WO2017082345A1 - Additif pour catalyseur de craquage catalytique de fluide utilisé dans la fabrication d'oléfines inférieures et procédé de fabrication dudit additif - Google Patents

Additif pour catalyseur de craquage catalytique de fluide utilisé dans la fabrication d'oléfines inférieures et procédé de fabrication dudit additif Download PDF

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Publication number
WO2017082345A1
WO2017082345A1 PCT/JP2016/083367 JP2016083367W WO2017082345A1 WO 2017082345 A1 WO2017082345 A1 WO 2017082345A1 JP 2016083367 W JP2016083367 W JP 2016083367W WO 2017082345 A1 WO2017082345 A1 WO 2017082345A1
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Prior art keywords
additive
mass
zsm
slurry
catalytic cracking
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PCT/JP2016/083367
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English (en)
Japanese (ja)
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由佳 瀬戸
雄二 白浜
隆喜 水野
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日揮触媒化成株式会社
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Priority to JP2017550387A priority Critical patent/JP6564875B2/ja
Publication of WO2017082345A1 publication Critical patent/WO2017082345A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J35/60—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to an additive for a fluid catalytic cracking catalyst for producing a lower olefin and a method for producing the same.
  • FCC refinery fluid catalytic cracking
  • the main purpose is to produce gasoline fractions by catalytic cracking of raw material hydrocarbons, and gasoline is desired to have a high octane number.
  • it is required to increase the production of petrochemical raw materials such as lower olefins, especially propylene and butene, at the same time to produce gasoline fraction by catalytic cracking of raw material hydrocarbons with FCC equipment.
  • Patent Document 1 discloses a composition comprising a pentasil-type zeolite and an inorganic oxide matrix having a large number of macropores having a pore diameter of about 100 nm.
  • 2 discloses a composition which is a particle composed of pentasil-type zeolite, a porous inorganic oxide, and phosphorus pentoxide, and has a higher content of phosphorus pentoxide in the surface portion than in the center portion of the particle.
  • Patent Document 3 also discloses an FCC catalyst additive containing a binder containing zeolite such as ZSM-5, phosphate, clay, and silica as an additive capable of increasing the production amount of propylene and the like. Yes.
  • Non-Patent Document 1-3 and the like describe that mesopores are formed by treating ZSM-5 type zeolite with NaOH aqueous solution, and Non-Patent Document 3 further describes that ZSM- treated with NaOH aqueous solution. The performance of type 5 zeolite as a cracking catalyst for hexane has been evaluated.
  • the fluid catalytic cracking in the presence of the conventional FCC catalyst and FCC catalyst additive has room for further improvement in terms of the yield of the lower olefins such as propylene and butene obtained.
  • the present invention is an additive for FCC catalyst used together with an FCC catalyst in fluid catalytic cracking, and is an additive for FCC catalyst capable of increasing the yield of lower olefins such as propylene and butene. It is an object to provide a product and a method for manufacturing the product.
  • the gist of the present invention is the following [1] to [5].
  • [1] (1) The pore volume with a pore diameter of 2 nm or less in the pore volume measurement by the MP method is in the range of 0.15 to 0.20 ml / g, (2) The pore volume with a pore diameter of 2.4 to 50 nm in the pore volume measurement by the BJH method is in the range of 0.05 to 0.15 ml / g, (3) 20 to 70% by mass of a modified ZSM-5 type zeolite having an ammonia adsorption amount in the range of 1.0 to 2.0 mmol / g; Filling material, Containing the modified ZSM-5 type zeolite and a binder comprising phosphorus and an aluminum-containing component for binding the filler particles; An additive for fluid catalytic cracking catalyst for the production of lower olefins having a phosphorus content (measured by ICP emission spectrometry) of 5 to 20% by mass in terms of P 2
  • the average particle diameter is 30 to 200 ⁇ m, the specific surface area is 70 to 250 m 2 / g, and the pore volume in the range of pore diameter 50 to 500 nm measured by mercury porosimetry is 0.3 to 0.5 ml / g.
  • ZSM-5 type zeolite and alkali metal-containing alkaline solution are contacted under the condition that the molar ratio of SiO 2 to alkali metal (SiO 2 : alkali metal) in ZSM-5 type zeolite is 15: 1 to 3: 1.
