WO2010102430A1 - 一种高固体含量流化催化裂化催化剂制备方法 - Google Patents

一种高固体含量流化催化裂化催化剂制备方法 Download PDF

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Publication number
WO2010102430A1
WO2010102430A1 PCT/CN2009/000500 CN2009000500W WO2010102430A1 WO 2010102430 A1 WO2010102430 A1 WO 2010102430A1 CN 2009000500 W CN2009000500 W CN 2009000500W WO 2010102430 A1 WO2010102430 A1 WO 2010102430A1
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catalyst
solid content
slurry
molecular sieve
boehmite
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French (fr)
Inventor
高雄厚
张海涛
谭争国
段宏昌
季东
刘引定
汪毅
马燕青
刘涛
张爱群
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Petrochina Co Ltd
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Petrochina Co Ltd
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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
    • 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
    • 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
    • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
    • 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
    • B01J29/80—Mixtures of different zeolites
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—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

Definitions

  • the present invention relates to a process for the preparation of a fluid catalytic cracking (FCC) catalyst, and more particularly to a process for the preparation of a high solids fluid catalytic cracking catalyst.
  • FCC fluid catalytic cracking
  • Technical Background Fluid catalytic cracking CFCC Process is the main process of secondary processing of crude oil, and it is an important means for deep processing of heavy oil at home and abroad to produce fuel for vehicles. As the processing materials are heavier, the degree of inferiority is increased, and the demand for vehicle fuels increases, the consumption of FCC catalysts required for this process is increasing. At the same time, due to the development of processing heavy oil and FCC process technology, the active components of molecular sieves are The proportion in the FCC catalyst also shows an increasing trend.
  • a process for preparing a semi-synthetic FCC catalyst is to slurry a raw material such as a binder (e.g., aluminum sol), pseudoboehmite, clay, inorganic acid, and molecular sieve, and obtain a catalyst product by spray molding and post-treatment.
  • a raw material such as a binder (e.g., aluminum sol), pseudoboehmite, clay, inorganic acid, and molecular sieve
  • this process has a low solid content of the colloid before the spray molding of the catalyst, and a problem of uneven mixing of the active component of the molecular sieve with other components (referred to as a matrix component), resulting in a low production cost of the catalyst and uneven particle size of the formed microspheres.
  • the sphericity difference and the active center of the catalyst are poor in thermal stability, and the reaction performance of the molecular sieve in the catalyst cannot be sufficiently exerted. Therefore, a preparation method of a high solid content FCC catalyst has been
  • USP 4,476, 239 and US Pat. No. 4,443, 355 disclose the preparation of a cracking catalyst characterized by adding a dispersant [Al 2 (0H) 6 - y Cl or A1 2 (0H) S N0 3 to the catalyst slurry to reduce the viscosity of the catalyst slurry. Increase the solids content of the catalyst spray slurry.
  • a catalyst slurry containing an aluminum-based binder, a clay, a silicon source and a molecular sieve the solid content of the catalyst slurry is 20 to 25% without a dispersant, and the solid content of the catalyst liquid after the addition of the dispersant Can be increased to 30%.
  • the preparation process comprises the following steps: adding chemical water and pseudo-boehmite in sequence in the reaction kettle, and then adding mineral acid to perform acidification peptization reaction after the beating is uniform, and then adding kaolin and molecular sieve slurry after the reaction is finished, mixing and homogenizing and then adding polypolymer.
  • the ammonium silicate is dispersed to reduce the viscosity of the catalyst slurry, and the obtained catalyst slurry is spray-dried to obtain a finished catalyst.
  • the polymer having a molecular weight of from 250 to 5 million units is added to the spray slurry before the catalyst is dried.
  • the acrylamide can reduce the viscosity of the catalyst slurry by 10 to 50% under the premise of ensuring that the performance of the catalyst is not affected, thereby not only greatly improving the solid content of the water liquid, but also improving the drying efficiency and saving. Energy consumption, Moreover, the adhesion of materials on the inner wall of the pipe wall and the spray dryer is greatly reduced.
  • CN1081219C discloses a method for increasing the solid content of a catalyst spray slurry, the method comprising beating a molecular sieve slurry, an aluminum sol, a pseudoboehmite, a clay and a mineral acid, characterized in that the molecular sieve is added before the clay and the inorganic acid, and the inorganic
  • the acid is added after the aluminum sol, preferably the mineral acid is added after the aluminum sol and the pseudoboehmite.
  • the method can significantly improve the solid content of the catalyst liquid before spray drying (up to 45m%), shorten the gelation time, thereby improving the catalyst production efficiency, and reducing energy consumption and production cost.
  • CN1081218C discloses a method for increasing the solid content of a catalyst spray slurry, which comprises beating a molecular sieve slurry, an aluminum glue, a pseudoboehmite, a clay and a mineral acid to make the slurry have a solid content of 25 to 45%, and the characteristics thereof.
  • the aluminum sol is added prior to the clay and the mineral acid, and the molecular sieve slurry is added after the mineral acid, preferably the mineral acid is added after the aluminum sol and the pseudoboehmite.
  • the method can also improve the solid content of the catalyst slurry before spray drying.
  • CN1362472A discloses a preparation method of a cracking catalyst, which comprises uniformly mixing a molecular sieve slurry, pseudoboehmite, clay and inorganic acid with or without adding an aluminum sol to prepare a catalyst slurry, which is then spray-dried;
  • the amount of inorganic acid added to the pseudo-boehmite peptizer is determined by the viscosity of the catalyst slurry, and the amount of hydrochloric acid added is such that the viscosity of the catalyst slurry is controlled in the range of 10,000 to 100,000 cp.
  • the method provided by the patent can avoid fluctuations in catalyst strength and pore volume caused by fluctuations in acid consumption of pseudo-boehmite, and the solid content of the catalyst is 25 to 52%.
  • CN1270203A discloses a preparation method of a cracking catalyst, which comprises mixing molecular sieve liquid, aluminum sol, pseudoboehmite, clay and inorganic acid into a catalyst slurry, followed by spray drying; and characterized by molecular sieve And/or the aluminum sol is added before the clay and the inorganic acid, the inorganic acid is added after the aluminum sol, the order of addition of the remaining materials is not particularly limited, and the catalyst slurry contains a viscosity reducing agent; wherein the viscosity reducing agent 1 ⁇ 2% ⁇ In the case of ammonium phosphate, diammonium hydrogen phosphate or ammonium dihydrogen phosphate, or a mixture thereof, the amount of the viscosity reducer is 0.1 to 2% of the weight of the catalyst ; The weight ratio of the A1203 is from 0.02 to 0.25; the catalyst slurry has a solid content of 30 to 55%.
