CN110523428B - Catalytic cracking catalyst containing NaY molecular sieve composite material and preparation method thereof - Google Patents

Catalytic cracking catalyst containing NaY molecular sieve composite material and preparation method thereof Download PDF

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CN110523428B
CN110523428B CN201810504993.4A CN201810504993A CN110523428B CN 110523428 B CN110523428 B CN 110523428B CN 201810504993 A CN201810504993 A CN 201810504993A CN 110523428 B CN110523428 B CN 110523428B
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molecular sieve
composite material
nay molecular
soil
kaolin
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CN110523428A (en
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胡清勋
刘宏海
王久江
田爱珍
张忠东
张莉
赵晓争
熊晓云
曹庚振
赵红娟
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Petrochina Co Ltd
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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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—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
    • B01J29/80—Mixtures of different zeolites
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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

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

Abstract

The invention provides a catalytic cracking catalyst containing NaY molecular sieve composite material and a preparation method thereof, wherein the preparation method mainly comprises the following steps: respectively roasting kaolin at high temperature and low temperature to obtain high soil and partial soil, carrying out alkali treatment on the high soil, mixing the high soil with a guiding agent and alkali liquor, carrying out hydrothermal crystallization for a period of time, adding the partial soil after acid treatment, continuing crystallization, filtering, washing with water, and drying to obtain the NaY molecular sieve composite material. The method does not reduce the crystallinity of the molecular sieve under the condition of not adding an additional silicon source, the silicon-aluminum ratio is more than 5.5, and the volume of the mesopores and the macropores of the composite material accounts for more than 35 percent of the total pore volume. After the NaY molecular sieve composite material is modified, it is mixed with clay, other molecular sieve and adhesive, and then pulped, spray-dried and washed, so that the prepared catalyst gasoline has high yield, low coke yield and strong heavy oil cracking capability.

Description

Catalytic cracking catalyst containing NaY molecular sieve composite material and preparation method thereof
Technical Field
The invention relates to a catalytic cracking catalyst containing a NaY molecular sieve composite material and a preparation method thereof, in particular to a catalytic cracking catalyst containing a NaY molecular sieve and a kaolin composite material and a preparation method thereof.
Background
The world's trend toward heavy crude oil has led to an increasing desire by refiners to convert heavy residues to lighter, more expensive products. Fluid Catalytic Cracking (FCC) is one of the most effective and economical methods for upgrading heavy raw materials at present, the proportion of the FCC raw materials mixed into residual oil is increased day by day, the yield of target products is increased by improving the conversion rate of heavy oil, and the method has great significance for improving the economic benefit of an oil refinery.
For the catalytic cracking reaction of heavy oil, the catalyst is a key technology, and the Y-type molecular sieve is still the most important active component of the catalyst. The gel guiding agent method is the main technical method for industrially producing the NaY molecular sieve at present. However, as crude oil heaviness increases, the content of polycyclic compounds in the catalytic cracking feedstock increases significantly, and their diffusion capacity in the molecular sieve channels decreases significantly. While the pore size of NaY molecular sieves is only 0.74nm for processing heavy fractions, the accessibility of the catalyst active sites will be a major obstacle to cracking of the polycyclic compounds contained therein. The solution of manufacturing mesopores in molecular sieve crystals is often adopted at present, and by this method, the micropore channels of the molecular sieve can be shortened, and more pore openings can be exposed, so as to improve the accessibility of the active center of the molecular sieve. However, this method causes the crystallinity and specific surface area of the molecular sieve to be significantly reduced. In order to overcome the defect of small pore diameter of microporous materials, the synthesis of mesoporous materials is increasingly paid attention by people. However, the mesoporous material needs to use an expensive template agent in the synthesis process, and the acidity and hydrothermal stability of the mesoporous material are far from the use requirements of catalytic cracking.
