WO2015182329A1 - Method for fluid catalytic cracking of heavy oil - Google Patents

Method for fluid catalytic cracking of heavy oil Download PDF

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WO2015182329A1
WO2015182329A1 PCT/JP2015/062967 JP2015062967W WO2015182329A1 WO 2015182329 A1 WO2015182329 A1 WO 2015182329A1 JP 2015062967 W JP2015062967 W JP 2015062967W WO 2015182329 A1 WO2015182329 A1 WO 2015182329A1
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catalyst
catalytic cracking
fluid catalytic
heavy oil
mass
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PCT/JP2015/062967
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French (fr)
Japanese (ja)
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太 大内
秀樹 尾野
真理絵 岩間
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Ｊｘ日鉱日石エネルギー株式会社
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Priority to US15/313,617 priority Critical patent/US20170218281A1/en
Priority to KR1020167033344A priority patent/KR20170015301A/en
Publication of WO2015182329A1 publication Critical patent/WO2015182329A1/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
    • 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins

Definitions

  • the present invention relates to a fluid catalytic cracking method of heavy oil, and more particularly to a fluid catalytic cracking method for obtaining light olefins such as propylene and butene from heavy oil in high yield.
  • Such a method of using a fluid catalytic cracker has an economic advantage particularly in a refinery where oil refining and a petrochemical factory are highly coupled.
  • Examples of the method for producing light olefins by fluid catalytic cracking of heavy oil include, for example, a method of shortening the contact time between the catalyst and the feedstock (Patent Documents 1 to 4), a method of performing a reaction at a high temperature (Patent Document 5), Examples thereof include methods using pentasil-type zeolite (Patent Documents 6 to 7).
  • the selectivity for light olefins has not been sufficiently improved.
  • the pyrolysis is combined with an increase in unnecessary dry gas yield, and the yield of useful light olefin is sacrificed accordingly.
  • the quality of gasoline obtained together with the light olefin deteriorates.
  • the method of shortening the contact time can suppress the hydrogen transfer reaction and reduce the rate of conversion of light olefins to light paraffin, but the conversion rate cannot be increased, so the yield of light olefins is still insufficient. It is.
  • Patent Document 8 a method (Patent Document 8) has been proposed that combines these techniques such as high temperature reaction, high catalyst / oil ratio, and short contact time to suppress thermal decomposition and achieve high conversion (Patent Document 8).
  • the olefin yield is not sufficient.
  • the method using pentasil-type zeolite only increases the light olefin yield by overdecomposing gasoline, so the light olefin yield is not sufficiently increased, and the gasoline yield is significantly reduced. . Therefore, it is difficult to obtain light olefins from heavy oil in high yield by these methods.
  • Patent Document 9 In addition to high temperature reaction, high catalyst / oil ratio, short contact time, a down flow type reaction zone that can suppress back mixing in the reaction zone, and content and shape selectivity of rare earth metal oxide in fluid catalytic cracking catalyst. There has been proposed a method (Patent Document 9) for further improving the light olefin yield by adjusting the mixing ratio of the additive containing zeolite. However, even if these methods are used, when the activity of the fluid catalytic cracking catalyst is not sufficient, the cracking of the heavy feedstock is insufficient and the light olefin yield has not been maximized.
  • the object of the present invention is an improved heavy material that can produce light olefins in a high yield by combining the reaction mode, reaction conditions, catalyst, etc., with a small amount of dry gas generated by thermal decomposition and a small amount of paraffin generated by hydrogen transfer reaction. It is to provide a fluid catalytic cracking process of oil.
  • the present inventors diligently focused on obtaining a light olefin in a high yield in a fluid catalytic cracking process for obtaining light olefins such as propylene and butene by fluid catalytic cracking of heavy oil at a high temperature and a short contact time.
  • the inventors have found that the object can be achieved by using a catalyst containing a specific fluid catalytic cracking catalyst and subjecting heavy oil to fluid catalytic cracking under specific conditions, and have reached the present invention. .
  • the present invention relates to a process for producing light olefins by fluid catalytic cracking of heavy oil, in which the reaction zone outlet temperature is 580 to 630 ° C., the catalyst / oil ratio is 15 to 40 weight / weight, and carbonization in the reaction zone is performed.
  • a catalyst containing 12 to 24% by mass of a shape-selective zeolite is brought into contact with heavy oil under conditions where the hydrogen residence time is 0.1 to 1.0 second, and the secondary cracking activity (C2 olefin concentration /
  • This is a heavy oil fluidized catalytic cracking method characterized in that a cracked product having a value of (C4 olefin concentration) in the range of 0.30 to 0.55 is obtained.
  • the catalyst is a catalyst comprising an additive containing a fluid catalytic cracking catalyst and a shape selective zeolite, and the content of the ultrastable Y-type zeolite in the fluid catalytic cracking catalyst is 5 to 50% by mass.
  • the present invention relates to a fluid catalytic cracking process of the heavy oil.
  • the catalyst is a catalyst comprising an additive containing a fluid catalytic cracking catalyst and a shape-selective zeolite, and the content of the shape-selective zeolite in the additive is 20 to 70% by mass.
  • the present invention relates to a fluid catalytic cracking method of the heavy oil.
  • the catalyst is a catalyst comprising an additive containing a fluid catalytic cracking catalyst and a shape-selective zeolite, wherein the ratio of the additive in the catalyst is 17 to 60% by mass.
  • the present invention relates to fluid catalytic cracking of heavy oil.
  • the present invention also relates to the above-described fluid catalytic cracking method of heavy oil, characterized in that the crystal lattice constant of the ultrastable Y-type zeolite is 24.20 to 24.60 ⁇ .
  • the catalyst is a catalyst comprising an additive containing a fluid catalytic cracking catalyst and a shape selective zeolite, and the content of the rare earth metal oxide in the fluid catalytic cracking catalyst is 1.5% by mass or less.
  • the present invention relates to a fluid catalytic cracking process for heavy oil as described above. Furthermore, the present invention relates to the above-described fluid catalytic cracking method of heavy oil, characterized by using a fluid catalytic cracking reactor having a down flow type reaction zone, a gas-solid separation zone, a stripping zone and a catalyst regeneration zone.
  • the amount of dry gas generated by thermal decomposition and the amount of paraffin generated by hydrogen transfer reaction are small, and light olefins such as propylene and butene can be obtained in high yield.
  • the present invention is a fluid catalytic cracking process of heavy oil for producing light olefins.
  • fluid catalytic cracking is one in which heavy oil is continuously brought into contact with a catalyst held in a fluid state to decompose heavy oil into light hydrocarbons mainly composed of light olefins and gasoline.
  • a fluid catalytic cracker having a reaction zone, a gas-solid separation zone, a stripping zone and a catalyst regeneration zone is used.
  • reaction zone examples include a so-called riser reaction zone in which both catalyst particles and feedstock oil rise in the pipe, and a downflow type (downer) reaction zone in which both catalyst particles and feedstock oil fall in the pipe.
  • riser reaction zone in which both catalyst particles and feedstock oil rise in the pipe
  • downflow type (downer) reaction zone in which both catalyst particles and feedstock oil fall in the pipe.
  • thermal decomposition is undesirable because it increases the generation of unnecessary dry gas and decreases the yield of the desired light olefin and gasoline. Therefore, in the present invention, a down flow type (downer) reaction zone in which both catalyst particles and raw material oil descend in the pipe is preferably used.
  • the cracked reaction mixture comprising the mixture of cracked reaction product, unreacted material and spent catalyst that has undergone fluid catalytic cracking in the reaction zone is then sent to the gas-solid separation zone where the cracked reaction product, unreacted from the catalyst particles. Most of hydrocarbons such as waste are removed. In some cases, the decomposition reaction mixture is quenched immediately before or after the gas-solid separation zone in order to suppress unnecessary thermal decomposition or excessive decomposition.
  • the spent catalyst from which most of the hydrocarbons have been removed is further sent to the stripping zone, where hydrocarbons that could not be completely removed in the gas-solid separation zone are removed by the stripping gas.
  • the used catalyst with the carbonaceous material and some heavy hydrocarbons attached is regenerated from the stripping zone in order to regenerate the spent catalyst. Sent to the band.
  • the used catalyst is oxidized, and carbonaceous substances and heavy hydrocarbons deposited and deposited on the catalyst are removed and regenerated.
  • the catalyst regenerated by this oxidation treatment is sent again to the reaction zone and continuously circulated.
  • FIG. 1 shows an example of a fluid catalytic cracking reaction apparatus having a downflow type reaction zone, a gas-solid separation zone, a stripping zone, and a catalyst regeneration zone. The present invention will be described below with reference to FIG.
  • the heavy oil as the raw material is supplied to the mixing region 7 through the line 10 and mixed with the regenerated catalyst circulated from the catalyst storage tank 6.
  • the mixture flows down in the reaction zone 1 in a parallel flow, and during this time, the raw heavy oil and the catalyst are brought into contact with each other at a high temperature for a short time, and the heavy oil is decomposed.
  • the decomposition reaction mixture from reaction zone 1 flows down to gas-solid separation zone 2 located below reaction zone 1, where spent catalyst is separated from decomposition reaction products and unreacted raw materials, and dipleg 9 is Then, it is guided to the upper part of the stripping band 3.
  • the hydrocarbon gas from which most of the spent catalyst has been removed is then led to the secondary separator 8.
  • a small amount of spent catalyst remaining in the gas is removed, and the hydrocarbon gas is extracted out of the system and recovered.
  • a tangential cyclone is preferably used as the secondary separator 8.
  • the spent catalyst in the stripping zone 3 is removed by the stripping gas introduced from the line 11 to remove remaining hydrocarbons adhering to the surface of the used catalyst or between the catalysts.
  • the stripping gas an inert gas such as nitrogen generated by a steam or a compressor generated by a boiler is used.
  • a temperature of 500 to 900 ° C., preferably 500 to 700 ° C., and a catalyst particle residence time of 1 to 10 minutes are usually employed.
  • the stripping zone 3 the decomposition reaction products and unreacted raw materials adhering to the spent catalyst are removed, and the stripping gas is extracted from the line 12 at the top of the stripping zone 3 and led to the recovery system.
  • the spent catalyst that has undergone the stripping process is supplied to the catalyst regeneration zone 4 through a line including the first flow rate regulator 13.
  • the gas superficial velocity in the stripping zone 3 is usually preferably maintained in the range of 0.05 to 0.4 m / s, so that the fluidized bed in the stripping zone can be a bubble fluidized bed. Since the gas velocity is relatively small in the bubbling fluidized bed, the consumption of the stripping gas can be reduced, and since the bed density is relatively large, the pressure control width of the first flow rate regulator 13 can be increased. Therefore, the transfer of the catalyst particles from the stripping zone 3 to the catalyst regeneration zone 4 is facilitated.
  • a horizontal perforated plate and other insertions can be provided in multiple stages for the purpose of improving the contact between the used catalyst and the stripping gas and improving the stripping efficiency.
  • the catalyst regeneration zone 4 is partitioned by a container having a conical upper portion and a cylindrical lower portion, and the upper conical portion communicates with an upright conduit (riser type regeneration tower) 5.
  • the apex angle of the upper cone portion is usually in the range of 30 to 90 degrees, and the height of the upper cone portion is preferably in the range of 1/2 to 2 times the diameter of the lower cylindrical portion.
  • the spent catalyst supplied from the stripping zone 3 to the catalyst regeneration zone 4 is fluidized by a regeneration gas (typically an oxygen-containing gas such as air) 14 introduced from the bottom of the catalyst regeneration zone 4. It is regenerated by burning and removing substantially all of the carbonaceous material and heavy hydrocarbons adhering to the catalyst surface.
  • a temperature of 600 to 1000 ° C., preferably 650 to 750 ° C., a catalyst residence time of 1 to 5 minutes is adopted, and a gas superficial velocity is preferably 0.4 to 1.2 m / s. Adopted.
  • the regenerated catalyst regenerated in the catalyst regeneration zone 4 and jumped out from the upper part of the turbulent fluidized bed is transferred to the riser type regeneration tower 5 from the upper conical portion along with the used regeneration gas.
  • the diameter of the riser type regeneration tower 5 communicating with the upper conical portion of the catalyst regeneration zone 4 is preferably 1/6 to 1/3 of the diameter of the lower cylindrical portion.
  • the regenerated catalyst rising in the riser type regeneration tower 5 is carried to a catalyst storage tank 6 installed at the top of the riser type regeneration tower.
  • the catalyst storage tank 6 also functions as a gas-solid separator, and the used regeneration gas containing carbon dioxide gas or the like is separated from the regeneration catalyst here and discharged out of the system via the cyclone 15.