  • the method provided by the invention can greatly improve the solid content of the catalyst polyliquid before spray drying, shorten the gelation time, thereby improving the production efficiency of the catalyst, and reducing energy consumption and production cost.
  • the above patented method improves the solid content of the colloid before the spray molding of the FCC catalyst to a certain extent, it is 25 to 50%, but the common feature is that the inorganic acid must be added after the addition of the pseudoboehmite in the preparation process.
  • the diaspore is acidified and peptized, so the following problems are inevitable: 1) due to the inorganic acid in the pseudo-thick aluminum After the addition of stone, the reaction between the inorganic acid and the pseudo-boehmite is difficult to occur uniformly, and there is always a local over-reaction phenomenon, which leads to a rapid increase in the viscosity of the slurry; 2) when the molecular sieve liquid is first added, the inorganic acid added later Localized molecular sieve phenomenon occurs, and because the acidity of the system cannot be controlled too low (generally pH is greater than 2.8), the pseudo-boehmite is difficult to be sufficiently refined, especially when the molecular sieve content is high, the anti-wear strength of the catalyst is deteriorated.
  • the performance is greatly affected; 3) The addition of inorganic acid seriously corrodes the equipment, and the acid gas generated during spray drying pollutes the surrounding environment.
  • the present invention provides a novel high solid content FCC catalyst preparation method, that is, in the preparation process of the catalyst, the inorganic acid is not added to carry out the acidification pseudo-boehmite reaction, but the mechanical physical idling dispersion method is used to disperse the fine It can effectively solve the effect of plywood plywood state on the solid content and wear index of the catalyst, can improve the solid content of the colloid before spray molding, and achieve the clean and efficient production target of FCC catalyst.
  • the high solid content FCC catalyst provided by the invention is prepared by adding various materials required for preparing the catalyst, water, clay, molecular sieve slurry, aluminum-containing binder, pseudoboehmite and dispersant to the reaction kettle, and mixing and mixing evenly.
  • the catalyst slurry is prepared, and then aged at 25 to 80 ° C for 10 min to 100 min, and finally homogenized spray drying to obtain a high solid content FCC catalyst.
  • the technical feature of the present invention is that the pseudo-boehmite is added to the reaction vessel after the aluminum sol, and is fully beaten for 20 min to 120 m in, and then the pseudo-boehmite is dispersed at a high speed by mechanical physics to make the pseudo-boehmite grain size D.
  • [V, 0.5] is not more than 4 ⁇ ⁇ , reducing its effect on the catalyst wear index. This method does not limit the order in which the remaining materials are added.
  • the composition of the catalyst slurry (according to the mass of the dry basis of the catalyst) is 15-50% of molecular sieve, 15 ⁇ 60% of clay, 8 ⁇ 30% of pseudoboehmite, and aluminum binder (as alumina) 3 ⁇ 18%
  • the obtained prize liquid solid content is 35 to 55%.
  • the catalyst slurry further comprises 0 to 8% of one or more oxides of rare earth oxide, zinc oxide, silicon oxide, magnesium oxide, titanium oxide, vanadium oxide, copper oxide or a precursor thereof; wherein oxidation is preferred Rare earths, silica or their precursors.
  • the invention provides a method for preparing a high solid content FCC catalyst, wherein the molecular sieve is a cerium type zeolite (including various modified cerium type zeolites) or a cerium type zeolite and a ZSM zeolite, a beta zeolite, an ⁇ zeolite, an MCM zeolite, and an SAP0 zeolite.
  • a cerium type zeolite including various modified cerium type zeolites
  • a cerium type zeolite and a ZSM zeolite a beta zeolite, an ⁇ zeolite, an MCM zeolite, and an SAP0 zeolite.
  • the modified cerium type zeolite is one of HY, NH 4 Y, REY, USY, REUSY, other element-modified
  • the clay for preparing a high solid content FCC catalyst provided by the present invention is kaolinite, sepiolite, halloysite, One of montmorillonite or a mixture thereof; among them, kaolin, halloysite or a mixture thereof is preferred; kaolin is most preferred.
  • the pseudo-boehmite according to the preparation method of the high solid content rcc catalyst provided by the invention may be boehmite, boehmite, bayerite, preferably boehmite.
  • the aluminum-containing binder of the present invention comprises an aluminum sol, a basic aluminum chloride, and an acid-modified kaolin, which can be obtained by one of the following methods:
  • a preferred embodiment of the method for preparing a high solids FCC catalyst provided by the present invention is that the aluminum sol is added before all the materials, and the pseudoboehmite is added before the molecular sieve. If the aluminum-containing binder and water are first added to the reaction vessel, then the clay and the pseudo-boehmite are added thereto, stirred uniformly, and then dispersed at a high speed until the material particle size [V, 0.5] is not more than 4 ⁇ ⁇ , and then added. Molecular sieve slurry, mix well and add dispersant, then heat up and age lOmir! ⁇ lOOmin, the resulting slurry was spray dried to obtain a catalyst.
  • the method for preparing a high solid content FCC catalyst provided by the invention may further comprise: first adding an aluminum-containing binder and water to the reaction vessel, and then adding a pseudo-boehmite tempering reaction 20 ⁇ ⁇ to 120 ⁇ , and dispersing at a high speed to a material particle size [V, 0. 5] not more than 4 um, finally added molecular sieve and clay, after stirring evenly, adding a dispersing agent, stirring uniformly, and then heating and aging for 10 m to 100 min, and spraying the obtained slurry to obtain a catalyst.
  • the preparation method of the high solid content FCC catalyst provided by the invention may further comprise: first adding an aluminum-containing binder and chemical water to the reaction kettle, and then adding the pseudo-boehmite to carry out the relaxation reaction for 20 min to 120 min, and dispersing at a high speed to the material particle size [ ⁇ , 0. 5] is not more than 44 111, and then aging for 10 min to 100 min, and finally adding molecular sieve and clay, stirring and hooking, and then drying the obtained slurry to obtain a catalyst.