The natural clay minerals such as kaolin and the like are widely applied in the preparation process of the catalytic cracking catalyst due to rich resources and low cost. The NaY molecular sieve composite material prepared by adopting the in-situ crystallization technology and taking the kaolin fine powder as the raw material has a plurality of advantages: in the in-situ crystallization process, a microporous Y molecular sieve and a medium-large pore alkali modified kaolin material are simultaneously generated, and the distribution of mesopores is concentrated; the molecular sieve is uniformly distributed on the pore wall of the modified kaolin, and the crystal grain is smaller than the crystal grain of NaY synthesized by a gel method, so that the active surface of the molecular sieve is improved, the accessibility of the active center of the catalyst is greatly improved, meanwhile, the rich meso-macroporous structure improves the diffusion speed of target components, and the synergy and relay effects of the molecular sieve and a matrix in the cracking reaction process are enhanced; due to the special process of in-situ crystallization molecular sieve synthesis and the special combination mode of the in-situ crystallization molecular sieve and the modified kaolin, the NaY molecular sieve composite material shows excellent performance in the catalytic cracking reaction process.
Research on this aspect has been ongoing since the 1964 publication of USP3119659 for the synthesis of molecular sieves starting from kaolin. Early work was primarily directed to the synthesis of pure phase molecular sieves, such as USP3574538, which discloses a process for synthesizing Y-type molecular sieves from kaolin clay by calcining the kaolin clay to amorphous metakaolin clay, adding a quantity of sodium silicate and sodium hydroxide to bring the silica/alumina molar ratio to approximately that of the molecular sieve to be synthesized, then adding 0.1 to 10 wt.% of a directing agent, and crystallizing at 60 to 110 ℃ to obtain very pure Y-type molecular sieves having a silica/alumina molar ratio of 4.5 to 5.95. EP0209332A discloses a method for preparing NaY molecular sieve by in-situ crystallization of kaolin under stirring, which comprises roasting kaolin at 550-925 deg.C to obtain metakaolin, adding sodium source compound and water, adjusting the molar ratio of sodium oxide/alumina to 2.1-15/1 and the molar ratio of water/sodium oxide to 15-70/1, crystallizing the reactant under stirring to form NaY molecular sieve, and optionally adding guiding agent. The average grain diameter of the synthesized NaY molecular sieve is 3000nm, and the purity of NaY reaches 97 percent.
Patent CN1334142A discloses a method for synthesizing molecular sieve from kaolin, which is characterized in that kaolin is used as raw material, a part of kaolin raw powder is calcined at high temperature to obtain high-temperature calcined clay, the other part of kaolin is calcined at lower temperature to obtain metakaolin, and after two types of calcined kaolin are mixed according to a certain ratio or in the presence of one of the calcined kaolin, crystallization reaction is carried out under hydrothermal condition to obtain a crystallization product with NaY molecular sieve content of 40-90% and silica-alumina ratio of 3.5-5.5. Different types of modified molecular sieves can be prepared by different post-treatment methods for the crystallized product.
The patent CN101746778A discloses a method for preparing a NaY type molecular sieve composite material with a double-pore structure by kaolin in-situ crystallization, the method adopts a two-stage crystallization mode, in the prepared composite material, the NaY molecular sieve accounts for 40-85%, the secondary structure of the composite material is a similar sphere, the similar sphere is formed by alternately stacking the NaY type molecular sieve generated by crystallization and a metakaolin amorphous intermediate generated in a crystal transformation process, gaps and holes exist, a nest channel is arranged in the sphere, the granularity is 3000-25000nm, and the surface area measured by a BET method is 280-800 m-one-shot2The volume of the total pores is 0.35-0.45ml/g, the pore volume of the medium and large pores with the diameter of 1.7-300nm is 0.05-0.150ml/g, and the pore volume accounts for 20-35% of the total pore volume. However, the medium and large pores of the composite material are mainly stacking pores, which have certain influence on stability, and two sections of crystallization are needed, so that the process is complicated.
Patent CN102757065A discloses a method for synthesizing a hybrid composite material of NaY molecular sieve and kaolin, which comprises in-situ crystallization, and controlling the proportion of high clay to low clay, aging time, aging temperature and crystallization time to synthesize the hybrid composite material of NaY molecular sieve and kaolin. The method is characterized in that a NaY molecular sieve is directly obtained by hydrothermal crystallization of raw materials without using a guiding agent or pretreating kaolin, the crystallinity of the molecular sieve is 35-70%, and the silicon-aluminum ratio is 3.5-4.2.