  • the regenerated catalyst in the catalyst storage tank 6 is supplied to the mixing region 7 via a downflow pipe equipped with a second flow rate regulator 17. Further, if necessary, a part of the regenerated catalyst in the catalyst storage tank 6 is regenerated through a bypass conduit having a third flow rate regulator 16 in order to facilitate control of the catalyst circulation amount in the riser type regenerating tower 5. It can be returned to 4. In this way, the catalyst passes through the downflow type reaction zone 1, the gas-solid separation zone 2, the stripping zone 3, the catalyst regeneration zone 4, the riser type regeneration tower 5, the catalyst storage tank 6, and the mixing region 7, and again the downflow type. It circulates in the system in the order of reaction zone 1.
  • Examples of the heavy oil used as a raw material in the present invention include vacuum gas oil, atmospheric residue, vacuum residue, pyrolysis gas oil, and heavy oil obtained by hydrorefining these. These heavy oils may be used alone, or a mixture of these heavy oils or a mixture of these heavy oils with a part of light oil may be used.
  • the distillation properties of heavy oils used as raw material oils are preferably those having a boiling range of 170 to 800 ° C, more preferably 190 to 780 ° C.
  • the reaction zone outlet temperature as used in the present invention is the outlet temperature of the reaction zone, and when the decomposition reaction product is rapidly cooled immediately before the separation from the catalyst or before the gas-solid separation zone, it is rapidly cooled.
  • the reaction zone outlet temperature is 580 to 630 ° C., preferably 590 to 620 ° C. If the temperature is lower than 580 ° C., a light olefin cannot be obtained in a high yield, and if it is higher than 630 ° C., thermal decomposition becomes remarkable and the amount of dry gas generated is not preferable.
  • the catalyst / oil ratio indicates the ratio of the catalyst circulation rate (ton / h) to the feed oil supply rate (ton / h).
  • the catalyst / oil ratio needs to be 15 to 40 weight / weight, preferably 20 to 30 weight / weight.
  • the catalyst / oil ratio is smaller than 15 weight / weight, the temperature of the regenerated catalyst supplied to the reaction zone becomes high in view of heat balance, which is not preferable because the amount of dry gas generated by thermal decomposition increases.
  • the catalyst / oil ratio is larger than 40 weight / weight, the catalyst circulation amount becomes large, and the capacity of the catalyst regeneration zone becomes too large to secure the catalyst residence time necessary for catalyst regeneration in the catalyst regeneration zone. Therefore, it is not preferable.
  • the hydrocarbon residence time as used in the present invention is the time from when the catalyst comes into contact with the raw material oil until the catalyst and the decomposition reaction product are separated at the outlet of the reaction zone, or immediately before the gas-solid separation zone. In the case, the time until quenching is shown.
  • the residence time needs to be 0.1 to 1.0 seconds, and preferably 0.4 to 0.9 seconds.
  • the residence time of hydrocarbons in the reaction zone is shorter than 0.1 seconds, the decomposition reaction becomes insufficient and light olefins cannot be obtained in high yield.
  • the residence time is longer than 1.0 seconds, the contribution of thermal decomposition becomes large, which is not preferable.
  • the operating conditions of the fluid catalytic cracking reactor in the present invention are not particularly limited except for the above, but usually, the operation is preferably carried out at a reaction pressure of 150 to 400 kPa.
  • the catalyst used in the present invention comprises a fluid catalytic cracking catalyst and an additive.
  • the fluid catalytic cracking catalyst comprises a zeolite which is an active component and a matrix which is a supporting matrix thereof.
  • the main component of the zeolite is ultrastable Y-type zeolite.
  • the matrix is composed of an active matrix, a binder (such as silica), a filler (such as clay mineral), and other components (such as rare earth metal oxides and metal trap components).
  • the active matrix has decomposition activity, and examples thereof include alumina and silica alumina.
  • the additive that is a constituent of the catalyst used in the present invention contains a shape-selective zeolite.
  • Constituent components other than the shape-selective zeolite include a binder (such as silica) and a filler (such as clay mineral).
  • Shape-selective zeolite is a zeolite whose pore diameter is smaller than that of Y-type zeolite, and only limited-shaped hydrocarbons can enter the pores. Examples of such zeolite include ZSM-5, ⁇ , omega, SAPO-5, SAPO-11, SAPO-34, and pentasil-type metallosilicate. Of these shape selective zeolites, ZSM-5 is most preferred.
  • C2 olefin concentration (wt%) and C4 olefin concentration (wt%) in all fractions (cracked product) distilled from a fluid catalytic cracking apparatus are used as indicators for measuring the balance between primary cracking and secondary cracking.
  • C2 olefin concentration / C4 olefin concentration (referred to as secondary cracking activity in the present invention).
  • the secondary decomposition activity needs to be in the range of 0.30 to 0.55, preferably 0.35 to 0.50.
  • the secondary cracking activity is less than 0.30, the secondary cracking ability is insufficient with respect to the primary cracking ability, and a light olefin cannot be obtained in a high yield.
  • the secondary cracking activity is larger than 0.55, the secondary cracking ability is too high with respect to the primary cracking ability, and the light olefin cannot be obtained in high yield due to the excessive cracking of the light olefin.
  • the content of the shape selective zeolite in the catalyst used in the present invention needs to be 12 to 24% by mass, preferably 14 to 24% by mass, more preferably 16 to 23% by mass, and 18 to 22% by mass. % Is particularly preferred.
  • the secondary cracking activity can be controlled in the range of 0.30 to 0.55.
  • the shape selective zeolite in the catalyst is more than 24% by mass, the hydrogen transfer reaction proceeds, the light olefin becomes light paraffin, and the light olefin decreases.
  • the shape-selective zeolite in the catalyst is less than 12% by mass, the progress of secondary cracking becomes insufficient and light olefins are reduced.
  • the content of the rare earth metal oxide in the fluid catalytic cracking catalyst is preferably 1.5% by mass or less, more preferably 1.2% by mass or less, and particularly preferably 1.0% by mass or less.
  • the content of the rare earth metal oxide in the fluid catalytic cracking catalyst is more than 1.5% by mass, the hydrogen transfer activity becomes too high, and the cracking activity increases, but the light olefin yield decreases.
  • the rare earth oxide content in the fluid catalytic cracking catalyst increases, so the steaming resistance increases, so the activity of the catalyst increases.
  • a catalyst containing a large amount of rare earth metal oxide also has high hydrogen transfer activity.
  • the hydrogen transfer activity of the fluid catalytic cracking catalyst increases, the olefin in the product decreases and the paraffin increases.
  • Olefins mainly in gasoline fractions are decomposed into light olefins by additives containing shape selective zeolite.
  • the crystal lattice constant of the ultrastable Y-type zeolite is preferably 24.20 to 24.60 ⁇ , more preferably 24.36 to 24.45 ⁇ . In this range, the gasoline yield decreases as the crystal lattice constant decreases, but the light olefin yield increases. However, when the crystal lattice constant is smaller than 24.20 ⁇ , the cracking activity of the fluid catalytic cracking catalyst is too low to obtain a high conversion rate, so that the light olefin yield decreases. On the other hand, when the lattice constant is larger than 24.60 mm, the hydrogen transfer activity becomes too high.
  • the crystal lattice constant of zeolite here is measured by ASTM D-3942-80.
  • the ultrastable Y-type zeolite content in the fluid catalytic cracking catalyst is preferably 5 to 50% by mass, more preferably 15 to 40% by mass.
  • the bulk density of the fluid catalytic cracking catalyst is 0.5 to 1.0 g / ml, the average particle size is 50 to 90 ⁇ m, the surface area is 50 to 350 m 2 / g, and the pore volume is 0.05 to 0.5 ml / g. A range is preferred.
  • the shape-selective zeolite content in the additive is preferably 20 to 70% by mass, more preferably 30 to 60% by mass.
  • the bulk density of the additive is in the range of 0.5 to 1.0 g / ml, the average particle size is 50 to 90 ⁇ m, the surface area is 10 to 200 m 2 / g, and the pore volume is in the range of 0.01 to 0.3 ml / g. Preferably there is.
  • the ratio of the fluid catalytic cracking catalyst and the additive in the catalyst used in the present invention is 40 to 83% by mass, preferably 40 to 80% by mass, more preferably 40 to 70% by mass for the fluid catalytic cracking catalyst,
  • the additive containing the selective zeolite is 17 to 60% by mass, preferably 20 to 60% by mass, more preferably 30 to 60% by mass.
  • the amount of additive in the catalyst is relatively high, the production of coke can be suppressed. Since the additive has a low acid density, the reaction that becomes an aroma by the hydrogen transfer reaction from naphthene is suppressed, so that coke is hardly generated. Since hydrogen is generated as coke is generated, when coke generation is suppressed, the reaction from olefins to paraffin is suppressed, and the yield of light olefins is improved. However, even if the amount of the additive in the catalyst is too high, overdecomposition from olefin to paraffin occurs, and the light olefin yield decreases.
  • ⁇ Coke / Kinetic Conversion Coke yield (mass%) / (decomposition rate (mass%) / (100 ⁇ decomposition ratio (mass%)) is used (hereinafter referred to as ⁇ Coke / Kinetic Conversion). Is ⁇ Coke / K).
  • Example 1 Heavy oil fluidized catalytic cracking was carried out using a downflow reactor (downer) type FCC pilot device.
  • the equipment scale is inventory-5 kg, feed amount 1 kg / h, operating conditions are reaction zone outlet temperature 600 ° C., reaction pressure 196 kPa (1.0 kg / cm 2 G), catalyst / oil ratio 25 weight / weight.
  • the catalyst regeneration zone temperature is 720 ° C.
  • the raw material oil used was a desulfurized atmospheric residue oil (desulfurized AR) of the Middle East (Arabian Light).
  • the properties of desulfurization AR are as follows.
  • the 5% distillation temperature in distillation is 362 ° C., and the 95% distillation temperature is 703 ° C.
  • the 15 ° C. density is 0.931 g / cm 3 .
  • the residual carbon content is 2.57% by mass.
  • the sulfur content is 0.38% by mass.
  • the catalyst (A) used is a mixture of 70% by mass of a fluid catalytic cracking catalyst containing 37% by mass of an ultrastable Y-type zeolite and 30% by mass of an additive containing 43% by mass of a shape-selective zeolite.
  • the crystal lattice constant of the ultrastable Y-type zeolite contained in the fluid catalytic cracking catalyst is 24.40 ⁇ .
  • Each of the fluid catalytic cracking catalyst and the additive was separately steamed at 100% steam for 6 hours at 810 ° C. before being charged to the apparatus.
  • the results of the decomposition reaction are shown in Table 1.
  • the cut temperatures of gasoline / LCO / CLO were 221 ° C. and 343 ° C., respectively.
  • Example 2 Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
  • the raw material oil used was desulfurized vacuum gas oil (desulfurized VGO) of Middle Eastern (Arabian Light).
  • the properties of desulfurized VGO are as follows.
  • the 5% distillation temperature in distillation is 305 ° C, and the 95% distillation temperature is 538 ° C.
  • the 15 ° C. density is 0.0.895 g / cm 3 .
  • the residual carbon content is 0.02% by mass.
  • the sulfur content is 0.23% by mass.
  • the catalyst used is the same catalyst (A) as in Example 1.
  • the results of the decomposition reaction are shown in Table 1.
  • Example 3 Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
  • the raw material oil used was the same Middle Eastern (Arabian light) desulfurized atmospheric residue oil (desulfurized AR) as in Example 1.
  • the used catalyst (B) is a mixture of 65% by mass of a fluid catalytic cracking catalyst containing 31% by mass of ultrastable Y-type zeolite and 35% by mass of an additive containing 54% by mass of shape-selective zeolite.
  • the crystal lattice constant of the ultrastable Y-type zeolite contained in the fluid catalytic cracking catalyst is 24.40 ⁇ .
  • Each of the fluid catalytic cracking catalyst and the additive was separately steamed at 100% steam for 6 hours at 810 ° C. before being charged to the apparatus. The results of the decomposition reaction are shown in Table 1.
  • Example 4 Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
  • the feedstock used was the same Middle Eastern (Arabyanlite) desulfurized vacuum gas oil (desulfurized VGO) as in Example 2.
  • the catalyst used is the same catalyst (B) as in Example 3.
  • the results of the decomposition reaction are shown in Table 1.
  • Example 5 Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
  • the raw material oil used was the same Middle Eastern (Arabian light) desulfurized atmospheric residue oil (desulfurized AR) as in Example 1.
  • the catalyst (C) used is a mixture of 50% by mass of a fluid catalytic cracking catalyst containing 36% by mass of an ultrastable Y-type zeolite and 50% by mass of an additive containing 42% by mass of a shape-selective zeolite.