  • USY molecular sieve (burning 4.8%, unit cell parameter a. 2.452 awake), REUSY molecular sieve (burning 5.3%, rare earth oxide 8.5%, unit cell parameter a. 2. 462nm ), REY (burning 4. 4%, oxidized rare earth 18.1%), are all qualified industrial products, taken from Lanzhou Petrochemical Company catalyst plant; high silicon ZSM-5 (slow reduction 5. 1%, silicon to aluminum ratio is greater than 300), industrial qualified products, produced by Shanghai Fudan University.
  • the zeolite slurry mixed with 2615 g of deionized water was stirred for 1 hour, then heated to 6 CTC for 60 minutes, and then homogenized by spray drying.
  • the obtained catalyst microspheres were calcined at 50 (TC calcined for 0.5 hours, then added 8 times. Ionized water, stirred well, washed at 8 CTC for 15 minutes, and dried by filtration to obtain the FCC catalyst prepared by the method of the present invention, which is referred to as Al.
  • the catalyst A- 1 spray slurry had a solids content of 43.5%, a slurry viscosity of 4058 cps, a wear index of the obtained catalyst of 1.5, and a pore volume of 0.43 mL.g-microreactivity 65.
  • Example 2 In the reaction kettle, 929 g of deionized water, 1622 g of aluminum sol, 1156 g of 1 # pseudoboehmite and 1902 g of kaolin were added, and the mixture was beaten for 60 minutes, and then dispersed by a high-speed disperser to a particle size [V, 0.5. Is equal to 2 ⁇ ⁇ , and then added to the molecular sieve slurry of 1573 g of REUSY molecular sieve, 43 g of Fudan ZSM 5 molecular sieve and 2468 g of deionized water, which have been finely ground with a colloid to a particle size of less than 5 ⁇ m, and then added with 13 ml of water.
  • the glass was stirred for 1 hour, then heated to 60 ° C for 120 minutes, then homogenized by spray drying, and the obtained catalyst microspheres were calcined at 50 CTC for 0.5 hours, then 8 times of deionized water was added, stirred uniformly, and washed at 80 ° C.
  • the FCC catalyst prepared by the process of the present invention was obtained by filtration and drying for 15 minutes, and was designated as A-2.
  • the catalyst A-2 spray slurry had a solids content of 41% and a slurry viscosity of 4,319 cps.
  • the obtained catalyst had an abrasion index of 1.2 and a pore volume of 0.42 mL.g.
  • the catalyst A- 3 spray slurry had a solids content of 44.2%, a slurry viscosity of 4,835 cps, and a wear index of the obtained catalyst of 1.6, a pore volume of 0.43 mL g-microreactivity 64.
  • the particle size [V, 0.5] is equal to 1.5 ⁇ m, and then 814 g of USY molecular sieve, 629 g of REUSY, 43 g of Fudan ZSM-5 molecular sieve, which have been finely ground with a colloid to an average particle diameter of less than 5 ⁇ m, 18 g of zeolite zeolite mixed with 2482 g of deionized water in a molecular sieve slurry, then added with 79 ml of water glass, stirred for 1 hour, heated to 40 ⁇ for 80 minutes, then homogenized spray dried, and the obtained catalyst microspheres were calcined at 500 ° C. After 5 hours, 8 times of deionized water was added, stirred uniformly, and washed at 80 ° C for 15 minutes, and dried by filtration to obtain the FCC catalyst prepared by the method of the present invention, which was designated as A-4.
  • the catalyst A- 4 spray slurry has a solid content of 38%, a slurry viscosity of 3,549 cps, and a wear index of the obtained catalyst of 0.88, a pore volume of 0.40 mL of micro-reaction activity 65.
  • Example 5 In the reaction kettle, 1871 g of deionized water, 326 g of USY molecular sieve and 764 g of REUSY molecular sieve were added, and after mixing, 1622 g of aluminum sol, 2603 g of kaolin and 899 g of 1 # pseudoboehmite were sequentially added, and stirred for 30 minutes. After that, it is dispersed by a high-speed disperser until the particle size [V, 0.5] is equal to 2. 5 ⁇ ⁇ , and then heated to 80 ° C for 15 minutes, then homogenized spray drying, and the obtained catalyst microspheres are calcined at 500 ° C. 0. 5 hours, then adding 8 times of deionized water, stirring and hooking, washing at 80 ° C for 15 minutes, filtering and drying to obtain the FCC catalyst prepared by the method of the present invention, which is recorded as A-5.
  • the catalyst A-5 spray slurry had a solids content of 49%, a slurry viscosity of 5327 cps, a wear index of 1.00, and a pore volume of 0.44 mL of micro-reaction 65.
  • the catalyst has a solids content of 52%, a slurry viscosity of 4,905 cps, a catalyst wear index of 1.4, a pore volume of 0. ASmL-g- 1 , and a microreaction activity of 63.
  • the mixture of the deionized water was stirred for 1 hour, and then heated to 7 CTC for 50 minutes, and then homogenized by spray drying.
  • the obtained catalyst microspheres were calcined at 50 CTC for 0.5 hours, then 8 times of deionized water was added, and the mixture was stirred.
  • the FCC catalyst prepared by the method of the present invention was obtained by washing at 8 (TC for 15 minutes), and was designated as A-7.
  • the catalyst A- 7 spray slurry had a solids content of 40% and a slurry viscosity of 4,195 cps.
  • the obtained catalyst had an abrasion index of 1.8 and a pore volume of 0.42 laL_g - microreactivity 66.
  • the catalyst A- 8 spray slurry had a solids content of 46%, a slurry viscosity of 5028 cps, a wear index of the obtained catalyst of 1.5, and a pore volume of 0.42 mL.g-', a microreactivity 65. Comparative example 1
  • the spray slurry of the catalyst B-1 had a solid content of 43. 2%, a slurry viscosity of 13092 cps, and a wear index of the obtained catalyst of 2.7, a pore volume of 0.40 mLg-microreactivity 63.
  • the granules have a solids content of 41%, a slurry viscosity of 12,653 cps, a wear index of the resulting catalyst of 1.7, a pore volume of 0.38 mL_g ⁇ , and a microreaction activity of 62.
  • the spray slurry of the catalyst B-3 had a solid content of 38.7%, a slurry viscosity of 7248 cps, a wear index of the obtained catalyst of 3.9, and a pore volume of 0.41 mL_g-microreactivity 63.
  • the spray slurry of the catalyst A 3 has a solid content of 44.2%, a slurry viscosity of 5638 cps, and a wear index of the obtained catalyst of 3.8.