  • a process for producing an additive for fluid catalytic cracking catalyst comprising:
  • [5] A method for producing a decomposition product mixture by fluid catalytic cracking, wherein the fluid catalytic cracking is carried out in the presence of a fluid catalytic cracking catalyst and the additive for fluid catalytic cracking catalyst according to the above [1] or [2].
  • fluid catalytic cracking preferably fluidized catalytic cracking using hydrodepressurized vacuum gas oil, hydrotreated vacuum gas oil (DSVGO), residual oil, etc. for cracking
  • DSVGO hydrotreated vacuum gas oil
  • residual oil etc.
  • the FCC catalyst additive according to the present invention is: (1) The pore volume with a pore diameter of 2 nm or less in the pore volume measurement by the MP method is in the range of 0.15 to 0.20 ml / g, (2) The pore volume with a pore diameter of 2.4 to 50 nm in the pore volume measurement by the BJH method is in the range of 0.05 to 0.15 ml / g, (3) 20 to 70% by mass of a modified ZSM-5 type zeolite having an ammonia adsorption amount in the range of 1.0 to 2.0 mmol / g; Containing a filler, a binder containing phosphorus and an aluminum-containing component, which binds the modified ZSM-5 type zeolite and particles of the filler, This is an FCC catalyst additive having a phosphorus
  • the modified ZSM-5 type zeolite is (1) In the pore volume measurement by the MP method (details of measurement conditions are as described in the column of Examples described later), the pore volume having a pore diameter of 2 nm or less is 0.15 to 0.20 ml / g. In the range of (2) Pore volume in a pore diameter range of 2.4 to 50 nm in pore volume measurement by BJH method (details of measurement conditions are as described in the column of Examples described later) is 0.05.
  • the pore volume with a pore diameter of 2 nm or less in the pore volume measurement by the MP method is 0.15 to 0.20 ml / g, preferably 0.16 to 0.20 ml / g. If it is less than 0.15 ml / g, the reaction field decreases and the production amount of lower olefins may be reduced. If it exceeds 0.20 ml / g, the treatment with NaOH or the like, which will be described later, in the production of the modified ZSM-5 type zeolite is not sufficiently performed, and the diffusibility of the reaction product is lowered, so that the expected effect is obtained. There is a risk of not.
  • the pore volume in the pore diameter range of 2.4 to 50 nm in the pore volume measurement by the BJH method is 0.05 to 0.15 ml / g, and 0.05 to 0.14 ml / g. preferable. If it is less than 0.05 ml / g, the diffusibility of the reaction product is lowered, so that the amount of lower olefin produced may be reduced. When the amount exceeds 0.15 ml / g, the treatment with NaOH or the like, which will be described later, is excessively performed in the production of the modified ZSM-5 type zeolite, and the micropore volume and the ammonia adsorption amount are below the lower limit, thereby improving the activity. Cannot be obtained. In addition, the moldability decreases due to the increase in viscosity during catalyst preparation, and physical properties such as bulk density and wear resistance deteriorate.
  • the ammonia adsorption amount is 1.0 to 2.0 mmol / g, preferably 1.0 to 1.8 mmol / g. If it is less than 1.0 mmol / g, the acid sites necessary for the reaction may be insufficient and the activity may be reduced. If it exceeds 2.0 mmol / g, it is not sufficiently performed by the NaOH treatment described later in the production of the modified ZSM-5 type zeolite, and the diffusibility of the reaction product is lowered, so that the expected effect can be obtained. There is a risk of not.
  • the modified ZSM-5 type zeolite is usually contained in the FCC catalyst additive according to the present invention in an amount of 20 to 70% by mass, preferably 30 to 60% by mass.
  • the filler is blended as a bulking material.
  • the filler include clay materials such as kaolin, metakaolin, hydrotalcite, and montmorillonite, and kaolin is preferable.
  • the filler is usually contained in the FCC catalyst additive according to the present invention in an amount of 20 to 73% by mass, preferably 25 to 60% by mass.
  • binder The binder for binding the modified ZSM-5 type zeolite and the filler particles contains phosphorus and aluminum.
