference between the temperature of the catalyst rich phase in the regeneration zone and the reaction zone outlet temperature is preferably within 150 ° C, more preferably within 100 ° C. If this temperature difference exceeds 150 ° C, heat balance cannot be achieved.
  • the “temperature of the catalyst rich phase in the regeneration zone” refers to the temperature of the portion immediately before the catalyst particles exiting the regeneration zone. Point to.
  • the regeneration zone pressure is as described above;! To 3 kg / cm 2 G.
  • the regeneration zone pressure is less than 1 kg / cm 2 G, the residence time of the gas necessary for regeneration is ensured, and the container in the regeneration zone becomes large, which is not economically preferable.
  • the regeneration zone pressure exceeds 3 kg / cm 2 G, the pressure in the reaction zone increases accordingly, which is not favorable for an economy such as a hydrogen transfer reaction in the reaction zone.
  • the oxygen concentration in the exhaust gas at the outlet of the regeneration zone is 0 to 3 mol%. If the oxygen concentration exceeds 3 mol%, excess air is sent to the regeneration zone using excess power, which is not economically preferable.
  • the catalyst that has been subjected to the above oxidation treatment is a regenerated catalyst, and coke and heavy hydrocarbons deposited on the catalyst are reduced by combustion.
  • This regenerated catalyst is continuously circulated in the reaction zone.
  • the decomposition products are quenched immediately before or after the separation zone in order to suppress unnecessary thermal decomposition or excessive decomposition.
  • the catalyst is heated by the amount of heat generated by the combustion of carbonaceous material in the regeneration zone, and the heat is brought into the reaction zone together with the catalyst.
  • the raw oil is heated and vaporized by this amount of heat. Since the decomposition reaction is an endothermic reaction, this amount of heat is also used as the heat of decomposition reaction.
  • balancing the heat generation in the regeneration zone and the heat absorption in the reaction zone is an essential condition for FCC operation!
  • a countermeasure when the heat becomes excessive there is a method of cooling the catalyst. In this method, a part of the catalyst in the regeneration zone is extracted and the heat is used to generate steam and the heat of the catalyst is taken away.
  • a countermeasure against excess heat there is a method in which the regeneration zone is divided into two stages and the first regeneration zone is operated in an oxygen-deficient atmosphere.
  • the upper limit of the amount of coke generated by catalytic cracking is generally determined for each FCC.
  • the allowable amount of coke is determined by the amount of heat that can be discharged out of the system as a result of the above-described measures for excess heat.
  • the upper limit of the amount of carbon dioxide generated by the location of the FCC may be determined, and the allowable value for the amount of coke is limited by that value. Normally, FCC is operated with as much oil flow as possible and as high a cracking rate as possible, resulting in operation at the upper limit of coke volume.
  • the amount of coke produced (mass%) per raw oil is referred to as “coke yield”.
  • the coke yield in the present invention is preferably 2 to 10% by mass, more preferably 5 to 9% by mass, and still more preferably 6 to 8% by mass. If the coke yield is less than the above lower limit, the amount of carbon monoxide and gaseous products supplied to the regeneration zone to supply the heat necessary for the reaction increases, which is not economically preferable. In addition, if the coke yield exceeds the above upper limit, the amount of heat generated in the regeneration zone becomes excessively large, which is not preferable because it is subject to operational restrictions such as a decrease in decomposition rate and a decrease in oil flow rate.
  • the coke yield in the present invention is preferably 0.2 to 1.5% by mass, more preferably 0.3 to 1.0% by mass. If the coke yield is less than 0.2% by mass, the heat required for the reaction tends to be insufficient. On the other hand, if the coke yield exceeds 1.5% by mass, the amount of heat generated in the regeneration zone becomes excessive, which is not preferable because it is subject to operational restrictions such as a reduction in decomposition rate and a reduction in oil flow rate.
  • “delta coke” on the catalyst means a value represented by the following formula.
  • the FCC in the present invention preferably further comprises a decomposition product recovery zone.
  • a decomposition product recovery zone is a decomposition product recovery facility that separates and recovers decomposition products based on their boiling points.
  • the decomposition product recovery equipment includes a plurality of distillation towers, absorption towers, A presser, a stripper, a heat exchanger and the like are included. With the decomposition product recovery facility, as described later, it is possible to recover each of the various fuel base materials and petrochemical raw materials more reliably.