  • the crystal lattice constant of the ultrastable Y-type zeolite contained in the fluid catalytic cracking catalyst is 24.40 ⁇ .
  • Each of the fluid catalytic cracking catalyst and the additive was separately steamed at 100% steam for 6 hours at 810 ° C. before being charged to the apparatus. The results of the decomposition reaction are shown in Table 1.
  • Example 6 Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
  • the feedstock used was the same Middle Eastern (Arabyanlite) desulfurized vacuum gas oil (desulfurized VGO) as in Example 2.
  • the catalyst used is the same catalyst (C) as in Example 5.
  • the results of the decomposition reaction are shown in Table 1.
  • Example 7 Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
  • the raw material oil used was the same Middle Eastern (Arabian light) desulfurized atmospheric residue oil (desulfurized AR) as in Example 1.
  • the catalyst (D) used was a mixture of 40% by mass of a fluid catalytic cracking catalyst containing 40% by mass of ultrastable Y-type zeolite and 60% by mass of an additive containing 39% by mass of shape-selective zeolite.
  • the crystal lattice constant of the ultrastable Y-type zeolite contained in the fluid catalytic cracking catalyst is 24.40 ⁇ .
  • Each of the fluid catalytic cracking catalyst and the additive was separately steamed at 100% steam for 6 hours at 810 ° C. before being charged to the apparatus. The results of the decomposition reaction are shown in Table 1.
  • Example 8 Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
  • the feedstock used was the same Middle Eastern (Arabyanlite) desulfurized vacuum gas oil (desulfurized VGO) as in Example 2.
  • the catalyst used is the same catalyst (D) as in Example 7.
  • the results of the decomposition reaction are shown in Table 1.
  • Example 1 (Comparative Example 1) Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
  • the raw material oil used was the same Middle Eastern (Arabian light) desulfurized atmospheric residue oil (desulfurized AR) as in Example 1.
  • the catalyst (E) used is a mixture of 80% by mass of a fluid catalytic cracking catalyst containing 40% by mass of an ultrastable Y-type zeolite and 20% by mass of an additive containing 30% by mass of a shape-selective zeolite.
  • the crystal lattice constant of the ultrastable Y-type zeolite contained in the fluid catalytic cracking catalyst is 24.40 ⁇ .
  • Each of the fluid catalytic cracking catalyst and the additive was separately steamed at 100% steam for 6 hours at 810 ° C. before being charged to the apparatus. The results of the decomposition reaction are shown in Table 1.
  • Comparative Example 2 (Comparative Example 2) Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
  • the feedstock used was the same Middle Eastern (Arabyanlite) desulfurized vacuum gas oil (desulfurized VGO) as in Example 2.
  • the catalyst used is the same catalyst (E) as in Comparative Example 1.
  • Table 1 The results of the decomposition reaction are shown in Table 1.
  • Example 3 (Comparative Example 3) Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
  • the raw material oil used was the same Middle Eastern (Arabian light) desulfurized atmospheric residue oil (desulfurized AR) as in Example 1.
  • the catalyst (F) used is a mixture of 34% by mass of a fluid catalytic cracking catalyst containing 34% by mass of an ultrastable Y-type zeolite and 66% by mass of an additive containing 42% by mass of a shape-selective zeolite.
  • the crystal lattice constant of the ultrastable Y-type zeolite contained in the fluid catalytic cracking catalyst is 24.40 ⁇ .
  • Each of the fluid catalytic cracking catalyst and the additive was separately steamed at 100% steam for 6 hours at 810 ° C. before being charged to the apparatus. The results of the decomposition reaction are shown in Table 1.
  • Examples 1 to 8 fluid catalytic cracking was performed in an appropriate range of secondary cracking activity as compared with Comparative Examples 1 to 4, and as a result, light olefins were obtained in high yields.
  • ⁇ Coke / K which is an indicator of coke selectivity, is kept low while keeping the light olefin high, which is a preferable condition for the activity of the fluid catalytic cracking catalyst.

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Abstract

A method for the fluid catalytic cracking of a heavy oil, the method being for obtaining light olefins such as propylene and butene in high yield by subjecting a heavy oil to fluid catalytic cracking at a high temperature for a short contact time, characterized in that a catalyst containing 12-24 mass% shape-selective zeolite is brought into contact with the heavy oil under such conditions that the reaction zone outlet temperature is 580-630°C, the catalyst/oil ratio is 15-40 by weight, and the hydrocarbon residence time in the reaction zone is 0.1-1.0 second, thereby obtaining a product of cracking which has a value of secondary cracking activity ((C2 olefin concentration)/(C4 olefin concentration)) in the range of 0.30-0.55.

Description

重質油の流動接触分解法Fluid catalytic cracking of heavy oil
　本発明は、重質油の流動接触分解法に関し、詳しくは重質油からプロピレン、ブテン等の軽質オレフィンを高収率で得るための流動接触分解法に関する。 The present invention relates to a fluid catalytic cracking method of heavy oil, and more particularly to a fluid catalytic cracking method for obtaining light olefins such as propylene and butene from heavy oil in high yield.
　通常の流動接触分解は、石油系炭化水素を触媒と接触させて分解し、主生成物としてのガソリンと少量のＬＰＧと分解軽油等を得、さらに触媒上に堆積したコ－クを空気で燃焼除去して触媒を循環再使用するものである。
　しかしながら最近では、流動接触分解装置をガソリン製造装置としてではなく、石油化学原料としての軽質オレフィン（特にプロピレン）製造装置として利用していこうという動きがある。また一方、プロピレン、ブテン等は高オクタン価ガソリン基材であるアルキレート、メチル－ｔ－ブチルエーテル（ＭＴＢＥ）の原料となる。このような流動接触分解装置の利用法は、石油精製と石油化学工場が高度に結びついた製油所において特に経済的なメリットがある。
　重質油の流動接触分解により軽質オレフィンを製造する方法としては、例えば、触媒と原料油の接触時間を短くする方法（特許文献１～４）、高温で反応を行う方法（特許文献５）、ペンタシル型ゼオライトを用いる方法（特許文献６～７）等が挙げられる。 In normal fluid catalytic cracking, petroleum hydrocarbons are brought into contact with a catalyst and decomposed to obtain gasoline, a small amount of LPG, cracked light oil, etc. as main products, and the coal deposited on the catalyst is combusted with air. It is removed and the catalyst is recycled and reused.
Recently, however, there is a movement to use the fluid catalytic cracking apparatus not as a gasoline production apparatus but as a light olefin (particularly propylene) production apparatus as a petrochemical raw material. On the other hand, propylene, butene, and the like are raw materials for alkylate, methyl-t-butyl ether (MTBE), which is a high octane gasoline base material. Such a method of using a fluid catalytic cracker has an economic advantage particularly in a refinery where oil refining and a petrochemical factory are highly coupled.
Examples of the method for producing light olefins by fluid catalytic cracking of heavy oil include, for example, a method of shortening the contact time between the catalyst and the feedstock (Patent Documents 1 to 4), a method of performing a reaction at a high temperature (Patent Document 5), Examples thereof include methods using pentasil-type zeolite (Patent Documents 6 to 7).
　しかし、これらの方法においてもまだ軽質オレフィン選択性を十分高めるまでには至っていない。例えば、高温反応による方法おいては熱分解を併発して不必要なドライガス収率が増大し、その分有用な軽質オレフィンの収率が犠牲となる。また高温反応ではジエンの生成が増加するため軽質オレフィンとともに得られるガソリンの品質が劣化するという欠点もある。接触時間を短くする方法では、水素移行反応を抑制し、軽質オレフィンが軽質パラフィンへ転化する割合を低減することはできるが、転化率を増加させることはできないため、軽質オレフィン収率はまだ不十分である。また、これらの高温反応、高触媒／油比、短接触時間などの技術を組み合わせて熱分解を抑制し、しかも高い転化率を達成する方法（特許文献８）が提案されているが、まだ軽質オレフィン収率は十分とはいえない。またペンタシル型ゼオライトを用いた方法ではガソリンを過分解して軽質オレフィン収率を高めているだけであるから、軽質オレフィン収率の増加も十分ではなく、ガソリン収率が著しく減少するという欠点がある。従ってこれらの方法で重質油から高い収率で軽質オレフィンを得ることは困難である。
　高温反応、高触媒／油比、短接触時間に加えて、反応帯域での逆混合を抑制できるダウンフロー形式反応帯域とし、さらに流動接触分解触媒中の希土類金属酸化物の含有量および形状選択性ゼオライトを含む添加剤の混合比率を調節することでさらに軽質オレフィン収率を向上させる方法（特許文献９）が提案されている。しかし、これらの方法を用いても、流動接触分解触媒の活性が十分でない場合は重質な原料油の分解が不足し、軽質オレフィン収率を最大化するまでには至っていなかった。 However, even in these methods, the selectivity for light olefins has not been sufficiently improved. For example, in the method using a high temperature reaction, the pyrolysis is combined with an increase in unnecessary dry gas yield, and the yield of useful light olefin is sacrificed accordingly. Moreover, since the production of diene increases in the high temperature reaction, there is a disadvantage that the quality of gasoline obtained together with the light olefin deteriorates. The method of shortening the contact time can suppress the hydrogen transfer reaction and reduce the rate of conversion of light olefins to light paraffin, but the conversion rate cannot be increased, so the yield of light olefins is still insufficient. It is. In addition, a method (Patent Document 8) has been proposed that combines these techniques such as high temperature reaction, high catalyst / oil ratio, and short contact time to suppress thermal decomposition and achieve high conversion (Patent Document 8). The olefin yield is not sufficient. In addition, the method using pentasil-type zeolite only increases the light olefin yield by overdecomposing gasoline, so the light olefin yield is not sufficiently increased, and the gasoline yield is significantly reduced. . Therefore, it is difficult to obtain light olefins from heavy oil in high yield by these methods.
In addition to high temperature reaction, high catalyst / oil ratio, short contact time, a down flow type reaction zone that can suppress back mixing in the reaction zone, and content and shape selectivity of rare earth metal oxide in fluid catalytic cracking catalyst There has been proposed a method (Patent Document 9) for further improving the light olefin yield by adjusting the mixing ratio of the additive containing zeolite. However, even if these methods are used, when the activity of the fluid catalytic cracking catalyst is not sufficient, the cracking of the heavy feedstock is insufficient and the light olefin yield has not been maximized.
米国特許第４，４１９，２２１号公報U.S. Pat. No. 4,419,221 米国特許第３，０７４，８７８号公報U.S. Pat. No. 3,074,878 米国特許第５，４６２，６５２号公報US Pat. No. 5,462,652 ヨーロッパ特許第３１５，１７９Ａ号公報European Patent No. 315,179A 米国特許第４，９８０，０５３号公報U.S. Pat. No. 4,980,053 米国特許第５，３２６，４６５号公報US Pat. No. 5,326,465 特公表７－５０６３８９号公報Special Publication 7-506389 特開平１０－６０４５３号公報Japanese Patent Laid-Open No. 10-60453 特許第３９４８９０５号公報Japanese Patent No. 3948905
　本発明の目的は、反応形式、反応条件、触媒等の組み合わせにより、熱分解によるドライガス発生量および水素移行反応によるパラフィン発生量が少なく、軽質オレフィンが高収率で得られる改良された重質油の流動接触分解法を提供することにある。 The object of the present invention is an improved heavy material that can produce light olefins in a high yield by combining the reaction mode, reaction conditions, catalyst, etc., with a small amount of dry gas generated by thermal decomposition and a small amount of paraffin generated by hydrogen transfer reaction. It is to provide a fluid catalytic cracking process of oil.
　本発明者らは重質油を高温・短接触時間で流動接触分解し、プロピレン、ブテン等の軽質オレフィンを得るための流動接触分解法において、高収率で軽質オレフィンを得ることを主眼に鋭意研究した結果、特定の流動接触分解触媒を含む触媒を用い、かつ特定の条件下に重質油を流動接触分解することによりその目的が達成されることを見出し、本発明に到達したものである。 The present inventors diligently focused on obtaining a light olefin in a high yield in a fluid catalytic cracking process for obtaining light olefins such as propylene and butene by fluid catalytic cracking of heavy oil at a high temperature and a short contact time. As a result of research, the inventors have found that the object can be achieved by using a catalyst containing a specific fluid catalytic cracking catalyst and subjecting heavy oil to fluid catalytic cracking under specific conditions, and have reached the present invention. .