  • Examples of the phosphorus- and aluminum-containing component include compounds containing phosphorus, aluminum, and oxygen.
  • Examples of the compound containing phosphorus, aluminum, and oxygen include oxides containing phosphorus and aluminum (for example, a composite oxide of phosphorus and aluminum).
  • the binder is usually contained in the FCC catalyst additive according to the present invention in an amount of 7 to 25% by mass, preferably 9 to 20% by mass, more preferably 9 to 15% by mass.
  • the binder preferably contains phosphorus in an amount of 5 to 20% by mass in terms of P 2 O 5 , more preferably 6 to 15% by mass, more preferably 6 to 12% by mass (of the FCC catalyst additive according to the present invention). The amount is 100% by mass).
  • the form of the FCC catalyst additive according to the present invention is preferably particulate.
  • the content of phosphorus measured by ICP emission spectroscopic analysis is P 2 O. In terms of 5, it is 5 to 20% by mass, preferably 6 to 15% by mass. When the content is within this range, the heat resistance and the diffusibility of the reaction product are high, and sufficient activity can be obtained. Further, the physical properties such as the apparent bulk density and wear resistance of the catalyst are also excellent.
  • the FCC catalyst additive according to the present invention preferably comprises one or more of the following physical properties (i) to (vi), and more preferably comprises one or more of the following physical properties (iii) to (vi). More preferably, the following physical properties (iii), (iv), (v) and (vi) are provided.
  • the average particle size measured by the method employed in the examples described later is 30 to 200 ⁇ m, preferably 50 to 150 ⁇ m. When the average particle size is within this range, the FCC reaction has sufficient fluidity and good reactivity.
  • the average particle diameter can be increased or decreased, for example, by changing the atomizer rotation speed, the spray pressure, or the like in the step (e) described later.
  • the pore volume in the range of the pore diameter of 50 to 500 nm measured by the mercury intrusion method employed in the examples described later is 0.3 to 0.5 ml / g, preferably 0.30 to 0.45 ml. / G.
  • the pore volume is below this range, the diffusibility of the reactant is lowered, and the amount of lower olefin produced is lowered.
  • the ABD of the catalyst is lowered, the fluidity in the FCC reaction is deteriorated, and the wear resistance is also lowered.
  • the pore volume can be increased or decreased by adjusting the content of aluminum biphosphate used as a raw material for the binder, for example.
  • the pore diameter (the details of the measurement conditions are as described in the column of Examples described later) is in the range of 2.5 to 5.0 nm.
  • the pore volume with a pore diameter of 2 nm or less is 0.020 to 0.130 ml / g. It is in the range.
  • the pore volume in the pore diameter range of 2.4 to 50 nm is 0.010. It is in the range of ⁇ 0.070 ml / g.
  • the FCC catalyst additive according to the present invention is, for example, ZSM-5 type zeolite and alkali metal-containing alkaline solution are contacted under the condition that the molar ratio of SiO 2 to alkali metal (SiO 2 : alkali metal) in ZSM-5 type zeolite is 15: 1 to 3: 1.
  • a process for producing an additive for fluid catalytic cracking catalyst comprising: Can be manufactured by.
  • step (a) ZSM-5 type zeolite is contacted with an alkali metal-containing alkaline solution.
  • ZSM-5 type zeolite In the synthesis of the ZSM-5 type zeolite, a method using a template (for example, H. Mochizuki et al., Microporous and Mesoporous Materials, 145 (2011) 165-171, etc.) or a method not using a template (for example, Japanese Patent Laid-Open No. 2011-2011) ZSM-5 type zeolites with various Si / Al 2 ratios can be produced.
  • a template for example, H. Mochizuki et al., Microporous and Mesoporous Materials, 145 (2011) 165-171, etc.
  • a method not using a template for example, Japanese Patent Laid-Open No. 2011-2011
  • the alkali metal-containing alkaline solution is preferably an aqueous solution of an alkali metal hydroxide.
  • alkali metal hydroxide examples include sodium hydroxide and potassium hydroxide, and preferably sodium hydroxide.