Patent CN101618881A discloses a method for rapid in-situ crystallization synthesis of faujasite, which comprises dissolving or mixing alkaline sodium salt, aluminum-containing compound and water glass in water; then adding kaolin into the mixture for pulping, aging the mixed slurry under stirring, and adding a metered NaY molecular sieve guiding agent; and (3) transferring the mixture into a reaction kettle for crystallization, wherein the crystallization time is less than 20 hours. The method synthesizes the faujasite by in-situ crystallization in a mode of adding an aluminum source, can greatly shorten crystallization time and improve product properties, and the synthesized faujasite can be used as a component of catalysts for hydrocracking and the like.
Chinese patent CN1709794A discloses a method for synthesizing NaY zeolite composite material, which comprises the steps of roasting and dehydrating kaolin at the temperature of 500-900 ℃ to convert the kaolin into metakaolin, crushing the metakaolin into powder with the particle size of less than 230 microns, treating the powder with alkali or acid, adding sodium silicate, a guiding agent, sodium hydroxide and water, crystallizing, filtering, collecting mother liquor, and directly recycling the collected mother liquor to play the role of partial or all of the sodium silicate and the sodium hydroxide for utilization.
Patent CN101676207A discloses a method for preparing NaY molecular sieve, which comprises mixing kaolin and bentonite, roasting, or respectively roasting and mixing, and then mixing with silicon source, directing agent, sodium hydroxide and water to prepare molecular sieve synthetic liquid for hydrothermal crystallization.
CN1533982 and USP7067449 use metakaolin calcined at 690 ℃ of 500-one temperature as an aluminum source and part of silicon source synthesized by NaY molecular sieve, add sodium silicate as an additional silicon source, add a guiding agent, sodium hydroxide solution and water to prepare Na with a molar ratio of (1-2.5)2O∶(4-9)SiO2∶Al2O3∶(40-100)H2And (3) crystallizing the reaction raw material of O under stirring at 88-98 ℃, and filtering to obtain the molecular sieve with the NaY mass percentage of 30-85%.
At present, the catalytic cracking catalyst is prepared by synthesizing a NaY molecular sieve composite material by taking kaolin as a raw material and then preparing the NaY molecular sieve composite material, and the catalyst has good heavy oil conversion capacity and excellent target product selectivity. However, in the reports, a certain amount of additional chemical silicon source or aluminum source is required to be added in the process of synthesizing the NaY molecular sieve composite material, and the utilization rates of the silicon source and the aluminum source are low, so that the cost is increased; the silicon-aluminum ratio of the skeleton of the NaY molecular sieve in the composite material is lower, usually about 5.0, and generally lower than 5.2, and the silicon-aluminum ratio of the Y-type molecular sieve has a direct relation with the ratio of cracking/hydrogen transfer activity on one hand, so that the silicon-aluminum ratio of the skeleton is improved, the Al center density is reasonably reduced, the relative strength of an acid center is improved, the ratio of cracking/hydrogen transfer activity is favorably changed, the generation of catalytic coke is reduced, and the octane number of a product is improved; on the other hand, the silicon-aluminum ratio of the framework of the NaY molecular sieve is closely connected with the hydrothermal stability of the NaY molecular sieve, the NaY molecular sieve needs to undergo the processes of exchange, roasting and the like to cause partial crystallinity loss, and in the using process of the catalytic cracking catalyst, the framework of the molecular sieve can be dealuminated by the hydrothermal environment in a regenerator, so that the activity stability of the catalyst is poor. The preparation method for directly synthesizing the NaY molecular sieve with high silicon-aluminum ratio mainly comprises a template method and a non-template method, wherein the NaY molecular sieve prepared by the template method has high silicon-aluminum ratio, but has high cost, expensive template agent, long crystallization time, crystallization time of dozens of days and low yield. The non-template method is that no template agent is added into the gel, and the silicon-aluminum ratio of the NaY molecular sieve is improved by adjusting the proportion of silicon source, aluminum source, alkali and water in the reactant gel, adjusting the crystallization time and the preparation method of the guiding agent or the crystal seed. However, the silicon source such as white carbon black and the like used by the method is relatively expensive, the utilization rate of the silicon source is low, and the silicon-aluminum ratio of the product is not greatly improved. In addition, the medium-large pore structure is helpful for the diffusion of target components, the medium-large pore structure of the NaY molecular sieve composite material prepared by taking kaolin as a raw material is not rich enough at present, the medium-large pore volume/the total pore volume is generally less than 35%, and the pore structure needs to be improved. The addition of the templating agent can improve the pore structure of the composite, but can add cost and make handling difficult. The NaY molecular sieve composite material with the silicon-aluminum ratio of more than 5.5 and the medium-large pore volume/total pore volume of more than 35 percent is synthesized by taking kaolin as a raw material without adding a chemical silicon-aluminum source and a template agent, and then the NaY molecular sieve composite material is prepared into the catalytic cracking catalyst, so that the catalyst has good industrial prospect.