　すなわち、本発明は、重質油を流動接触分解して軽質オレフィンを製造する方法において、反応帯域出口温度が５８０～６３０℃、触媒／油比が１５～４０重量／重量、反応帯域での炭化水素の滞留時間が０．１～１．０秒の条件下に、形状選択性ゼオライトを１２～２４質量％含有する触媒を重質油と接触させて、二次分解活性度（Ｃ２オレフィン濃度／Ｃ４オレフィン濃度）の値が０．３０～０．５５の範囲の分解生成物を得ることを特徴とする重質油の流動接触分解法である。 That is, the present invention relates to a process for producing light olefins by fluid catalytic cracking of heavy oil, in which the reaction zone outlet temperature is 580 to 630 ° C., the catalyst / oil ratio is 15 to 40 weight / weight, and carbonization in the reaction zone is performed. A catalyst containing 12 to 24% by mass of a shape-selective zeolite is brought into contact with heavy oil under conditions where the hydrogen residence time is 0.1 to 1.0 second, and the secondary cracking activity (C2 olefin concentration / This is a heavy oil fluidized catalytic cracking method characterized in that a cracked product having a value of (C4 olefin concentration) in the range of 0.30 to 0.55 is obtained.
　また本発明は、前記触媒が、流動接触分解触媒と形状選択性ゼオライトを含む添加剤からなる触媒であって、流動接触分解触媒中の超安定Ｙ型ゼオライトの含有量が５～５０質量％であることを特徴とする前記の重質油の流動接触分解法に関する。
　また本発明は、前記触媒が、流動接触分解触媒と形状選択性ゼオライトを含む添加剤からなる触媒であって、添加剤中の形状選択性ゼオライトの含有量が２０～７０質量％であることを特徴とする前記の重質油の流動接触分解法に関する。
　また本発明は、前記触媒が、流動接触分解触媒と形状選択性ゼオライトを含む添加剤からなる触媒であって、触媒における添加剤の割合が１７～６０質量％であることを特徴とする前記の重質油の流動接触分解法に関する。
　また本発明は、超安定Ｙ型ゼオライトの結晶格子定数が２４．２０～２４．６０Åであることを特徴とする前記の重質油の流動接触分解法に関する。
　また本発明は、前記触媒が、流動接触分解触媒と形状選択性ゼオライトを含む添加剤からなる触媒であって、流動接触分解触媒中の希土類金属酸化物の含有量が１．５質量％以下であること特徴とする前記の重質油の流動接触分解法に関する。
　さらに本発明は、ダウンフロー形式反応帯域、気固分離帯域、ストリッピング帯域および触媒再生帯域を有する流動接触分解反応装置を使用することを特徴とする前記の重質油の流動接触分解法に関する。 In the present invention, the catalyst is a catalyst comprising an additive containing a fluid catalytic cracking catalyst and a shape selective zeolite, and the content of the ultrastable Y-type zeolite in the fluid catalytic cracking catalyst is 5 to 50% by mass. The present invention relates to a fluid catalytic cracking process of the heavy oil.
In the present invention, the catalyst is a catalyst comprising an additive containing a fluid catalytic cracking catalyst and a shape-selective zeolite, and the content of the shape-selective zeolite in the additive is 20 to 70% by mass. The present invention relates to a fluid catalytic cracking method of the heavy oil.
In the present invention, the catalyst is a catalyst comprising an additive containing a fluid catalytic cracking catalyst and a shape-selective zeolite, wherein the ratio of the additive in the catalyst is 17 to 60% by mass. The present invention relates to fluid catalytic cracking of heavy oil.
The present invention also relates to the above-described fluid catalytic cracking method of heavy oil, characterized in that the crystal lattice constant of the ultrastable Y-type zeolite is 24.20 to 24.60 Å.
In the present invention, the catalyst is a catalyst comprising an additive containing a fluid catalytic cracking catalyst and a shape selective zeolite, and the content of the rare earth metal oxide in the fluid catalytic cracking catalyst is 1.5% by mass or less. The present invention relates to a fluid catalytic cracking process for heavy oil as described above.
Furthermore, the present invention relates to the above-described fluid catalytic cracking method of heavy oil, characterized by using a fluid catalytic cracking reactor having a down flow type reaction zone, a gas-solid separation zone, a stripping zone and a catalyst regeneration zone.
　本発明により、熱分解によるドライガス発生量および水素移行反応によるパラフィン発生量が少なく、プロピレン、ブテンなどの軽質オレフィンを高い収率で得ることができる。 According to the present invention, the amount of dry gas generated by thermal decomposition and the amount of paraffin generated by hydrogen transfer reaction are small, and light olefins such as propylene and butene can be obtained in high yield.
ダウンフロー形式反応帯域、気固分離帯域、ストリッピング帯域および触媒再生帯域を有する流動接触分解反応装置の一例示す図である。It is a figure which shows an example of the fluid catalytic cracking reaction apparatus which has a downflow type | mold reaction zone, a gas-solid separation zone, a stripping zone, and a catalyst regeneration zone.
　以下、本発明について詳述する。 Hereinafter, the present invention will be described in detail.
　本発明は、軽質オレフィンを製造する重質油の流動接触分解法である。本発明において流動接触分解は、重質油を流動状態に保持されている触媒に連続的に接触させて重質油を軽質オレフィンおよびガソリンを主体とした軽質な炭化水素に分解するものである。 The present invention is a fluid catalytic cracking process of heavy oil for producing light olefins. In the present invention, fluid catalytic cracking is one in which heavy oil is continuously brought into contact with a catalyst held in a fluid state to decompose heavy oil into light hydrocarbons mainly composed of light olefins and gasoline.
　流動接触分解装置としては、反応帯域、気固分離帯域、ストリッピング帯域および触媒再生帯域を有する流動接触分解装置が用いられる。 As the fluid catalytic cracker, a fluid catalytic cracker having a reaction zone, a gas-solid separation zone, a stripping zone and a catalyst regeneration zone is used.
　反応帯域としては、例えば、触媒粒子と原料油が共に管中を上昇するいわゆるライザー反応帯域、触媒粒子と原料油が共に管中を降下するダウンフロー形式（ダウナー）反応帯域が挙げられ、いずれも採用することができる。
　しかし、通常のライザー反応帯域を用いた場合には逆混合が起こり、局部的にガスの滞留時間が長くなり熱分解を併発するおそれがある。特に、本発明のように触媒／油比が通常の流動接触分解法に比べて極端に大きい場合には逆混合の程度は大きくなる。そして熱分解は不必要なドライガスの発生を増加させ、目的とする軽質オレフィンおよびガソリンの収率を減少させるため好ましくない。そのため本発明においては、触媒粒子と原料油が共に管中を降下するダウンフロー形式（ダウナー）反応帯域が好ましく用いられる。 Examples of the reaction zone include a so-called riser reaction zone in which both catalyst particles and feedstock oil rise in the pipe, and a downflow type (downer) reaction zone in which both catalyst particles and feedstock oil fall in the pipe. Can be adopted.
However, when a normal riser reaction zone is used, backmixing occurs, and the residence time of the gas is locally increased, possibly causing thermal decomposition. In particular, when the catalyst / oil ratio is extremely large as compared with a normal fluid catalytic cracking method as in the present invention, the degree of backmixing becomes large. Thermal decomposition is undesirable because it increases the generation of unnecessary dry gas and decreases the yield of the desired light olefin and gasoline. Therefore, in the present invention, a down flow type (downer) reaction zone in which both catalyst particles and raw material oil descend in the pipe is preferably used.
　反応帯域で流動接触分解を受けた分解反応生成物、未反応物および使用済み触媒の混合物からなる分解反応混合物は、次に気固分離帯域に送られ、触媒粒子から分解反応生成物、未反応物等の炭化水素類の大部分が除去される。なお、場合によっては、不必要な熱分解あるいは過分解を抑制するため、分解反応混合物は気固分離帯域の直前あるいは直後で急冷される。 The cracked reaction mixture comprising the mixture of cracked reaction product, unreacted material and spent catalyst that has undergone fluid catalytic cracking in the reaction zone is then sent to the gas-solid separation zone where the cracked reaction product, unreacted from the catalyst particles. Most of hydrocarbons such as waste are removed. In some cases, the decomposition reaction mixture is quenched immediately before or after the gas-solid separation zone in order to suppress unnecessary thermal decomposition or excessive decomposition.
　大部分の炭化水素類が除去された使用済み触媒は、さらにストリッピング帯域に送られ、ストリッピング用ガスにより気固分離帯域で除去しきれなかった炭化水素類の除去が行われる。このようにして使用済み触媒と炭化水素類を分離した後、使用済み触媒を再生するため、炭素質物質および一部重質の炭化水素類が付着した使用済み触媒は、ストリッピング帯域から触媒再生帯域に送られる。触媒再生帯域においては使用済み触媒に酸化処理が施され、触媒上に沈着・付着した炭素質物質および重質炭化水素類が除去され再生される。この酸化処理を受けて再生された触媒は前記反応帯域に再び送られ、連続的に循環される。 The spent catalyst from which most of the hydrocarbons have been removed is further sent to the stripping zone, where hydrocarbons that could not be completely removed in the gas-solid separation zone are removed by the stripping gas. After separating the spent catalyst and hydrocarbons in this way, the used catalyst with the carbonaceous material and some heavy hydrocarbons attached is regenerated from the stripping zone in order to regenerate the spent catalyst. Sent to the band. In the catalyst regeneration zone, the used catalyst is oxidized, and carbonaceous substances and heavy hydrocarbons deposited and deposited on the catalyst are removed and regenerated. The catalyst regenerated by this oxidation treatment is sent again to the reaction zone and continuously circulated.
　図１に、ダウンフロー形式反応帯域、気固分離帯域、ストリッピング帯域および触媒再生帯域を有する流動接触分解反応装置の一例を示す。以下、図１を参照しながら本発明について説明する。 FIG. 1 shows an example of a fluid catalytic cracking reaction apparatus having a downflow type reaction zone, a gas-solid separation zone, a stripping zone, and a catalyst regeneration zone. The present invention will be described below with reference to FIG.
　原料である重質油は、ライン１０を通って混合領域７に供給され、触媒貯槽６から循環される再生触媒と混合される。その混合物は反応帯域１内を並流で流下し、この間に原料重質油と触媒は高温で短時間接触して重質油の分解反応が行われる。反応帯域１からの分解反応混合物は、反応帯域１の下方に位置する気固分離帯域２に流下し、ここで使用済み触媒は、分解反応生成物及び未反応原料から分離され、ディップレッグ９を経てストリッピング帯域３の上部に導かれる。 The heavy oil as the raw material is supplied to the mixing region 7 through the line 10 and mixed with the regenerated catalyst circulated from the catalyst storage tank 6. The mixture flows down in the reaction zone 1 in a parallel flow, and during this time, the raw heavy oil and the catalyst are brought into contact with each other at a high temperature for a short time, and the heavy oil is decomposed. The decomposition reaction mixture from reaction zone 1 flows down to gas-solid separation zone 2 located below reaction zone 1, where spent catalyst is separated from decomposition reaction products and unreacted raw materials, and dipleg 9 is Then, it is guided to the upper part of the stripping band 3.
　大部分の使用済み触媒が除去された炭化水素気体は、次に二次分離器８へ導かれる。ここで気体中に少量残存した使用済み触媒が取り除かれ、炭化水素気体は系外へ抜き出されて回収される。二次分離器８としては接線型サイクロンが好ましく用いられる。 The hydrocarbon gas from which most of the spent catalyst has been removed is then led to the secondary separator 8. Here, a small amount of spent catalyst remaining in the gas is removed, and the hydrocarbon gas is extracted out of the system and recovered. A tangential cyclone is preferably used as the secondary separator 8.
　ストリッピング帯域３内の使用済み触媒は、ライン１１から導入されるストリッピング用ガスにより、使用済み触媒の表面や触媒間に付着残存した炭化水素類が取り除かれる。ストリッピング用ガスとしては、ボイラーにより発生されたスチームやコンプレッサー等により昇圧された窒素等の不活性ガスなどが用いられる。 The spent catalyst in the stripping zone 3 is removed by the stripping gas introduced from the line 11 to remove remaining hydrocarbons adhering to the surface of the used catalyst or between the catalysts. As the stripping gas, an inert gas such as nitrogen generated by a steam or a compressor generated by a boiler is used.
　ストリッピング条件としては、通常、温度５００～９００℃、好ましくは５００～７００℃、触媒粒子の滞留時間１～１０分が採用される。ストリッピング帯域３においては、使用済み触媒に付着残存する分解反応生成物並びに未反応原料が除去され、ストリッピング用ガスと共にストリッピング帯域３頂部のライン１２から抜き出され、回収系に導かれる。一方、ストリッピング処理を受けた使用済み触媒は、第１流量調節器１３を備えたラインを通って、触媒再生帯域４に供給される。 As stripping conditions, a temperature of 500 to 900 ° C., preferably 500 to 700 ° C., and a catalyst particle residence time of 1 to 10 minutes are usually employed. In the stripping zone 3, the decomposition reaction products and unreacted raw materials adhering to the spent catalyst are removed, and the stripping gas is extracted from the line 12 at the top of the stripping zone 3 and led to the recovery system. On the other hand, the spent catalyst that has undergone the stripping process is supplied to the catalyst regeneration zone 4 through a line including the first flow rate regulator 13.