  • the conditions for contacting the ZSM-5 type zeolite with the alkali metal-containing alkaline solution are, for example, as follows. Concentration of slurry A: 5 to 30% by weight Molar ratio of SiO 2 to alkali metal in ZSM-5 type zeolite (SiO 2 : alkali metal): 15: 1 to 3: 1 Time: 0.5-5 hours Temperature: 70-90 ° C By bringing the ZSM-5 type zeolite into contact with the alkali metal-containing alkaline solution, a slurry (A) containing the ZSM-5 type zeolite modified with an alkali metal is obtained.
  • the solid content is separated from the slurry (A), and the solid content is washed.
  • a conventionally known method such as filtration can be applied to the separation of the solid content.
  • the washing of the solid content is preferably washing with water.
  • the temperature of the water is preferably 25 to 70 ° C.
  • the washed product (B) obtained in the step (B) is dispersed in water, and then alkali metal ions are removed by an ion exchange method to obtain a slurry of a modified ZSM-5 type zeolite.
  • alkali metal ions are removed by an ion exchange method to obtain a slurry of a modified ZSM-5 type zeolite.
  • ammonium sulfate, ammonium nitrate or the like is added to and reacted with the aqueous dispersion slurry of the washed product (B), the solid content is separated, and the solid content is washed repeatedly.
  • the conditions for ion exchange are, for example, as follows. Time: 10 minutes to 2 hours Temperature: 25 to 70 ° C Molar ratio of Al 2 O 3 and ammonium salt (as NH 4+ ) in the zeolite (Al 2 O 3 : NH 4+ ): 1: 1 to 1:10 Repeat count: 1 to 5 times
  • the binder raw material is a raw material for the binder contained in the FCC catalyst additive according to the present invention.
  • the binder material include compounds containing phosphorus, aluminum, and oxygen.
  • the compound containing phosphorus, aluminum and oxygen include aluminum deuterium phosphate (Al (H 2 PO 4 ) 3 ), dibasic aluminum phosphate (Al 2 (HPO 4 ) 3 ), and aluminum phosphate (AlPO 4 ).
  • aluminum biphosphate is used.
  • the blending ratios of the modified ZSM-5 type zeolite slurry, the filler, and the binder raw material are respectively the modified ZSM-5 type zeolite, the filler, and the binder contained in the FCC catalyst additive according to the present invention. It is appropriately set so as to correspond to the ratio of the binder.
  • the modified ZSM-5 type zeolite is 20 to 70% by mass, preferably 30 to 60% by mass
  • the filler is 20 to 73% by mass, preferably 25 to 60% by mass
  • the binder raw material is 7 to 25% by mass.
  • % Preferably 9 to 20% by mass, more preferably 9 to 15% by mass (the total amount of these three components is 100% by mass).
  • the binder raw material may be, for example, an amount such that phosphorus is 5 to 20% by mass, preferably 6 to 15% by mass, more preferably 6 to 12% by mass in terms of P 2 O 5 .
  • the slurry (D) is spray-dried, and then the obtained solid is fired.
  • the solid obtained by spray drying is preferably classified before firing.
  • Each operation in the step (e) can be performed by a conventionally known method, for example, under the following conditions.
  • ⁇ Spray drying is set at a spray inlet temperature range of 200 to 450 ° C and an outlet temperature range of 110 to 350 ° C.
  • ⁇ Classification ⁇ Classification is preferably performed so that the average particle size is about 30 to 200 ⁇ m, preferably about 50 to 150 ⁇ m.
  • the method for producing a decomposition product mixture by fluid catalytic cracking according to the present invention is characterized in that the fluid catalytic cracking is carried out in the presence of the FCC catalyst and the FCC catalyst additive according to the present invention.
  • the raw material hydrocarbon to be subjected to fluid catalytic cracking non-depressurized vacuum gas oil, hydrotreated vacuum gas oil (DSVGO), residual oil and the like are preferable.
  • the fluidity in the FCC reactor can be improved.
  • the production conditions of the decomposition product mixture can be appropriately set with reference to the prior art except that the FCC catalyst additive according to the present invention is used as the FCC catalyst additive.