Disclosure of Invention
The invention aims to provide a catalytic cracking catalyst containing a NaY molecular sieve composite material and a preparation method thereof.
A preparation method of a catalytic cracking catalyst containing a NaY molecular sieve composite material comprises the following steps: (1) roasting a part of kaolin at 940-1000 ℃ for 1-3 hours to obtain high soil, and roasting the other part of kaolin at 700-900 ℃ for 1-3 hours to form partial soil; (2) mixing partial soil and inorganic acid solution, and treating at 90-95 deg.C for 1-6 hr, wherein the partial soil (dry basis) is mixed with inorganic acid H+The mass ratio of partial soil (dry basis) to high soil (dry basis) is 80-160: 10.1-10: 1; (3) mixing high soil and alkali solution, and treating at 90-95 deg.C for 1-6 hr, wherein the high soil (dry basis) is OH-The mass ratio is 4-11: 1, then the guiding agent and the alkali liquor are added to prepare the Na with the raw material molar ratio of (5-10)2O∶Al2O3∶(8-25)SiO2∶(80-380) H2Crystallizing the mixture of O, adding the treated meta-soil in the step (2) after crystallizing for 4-6 hours, continuously crystallizing for 16-32 hours, filtering, washing with water, and drying to obtain a composite material containing the NaY molecular sieve; (4) modifying the composite material obtained in the step (3) according to a commonly used industrial two-way two-baking process to obtain a modified NaY molecular sieve composite material; (5) mixing and pulping the modified NaY molecular sieve composite material, clay, other molecular sieves and a binder, and spray-drying to obtain the catalytic cracking catalyst containing the NaY molecular sieve composite material.
The invention discloses a preparation method of a catalytic cracking catalyst containing a NaY molecular sieve composite material, which comprises the step (2) of mixing partial soil and an inorganic acid solution, preferably for 1-3 hours, wherein the partial soil (dry basis) is mixed with the inorganic acid H+The mass ratio is 80-160: 1, preferably 100-120: 1, the mass ratio of partial soil (dry basis) to high soil (dry basis) is 0.1-10: 1, preferably 0.5-2: 1.
The invention discloses a preparation method of a catalytic cracking catalyst containing a NaY molecular sieve composite material, wherein the crystallinity of the NaY molecular sieve composite material in the step (3) is 60-70%, the silicon-aluminum ratio is more than 5.5, and the volume of medium and large pores accounts for more than 35% of the total pore volume.
The invention discloses a preparation method of a catalytic cracking catalyst containing a NaY molecular sieve composite material, which comprises the following steps of (3) mixing kaolin and alkali liquor, treating for 1-6 hours at 90-95 ℃, preferably for 1-3 hours, wherein the kaolin (dry basis) is mixed with the alkali liquor OH-The mass ratio is 4-11: 1, preferably 6-8: 1.
The invention discloses a preparation method of a catalytic cracking catalyst containing a NaY molecular sieve composite material, wherein in the preparation method of the NaY molecular sieve composite material, partial soil and high soil are respectively mixed with inorganic acid and alkali liquor, and the liquid-solid ratio of the inorganic acid to the partial soil (dry basis) and the liquid-solid ratio of the alkali liquor to the high soil (dry basis) are 3-1.5: 1.