　ストリッピング帯域３のガス空塔速度は、通常、０．０５～０．４ｍ／ｓの範囲に保持することが好ましく、これによってストリッピング帯域の流動層を気泡流動層とすることができる。気泡流動層ではガス速度が比較的小さいため、ストリッピング用ガスの消費量を少なくすることができ、また、層密度が比較的大きいことから、第１流量調節器１３の圧力制御幅を大きくできるので、ストリッピング帯域３から触媒再生帯域４への触媒粒子の移送が容易となる。ストリッピング帯域３には、使用済み触媒とストリッピング用ガスとの接触を良くし、ストリッピングの効率向上を図る目的で、水平多孔板やその他の内挿物を多段に設けることができる。 The gas superficial velocity in the stripping zone 3 is usually preferably maintained in the range of 0.05 to 0.4 m / s, so that the fluidized bed in the stripping zone can be a bubble fluidized bed. Since the gas velocity is relatively small in the bubbling fluidized bed, the consumption of the stripping gas can be reduced, and since the bed density is relatively large, the pressure control width of the first flow rate regulator 13 can be increased. Therefore, the transfer of the catalyst particles from the stripping zone 3 to the catalyst regeneration zone 4 is facilitated. In the stripping zone 3, a horizontal perforated plate and other insertions can be provided in multiple stages for the purpose of improving the contact between the used catalyst and the stripping gas and improving the stripping efficiency.
　触媒再生帯域４は、上部域が円錐状で下部域が円筒状を呈する容器で区画され、その上部円錐部分は直立導管（ライザー型再生塔）５と連通している。触媒再生帯域４は、上部円錐部分の頂角が通常３０～９０度の範囲にあり、上部円錐部分の高さが下部円筒部分の直径の１／２～２倍の範囲にあることが好ましい。ストリッピング帯域３から触媒再生帯域４に供給された使用済み触媒は、触媒再生帯域４の底部から導入される再生用ガス（典型的には空気などの酸素含有ガス）１４により、流動化されながら触媒表面に付着した炭素質物質並びに重質炭化水素の実質的に全てが燃焼除去されることで再生される。再生条件としては、通常、温度６００～１０００℃、好ましくは６５０～７５０℃、触媒滞留時間１～５分が採用され、ガス空塔速度は、通常、０．４～１．２ｍ／ｓが好ましく採用される。 The catalyst regeneration zone 4 is partitioned by a container having a conical upper portion and a cylindrical lower portion, and the upper conical portion communicates with an upright conduit (riser type regeneration tower) 5. In the catalyst regeneration zone 4, the apex angle of the upper cone portion is usually in the range of 30 to 90 degrees, and the height of the upper cone portion is preferably in the range of 1/2 to 2 times the diameter of the lower cylindrical portion. The spent catalyst supplied from the stripping zone 3 to the catalyst regeneration zone 4 is fluidized by a regeneration gas (typically an oxygen-containing gas such as air) 14 introduced from the bottom of the catalyst regeneration zone 4. It is regenerated by burning and removing substantially all of the carbonaceous material and heavy hydrocarbons adhering to the catalyst surface. As regeneration conditions, a temperature of 600 to 1000 ° C., preferably 650 to 750 ° C., a catalyst residence time of 1 to 5 minutes is adopted, and a gas superficial velocity is preferably 0.4 to 1.2 m / s. Adopted.
　触媒再生帯域４内で再生され、乱流流動層の上部から飛び出した再生触媒は、使用済みの再生用ガスに同伴されて上部円錐部分からライザー型再生塔５に移送される。触媒再生帯域４の上部円錐部分と連通するライザー型再生塔５の直径は、下部円筒部分の直径の１／６～１／３であることが好ましい。こうすることで、触媒再生帯域４内の流動層のガス空塔速度を、乱流流動層の形成に適した０．４～１．２ｍ／ｓの範囲に維持することができ、ライザー型再生塔５のガス空塔速度を、再生触媒の上昇移送に適した４～１２ｍ／ｓの範囲に維持できる。 The regenerated catalyst regenerated in the catalyst regeneration zone 4 and jumped out from the upper part of the turbulent fluidized bed is transferred to the riser type regeneration tower 5 from the upper conical portion along with the used regeneration gas. The diameter of the riser type regeneration tower 5 communicating with the upper conical portion of the catalyst regeneration zone 4 is preferably 1/6 to 1/3 of the diameter of the lower cylindrical portion. By doing so, the gas superficial velocity of the fluidized bed in the catalyst regeneration zone 4 can be maintained in the range of 0.4 to 1.2 m / s suitable for the formation of the turbulent fluidized bed. The gas superficial velocity of the column 5 can be maintained in a range of 4 to 12 m / s suitable for ascending transfer of the regenerated catalyst.
　ライザー型再生塔５内を上昇した再生触媒は、ライザー型再生塔頂部に設置された触媒貯槽６に運ばれる。触媒貯槽６は気固分離器としても機能し、炭酸ガスなどを含有する使用済み再生用ガスは、ここで再生触媒から分離され、サイクロン１５を経由して系外に排出される。 The regenerated catalyst rising in the riser type regeneration tower 5 is carried to a catalyst storage tank 6 installed at the top of the riser type regeneration tower. The catalyst storage tank 6 also functions as a gas-solid separator, and the used regeneration gas containing carbon dioxide gas or the like is separated from the regeneration catalyst here and discharged out of the system via the cyclone 15.
　一方、触媒貯槽６内の再生触媒は、第２流量調節器１７を備えた流下管を経て混合領域７に供給される。また必要に応じ、ライザー型再生塔５における触媒循環量の制御を容易にするため、触媒貯槽６内の再生触媒の一部を第３流量調節器１６を備えたバイパス導管を経由して再生帯域４に戻すこともできる。このように触媒は、ダウンフロー形式反応帯域１、気固分離帯域２、ストリッピング帯域３、触媒再生帯域４、ライザー型再生塔５、触媒貯槽６、および混合領域７を経て、再びダウンフロー形式反応帯域１の順で系内を循環している。 On the other hand, the regenerated catalyst in the catalyst storage tank 6 is supplied to the mixing region 7 via a downflow pipe equipped with a second flow rate regulator 17. Further, if necessary, a part of the regenerated catalyst in the catalyst storage tank 6 is regenerated through a bypass conduit having a third flow rate regulator 16 in order to facilitate control of the catalyst circulation amount in the riser type regenerating tower 5. It can be returned to 4. In this way, the catalyst passes through the downflow type reaction zone 1, the gas-solid separation zone 2, the stripping zone 3, the catalyst regeneration zone 4, the riser type regeneration tower 5, the catalyst storage tank 6, and the mixing region 7, and again the downflow type. It circulates in the system in the order of reaction zone 1.
　本発明で原料に用いる重質油としては、減圧軽油、常圧残油、減圧残油、熱分解軽油、およびこれらを水素化精製した重質油等が例示できる。これらの重質油を単独で用いても良いし、これら重質油の混合物あるいはこれら重質油に一部軽質油を混合したものも用いることができる。
　原料油として用いる重質油の蒸留性状としては、沸点範囲が１７０～８００℃のものが好ましく、１９０～７８０℃がより好ましい。 Examples of the heavy oil used as a raw material in the present invention include vacuum gas oil, atmospheric residue, vacuum residue, pyrolysis gas oil, and heavy oil obtained by hydrorefining these. These heavy oils may be used alone, or a mixture of these heavy oils or a mixture of these heavy oils with a part of light oil may be used.
The distillation properties of heavy oils used as raw material oils are preferably those having a boiling range of 170 to 800 ° C, more preferably 190 to 780 ° C.
　本発明でいう反応帯域出口温度とは反応帯域の出口温度のことであり、分解反応生成物が触媒と分離される直前の温度、あるいは気固分離帯域の手前で急冷される場合は急冷される直前の温度である。本発明において反応帯域出口温度は５８０～６３０℃であり、好ましくは５９０～６２０℃である。５８０℃より低い温度では高い収率で軽質オレフィンを得ることができず、６３０℃より高い温度では熱分解が顕著になりドライガス発生量が多くなるため好ましくない。 The reaction zone outlet temperature as used in the present invention is the outlet temperature of the reaction zone, and when the decomposition reaction product is rapidly cooled immediately before the separation from the catalyst or before the gas-solid separation zone, it is rapidly cooled. The temperature just before. In the present invention, the reaction zone outlet temperature is 580 to 630 ° C., preferably 590 to 620 ° C. If the temperature is lower than 580 ° C., a light olefin cannot be obtained in a high yield, and if it is higher than 630 ° C., thermal decomposition becomes remarkable and the amount of dry gas generated is not preferable.
　本発明でいう触媒／油比とは触媒循環量（ｔｏｎ／ｈ）と原料油供給速度（ｔｏｎ／ｈ）の比を示す。本発明において該触媒／油比は、１５～４０重量／重量であることが必要であり、好ましくは２０～３０重量／重量である。触媒／油比が１５重量／重量より小さい場合には、ヒートバランス上、反応帯域へ供給される再生触媒の温度が高くなるため、熱分解によるドライガス発生量が多くなり好ましくない。また触媒／油比が４０重量／重量より大きい場合には、触媒循環量が大きくなり、触媒再生帯域での触媒再生に必要な触媒滞留時間を確保するには触媒再生帯域の容量が大きくなり過ぎるため好ましくない。 In the present invention, the catalyst / oil ratio indicates the ratio of the catalyst circulation rate (ton / h) to the feed oil supply rate (ton / h). In the present invention, the catalyst / oil ratio needs to be 15 to 40 weight / weight, preferably 20 to 30 weight / weight. When the catalyst / oil ratio is smaller than 15 weight / weight, the temperature of the regenerated catalyst supplied to the reaction zone becomes high in view of heat balance, which is not preferable because the amount of dry gas generated by thermal decomposition increases. Further, when the catalyst / oil ratio is larger than 40 weight / weight, the catalyst circulation amount becomes large, and the capacity of the catalyst regeneration zone becomes too large to secure the catalyst residence time necessary for catalyst regeneration in the catalyst regeneration zone. Therefore, it is not preferable.
　本発明でいう炭化水素の滞留時間とは、触媒と原料油が接触してから反応帯域出口において触媒と分解反応生成物が分離されるまでの時間、あるいは気固分離帯域の手前で急冷される場合は急冷されるまでの時間を示す。本発明において該滞留時間は０．１～１．０秒であることが必要であり、好ましくは０．４～０．９秒である。反応帯域内での炭化水素の滞留時間が０．１秒より短い場合、分解反応が不充分となり軽質オレフィンを高い収率で得ることができない。また該滞留時間が１．０秒より長い場合、熱分解の寄与が大きくなり好ましくない。
　なお、本発明における流動接触分解反応装置の操作条件のうち上記以外については特に限定されないが、通常、反応圧力１５０～４００ｋＰａで好ましく運転される。 The hydrocarbon residence time as used in the present invention is the time from when the catalyst comes into contact with the raw material oil until the catalyst and the decomposition reaction product are separated at the outlet of the reaction zone, or immediately before the gas-solid separation zone. In the case, the time until quenching is shown. In the present invention, the residence time needs to be 0.1 to 1.0 seconds, and preferably 0.4 to 0.9 seconds. When the residence time of hydrocarbons in the reaction zone is shorter than 0.1 seconds, the decomposition reaction becomes insufficient and light olefins cannot be obtained in high yield. On the other hand, if the residence time is longer than 1.0 seconds, the contribution of thermal decomposition becomes large, which is not preferable.
The operating conditions of the fluid catalytic cracking reactor in the present invention are not particularly limited except for the above, but usually, the operation is preferably carried out at a reaction pressure of 150 to 400 kPa.
　本発明に用いる触媒は、流動接触分解触媒と添加剤よりなる。
　該流動接触分解触媒は、活性成分であるゼオライトとその支持母体であるマトリックスよりなっている。
　該ゼオライトの主成分は超安定Ｙ型ゼオライトである。
　マトリックスは、活性マトリックス、バインダー（シリカ等）、フィラー（粘土鉱物等）、その他成分（希土類金属酸化物、メタルトラップ成分等）で構成される。
　ここで、活性マトリックスとは、分解活性を持つもので、アルミナやシリカアルミナなどが挙げられる。 The catalyst used in the present invention comprises a fluid catalytic cracking catalyst and an additive.