  • the pore volume is ⁇ . ⁇ 1 , and the microreaction activity is 65.
  • the existence state of pseudo-boehmite is an important factor affecting the solid content of catalyst liquid and the anti-wear strength of the catalyst.
  • the key is to control the existence state of the pseudo-boehmite.
  • the inorganic acid acidified pseudo-boehmite is not added, but the surface of the pseudo-boehmite is softened by the free H + ion of the catalyst preparation system.
  • the solid content of the catalyst slurry prepared by the method for preparing a high solid content FCC catalyst provided by the present invention can be increased to 35% to 55% without affecting the fluidity of the catalyst liquid.
  • the physical and chemical properties and reaction properties of the resulting catalyst are not adversely affected.
  • the implementation of this technology can significantly improve the production efficiency of the catalyst, reduce the pollutant emissions in the production process, and reduce the catalyst flash energy consumption and production costs.
  • the evaluation results show that the FCC catalyst prepared by this technology has an open medium-large pore structure, and the heavy oil conversion ability of the catalyst is obviously improved, and the yield of the high value-added product is increased.
  • Table 2 shows the evaluation results of the catalyst prepared by the method of the present invention and the comparative catalyst on a fixed fluidized bed apparatus.
  • the fixed fluidized bed has a reaction temperature of 500 ⁇ , a ratio of agent to oil of 4, and a space velocity of 151.
  • the feedstock oil is a vacuum residue of 30% blended with Xinjiang oil.
  • the catalyst A-1 prepared by the process of the present invention has the best heavy oil conversion ability and the highest total liquid recovery compared with the catalysts B1 and B-3 prepared in the comparative example, and at the same time, the olefin content of the gasoline is relatively high. Low, the overall reaction performance of the catalyst is improved.

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Description

一种高固休含量流化催化裂化催化剂制备方法
技术领域 本发明涉及流化催化裂化 （FCC)催化剂的制备方法， 具体涉及一种高固体含量的 流化催化裂化催化剂的制备方法。 技术背景 流化催化裂化 CFCC) 工艺是原油二次加工的主要过程， 是国内外重油深度加工生 产车用燃料的重要手段。隨着加工原料重质化、劣质化程度加重以及车用燃料需求量上 升，该工艺所需的 FCC催化剂消耗量在不断增加； 同时由于加工重油和 FCC工艺技术发 展的需求， 分子筛活性组分在 FCC催化剂中的比例也呈现增加趋势。通常， 制备半合成 FCC催化剂的工艺过程是将粘结剂 （如铝溶胶)、 拟薄水铝石、 粘土、 无机酸以及分子 筛等原料制成浆液，通过喷雾成型和后处理得到催化剂产品。但是该工艺存在催化剂喷 雾成型前的胶体固含量低， 分子筛活性组分与其它组分（称作基质组分）混合不均勾等 突出问题， 导致催化剂生产成本髙、成型微球颗粒大小不均匀、球形度差和催化剂活性 中心热稳定性差， 不能充分发挥催化剂中分子筛的反应性能。因此，人们开发了高固含 量 FCC催化剂的制备方法。