The invention discloses a preparation method of a catalytic cracking catalyst containing a NaY molecular sieve composite material, wherein inorganic acid in the step (2) is selected from any one of hydrochloric acid, sulfuric acid and nitric acid; the alkali liquor in the step (3) is selected from one of sodium hydroxide solution and potassium hydroxide solution.
The invention discloses a preparation method of a catalytic cracking catalyst containing a NaY molecular sieve composite material, wherein in the step (1), kaolin comprises soft kaolin, hard kaolin and coal gangue, wherein the particle size is 2.5-3.5 mu m, the content of crystal kaolinite is higher than 80%, the content of iron oxide is lower than 1.7%, and the sum of sodium oxide and potassium oxide is lower than 0.5%.
The invention discloses a preparation method of a catalytic cracking catalyst containing a NaY molecular sieve composite material, wherein in the preparation method of the NaY molecular sieve composite material, a directing agent is only required to be a common directing agent, for example, the directing agent is prepared according to the directing agent composition in CN1232862A, and the material molar ratio composition of the directing agent recommended by the invention is as follows: (14-16) SiO2:(0.7～1.3)Al2O3:(14～16)Na2O:(300～330)H2And O. The addition amount of the guiding agent is 1-10% of the weight of the synthetic material.
The invention discloses a preparation method of a catalytic cracking catalyst containing a NaY molecular sieve composite material, wherein in the preparation method of the NaY molecular sieve composite material, the post-modification of the composite material is carried out according to a two-way two-baking process commonly used in industry, and the modification process is well known by persons of ordinary skill in the art.
The invention discloses a preparation method of a catalytic cracking catalyst containing NaY molecular sieve composite material, wherein the clay is selected from one or more of clays which are commonly used as catalytic cracking catalyst components, such as one or more of kaolin, halloysite, acid-extracted kaolin, alkali-extracted kaolin, montmorillonite, diatomite, rectorite, halloysite, sepiolite and bentonite, and the clays are well known to those skilled in the art.
The invention discloses a preparation method of a catalytic cracking catalyst containing a NaY molecular sieve composite material, wherein other molecular sieves comprise one or more of REY, REUSY and ZSM-5.
The invention discloses a preparation method of a catalytic cracking catalyst containing a NaY molecular sieve composite material, wherein the binder is selected from one or more of binders commonly used in cracking catalysts, such as one or more of silica sol, aluminum sol, modified silica sol, modified aluminum sol, amorphous silica-alumina gel and pseudo-boehmite, and is preferably pseudo-boehmite and/or aluminum sol.
The catalyst prepared by the preparation method of the catalytic cracking catalyst containing the NaY molecular sieve composite material comprises, by mass, 100% of the catalyst, 30-70% of the modified NaY molecular sieve composite material on a dry basis, 10-80% of clay on a dry basis, 0-30% of one or more other molecular sieves on a dry basis, and 5-40% of a binder on an oxide basis; preferably, the catalyst comprises, by mass, 100% of the modified NaY molecular sieve composite material in terms of dry basis 35-60%, clay in terms of dry basis 20-65%, one or more other molecular sieves in terms of dry basis 0-15%, and a binder in terms of oxide 5-30%.