  • Example 1 ZSM-5 type zeolite produced according to Example 1 of JP 2011-213525 A was added to pure water to prepare 10,000 g of an aqueous dispersion slurry of ZSM-5 type zeolite having a concentration of 10% by mass. To this slurry, 166.7 g of a 48 mass% NaOH aqueous solution was added and mixed with stirring. The obtained mixture was heated to 80 ° C. and held at 80 ° C. for 2 hours, and then filtered to obtain a cake. Washing was performed by applying 20,000 g of warm water of 60 ° C. to the obtained cake in four portions.
  • the washed cake is suspended in pure water to prepare a 10,000 g slurry, 116.7 g of ammonium sulfate is added thereto, and the mixture is heated to 60 ° C. and stirred and mixed at 60 ° C. for 30 minutes. , Filtered and washed the cake. This operation, that is, ion exchange with ammonium sulfate, was performed twice in total. Washing was performed by applying 20,000 g of 60 ° C. warm water in four portions on the cake.
  • NaOH-treated (a) ZSM-5 slurry a modified ZSM-5 type zeolite slurry having a concentration of 25% by mass.
  • Table 1 shows the physical properties and the like of NaOH-treated (a) ZSM-5.
  • Steps (d) to (e)) 2,400 g of the NaOH-treated (a) ZSM-5 slurry (amount of NaOH-treated (a) ZSM-5 to be 40% by mass based on the mass of the target product (additive for catalyst)). This was mixed with 885.5 g of kaolin (containing 19.5% by mass water) (amount of kaolin (without water) 47.5% by mass based on the mass of the target product), and aluminum was mixed with Al.
  • ZSM-5 type zeolite produced in accordance with Example 1 of JP 2011-213525 A is suspended in pure water, ground to an average particle size of 2.5 ⁇ m or less by a bead mill, and a ZSM-5 slurry having a concentration of 25% by mass ( Hereinafter also referred to as “ZSM-5 pulverized slurry”).
  • Example 2 Except that the amount of the NaOH aqueous solution was changed to 250.0 g, the same operation as in steps (a) to (c) of Example 1 was carried out to obtain a slurry having a concentration of 25% by mass (hereinafter referred to as “NaOH treatment (b) ZSM-5”. Also referred to as “slurry”). Except that the NaOH-treated (a) ZSM-5 slurry was changed to 2,400 g of the NaOH-treated (b) ZSM-5 slurry, the same operations as in steps (d) to (e) of Example 1 were performed. FCC catalyst additive C was obtained. Table 2 shows the physical properties and the like of the FCC catalyst additive C.
  • Example 3 Except that the amount of the NaOH aqueous solution was changed to 333.4 g, the same operation as in steps (a) to (c) of Example 1 was performed to obtain a slurry having a concentration of 25% by mass (hereinafter referred to as “NaOH-treated (c) ZSM-5”). Also referred to as “slurry”). Except that the NaOH-treated (a) ZSM-5 slurry was changed to 2,400 g of the NaOH-treated (c) ZSM-5 slurry, the same operations as in steps (d) to (e) of Example 1 were performed. FCC catalyst additive D was obtained. Table 2 shows the physical properties and the like of FCC catalyst additive D.
  • Example 4 The same operations as in steps (a) to (c) of Example 1 were performed to prepare a NaOH-treated (a) ZSM-5 slurry having a concentration of 25% by mass.
  • the silica hydrosol is weighed so that the SiO 2 content is 17.5% by mass based on the mass of the target product (excluding the mass of P 2 O 5 ), and kaolin is added to the silica hydrosol.
  • the contents of kaolin and the NaOH-treated (a) ZSM-5 are based on the mass of the target product (however, the mass of P 2 O 5 is not included). 42.5% by mass and 40% by mass to obtain a mixed slurry having a pH of 1.88 and 35 ° C.
  • a magnesium hydroxide slurry having a concentration of 20% by mass was added to the mixed slurry to prepare a mixed slurry having a pH of 3.60 and 35 ° C.
  • This mixed slurry is spray-dried to prepare microspherical particles having an average particle diameter of 80 ⁇ m, and then the microspherical particles have an Na 2 O content of 0.1% by mass or less and an MgO content of 0.1% by mass or less. It was washed with a 5% by mass ammonium sulfate aqueous solution until it became, and then dried in a dryer at 135 ° C. for 10 hours. What was obtained by impregnating dried microspherical particles with a diammonium hydrogen phosphate aqueous solution so that the ratio of phosphorus converted to P 2 O 5 was 6% by mass based on the mass of the target product It was dried at 135 ° C. overnight and then calcined at 600 ° C. for 2 hours to obtain FCC catalyst additive G. Table 2 shows the physical properties and the like of the FCC catalyst additive G.