USP4476239和 USP4443553报道了一种裂化催化剂的制备方法，其特征是在催化剂 浆液中加入分散剂 [Al2 (0H)6-yCl 或 A12 (0H)SN03, 降低催化剂浆液的粘度， 从而提高催 化剂喷雾浆液的固含量。该专利中， 含有铝基粘结剂、粘土、硅源和分子筛的催化剂浆 液， 不加分散剂时催化剂浆液的固含量为 20〜25%， 加入所说的分散剂后催化剂衆液的 固含量可增加至 30%。 其制备流程为： 在反应釜内依次加入化学水和拟薄水铝石， 打浆 均匀后再加入无机酸进行酸化胶溶反应，反应结束后依次加入高岭土和分子筛浆液，打 浆混合均匀后加入多聚硅酸铵进行分散， 降低催化剂浆液粘度，将所得催化剂漿液喷雾 干燥， 获得催化剂成品。
CN1032498A介绍了一种半合成流化催化裂化催化剂的制备方法， 即在催化剂干燥 前， 在喷雾浆液中加入占催化剂千基含量 0. 01〜0. 15%的分子量为 250〜500万单位的 聚丙烯酰胺作为分散剂，该方法可在保证催化剂性能不受影响的前提下， 降低催化剂浆 液粘度 10〜50%， 由此不但大大提髙了水衆液的固含量，提高了干燥效率，节省了能耗, 而且大大减少了管壁和喷雾千燥装置内壁上物料的粘结现象。
CN1081219C公开了一种提高催化剂喷雾浆液固含量的方法， 该方法包括将分子筛 浆液、铝溶胶、拟薄水铝石、粘土以及无机酸进行打浆， 其特征在于分子筛在粘土和无 机酸之前加入，无机酸在铝溶胶之后加入，优选的是无机酸在铝溶胶和拟薄水铝石之后 加入。 该方法可以明显提高喷雾干燥前催化剂衆液的固含量（最高为 45m%)， 缩短成胶 时间， 从而提高催化剂生产效率， 并降低能耗和生产成本。
CN1081218C公开了一种提高催化剂喷雾浆液固含量的方法， 该方法包括将分子筛 浆液、 铝胶、 拟薄水铝石、 粘土以及无机酸进行打浆， 使浆液的固含量为 25〜45%， 其 特征在于铝溶胶在粘土和无机酸之前加入，分子筛浆液在无机酸之后加入，优选的是无 机酸在铝溶胶和拟薄水铝石之后加入。该方法也可以提高喷雾干燥前催化剂浆液的固含
CN1362472A公开了一种裂化催化剂的制备方法， 包括将分子筛浆液、拟薄水铝石、 粘土以及无机酸打浆混合均匀，加入或不加入铝溶胶，制成催化剂浆液，然后喷雾干燥； 其特征在于使拟薄水铝石胶溶所加入无机酸的量以催化剂浆液粘度为控制指标，盐酸的 加入量以使催化剂桨液粘度控制在 10000〜100000cp范围为准。该专利提供的方法与现 有工艺技术相比，可以避免因为拟薄水铝石耗酸量的波动引起的催化剂强度和孔体积的 波动， 催化剂固质量含量为 25〜52%。
CN1270203A公幵了一种裂化催化剂的制备方法， 该方法包括将分子筛衆液、 铝溶 胶、 拟薄水铝石、粘土以及无机酸打浆混合均勾制成催化剂浆液， 然后喷雾干燥； 其特 征在于分子筛和 /或铝溶胶在粘土和无机酸之前加入， 无机酸在铝溶胶之后加入， 其余 物料的加入顺序没有特别的限制，并且所说催化剂浆液中含有一种减粘剂；其中所说减 粘剂为磷酸铵、磷酸氢二铵或磷酸二氢铵， 或者是它们的混合物， 减粘剂的加入量为催 化剂干基重量的 0. 1〜2% ; 所说无机酸与拟薄水铝石中的 A1203 的重量比为 0. 02~ 0. 25； 所说催化剂桨液的固重量含量为 30〜55%。 本发明提供的方法与现有技术的方 法相比，可以大大提高喷雾干燥前催化剂聚液的固含量，缩短成胶时间， 从而提高催化 剂的生产效率， 并降低能耗和生产成本。 上述专利方法虽然在一定程度上提高了 FCC催化剂喷雾成型前的胶体固质量含量， 为 25〜50%，但共同的特点是在制备过程中加入拟薄水铝石之后必须加入无机酸对拟薄 水铝石进行酸化胶溶反应， 因而不可避免地存在以下问题： 1 ) 由于无机酸在拟薄水铝 石之后加入，无机酸与拟薄水铝石之间的反应难以均匀发生，总是存在局部过度反应现 象， 导致浆液粘度迅速增加； 2) 当分子筛衆液先加入时， 后加入的无机酸会发生局部 破坏分子筛现象， 同时由于体系酸度不能控制太低（一般 pH大于 2. 8)， 拟薄水铝石难 以充分细化， 尤其是当分子筛含量较高时， 催化剂的抗磨损强度变差， 使用性能大受影 响； 3) 无机酸的加入严重腐蚀设备， 同时喷雾干燥时产生的酸性气体对周围环境产生 污染。 发明内容 本发明提供一种新型高固含量 FCC催化剂制备方法，即在催化剂制备过程中不加入 无机酸进行酸化拟薄水铝石反应， 而是采用机械物理髙速分散的方法对其进行分散细 化，有效解决拟薄水铝石胶溶状态对催化剂固含量和磨损指数的影响，可提高催化剂喷 雾成型前胶体固含量， 实现 FCC催化剂清洁高效的生产目标。
本发明提供的高固含量 FCC催化剂制备方法是:将制备催化剂所需的各种物料，水、 粘土、分子筛浆液、含铝粘结剂、拟薄水铝石和分散剂加入反应釜， 打浆混合均匀制成 催化剂浆液，然后在 25〜80°C下老化反应 10min〜100min，最后均质喷雾干燥制得高固 含量 FCC催化剂。本发明的技术特征在于拟薄水铝石在铝溶胶之后加入反应釜，并充分 打浆 20min〜120min， 之后用机械物理法将拟薄水铝石高速分散， 使拟薄水铝石粒度 D [V，0. 5]不大于 4 μ πι， 减小其对催化剂磨损指数的影响。 本方法对其余物料加入顺序 不限制。催化剂浆液的组成（按照催化剂干基质量计）为分子筛 15-50%，粘土 15〜60%， 拟薄水铝石 8〜30%， 含铝粘结剂 （按氧化铝计） 3〜18%， 所得奖液固含量为 35〜55%。 所说的催化剂浆液还含有 0〜8%的氧化稀土、 氧化锌、 氧化硅、 氧化镁、 氧化钛、 氧化 钒、氧化铜的一种或几种氧化物或者其前驱物； 其中优选的是氧化稀土、氧化硅或者它 们的前驱物。
本发明提供的高固含量 FCC催化剂制备方法，所说的分子筛为 Υ型沸石（包括各种 改性 Υ型沸石）或者是 Υ型沸石与 ZSM沸石、 β沸石、 Ω沸石、 MCM沸石、 SAP0沸石之 一或几个的混合物；其中优选 Υ型沸石或是 Υ型沸石与 ZSM-5沸石的混合物。其中所说 的改性 Υ型沸石为 HY、 NH4Y、 REY、 USY、 REUSY、 其它元素改性 Y沸石的一种， 或者它 们的混合物。