The fluid catalytic cracking catalyst comprises a zeolite which is an active component and a matrix which is a supporting matrix thereof.
The main component of the zeolite is ultrastable Y-type zeolite.
The matrix is composed of an active matrix, a binder (such as silica), a filler (such as clay mineral), and other components (such as rare earth metal oxides and metal trap components).
Here, the active matrix has decomposition activity, and examples thereof include alumina and silica alumina.
　本発明に用いる触媒の構成要素である添加剤は形状選択性ゼオライトを含む。形状選択性ゼオライト以外の構成成分は、バインダー(シリカ等)、フィラー(粘土鉱物等)などである。
　形状選択性ゼオライトはその細孔径がＹ型ゼオライトの細孔径よりも小さく、限られた形状の炭化水素のみがその細孔内へ進入できるというゼオライトである。そのようなゼオライトとして、ＺＳＭ－５、β、オメガ、ＳＡＰＯ－５、ＳＡＰＯ－１１、ＳＡＰＯ－３４、ペンタシル型メタロシリケート等が例示できる。これらの形状選択性ゼオライトのなかでＺＳＭ－５が最も好ましい。 The additive that is a constituent of the catalyst used in the present invention contains a shape-selective zeolite. Constituent components other than the shape-selective zeolite include a binder (such as silica) and a filler (such as clay mineral).
Shape-selective zeolite is a zeolite whose pore diameter is smaller than that of Y-type zeolite, and only limited-shaped hydrocarbons can enter the pores. Examples of such zeolite include ZSM-5, β, omega, SAPO-5, SAPO-11, SAPO-34, and pentasil-type metallosilicate. Of these shape selective zeolites, ZSM-5 is most preferred.
　重質な原料油が流動接触分解される場合、まず超安定Ｙ型ゼオライトを含む流動接触分解触媒によって粗分解（一次分解）され、粗分解された炭化水素は、形状選択性ゼオライトを含む添加剤によってさらに分解（二次分解）されて軽質オレフィンとなる。一次分解の能力が不足すると、中間生成物のガソリン留分が少なくなり、二次分解が進行しにくく軽質オレフィンが減少する。一方、一次分解能力が十分にある状態であって、二次分解能力が不足すると軽質オレフィンは減少し、二次分解能力が高すぎても軽質オレフィンがパラフィンまで過分解されるため軽質オレフィンが減少する。つまり、軽質オレフィンを高い収率で得るためには、一次分解と二次分解のバランスが重要である。 When heavy feedstock oil is subjected to fluid catalytic cracking, it is first roughly cracked (primary cracking) with a fluid catalytic cracking catalyst containing ultrastable Y-type zeolite, and the roughly cracked hydrocarbon is an additive containing shape selective zeolite Is further decomposed (secondary decomposition) into light olefins. If the ability of primary cracking is insufficient, the gasoline fraction of the intermediate product decreases, and secondary cracking does not proceed easily and light olefins decrease. On the other hand, if the primary cracking capacity is sufficient and the secondary cracking capacity is insufficient, the light olefins will decrease, and even if the secondary cracking capacity is too high, the light olefins will be excessively decomposed to paraffin, so the light olefins will decrease. To do. That is, in order to obtain a light olefin in a high yield, the balance between primary cracking and secondary cracking is important.
　本発明では一次分解と二次分解のバランスを計る指標として、流動接触分解装置から留出する全留分（分解生成物）中のＣ２オレフィン濃度（重量％）とＣ４オレフィン濃度（重量％）との比（Ｃ２オレフィン濃度／Ｃ４オレフィン濃度）（本発明において、二次分解活性度と呼ぶ。）を用いる。
　本発明においては、該二次分解活性度が０．３０～０．５５の範囲であることが必要であり、好ましくは０．３５～０．５０である。二次分解活性度が０．３０より小さい場合、一次分解能力に対して二次分解能力が不足しており、軽質オレフィンを高い収率で得られない。また、該二次分解活性度が０．５５より大きい場合、一次分解能力に対して二次分解能力が高すぎて軽質オレフィンの過分解により軽質オレフィンを高い収率で得られない。 In the present invention, C2 olefin concentration (wt%) and C4 olefin concentration (wt%) in all fractions (cracked product) distilled from a fluid catalytic cracking apparatus are used as indicators for measuring the balance between primary cracking and secondary cracking. (C2 olefin concentration / C4 olefin concentration) (referred to as secondary cracking activity in the present invention).
In the present invention, the secondary decomposition activity needs to be in the range of 0.30 to 0.55, preferably 0.35 to 0.50. When the secondary cracking activity is less than 0.30, the secondary cracking ability is insufficient with respect to the primary cracking ability, and a light olefin cannot be obtained in a high yield. On the other hand, when the secondary cracking activity is larger than 0.55, the secondary cracking ability is too high with respect to the primary cracking ability, and the light olefin cannot be obtained in high yield due to the excessive cracking of the light olefin.
　本発明に用いる触媒中の形状選択性ゼオライトの含有量は、１２～２４質量％であることが必要であり、１４～２４質量％が好ましく、１６～２３質量％がさらに好ましく、１８～２２質量％が特に好ましい。
　触媒中の形状選択性ゼオライトを上記範囲にすることにより、前述の二次分解活性度を０．３０～０．５５の範囲に制御することができる。触媒中の形状選択性ゼオライトが２４質量％より多い場合、水素移行反応が進行し、軽質オレフィンが軽質パラフィンになり、軽質オレフィンが減少する。触媒中の形状選択性ゼオライトが１２質量％より少ない場合、二次分解の進行が不十分になり、軽質オレフィンが減少する。 The content of the shape selective zeolite in the catalyst used in the present invention needs to be 12 to 24% by mass, preferably 14 to 24% by mass, more preferably 16 to 23% by mass, and 18 to 22% by mass. % Is particularly preferred.
By making the shape selective zeolite in the catalyst in the above range, the secondary cracking activity can be controlled in the range of 0.30 to 0.55. When the shape selective zeolite in the catalyst is more than 24% by mass, the hydrogen transfer reaction proceeds, the light olefin becomes light paraffin, and the light olefin decreases. When the shape-selective zeolite in the catalyst is less than 12% by mass, the progress of secondary cracking becomes insufficient and light olefins are reduced.
　流動接触分解触媒における希土類金属酸化物の含有量は１．５質量％以下であることが好ましく、１．２質量％以下がさらに好ましく、１．０質量％以下が特に好ましい。流動接触分解触媒中の希土類金属酸化物の含有量が１．５質量％より多い場合は、水素移行活性が高くなりすぎ、分解活性は高くなるものの軽質オレフィン収率は低下する。 The content of the rare earth metal oxide in the fluid catalytic cracking catalyst is preferably 1.5% by mass or less, more preferably 1.2% by mass or less, and particularly preferably 1.0% by mass or less. When the content of the rare earth metal oxide in the fluid catalytic cracking catalyst is more than 1.5% by mass, the hydrogen transfer activity becomes too high, and the cracking activity increases, but the light olefin yield decreases.
　一般に流動接触分解触媒中の希土類酸化物含有量が増加するほど耐スチーミング性が増加するため触媒の活性は高くなる。一方、希土類金属酸化物を多く含む触媒は水素移行活性も高くなる。流動接触分解触媒の水素移行活性が高くなると生成物中のオレフィンが減少しパラフィンが増加する。主にガソリン留分中のオレフィン類は形状選択性ゼオライトを含む添加剤により軽質オレフィンに分解される。しかし、該添加剤によるガソリン留分中のパラフィン類の分解速度はオレフィン類の分解に比べて著しく遅いため、流動接触分解触媒の水素移行活性が高くなるほど該添加剤による軽質オレフィンの生成速度は小さくなる。 Generally, as the rare earth oxide content in the fluid catalytic cracking catalyst increases, the steaming resistance increases, so the activity of the catalyst increases. On the other hand, a catalyst containing a large amount of rare earth metal oxide also has high hydrogen transfer activity. When the hydrogen transfer activity of the fluid catalytic cracking catalyst increases, the olefin in the product decreases and the paraffin increases. Olefins mainly in gasoline fractions are decomposed into light olefins by additives containing shape selective zeolite. However, since the decomposition rate of paraffins in gasoline fractions by the additive is remarkably slower than that of olefins, the higher the hydrogen transfer activity of the fluid catalytic cracking catalyst, the lower the rate of light olefin formation by the additive. Become.
　該超安定Ｙ型ゼオライトの好ましい結晶格子定数は２４．２０～２４．６０Åであり、より好ましくは２４．３６～２４．４５Åである。この範囲において結晶格子定数が小さいほどガソリン収率は減少するが軽質オレフィン収率は増加する。しかし該結晶格子定数が２４．２０Åより小さい場合、流動接触分解触媒の分解活性が低すぎて高い転化率を得ることができないため軽質オレフィン収率は減少する。また格子定数が２４．６０Åより大きい場合、水素移行活性が高くなり過ぎ好ましくない。
　なお、ここでいうゼオライトの結晶格子定数はＡＳＴＭ　Ｄ－３９４２－８０で測定したものである。 The crystal lattice constant of the ultrastable Y-type zeolite is preferably 24.20 to 24.60Å, more preferably 24.36 to 24.45Å. In this range, the gasoline yield decreases as the crystal lattice constant decreases, but the light olefin yield increases. However, when the crystal lattice constant is smaller than 24.20Å, the cracking activity of the fluid catalytic cracking catalyst is too low to obtain a high conversion rate, so that the light olefin yield decreases. On the other hand, when the lattice constant is larger than 24.60 mm, the hydrogen transfer activity becomes too high.
Here, the crystal lattice constant of zeolite here is measured by ASTM D-3942-80.
　流動接触分解触媒中の超安定Ｙ型ゼオライト含有量は５～５０質量％であることが好ましく、１５～４０質量％がさらに好ましい。また流動接触分解触媒のかさ密度は０．５～１．０ｇ／ｍｌ、平均粒径は５０～９０μｍ、表面積は５０～３５０ｍ２／ｇ、細孔容積は０．０５～０．５ｍｌ／ｇの範囲であるのが好ましい。 The ultrastable Y-type zeolite content in the fluid catalytic cracking catalyst is preferably 5 to 50% by mass, more preferably 15 to 40% by mass. The bulk density of the fluid catalytic cracking catalyst is 0.5 to 1.0 g / ml, the average particle size is 50 to 90 μm, the surface area is 50 to 350 m 2 / g, and the pore volume is 0.05 to 0.5 ml / g. A range is preferred.
　添加剤中の形状選択性ゼオライト含有量は２０～７０質量％であることが好ましく、３０～６０質量％がより好ましい。また添加剤のかさ密度は０．５～１．０ｇ／ｍｌ、平均粒径は５０～９０μｍ、表面積は１０～２００ｍ２／ｇ、細孔容積は０．０１～０．３ｍｌ／ｇの範囲であるのが好ましい。 The shape-selective zeolite content in the additive is preferably 20 to 70% by mass, more preferably 30 to 60% by mass. The bulk density of the additive is in the range of 0.5 to 1.0 g / ml, the average particle size is 50 to 90 μm, the surface area is 10 to 200 m 2 / g, and the pore volume is in the range of 0.01 to 0.3 ml / g. Preferably there is.
　本発明において使用する触媒中の流動接触分解触媒および添加剤の割合は、流動接触分解触媒が４０～８３質量％、好ましくは４０～８０質量％、より好ましくは４０～７０質量％であり、形状選択性ゼオライトを含む添加剤が１７～６０質量％、好ましくは２０～６０質量％、より好ましくは３０～６０質量％ある。該流動接触分解触媒の割合が４０質量％よりも少ない場合、あるいは該添加剤の割合が６０質量％よりも多い場合には、原料油である重質油の転化率が低下し、高い軽質オレフィン収率は得られない。一方、該流動接触分解触媒の割合が９５質量％よりも多い場合、あるいは該添加剤の割合が５質量％よりも少ない場合には、高い転化率は得られるが高い軽質オレフィン収率は得られない。 The ratio of the fluid catalytic cracking catalyst and the additive in the catalyst used in the present invention is 40 to 83% by mass, preferably 40 to 80% by mass, more preferably 40 to 70% by mass for the fluid catalytic cracking catalyst, The additive containing the selective zeolite is 17 to 60% by mass, preferably 20 to 60% by mass, more preferably 30 to 60% by mass. When the proportion of the fluid catalytic cracking catalyst is less than 40% by mass, or when the proportion of the additive is more than 60% by mass, the conversion rate of the heavy oil as the raw material oil decreases, and a high light olefin No yield is obtained. On the other hand, when the proportion of the fluid catalytic cracking catalyst is more than 95% by mass, or when the proportion of the additive is less than 5% by mass, a high conversion rate is obtained but a high light olefin yield is obtained. Absent.