  • the fluid catalytic cracking method of the present invention is excellent in terms of energy security and carbon dioxide reduction because it uses a hydrocarbon liquid product obtained by FT synthesis as a raw material.
  • the base material of various fuels is very useful when producing raw materials for petrochemical products.
  • the hydrogen obtained by the fluid catalytic cracking method of the present invention is reduced by the force S used as a fuel for fuel cells.
  • the fraction having a boiling point of 25 to 220 ° C obtained by the fluid catalytic cracking method of the present invention can be used as a gasoline substrate.
  • a fraction having a boiling point of 25 to 220 ° C may be a part of the fraction having a boiling point of 25 to 220 ° C.
  • the hydrogenation process is performed and the resulting hydride is used as a gasoline base material.
  • a fraction having a boiling point of 170 to 370 ° C obtained by the fluid catalytic cracking method of the present invention can be used as a diesel fuel base material.
  • a fraction having a boiling point of 170 to 370 ° C may be partially used as a diesel fuel base or may be used as a diesel fuel base with a force S.
  • the hydrocarbon having 3 or 4 carbon atoms obtained by the fluid catalytic cracking method of the present invention can be used as a liquefied petroleum gas base material.
  • propylene obtained by the fluid catalytic cracking method of the present invention can be used as a constituent monomer of a synthetic resin.
  • ether obtained by reacting isoprene obtained by the fluid catalytic cracking method of the present invention with methanol or ethanol can be used as a gasoline base material.
  • a reaction product obtained by reacting butylene obtained by the fluid catalytic cracking method of the present invention with isobutane using an alkylation apparatus can be used as a gasoline base material.
  • the dimerized butylene obtained by the fluid catalytic cracking method of the present invention is used with a force S to be used as a gasoline substrate.
  • the hydrogen / carbon monoxide molar ratio is 2: 1, the reaction temperature is 300 ° C, and the gas space velocity is 2000h— 1 . Went.
  • the resulting synthesis product was separated into a hydrocarbon liquid product and a mixture of unreacted hydrogen, carbon monoxide and gaseous products using a distillation apparatus.
  • an FCC pilot device manufactured by Xytel having a reaction zone (adiabatic downflow reactor), a separation zone, a stripping zone and a regeneration zone was used.
  • the catalyst prepared as follows was used as a catalytic cracking catalyst.
  • the catalyst obtained as described above was pseudo-equilibrated by 100% steaming treatment at 800 ° C for 6 hours before being supplied to the apparatus.
  • the equipment scale is 2 kg of inventory (total amount of catalyst) and feed amount is 1 kg / h
  • the reaction conditions for fluid catalytic cracking are catalyst /
  • the feed oil ratio was 20, the reaction zone outlet temperature was 600 ° C, the contact time was 0.5 seconds, and the gas linear velocity of the downflow reactor was 4 m / s.
  • the feedstock was supplied to the reaction zone by spraying the feedstock using a steam equivalent to 5% by mass of the feedstock.
  • the amount of coke required for heat balance was 8.5%.
  • the actual coke yield was 7.5%, and the insufficient heat was compensated as follows.
  • the unreacted hydrogen and carbon monoxide separated from the synthesis product of the FT synthesis and the unreacted hydrogen from the gas product mixture are removed, and the resulting carbon monoxide and gas product mixture is regenerated.
  • the zone was supplied as a heat source.
  • Table 1 shows the conversion rate from feedstock to cracked products, yield of cracked products, delta coke, and the research octane number of the gasoline obtained in the above catalytic cracking reaction.
  • the yields of the cracked products are all expressed as a percentage of the mass ratio of the cracked products to the feedstock oil.
  • C1 represents methane gas and C2 represents ethane gas (the same applies hereinafter).
  • a catalyst was prepared in the same manner as in Example 1, and this catalyst and a commercially available additive for improving octane number (GRACE Davison: Olef insmax) were 20% of the inventory (total amount of catalyst and additive).
  • the catalytic cracking reaction was carried out in the same manner as in Example 1 except that it was used in combination.
  • Table 1 shows the conversion rate from feedstock to cracked products, yield of cracked products, delta coke, and research octane number of the gasoline obtained.
  • Catalytic cracking was carried out in the same manner as in Example 1 except that Middle Eastern desulfurization VGO was used as the feedstock.
  • Table 1 shows the conversion rate from feedstock to cracked products, cracked product yield, delta coke, and the research method octane number of the gasoline obtained.