  • Example 5 The same operations as in steps (a) to (c) of Example 1 were performed to prepare a 25 mass% NaOH-treated (a) ZSM-5 slurry.
  • the silica sol (cataloid SI-30 manufactured by JGC Catalysts & Chemicals Co., Ltd.) was weighed so that the content was 20% by mass based on the mass of the target product (excluding the mass of P 2 O 5 ).
  • the silica sol contains kaolin and the NaOH-treated (a) ZSM-5 slurry, and the contents of kaolin and NaOH-treated (a) ZSM-5 do not include the mass of the target product (however, the mass of P 2 O 5 is not included).
  • a basic aluminum chloride solution of a mass% was weighed, and kaolin and the NaOH-treated (a) ZSM-5 slurry were added to the basic aluminum chloride solution, respectively, and the contents of kaolin and the NaOH-treated (a) ZSM-5 were mass of the object (but not including the weight of P 2 O 5.) added in an amount of 45 wt% and 40 wt% based on to obtain a mixed slurry of pH3.11,36 °C.
  • a magnesium hydroxide slurry having a concentration of 20% by mass was added to the mixed slurry to obtain a mixed slurry having a pH of 5.6 and a temperature of 35 ° C.
  • This mixed slurry is spray-dried to prepare microspherical particles having an average particle diameter of 80 ⁇ m, and then the microspherical particles have an Na 2 O content of 0.1% by mass or less and an MgO content of 0.1% by mass or less. It was washed with a 5% by mass ammonium sulfate aqueous solution until it became, and then dried in a dryer at 135 ° C. for 10 hours. What was impregnated with a diammonium hydrogen phosphate aqueous solution so that the ratio of phosphorus converted to P 2 O 5 was 10% by mass with respect to the dried microspherical particles on the basis of the mass of the object was obtained at 135 ° C. It was dried overnight and calcined at 600 ° C. for 2 hours to obtain FCC catalyst additive I. Table 2 shows the physical properties and the like of FCC catalyst additive I.
  • Example 4 In the steps (d) to (e) of Example 1, the NaOH-treated (a) ZSM-5 slurry was weighed so that the NaOH-treated (a) ZSM-5 was 20% by mass based on the mass of the target product. Then, the aluminum phosphate solution is added so that the total concentration of aluminum and phosphorus converted to Al 2 O 3 and P 2 O 5 is 12.5% by mass based on the mass of the target product, and contains kaolin.
  • An FCC catalyst additive J was prepared in the same manner as in Example 1 except that the amount was balanced. Table 2 shows the physical properties and the like of FCC catalyst additive J.
  • Example 5 In the steps (d) to (e) of Example 1, the NaOH-treated (a) ZSM-5 slurry was weighed so that the NaOH-treated (a) ZSM-5 was 60% by mass based on the mass of the target product. Then, the aluminum phosphate solution is added so that the total concentration of aluminum and phosphorus converted to Al 2 O 3 and P 2 O 5 is 12.5% by mass based on the mass of the target product, and contains kaolin.
  • An FCC catalyst additive K was prepared in the same manner as in Example 1 except that the amount was balanced. Table 2 shows the physical properties of the FCC catalyst additive K.
  • Example 6 In the steps (d) to (e) of Example 1, the amount of the aluminum biphosphate solution was adjusted to the concentration of aluminum and phosphorus converted to Al 2 O 3 and P 2 O 5 on the basis of the mass of the target product.
  • the FCC catalyst additive L was prepared in the same manner as in Example 1 except that the total amount was changed to 9.0% by mass and the kaolin content was balanced. Table 2 shows the physical properties and the like of the FCC catalyst additive L.
  • Example 7 In the steps (d) to (e) of Example 1, the amount of the aluminum biphosphate solution was adjusted to the concentration of aluminum and phosphorus converted to Al 2 O 3 and P 2 O 5 on the basis of the mass of the target product.