　本発明においては、触媒中の添加剤量が比較的高いためコークの生成を抑制することができる。添加剤は酸密度が低いため、ナフテンから水素移行反応によってアロマとなる反応が抑制される結果、コークの生成がしにくい。コーク生成に伴い水素が発生するため、コーク生成が抑制されると、オレフィンからパラフィンへの反応が抑制され、軽質オレフィンの収率が向上する。しかし、触媒中の添加剤量が高すぎても、オレフィンからパラフィンへの過分解が生じてしまい、軽質オレフィン収率は減少してしまう。
　なお、コーク選択性の指標として、ΔＣｏｋｅ／Ｋｉｎｅｔｉｃ　Ｃｏｎｖｅｒｓｉｏｎ＝コーク収率（質量％）／（分解率（質量％）／（１００－分解率（質量％））が用いられる（以下、ΔＣｏｋｅ／Ｋｉｎｅｔｉｃ　ＣｏｎｖｅｒｓｉｏｎをΔＣｏｋｅ／Ｋとする）。 In the present invention, since the amount of additive in the catalyst is relatively high, the production of coke can be suppressed. Since the additive has a low acid density, the reaction that becomes an aroma by the hydrogen transfer reaction from naphthene is suppressed, so that coke is hardly generated. Since hydrogen is generated as coke is generated, when coke generation is suppressed, the reaction from olefins to paraffin is suppressed, and the yield of light olefins is improved. However, even if the amount of the additive in the catalyst is too high, overdecomposition from olefin to paraffin occurs, and the light olefin yield decreases.
As an index of coke selectivity, ΔCoke / Kinetic Conversion = Coke yield (mass%) / (decomposition rate (mass%) / (100−decomposition ratio (mass%)) is used (hereinafter referred to as ΔCoke / Kinetic Conversion). Is ΔCoke / K).
　以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。　 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples. *
（実施例１）
　ダウンフローリアクター（ダウナー）タイプＦＣＣパイロット装置を用いて重質油の流動接触分解を行なった。装置規模は、インベントリ－５ｋｇ、フィ－ド量１ｋｇ／ｈであり、運転条件は、反応帯域出口温度６００℃、反応圧力１９６ｋＰａ（１．０ｋｇ／ｃｍ２Ｇ）、触媒／油比２５重量／重量、触媒再生帯域温度７２０℃である。このときリアクター内の炭化水素滞留時間は０．５秒であった。
　用いた原料油は中東系（アラビアンライト）の脱硫した常圧残渣油（脱硫ＡＲ）である。脱硫ＡＲの性状は以下の通りである。蒸留における５％留出温度は３６２℃、９５％留出温度は７０３℃である。１５℃密度は０．９３１ｇ／ｃｍ３である。残留炭素分は２．５７質量％である。硫黄分は０．３８質量％である。
　用いた触媒（Ａ）は、超安定Ｙ型ゼオライトを３７質量％含む流動接触分解触媒７０質量％と形状選択性ゼオライトを４３質量％含む添加剤３０質量％の混合物である。流動接触分解触媒に含まれる超安定Ｙ型ゼオライトの結晶格子定数は２４．４０Åである。該流動接触分解触媒および該添加剤を装置に充填する前にそれぞれを別々に８１０℃で６時間、１００％スチ－ムでスチ－ミングした。分解反応の結果を表１に示す。
　ガソリン／ＬＣＯ／ＣＬＯのカット温度は、それぞれ２２１℃、３４３℃とした。 Example 1
Heavy oil fluidized catalytic cracking was carried out using a downflow reactor (downer) type FCC pilot device. The equipment scale is inventory-5 kg, feed amount 1 kg / h, operating conditions are reaction zone outlet temperature 600 ° C., reaction pressure 196 kPa (1.0 kg / cm 2 G), catalyst / oil ratio 25 weight / weight. The catalyst regeneration zone temperature is 720 ° C. At this time, the hydrocarbon residence time in the reactor was 0.5 seconds.
The raw material oil used was a desulfurized atmospheric residue oil (desulfurized AR) of the Middle East (Arabian Light). The properties of desulfurization AR are as follows. The 5% distillation temperature in distillation is 362 ° C., and the 95% distillation temperature is 703 ° C. The 15 ° C. density is 0.931 g / cm 3 . The residual carbon content is 2.57% by mass. The sulfur content is 0.38% by mass.
The catalyst (A) used is a mixture of 70% by mass of a fluid catalytic cracking catalyst containing 37% by mass of an ultrastable Y-type zeolite and 30% by mass of an additive containing 43% by mass of a shape-selective zeolite. The crystal lattice constant of the ultrastable Y-type zeolite contained in the fluid catalytic cracking catalyst is 24.40Å. Each of the fluid catalytic cracking catalyst and the additive was separately steamed at 100% steam for 6 hours at 810 ° C. before being charged to the apparatus. The results of the decomposition reaction are shown in Table 1.
The cut temperatures of gasoline / LCO / CLO were 221 ° C. and 343 ° C., respectively.
（実施例２）
　実施例１と同じ装置を用い、同じ運転条件で重質油の流動接触分解を行なった。
　用いた原料油は中東系（アラビアンライト）の脱硫した減圧軽油（脱硫ＶＧＯ）である。脱硫ＶＧＯの性状は以下の通りである。蒸留における５％留出温度は３０５℃、９５％留出温度は５３８℃である。１５℃密度は０．０．８９５ｇ／ｃｍ３である。残留炭素分は０．０２質量％である。硫黄分は０．２３質量％である。用いた触媒は実施例１と同じ触媒（Ａ）である。分解反応の結果を表１に示す。 (Example 2)
Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
The raw material oil used was desulfurized vacuum gas oil (desulfurized VGO) of Middle Eastern (Arabian Light). The properties of desulfurized VGO are as follows. The 5% distillation temperature in distillation is 305 ° C, and the 95% distillation temperature is 538 ° C. The 15 ° C. density is 0.0.895 g / cm 3 . The residual carbon content is 0.02% by mass. The sulfur content is 0.23% by mass. The catalyst used is the same catalyst (A) as in Example 1. The results of the decomposition reaction are shown in Table 1.
（実施例３）
　実施例１と同じ装置を用い、同じ運転条件で重質油の流動接触分解を行なった。
　用いた原料油は実施例１と同じ中東系（アラビアンライト）の脱硫した常圧残渣油（脱硫ＡＲ）である。
　用いた触媒（Ｂ）は超安定Ｙ型ゼオライトを３１質量％含む流動接触分解触媒６５質量％と形状選択性ゼオライトを５４質量％含む添加剤３５質量％の混合物である。流動接触分解触媒に含まれる超安定Ｙ型ゼオライトの結晶格子定数は２４．４０Åである。該流動接触分解触媒および該添加剤を装置に充填する前にそれぞれを別々に８１０℃で６時間、１００％スチ－ムでスチ－ミングした。分解反応の結果を表１に示す。 Example 3
Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
The raw material oil used was the same Middle Eastern (Arabian light) desulfurized atmospheric residue oil (desulfurized AR) as in Example 1.
The used catalyst (B) is a mixture of 65% by mass of a fluid catalytic cracking catalyst containing 31% by mass of ultrastable Y-type zeolite and 35% by mass of an additive containing 54% by mass of shape-selective zeolite. The crystal lattice constant of the ultrastable Y-type zeolite contained in the fluid catalytic cracking catalyst is 24.40Å. Each of the fluid catalytic cracking catalyst and the additive was separately steamed at 100% steam for 6 hours at 810 ° C. before being charged to the apparatus. The results of the decomposition reaction are shown in Table 1.
（実施例４）
　実施例１と同じ装置を用い、同じ運転条件で重質油の流動接触分解を行なった。
　用いた原料油は実施例２と同じ中東系（アラビアンライト）の脱硫した減圧軽油（脱硫ＶＧＯ）である。用いた触媒は実施例３と同じ触媒（Ｂ）である。分解反応の結果を表１に示す。 Example 4
Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
The feedstock used was the same Middle Eastern (Arabyanlite) desulfurized vacuum gas oil (desulfurized VGO) as in Example 2. The catalyst used is the same catalyst (B) as in Example 3. The results of the decomposition reaction are shown in Table 1.
（実施例５）
　実施例１と同じ装置を用い、同じ運転条件で重質油の流動接触分解を行なった。
　用いた原料油は実施例１と同じ中東系（アラビアンライト）の脱硫した常圧残渣油（脱硫ＡＲ）である。
　用いた触媒（Ｃ）は超安定Ｙ型ゼオライトを３６質量％含む流動接触分解触媒５０質量％と形状選択性ゼオライトを４２質量％含む添加剤５０質量％の混合物である。流動接触分解触媒に含まれる超安定Ｙ型ゼオライトの結晶格子定数は２４．４０Åである。該流動接触分解触媒および該添加剤を装置に充填する前にそれぞれを別々に８１０℃で６時間、１００％スチ－ムでスチ－ミングした。分解反応の結果を表１に示す。 (Example 5)
Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
The raw material oil used was the same Middle Eastern (Arabian light) desulfurized atmospheric residue oil (desulfurized AR) as in Example 1.
The catalyst (C) used is a mixture of 50% by mass of a fluid catalytic cracking catalyst containing 36% by mass of an ultrastable Y-type zeolite and 50% by mass of an additive containing 42% by mass of a shape-selective zeolite. The crystal lattice constant of the ultrastable Y-type zeolite contained in the fluid catalytic cracking catalyst is 24.40Å. Each of the fluid catalytic cracking catalyst and the additive was separately steamed at 100% steam for 6 hours at 810 ° C. before being charged to the apparatus. The results of the decomposition reaction are shown in Table 1.
（実施例６）
　実施例１と同じ装置を用い、同じ運転条件で重質油の流動接触分解を行なった。
　用いた原料油は実施例２と同じ中東系（アラビアンライト）の脱硫した減圧軽油（脱硫ＶＧＯ）である。用いた触媒は実施例５と同じ触媒（Ｃ）である。分解反応の結果を表１に示す。 (Example 6)
Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
The feedstock used was the same Middle Eastern (Arabyanlite) desulfurized vacuum gas oil (desulfurized VGO) as in Example 2. The catalyst used is the same catalyst (C) as in Example 5. The results of the decomposition reaction are shown in Table 1.
（実施例７）
　実施例１と同じ装置を用い、同じ運転条件で重質油の流動接触分解を行なった。
　用いた原料油は実施例１と同じ中東系（アラビアンライト）の脱硫した常圧残渣油（脱硫ＡＲ）である。
　用いた触媒（Ｄ）は超安定Ｙ型ゼオライトを４０質量％含む流動接触分解触媒４０質量％と形状選択性ゼオライトを３９質量％含む添加剤６０質量％の混合物である。流動接触分解触媒に含まれる超安定Ｙ型ゼオライトの結晶格子定数は２４．４０Åである。該流動接触分解触媒および該添加剤を装置に充填する前にそれぞれを別々に８１０℃で６時間、１００％スチ－ムでスチ－ミングした。分解反応の結果を表１に示す。 (Example 7)
Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
The raw material oil used was the same Middle Eastern (Arabian light) desulfurized atmospheric residue oil (desulfurized AR) as in Example 1.
The catalyst (D) used was a mixture of 40% by mass of a fluid catalytic cracking catalyst containing 40% by mass of ultrastable Y-type zeolite and 60% by mass of an additive containing 39% by mass of shape-selective zeolite. The crystal lattice constant of the ultrastable Y-type zeolite contained in the fluid catalytic cracking catalyst is 24.40Å. Each of the fluid catalytic cracking catalyst and the additive was separately steamed at 100% steam for 6 hours at 810 ° C. before being charged to the apparatus. The results of the decomposition reaction are shown in Table 1.
（実施例８）
　実施例１と同じ装置を用い、同じ運転条件で重質油の流動接触分解を行なった。
　用いた原料油は実施例２と同じ中東系（アラビアンライト）の脱硫した減圧軽油（脱硫ＶＧＯ）である。用いた触媒は実施例７と同じ触媒（Ｄ）である。分解反応の結果を表１に示す。 (Example 8)
Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
The feedstock used was the same Middle Eastern (Arabyanlite) desulfurized vacuum gas oil (desulfurized VGO) as in Example 2. The catalyst used is the same catalyst (D) as in Example 7. The results of the decomposition reaction are shown in Table 1.