本发明提供的高固含量 FCC催化剂制备方法所说的粘土为髙岭土、海泡石、埃洛石、 蒙脱土中的一种或者是它们的混合物； 其中优选高岭土、埃洛石或是它们的混合物； 最 优选的是高岭土。
本发明提供的高固含量 rcc催化剂制备方法所说的拟薄水铝石可以为一水软铝石、 三水软铝石、 拜耳石， 优选的是一水软铝石。
本发明所述的含铝粘结剂包括铝溶胶、碱式氯化铝、酸改性高岭土， 可通过下述途 径之一获得：
( 1 ) 金属铝加盐酸 （或氯化铝）反应
(2) 结晶氯化铝热解过程
(3) 无机酸与高岭土或焙烧高岭土进行反应
(4) 其它途径， 如在压力下将盐酸和氢氧化铝反应
本发明提供的高固含量 FCC催化剂制备方法的优选方案是：铝溶胶在所有物料之前 加入， 拟薄水铝石在分子筛之前加入。如先将含铝粘结剂和水加入反应釜， 然后向其中 加入粘土和拟薄水铝石， 搅拌均匀后， 高速分散至物料粒度 [V， 0. 5]不大于 4 μ πι ， 再 加入分子筛浆液， 混合均匀后加入分散剂， 然后升温老化 lOmir！〜 lOOmin, 将所得浆液 喷雾干燥制得催化剂。
本发明提供的高固含量 FCC催化剂制备方法还可以是：先将含铝粘结剂和水加入反 应釜， 然后加入拟薄水铝石缓和反应 20πΰη〜120πΰη， 高速分散至物料粒度 [V， 0. 5]不 大于 4 u m， 最后加入分子筛与粘土， 搅拌均匀后， 加入分散剂， 搅拌均匀， 然后升温 老化 10min〜100min， 将所得浆液喷雾干燥制得催化剂。
本发明提供的高固含量 FCC催化剂制备方法还可以是：先将含铝粘结剂和化学水加 入反应釜， 然后加入拟薄水铝石进行缓和反应 20min〜120min， 高速分散至物料粒度 [¥，0. 5]不大于44 111 ， 然后升温老化 10min〜100min， 最后加入分子筛与粘土，搅拌均 勾后将所得浆液喷雾干燥制得催化剂。
具体实施方式
下面的实例对本发明的特点作进一步的说明，但本发明的保护范围并不受这些实例 的限制。
在各个实例中， 采用 C0le Parmer98936- 15旋转粘度计测量浆液的粘度， 测量条件 为： 转速 20rpm、 转轴 R4; 所得催化剂理化指标的测量方法如表 1所示。 催化剂分析评定方法
Figure imgf000007_0001
实例中所用原料规格如下-
1. 1#拟薄水铝石（山东铝厂， 灼减 39. 6%， 胶溶指数不小于 95%)、 2#拟薄水铝石（山 西铝厂， 灼减 40. 4%， 胶溶指数不小于 95°/。）、 高岭土 （灼减 25. 4%， 高岭石含量不 小于 85%)、 埃洛石（灼减 19. 2%, 埃洛石不小于 90%); 铝溶胶（含氧化铝 23. 0%); 氯化稀土（氧化稀土含量为 308. 75g/L)，水玻璃（含氧化硅 250g/L)， 均为工业合 格品， 采自兰州石化公司催化剂厂。
2. USY分子筛 （灼减 4. 8%, 晶胞参数 a。为 2. 452醒）、 REUSY分子筛 （灼减 5. 3%, 氧 化稀土 8. 5%, 晶胞参数 a。为 2. 462nm)、 REY (灼减 4. 4%, 氧化稀土 18. 1%)， 均为 合格工业品，采自兰州石化公司催化剂厂；高硅 ZSM- 5(灼减 5. 1%，硅铝比大于 300)， 工业合格品， 上海复旦大学生产。
实施例 1
在反应釜中加入 573克去离子水、 32ml的氯化稀土、 1441克铝溶胶和 1284克 1# 拟薄水铝石， 混合打浆 60分钟后再用高速分散机分散至物料粒度 [V， 0. 5]等于 3 μ ιη, 之后加入 1852克高岭土， 搅拌 30分钟， 之后再加入已用胶体磨磨细至平均粒径小于 5 微米的 1384克 REUSY分子筛、 19克复旦 ZSM- 5分子筛、 48克 β沸石与 2615克去离子水 混合的分子筛浆液， 搅拌 1小时后升温至 6CTC老化 60分钟， 然后均质喷雾干燥， 将所 得催化剂微球在 50(TC焙烧 0. 5小时， 然后加入 8倍去离子水， 搅拌均匀，在 8CTC洗涤 15分钟， 过滤干燥即得本发明方法制备的 FCC催化剂， 记做 A-l。
催化剂 A- 1喷雾浆液的固重量含量为 43. 5%， 浆液粘度为 4058厘泊， 所得催化剂 的磨损指数为 1. 5， 孔体积为 0. 43mL.g— 微反活性 65。
实施例 2 在反应釜中加入 929克去离子水、 1622克铝溶胶、 1156克 1#拟薄水铝石和 1902 克高岭土， 混合打浆 60分钟后， 再用高速分散机分散至物料粒度 [V, 0. 5]等于 2 μ ιη， 之后再加入已用胶体磨磨细至平均粒径小于 5微米的 1573克 REUSY分子筛、 43克复旦 ZSM 5分子筛与 2468克去离子水混合的分子筛浆液， 再加入 13ml的水玻璃， 搅拌 1小 时后升温至 60°C老化 120分钟， 然后均质喷雾干燥， 将所得催化剂微球在 50CTC焙烧 0. 5小时， 然后加入 8倍去离子水， 搅拌均匀， 在 80°C洗涤 15分钟， 过滤干燥即得本 发明方法制备的 FCC催化剂， 记做 A-2。
催化剂 A- 2喷雾浆液的固重量含量为 41%， 浆液粘度为 4319厘泊， 所得催化剂的 磨损指数为 1. 2， 孔体积为 0. 42mL.g 微反活性 65。
实施例 3
在反应釜中加入 3104克去离子水、 1465克 REUSY分子筛和 43克复旦 ZSM- 5分子 筛， 混合均匀后再依次加入 1261克铝溶胶、 2103克高岭土和 963克 1#拟薄水铝石， 搅 拌 100分钟后，用高速分散机分散至物料粒度 [V， 0. 5]等于 3. 6 μ πι，然后升温至 7(TC老 化 40分钟， 然后均质喷雾干燥， 将所得催化剂微球在 500°C焙烧 0. 5小时， 然后加入 8 倍去离子水， 搅拌均匀， 在 80Ό洗涤 15分钟， 过滤干燥即得本发明方法制备的 FCC催 化剂， 记做 A - 3。
催化剂 A- 3喷雾浆液的固重量含量为 44. 2%, 浆液粘度为 4835厘泊， 所得催化剂 的磨损指数为 1. 6， 孔体积为 0. 43mL g— 微反活性 64。
实施例 4