  • Catalytic cracking was carried out in the same manner as in Example 2 except that Middle Eastern desulfurization VGO was used as the feedstock.
  • Table 1 shows the conversion rate from feedstock to cracked products, cracked product yield, delta coke, and the research method octane number of the gasoline obtained.
  • Example 2 From the results shown in Table 1, in Examples 1 and 2, a high yield was obtained by decomposing FT synthetic oil using a catalyst containing ultrastable Y-type zeolite under the above reaction conditions. It can be seen that cracked product oil and light olefin are obtained. Further, in Example 2, it is possible to further increase the production of light olefins with higher added value by using a combination of a catalyst containing an ultrastable Y-type zeolite and a commercially available additive for improving octane number. Force S Force. In addition, the heat balance could be maintained by supplying the FT synthesis gas product to the regeneration tower. This experimental device has the power that can be adjusted by an external heater, and the commercial device does not have an external heater. Therefore, if the heat balance is not maintained, the reaction temperature will decrease and stable operation cannot be maintained.
  • Comparative Example 3 the FT synthetic oil was decomposed under the same conditions as the conventional FCC, with a catalyst / feed oil ratio of 5.5, a reaction zone outlet temperature of 500 ° C., and a contact time of 2 seconds. It is equivalent to.
  • Delta Coke has the same strength S as in Examples 1 and 2, the coke yield is extremely low, and generally 5-7% of coke is required to achieve heat balance. Unless the shortage of heat is compensated for, the decomposition reaction cannot be continued under these reaction conditions!
  • the output of the electric external heater is adjusted to compensate for the lack of heat! / Continued driving.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Cette invention concerne un procédé de craquage catalytique consistant à utiliser un dispositif de craquage catalytique fluide présentant une zone de réaction, une zone de séparation, une zone d'épuration et une zone de reproduction. Un produit de synthèse élaboré par synthèse FT est divisé en un produit liquide principalement constitué d'un hydrocarbure et d'un mélange d'hydrogène inaltéré et d'un monoxyde de carbone et en un produit gazeux. Dans la zone de réaction, une huile de charge contenant le produit liquide est traitée au moyen d'un catalyseur contenant de 10 à 50% en masse d'un zéolite Y ultrastable dans des conditions d'une température de sortie dans la zone de réaction comprise entre 550 et 650°C, un rapport catalyseur/huile de 10 à 40 poids/poids, une pression de reaction de 1 à 3 kg/cm2G, et une durée de contact entre l'huile de charge et le catalyseur dans la zone de réaction de 0,1 à 1 seconde. Dans la zone de reproduction, le catalyseur utilisé est traité dans des conditions d'une température d'une phase riche en catalyseur dans la zone de reproduction de 620 à 690˚C, une pression dans la zone de reproduction de 1 à 3 kg/cm2G, et d'une concentration en oxygène dans un gaz d'échappement à la sortie de la zone de reproduction de 0 à 3% en moles, pendant l'introduction de l'hydrogène inaltéré ou d'un élément similaire en tant que source de chaleur.
PCT/JP2007/066868 2006-08-31 2007-08-30 Procédé de craquage catalytique fluide Ceased WO2008026681A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2365409C1 (ru) * 2008-04-07 2009-08-27 Институт проблем переработки углеводородов Сибирского отделения Российской Академии Наук (ИППУ СО РАН) Катализатор для глубокого крекинга нефтяных фракций и способ его приготовления
WO2023234212A1 (fr) * 2022-05-31 2023-12-07 Ｅｎｅｏｓ株式会社 Procédé de production d'hydrocarbure
WO2023234211A1 (fr) * 2022-05-31 2023-12-07 Ｅｎｅｏｓ株式会社 Procédé de production d'hydrocarbures

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JPH1060453A (ja) * 1996-06-05 1998-03-03 Nippon Oil Co Ltd 重質油の流動接触分解法
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* Cited by examiner, † Cited by third party
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RU2365409C1 (ru) * 2008-04-07 2009-08-27 Институт проблем переработки углеводородов Сибирского отделения Российской Академии Наук (ИППУ СО РАН) Катализатор для глубокого крекинга нефтяных фракций и способ его приготовления
WO2023234212A1 (fr) * 2022-05-31 2023-12-07 Ｅｎｅｏｓ株式会社 Procédé de production d'hydrocarbure
WO2023234211A1 (fr) * 2022-05-31 2023-12-07 Ｅｎｅｏｓ株式会社 Procédé de production d'hydrocarbures
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