  • the FCC catalyst additive M was prepared in the same manner as in Example 1 except that the total amount was changed to 5.0% by mass and the kaolin content was balanced. Table 2 shows the physical properties and the like of the FCC catalyst additive M.
  • Example 7 In the steps (d) to (e) of Example 1, the amount of the aluminum biphosphate solution was adjusted to the concentration of aluminum and phosphorus converted to Al 2 O 3 and P 2 O 5 on the basis of the mass of the target product.
  • the FCC catalyst additive N was prepared in the same manner as in Example 1 except that the total amount was changed to 20.0% by mass and the kaolin content was balanced. Table 2 shows the physical properties and the like of the FCC catalyst additive N.
  • Example 8 In the steps (d) to (e) of Example 1, the amount of the aluminum biphosphate solution was adjusted to the concentration of aluminum and phosphorus converted to Al 2 O 3 and P 2 O 5 on the basis of the mass of the target product.
  • the FCC catalyst additive O was prepared in the same manner as in Example 1 except that the total amount was changed to 30.0% by mass and the kaolin content was balanced. Table 2 shows the physical properties and the like of the FCC catalyst additive O.
  • ⁇ Evaluation method> (Method for measuring the content of each element)
  • mass analysis of each element chemical analysis was performed with an atomic absorption photometer for Na and with an inductively coupled plasma spectrometer except for Na.
  • the zeolite (ZSM-5) or catalyst is heated by adding sulfuric acid and hydrofluoric acid to dryness, the dried solid is dissolved in concentrated hydrochloric acid, and diluted to a concentration of 10 to 100 mass ppm with water.
  • the solution was prepared and analyzed with an atomic absorption photometer (Z-2310) manufactured by Hitachi High-Tech Science Co., Ltd. and an inductively coupled plasma spectrometer (ICPS-8100) manufactured by Shimadzu Corporation.
  • the wavelengths are Na: 589.6 nm, Al: 396.2 nm, Si: 251.6 nm, P: 178.3 nm.
  • the SiO 2 elution amount indicates the ratio of the SiO 2 amount eluted in the filtrate by NaOH treatment to the SiO 2 content in the zeolite.
  • the filtrate was diluted with water and analyzed with ICPS-8100.
  • the particle size distribution of the sample was measured with a laser diffraction / scattering type particle size distribution measuring apparatus (LA-950V2) manufactured by Horiba, Ltd. Specifically, the sample was put into a solvent (water) so that the light transmittance was in the range of 70 to 95%, and the measurement was performed at a circulation rate of 2.8 L / min, an ultrasonic wave of 3 min, and the number of repetitions of 30.
  • the median diameter (D50) was adopted as the average particle diameter.
  • Pore diameter, specific surface area, pore volume of additive for zeolite and FCC catalyst The measurement of the pore volume of pores having a specific surface area (SA) and a pore diameter of 50 nm or less was performed with BELSORP-mini Ver2.5.6 manufactured by Microtrac Bell. Specifically, a sample pretreated with zeolite or catalyst at 500 ° C. for 1 hour was used, and measurement was performed using nitrogen as an adsorption gas.
  • SA Specific surface area of zeolite (ZSM-5) and FCC catalyst additive
  • BET method external surface area of zeolite (ZSM-5) and matrix SA (MSA) of FCC catalyst additive is t-plot method
  • FCC The catalyst additive zeolite SA (ZSA) was calculated by the difference between SA and MSA.
  • the volume of micropores having a pore diameter of 2 nm or less of zeolite (ZSM-5) and the additive for FCC catalyst was calculated by the MP method, and the volume of mesopores having a pore diameter of 2.4 to 50 nm was calculated by the BJH method.
  • ammonia adsorption amount of zeolite The ammonia adsorption amount of zeolite was measured by a temperature desorption (TPD) method using BELCAT Version 2.5.5 of Microtrac Bell Co., Ltd. Specifically, a sample pretreated at 500 ° C. for 1 hour was used as the zeolite. 0.2 g of the pretreated sample was heat-treated in a TPD apparatus at 500 ° C. for 1 hour under a helium flow, and then cooled to 100 ° C. Ammonia was adsorbed at 100 ° C. for 30 minutes and degassed for 30 minutes under the same temperature and helium flow. Thereafter, the ammonia desorption amount when the temperature was raised from 100 ° C. to 600 ° C. at 10 ° C./min was detected by TCD, and the ammonia adsorption amount was calculated from the desorption amount.