（比較例１）
　実施例１と同じ装置を用い、同じ運転条件で重質油の流動接触分解を行なった。
　用いた原料油は実施例１と同じ中東系（アラビアンライト）の脱硫した常圧残渣油（脱硫ＡＲ）である。
　用いた触媒（Ｅ）は超安定Ｙ型ゼオライトを４０質量％含む流動接触分解触媒８０質量％と形状選択性ゼオライトを３０質量％含む添加剤２０質量％の混合物である。流動接触分解触媒に含まれる超安定Ｙ型ゼオライトの結晶格子定数は２４．４０Åである。該流動接触分解触媒および該添加剤を装置に充填する前にそれぞれを別々に８１０℃で６時間、１００％スチ－ムでスチ－ミングした。分解反応の結果を表１に示す。 (Comparative Example 1)
Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
The raw material oil used was the same Middle Eastern (Arabian light) desulfurized atmospheric residue oil (desulfurized AR) as in Example 1.
The catalyst (E) used is a mixture of 80% by mass of a fluid catalytic cracking catalyst containing 40% by mass of an ultrastable Y-type zeolite and 20% by mass of an additive containing 30% by mass of a shape-selective zeolite. The crystal lattice constant of the ultrastable Y-type zeolite contained in the fluid catalytic cracking catalyst is 24.40Å. Each of the fluid catalytic cracking catalyst and the additive was separately steamed at 100% steam for 6 hours at 810 ° C. before being charged to the apparatus. The results of the decomposition reaction are shown in Table 1.
（比較例２）
　実施例１と同じ装置を用い、同じ運転条件で重質油の流動接触分解を行なった。
　用いた原料油は実施例２と同じ中東系（アラビアンライト）の脱硫した減圧軽油（脱硫ＶＧＯ）である。用いた触媒は比較例１と同じ触媒（Ｅ）である。分解反応の結果を表１に示す。 (Comparative Example 2)
Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
The feedstock used was the same Middle Eastern (Arabyanlite) desulfurized vacuum gas oil (desulfurized VGO) as in Example 2. The catalyst used is the same catalyst (E) as in Comparative Example 1. The results of the decomposition reaction are shown in Table 1.
（比較例３）
　実施例１と同じ装置を用い、同じ運転条件で重質油の流動接触分解を行なった。
　用いた原料油は実施例１と同じ中東系（アラビアンライト）の脱硫した常圧残渣油（脱硫ＡＲ）である。
　用いた触媒（Ｆ）は超安定Ｙ型ゼオライトを３４質量％含む流動接触分解触媒３４質量％と形状選択性ゼオライトを４２質量％含む添加剤６６質量％の混合物である。流動接触分解触媒に含まれる超安定Ｙ型ゼオライトの結晶格子定数は２４．４０Åである。該流動接触分解触媒および該添加剤を装置に充填する前にそれぞれを別々に８１０℃で６時間、１００％スチ－ムでスチ－ミングした。分解反応の結果を表１に示す。 (Comparative Example 3)
Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
The raw material oil used was the same Middle Eastern (Arabian light) desulfurized atmospheric residue oil (desulfurized AR) as in Example 1.
The catalyst (F) used is a mixture of 34% by mass of a fluid catalytic cracking catalyst containing 34% by mass of an ultrastable Y-type zeolite and 66% by mass of an additive containing 42% by mass of a shape-selective zeolite. The crystal lattice constant of the ultrastable Y-type zeolite contained in the fluid catalytic cracking catalyst is 24.40Å. Each of the fluid catalytic cracking catalyst and the additive was separately steamed at 100% steam for 6 hours at 810 ° C. before being charged to the apparatus. The results of the decomposition reaction are shown in Table 1.
（比較例４）
　実施例１と同じ装置を用い、同じ運転条件で重質油の流動接触分解を行なった。
　用いた原料油は実施例２と同じ中東系（アラビアンライト）の脱硫した減圧軽油（脱硫ＶＧＯ）である。用いた触媒は比較例３と同じ触媒（Ｆ）である。分解反応の結果を表１に示す。 (Comparative Example 4)
Using the same apparatus as in Example 1, fluid catalytic cracking of heavy oil was performed under the same operating conditions.
The feedstock used was the same Middle Eastern (Arabyanlite) desulfurized vacuum gas oil (desulfurized VGO) as in Example 2. The catalyst used is the same catalyst (F) as in Comparative Example 3. The results of the decomposition reaction are shown in Table 1.
　実施例１～８では、比較例１～４と比較して二次分解活性度が適正な範囲で流動接触分解された結果、軽質オレフィン高い収率で得られた。
　また、実施例１～８においては軽質オレフィンを高く保ちつつコーク選択性の指標であるΔＣｏｋｅ／Ｋが低い値となっており、流動接触分解触媒の活性上、好ましい条件となっている。 In Examples 1 to 8, fluid catalytic cracking was performed in an appropriate range of secondary cracking activity as compared with Comparative Examples 1 to 4, and as a result, light olefins were obtained in high yields.
In Examples 1 to 8, ΔCoke / K, which is an indicator of coke selectivity, is kept low while keeping the light olefin high, which is a preferable condition for the activity of the fluid catalytic cracking catalyst.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
１ ダウンフロー形式反応帯域
２ 気固分離帯域
３ ストリッピング帯域
４ 再生帯域
５ ライザー型再生塔
６ 触媒貯槽
７ 混合領域
８ 二次分離器
９ ディップレッグ
１０、１１、１２　ライン
１３　第１流量調節器
１４　再生用ガス
１５　サイクロン
１６　第１流量調節器
１７　第２流量調節器 DESCRIPTION OF SYMBOLS 1 Down flow type reaction zone 2 Gas-solid separation zone 3 Stripping zone 4 Regeneration zone 5 Riser type regeneration tower 6 Catalyst storage tank 7 Mixing zone 8 Secondary separator 9 Dipreg 10, 11, 12 Line 13 First flow controller 14 Gas for regeneration 15 Cyclone 16 First flow controller 17 Second flow controller

Claims (7)

  1. 　重質油を流動接触分解して軽質オレフィンを製造する方法において、反応帯域出口温度が５８０～６３０℃、触媒／油比が１５～４０重量／重量、反応帯域での炭化水素の滞留時間が０．１～１．０秒の条件下に、形状選択性ゼオライトを１２～２４質量％含有する触媒を重質油と接触させて、二次分解活性度（Ｃ２オレフィン濃度／Ｃ４オレフィン濃度）の値が０．３０～０．５５の範囲の分解生成物を得ることを特徴とする重質油の流動接触分解法。 In a process for producing light olefins by fluid catalytic cracking of heavy oil, the reaction zone outlet temperature is 580 to 630 ° C., the catalyst / oil ratio is 15 to 40 weight / weight, and the hydrocarbon residence time in the reaction zone is zero. The value of secondary cracking activity (C2 olefin concentration / C4 olefin concentration) by contacting a catalyst containing 12 to 24% by mass of a shape selective zeolite with heavy oil under conditions of 1 to 1.0 seconds. A fluid catalytic cracking process of heavy oil, characterized in that a cracked product having a ratio of 0.30 to 0.55 is obtained.
  2. 　触媒が、流動接触分解触媒と形状選択性ゼオライトを含む添加剤からなる触媒であって、流動接触分解触媒中の超安定Ｙ型ゼオライトの含有量が５～５０質量％であることを特徴とする請求項１に記載の重質油の流動接触分解法。 The catalyst is a catalyst comprising an additive containing a fluid catalytic cracking catalyst and a shape selective zeolite, and the content of the ultrastable Y-type zeolite in the fluid catalytic cracking catalyst is 5 to 50% by mass The fluid catalytic cracking method of heavy oil according to claim 1.
  3. 　触媒が、流動接触分解触媒と形状選択性ゼオライトを含む添加剤からなる触媒であって、添加剤中の形状選択性ゼオライトの含有量が２０～７０質量％であることを特徴とする請求項１または２に記載の重質油の流動接触分解法。 2. The catalyst comprising an additive containing a fluid catalytic cracking catalyst and a shape selective zeolite, wherein the content of the shape selective zeolite in the additive is 20 to 70% by mass. Or the fluid catalytic cracking method of heavy oil of 2.
  4. 　触媒が、流動接触分解触媒と形状選択性ゼオライトを含む添加剤からなる触媒であって、触媒における添加剤の割合が１７～６０質量％であることを特徴とする請求項１～３のいずれかに記載の重質油の流動接触分解法。 The catalyst according to any one of claims 1 to 3, wherein the catalyst is a catalyst comprising an additive containing a fluid catalytic cracking catalyst and a shape selective zeolite, and the ratio of the additive in the catalyst is 17 to 60% by mass. Fluid catalytic cracking method of heavy oil as described in 1.
  5. 　超安定Ｙ型ゼオライトの結晶格子定数が２４．２０～２４．６０Åであることを特徴とする請求項２～４のいずれかに記載の重質油の流動接触分解法。 The fluid catalytic cracking method of heavy oil according to any one of claims 2 to 4, wherein the crystal lattice constant of the ultrastable Y-type zeolite is 24.20 to 24.60 Å.
  6. 　触媒が、流動接触分解触媒と形状選択性ゼオライトを含む添加剤からなる触媒であって、流動接触分解触媒中の希土類金属酸化物の含有量が１．５質量％以下であること特徴とする請求項１～５のいずれかに記載の重質油の流動接触分解法。 The catalyst is a catalyst comprising an additive containing a fluid catalytic cracking catalyst and a shape selective zeolite, wherein the content of rare earth metal oxide in the fluid catalytic cracking catalyst is 1.5% by mass or less. Item 6. The fluid catalytic cracking method of heavy oil according to any one of Items 1 to 5.
  7. 　ダウンフロー形式反応帯域、気固分離帯域、ストリッピング帯域および触媒再生帯域を有する流動接触分解反応装置を使用することを特徴とする請求項１～６のいずれかに記載の重質油の流動接触分解法。
          The fluid contact of heavy oil according to any one of claims 1 to 6, wherein a fluid catalytic cracking reactor having a down flow type reaction zone, a gas-solid separation zone, a stripping zone and a catalyst regeneration zone is used. Decomposition method.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002241764A (en) * 2001-02-21 2002-08-28 Petroleum Energy Center Fluidized catalytic cracking process for heavy oil
JP2002530514A (en) * 1998-11-24 2002-09-17 モービル・オイル・コーポレイション Catalytic cracking for olefin production
JP2004261628A (en) * 2003-01-24 2004-09-24 Idemitsu Petrochem Co Ltd Catalyst for catalytic cracking of hydrocarbons, and production method of light olefins by use of the catalyst
JP2009073919A (en) * 2007-09-20 2009-04-09 Nippon Oil Corp Method of fluid catalytic cracking of heavy petroleum
JP2010509329A (en) * 2006-11-07 2010-03-25 サウジ アラビアン オイル カンパニー Advanced control of severe fluid catalytic cracking process to maximize propylene production from petroleum feedstock
US20130317271A1 (en) * 2012-05-25 2013-11-28 Saudi Arabian Oil Company Catalyst for Enhanced Propylene in Fluidized Catalytic Cracking

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3074878A (en) 1957-10-18 1963-01-22 Exxon Research Engineering Co Short contact time system
US4419221A (en) 1981-10-27 1983-12-06 Texaco Inc. Cracking with short contact time and high temperatures
CN1004878B (en) 1987-08-08 1989-07-26 中国石油化工总公司 Hydrocarbon catalytic conversion method for preparing low-carbon olefin
US4985136A (en) 1987-11-05 1991-01-15 Bartholic David B Ultra-short contact time fluidized catalytic cracking process
CN1031646C (en) 1992-10-22 1996-04-24 中国石油化工总公司 Method for catalytic conversion of hydrocarbons
US5462652A (en) 1993-09-24 1995-10-31 Uop Short contact FCC process with catalyst blending
JP3580518B2 (en) 1996-06-05 2004-10-27 新日本石油株式会社 Fluid catalytic cracking of heavy oil
US7069609B2 (en) 2004-10-20 2006-07-04 Patent Category Corp. Inflatable liquid furniture

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002530514A (en) * 1998-11-24 2002-09-17 モービル・オイル・コーポレイション Catalytic cracking for olefin production
JP2002241764A (en) * 2001-02-21 2002-08-28 Petroleum Energy Center Fluidized catalytic cracking process for heavy oil
JP2004261628A (en) * 2003-01-24 2004-09-24 Idemitsu Petrochem Co Ltd Catalyst for catalytic cracking of hydrocarbons, and production method of light olefins by use of the catalyst
JP2010509329A (en) * 2006-11-07 2010-03-25 サウジ アラビアン オイル カンパニー Advanced control of severe fluid catalytic cracking process to maximize propylene production from petroleum feedstock
JP2009073919A (en) * 2007-09-20 2009-04-09 Nippon Oil Corp Method of fluid catalytic cracking of heavy petroleum
US20130317271A1 (en) * 2012-05-25 2013-11-28 Saudi Arabian Oil Company Catalyst for Enhanced Propylene in Fluidized Catalytic Cracking

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