在反应釜中依次加入 1782克去离子水、 1662克铝溶胶和 2003克高岭土， 混合均 勾后再加入 1091克 1#拟薄水铝石，混合打浆 80分钟后再用高速分散机分散至物料粒度 [V, 0. 5]等于 1. 5 μ m， 之后再加入已用胶体磨磨细至平均粒径小于 5微米的 814克 USY 分子筛、 629克的 REUSY、 43克复旦 ZSM- 5分子筛、 18克 β沸石与 2482克去离子水混合 的分子筛浆液， 再加入 79ml的水玻璃， 搅拌 1小时后升温至 40Ό老化 80分钟， 然后 均质喷雾干燥， 将所得催化剂微球在 500°C焙烧 0. 5小时， 然后加入 8倍去离子水， 搅 拌均匀， 在 80°C洗涤 15分钟， 过滤干燥即得本发明方法制备的 FCC催化剂， 记做 A-4。
催化剂 A- 4喷雾浆液的固重量含量为 38%， 浆液粘度为 3549厘泊， 所得催化剂的 磨损指数为 0. 8， 孔体积为 0. 40mL 微反活性 65。
实施例 5 在反应釜中加入 1871克去离子水、 326克 USY分子筛和 764克的 REUSY分子筛， 混合均匀后再依次加入 1622克铝溶胶、 2603克高岭土和 899克 1#拟薄水铝石，搅拌 30 分钟后， 用高速分散机分散至物料粒度〔V， 0. 5]等于 2. 5 μ ηι， 然后升温至 80°C老化 15 分钟， 然后均质喷雾干燥， 将所得催化剂微球在 500°C焙烧 0. 5小时， 然后加入 8倍去 离子水，搅拌均勾，在 80°C洗漆 15分钟，过滤干燥即得本发明方法制备的 FCC催化剂， 记做 A-5。
催化剂 A-5喷雾浆液的固重量含量为 49%, 桨液粘度为 5327厘泊， 所得催化剂的 磨损指数为 1. 0， 孔体积为 0. 44mL 微反活性 65。
实施例 6
在反应釜中加入 1918克去离子水、 1124克 REUSY分子筛， 混合均匀后再依次加入 901克铝溶胶、 2904克高岭土和 770克 2#拟薄水铝石， 搅拌 40分钟后， 用高速分散机 分散至物料粒度〔V， 0. 5]等于 2. 0 μ ηι， 然后升温至 50°C老化 40分钟， 然后均质喷雾干 燥， 将所得催化剂微球在 500°C焙烧 0. 5小时， 然后加入 8倍去离子水， 搅拌均匀， 在 80Ό洗涤 15分钟， 过滤干燥即得本发明方法制备的 FCC催化剂， 记做 A - 6。
催化剂 A 6喷雾浆液的固重量含量为 52%， 浆液粘度为 4905厘泊， 所得催化剂磨 损指数为 1. 4， 孔体积为 0. ASmL-g—1, 微反活性 63。
实施例 7
在反应釜中加入 1370克去离子水、 1441克碱式氯化铝、 1156克 2#拟薄水铝石、 1502 克高岭土和 535克埃洛石，混合打桨 70分钟后，再用高速分散机分散至物料粒度 [V, 0. 5] 等于 2. 0 μ m， 之后再加入已用胶体磨磨细至平均粒径小于 5微米的 1528克 REUSY分子 筛、 43克复旦 ZSM- 5分子筛与 2397克去离子水混合的分子筛浆液， 搅拌 1小时后升温 至 7CTC老化 50分钟， 然后均质喷雾干燥， 将所得催化剂微球在 50CTC焙烧 0. 5小时， 然后加入 8倍去离子水， 搅拌均勾， 在 8(TC洗涤 15分钟， 过滤干燥即得本发明方法制 备的 FCC催化剂， 记做 A - 7。
催化剂 A- 7喷雾浆液的固重量含量为 40%， 浆液粘度为 4195厘泊， 所得催化剂的 磨损指数为 1. 8， 孔体积为 0. 42raL_g— 微反活性 66。
实施例 8
在反应釜中加入 2637克去离子水、 1483克 REUSY分子筛和 43克复旦 ZSM- 5分子 筛， 混合均匀后再依次加入 1261克碱式氯化铝、 83ml的氯化稀土、 2253克高岭土和 963克 1#拟薄水铝石， 搅拌 100分钟后， 用高速分散机分散至物料粒度 [V, 0. 5]等于 3. 0 m, 然后升温至 55Ό老化 120分钟， 然后均质喷雾干燥， 将所得催化剂微球在 500 °C焙烧 0. 5小时， 然后加入 8倍去离子水， 搅拌均匀， 在 80°C洗涤 15分钟， 过滤干燥 即得本发明方法制备的 FCC催化剂， 记做 A - 8。
催化剂 A- 8喷雾浆液的固重量含量为 46%， 浆液粘度为 5028厘泊， 所得催化剂的 磨损指数为 1. 5， 孔体积为 0. 42mL.g— '， 微反活性 65。 对比例 1
在反应釜中加入 1441克铝溶胶和 573克去离子水， 在搅拌的同时加入 1284克 1# 拟薄水铝石， 打浆 20分钟加入 1852克高岭土， ,搅拌打浆 40分钟后加入 305克浓度为 22%的盐酸，搅拌 30分钟后，加入已用胶体磨磨细至平均粒径小于 5微米的 1384克 REUSY 分子筛， 43克复旦 ZSM- 5分子筛与 2615克去离子水混合的分子筛柴液， 打浆 30分钟 后进行喷雾干燥， 将所得催化剂微球在 500°C焙烧 0. 5小时， 然后加入 8倍去离子水， 搅拌均匀， 在 80°C洗涤 15分钟， 过滤干燥即得 FCC催化剂， 记做 B - 1。
催化剂 B-1的喷雾浆液的固重量含量为 43. 2%， 浆液粘度为 13092厘泊， 所得催化 剂的磨损指数为 2. 7， 孔体积为 0. 40mLg— 微反活性 63。
数据表明，采用该方法提高固含量时催化剂浆液的粘度高、 流动性差， 在实际生产 中还可能存在催化剂抗磨损指数较高的问题；在喷雾成型中因加入大量盐酸所产生的酸 性气体部分破坏了分子筛结构， 降低了催化剂的微反活性。 对比例 2
在反应釜中加入 929克去离子水和 1902克高岭土，打浆 30分钟后加入 230克浓度 为 35%的盐酸， 混合均匀后反应 1小时， 在搅拌状态下加入 1156克 1#拟薄水铝石， 搅 拌后 0. 5小时后升温至 7CTC老化 1小时， 再加入 1622克铝溶胶， 搅拌 20分钟后， 加 入由 1573克 REUSY分子筛、 43克复旦 ZSM- 5分子筛与 2468克去离子水混合的分子筛 浆液， 打浆 30分钟后进行喷雾千燥， 将所得催化剂微球在 500°C焙烧 0. 5小时， 然后 加入去离子水， 搅拌均匀， 在 8(TC洗涤 15分钟， 过滤干燥即得 FCC催化剂， 记做 B-2。