In the preparation method of the NaY molecular sieve composite material, in the crystallization stage of the molecular sieve composite material, high soil is treated by alkali and partial soil is treated by acid, active silicon and aluminum in the high soil and the partial soil which are rich in active silicon and active aluminum are extracted, and the extracted silicon and aluminum enter a liquid phase and can be used as a raw material for in-situ growth of the NaY molecular sieve; the extracted high soil and partial soil have rich medium-large pore structures, the specific surfaces of the pore channels can provide growing points for the NaY molecular sieve, the existing pore channel structures are beneficial to mass transfer of crystallization reaction, and if the high soil and the partial soil are not subjected to alkali and acid treatment before crystallization, both pore-forming extraction and crystal growth are carried out in the crystallization process, so that the crystallization reaction efficiency is obviously influenced. In the method, the high soil subjected to alkali treatment, the guiding agent and the alkali liquor are mixed firstly, and after crystallization for a period of time, the meta soil subjected to acid treatment is added, so that a chemical silica-alumina source is not required to be added, alkali treatment is performed on the high soil, a silicon source is activated, and the utilization rate of the silicon source is improved; generally, under the condition that the fed silicon-aluminum ratio is not changed, the silicon-aluminum ratio of a product can be improved by reducing the alkalinity, but the low alkalinity causes difficulty in crystal nucleus formation, the induction period is prolonged, and the crystallization time is prolonged, so that after crystallization is carried out for a certain time, the acid-treated metasoil is added, the material can be fed with high alkalinity, crystallization is carried out for a certain time, and after crystal nuclei are formed, an acid substance and an aluminum source are added, so that the crystallization time is shortened, and the silicon-aluminum ratio of the product is ensured. Therefore, the catalytic cracking catalyst prepared from the NaY molecular sieve composite material with rich medium-large pore structure and high silica-alumina ratio has strong heavy oil conversion capability and good coke selectivity.
Detailed Description
The present invention will be further illustrated by the following specific examples, but the present invention is not limited to the following specific examples.
Source of raw materials
1. Kaolin: the medium particle size is 3.2 μm, the kaolinite content is 82%, the iron oxide content is 0.74%, and the sum of the potassium oxide content and the sodium oxide content is 0.35%. A guiding agent: the preparation method is characterized by being prepared according to the guiding agent composition in CN 1232862A.
2. Water glass (SiO)2 250.3g/L，Na2O87.4 g/L), alkali liquor (NaOH 14 m%), NaY molecular sieve and REY (RE)2O3 10.51％，Na2O 0.30％)、REUSY(RE2O3 4.02％，Na2O 1.24％)、 ZSM-5(Na20.10% of O, 14.6% of kaolin (ignition), 15.4% of diatomite and alumina sol (Al)2O319.4 percent), pseudo-boehmite (burned off by 17.0 percent), rare earth nitrate (RE)2O3230.5g/L) high alkali sodium metaaluminate: (Na)2O 281.1g/L，Al2O340.9g/L) are all industrial products and are collected from catalyst factories of Lanzhou petrochemical company.
3. Hydrochloric acid (HCl 36-37 m%) sulfuric acid (H) from Mimi European Chemicals Co., Tianjin2SO498 m%), nitric acid (HNO)398m percent), potassium hydroxide and ammonium chloride are permanent chemical reagents in TianjinManufactured by limited company.
Analytical method
The crystallinity and the silicon-aluminum ratio of the NaY molecular sieve in the composite material are determined by an X-ray powder diffraction method, and the pore volume of the composite material is determined by a low-temperature nitrogen adsorption-desorption method. (see the analysis methods in petrochemical analysis (RIPP methods), Yanggui, published by scientific publishers, 1990), the ratio of the synthetic liquid to the solid was calculated according to the weight ratio of the liquid to the solid in the raw material. The catalyst reaction performance was evaluated by using an ACE apparatus (Advanced Cracking Evaluation, Kayser, R + Multi Mode type reactor) under the following conditions: the catalyst is aged for 17 hours at 800 ℃ and 100 percent of water vapor, the reaction temperature is 530 ℃, the catalyst-oil ratio is 5, the raw oil is Xinjiang reduced pressure wide-cut wax oil and Xinjiang reduced pressure residual oil, the slag mixing ratio is 30 percent, and the properties of the raw oil are shown in Table 1.