  • TPD temperature desorption
  • the macropore diameter and the macropore volume of the FCC catalyst additive were measured using a mercury porosimeter (POREMASTER Ver 7.01) manufactured by Cantachrome Instruments Japan GK. Specifically, a sample pretreated with an FCC catalyst additive at 500 ° C. for 1 hour was measured by a mercury intrusion method using a mercury contact angle of 130 ° and a surface tension of 480 dyn / cm.
  • the average pore diameter (PD A ) represents the pore distribution of the FCC catalyst additive as a cumulative pore distribution curve, and is equivalent to 50% of the total pore volume (PV T ) in the pore diameter range of 50 to 500 nm. The pore diameter corresponding to a point on the pore distribution curve.
  • the particle size distribution of the sample was measured with a laser diffraction / scattering particle size distribution measuring apparatus (LA-300) manufactured by Horiba, Ltd. Specifically, the sample was put into a solvent (water) so that the light transmittance was in the range of 70 to 95%, and the measurement was performed at a circulation rate of 2.8 L / min, an ultrasonic wave of 3 min, and the number of repetitions of 30.
  • the median diameter (D50) was adopted as the average particle diameter.
  • Catalyst performance FCC catalyst additives A to O of Examples and Comparative Examples were subjected to catalyst evaluation tests using ACE-MAT under the same feedstock and the same reaction conditions. Prior to the catalyst evaluation test, each catalyst was pretreated at 750 ° C. for 13 hours in a 100 ° C. steam atmosphere.
  • the ACE-MAT activity test equipment was prepared by blending the FCC catalyst additive pretreated with the FCC equilibrium catalyst so that the amount of ZSM-5 in the mixed catalyst was a constant amount of 0.96% by mass.
  • the mixed catalyst was evaluated.
  • the fixed amount of 0.96% means that 4 FCC catalyst additives are contained in the mixed catalyst.
  • the amount is 2.4% by mass.
  • reaction conditions were as follows. -Reaction temperature: 510 ° C ⁇
  • Raw oil 100% by mass of desulfurized vacuum gas oil (DSVGO) ⁇ WHSV: 8 hr ⁇ 1
  • Catalyst / oil ratio 5% by mass /% by mass
  • the gasoline fraction was analyzed about the product liquid by the gas chromatography [GC System HP6890A] made from Agilent. The evaluation results are shown in Tables 3-1 and 3-2.

Abstract

[Problème] Fournir un additif pour un catalyseur de craquage de fluide (FCC) utilisé avec un catalyseur FCC dans FCC, l'additif permettant d'augmenter le rendement en oléfines inférieures. [Solution] La présente invention concerne un additif pour un catalyseur FCC utilisé dans la fabrication d'oléfines inférieures, ledit additif contenant : 20 à 70 % en masse de zéolite ZSM-5 modifiée de sorte que (1) le volume de pores ayant un diamètre de 2 nm ou moins dans des mesures de volume de pore au moyen du procédé MP est dans la plage de 0,15 à 0,20 ml/g, (2) le volume de pores ayant un diamètre de 2,4 à 50 nm dans des mesures de volume de pore au moyen de la méthode BJH est dans la plage de 0,05 à 0,15 ml/g, et (3) la quantité d'adsorption d'ammoniac est dans la plage de 1,0 à 2,0 mmol/g ; une charge ; et un liant comprenant des composants contenant du phosphore et de l'aluminium pour lier les particules de la charge et la zéolite ZSM-5 modifiée. La teneur en phosphore (conformément à la spectroscopie d'émission ICP) est de 5 à 20 % en masse exprimée en termes de P2O5.
PCT/JP2016/083367 2015-11-11 2016-11-10 Additif pour catalyseur de craquage catalytique de fluide utilisé dans la fabrication d'oléfines inférieures et procédé de fabrication dudit additif WO2017082345A1 (fr)

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