催化剂 B- 2的喷雾浆液的固重量含量为 41%, 浆液粘度为 12653厘泊， 所得催化剂 的磨损指数为 1. 7， 孔体积为 0. 38mL_g→， 微反活性 62。
数据表明， 采用该方法制备的高固含量催化剂， 由于拟薄水铝石胶溶状态的限制， 催化剂固含量已达到极限， 浆液粘度大、流动性差， 增加了工业生产的难度； 同时由于 桨液粘度大， 分子筛与基质混合不均勾， 导致催化剂微反活性偏低。 对比例 3
在反应釜中加入用胶体磨磨至平均粒径小于 5微米的由 3065克去离子水与 1628 克 REUSY分子筛组成的浆液，在加入 1622克铝溶胶，然后在搅拌的同时加入 1522克高 岭土， 搅拌 15分钟后加入 1284克 1 #拟薄水铝石， 搅拌 20分钟加入 305克浓度为 22% 的盐酸， 打浆 30分钟后进行喷雾干燥， 将所得催化剂微球在 50CTC焙烧 0. 5小时， 然 后加入 8倍去离子水， 搅拌均匀， 在 80°C洗涤 15分钟， 过滤干燥即得 FCC催化剂， 记 做 B-3。
催化剂 B- 3的喷雾浆液的固重量含量为 38. 7%， 浆液粘度为 7248厘泊， 所得催化 剂的磨损指数为 3. 9， 孔体积为 0. 41mL_g— 微反活性 63。
数据表明当催化剂中分子筛含量较高时，如果采用该方法提高催化剂桨液固含量， 催化剂的抗磨损指数较高， 同时催化剂的微反活性偏低。 对比例 4
在反应釜中加入 503克去离子水、 1261克铝溶胶和 963克 Is拟薄水铝石， 高速分 散至物料粒度 [V， 0. 5]等于 7. 5 μ m， 之后再加入已用胶体磨磨细至平均粒径小于 5微米 的 1465克 REUSY分子筛、 43克复旦 ZSM- 5分子筛与 2691克去离子水混合的分子筛浆 液， 混合均匀后加入 2103克高岭土， 搅拌 1小时后升温至 50°C老化 60分钟， 然后均 质喷雾干燥， 将所得催化剂微球在 50CTC焙烧 0. 5小时， 然后加入 8倍去离子水， 搅拌 均勾， 在 8CTC洗涤 15分钟， 过滤干燥即得 FCC催化剂， 记做 A - 3。
催化剂 A 3的喷雾浆液的固重量含量为 44. 2%， 浆液粘度为 5638厘泊， 所得催化 剂的磨损指数为 3. 8， 孔体积为 Ο. ϋ1, 微反活性 65。
数据表明釆用该方法当拟薄水铝石粒径较大时， 催化剂磨损指数不能满足工业指 标。 工业实用性
对于采用拟薄水铝石和含铝粘结剂复合制备的半合成 FCC催化剂，拟薄水铝石的存 在状态是影响催化剂柴液固含量高低和催化剂抗磨损强度的重要因素。本发明的技术关 键是着力控制拟薄水铝石的存在状态，在催化剂制备过程中不加入无机酸酸化拟薄水铝 石， 而是利用催化剂制备体系游离的 H+离子将拟薄水铝石表面进行软化， 消耗游离的 H+离子， 降低 H+离子在喷雾干燥时对分子筛的破坏， 提髙催化剂的初始裂化活性； 同时 在制备过程中对已经软化的拟薄水铝石粒子进行机械物理分散，降低其对催化剂磨损指 数的影响，并使之与其他组分充分混合均勾，增加了基质组分对分子筛组分的活性协同 保护作用。 因此， 与现有技术相比， 在不影响催化剂衆液流动性的前提下， 按照本发明 提供的高固含量 FCC催化剂制备方法所制备的催化剂浆液固质量含量可提高至 35%〜 55%， 所得催化剂理化性能和反应性能不受负面影响。 该技术的实施可以显著提高催化 剂的生产效率， 减少生产过程中的污染物排放量， 并降低催化剂闪蒸能耗和生产成本。 评价结果表明，采用该技术制备的 FCC催化剂具有开放式的中大孔孔道结构，催化剂的 重油转化能力得到明显改善， 增加了高附加值产品的收率。 表 2是本发明方法制备催化剂与对比催化剂在固定流化床装置上的评价结果。固定 流化床反应温度 500Ό , 剂油比为 4， 空速 151 原料油为新疆油掺炼 30%的减压渣油。 表 2催化剂在固定流化床上的评价结果
Figure imgf000012_0001
Figure imgf000013_0001
从表 2可知，与对比例制备的催化剂 B-l和 B- 3相比，本发明工艺方法制备的催化 剂 A-1具有最好的重油转化能力和最高的总液收， 同时生成汽油的烯烃含量较低，催化 剂的总体反应性能得到改善。

Claims

权利要求书
1.一种高固含量流化催化裂化催化剂制备方法， 将制备催化剂所需的物料， 水、 粘土、分子筛浆液、含铝粘结剂和拟薄水铝石加入反应釜，打桨混合均勾制成催化剂浆 液， 然后在 25〜80°C下老化反应 10min〜100min， 最后均质喷雾干燥制得催化剂； 其特 征在于：所述的拟薄水铝石在含铝粘结剂加入反应釜后加入反应釜，并进行机械物理高 速分散， 使拟薄水铝石粒度 D[V，0. 5]不大于 4 μ πι， 其它物料加料顺序不限。
2.按照权利要求 1所述的高固含量流化催化裂化催化剂制备方法， 其特征在于： 所述的催化剂浆液的组成按干基质量计， 至少含有分子筛 15〜50%， 粘土 15〜60%， 拟 薄水铝石 8〜30%, 含铝粘结剂按氧化铝计为 3〜18%。
3.按照权利要求 1所述的高固含量流化催化裂化催化剂制备方法， 其特征在于： 按质量计， 所述的催化剂浆液中含有 0〜8%的氧化稀土、 氧化锌、 氧化硅、 氧化镜、 氧 化钛、 氧化钒、 氧化铜的一种或多种氧化物或者其前驱物。
4.按照权利要求 1所述的高固含量流化催化裂化催化剂制备方法， 其特征在于： 所述的分子筛为 Υ型沸石或者是 Υ型沸石与 ZSM沸石、 β沸石、 Ω沸石、 MCM沸石、 SAP0 沸石中的一种或多种混合物。
5.按照权利要求 1所述的高固含量流化催化裂化催化剂制备方法， 其特征在于. - 所述的分子筛为 Υ型沸石与 ZSM-5沸石的混合物。
6.按照权利要求 5所述的高固含量流化催化裂化催化剂制备方法， 其特征在于： 所述的 Υ型沸石为改性 Υ型沸石。
7.按照权利要求 1所述的高固含量流化催化裂化催化剂制备方法， 其特征在于- 所述的粘土为高岭土。
8.按照权利要求 1所述的高固含量流化催化裂化催化剂制备方法， 其特征在于： 所述的含铝粘结剂为铝溶胶或碱式氯化铝。
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