TABLE 1 Properties of the feed oils
Figure DEST_PATH_IMAGE001
Figure DEST_PATH_IMAGE002
*: the above results are measured by the research and development center of lubricating oil in Lanzhou Petroleum
Example 1
The guiding agent is prepared by mixing 1.54kg of water glass and 0.945kg of high-alkali sodium metaaluminate and standing for 15 hours at 35 ℃. Roasting one part of kaolin at 940 ℃ for 2.4 hours to obtain high soil, roasting the other part of kaolin at 800 ℃ for 2.8 hours to obtain partial soil, uniformly mixing 2kg of partial soil and 3.65kg of hydrochloric acid solution with the concentration of 20 wt%, and stirring at 92 ℃ for 2 hours; mixing 2kg of kaolin and 4.6kg of alkali liquor uniformly, stirring for 2.5 hours at 90 ℃, sequentially adding 1.4kg of directing agent and 0.7kg of alkali liquor, crystallizing for 4 hours at 92 ℃, adding the treated meta-soil solution, continuously crystallizing for 20 hours, filtering, washing with water, and drying to obtain the NaY molecular sieve composite material. The crystallinity of NaY molecular sieve in the composite material is 68 percent and the crystallinity of SiO is measured by an X-ray diffraction method2/Al2O3Is 5.78, specific surface 609m2(g) total pore volume of 0.44m3Per g, medium and large pore volume of 0.16m3/g。
The NaY molecular sieve composite material is modified according to a double-cross double-baking process, and composite materials with different rare earth contents can be prepared according to different rare earth feeding amounts. The NaY molecular sieve composite material prepared by the method is modified, and RE in the modified composite material2O3The content of Na is 4.04 percent2The O content was 1.11% and the crystallinity was 41%. Mixing and pulping 1.7kg of kaolin (dry basis), 2.54kg of modified NaY molecular sieve composite material, 0.2kg of ZSM-5 molecular sieve, 3.26kg of alumina sol and 7.5kg of deionized water, stirring for 1.5 hours, carrying out colloid mill, spray drying and forming, roasting, washing, filtering and drying to obtain the catalytic cracking catalyst S-1 containing the NaY molecular sieve composite material.
Example 2
The guiding agent is prepared by mixing 0.624kg of water glass and 0.416kg of high-alkali sodium metaaluminate and standing for 20 hours at 33 ℃. Roasting part of kaolin at 970 ℃ for 1.5 hours to obtain high soil, roasting the other part of kaolin at 830 ℃ for 2 hours to obtain partial soil, uniformly mixing 2.5kg of partial soil and 4.3kg of sulfuric acid solution with the concentration of 18 weight percent, and stirring at 94 ℃ for 1 hour; 1.5kg of high soil and 4.2kg of alkali liquor are mixed uniformly, stirred for 1.2 hours at 93 ℃, then 0.8kg of directing agent and 1.0kg of alkali liquor are added in sequence, crystallized for 6 hours at 93 ℃, then the treated partial soil solution is added, and the crystallization is continued for 28 hours, and then the NaY molecular sieve composite material is obtained after filtration, washing and drying. The crystallinity of NaY molecular sieve in the composite material is 70 percent and the crystallinity of SiO is measured by an X-ray diffraction method2/Al2O3Is 5.67, the specific surface 623m2(g) total pore volume of 0.41m3Per g, medium and large pore volume of 0.15m3/g。
The NaY molecular sieve composite material prepared by the method is modified, and RE in the modified composite material2O3The content of Na is 1.84 percent2The O content was 1.20% and the crystallinity was 45%. Mixing and pulping 2.53kg of diatomite (dry basis), 1.06kg of modified NaY molecular sieve composite material, 0.51kgREY molecular sieve, 2.39kg of alumina sol, 0.55kg of pseudo-boehmite and 7.1kg of deionized water, and stirring for 1.3 hoursAfter passing through a colloid mill, spray drying and forming, roasting, washing, filtering and drying to obtain the catalytic cracking catalyst S-2 containing the NaY molecular sieve composite material.
Example 3
The guiding agent is prepared by mixing 1.53k g water glass and 0.98kg high-alkali sodium metaaluminate and standing at 34 ℃ for 32 h. Roasting one part of kaolin at 950 ℃ for 2 hours to obtain high soil, roasting the other part of kaolin at 900 ℃ for 1.5 hours to obtain partial soil, uniformly mixing 1.0kg of partial soil and 2.65g of nitric acid solution with the concentration of 22 weight percent, and stirring for 3 hours at 92.5 ℃; uniformly mixing 3.0kg of kaolin with 4.55g of alkali liquor, stirring for 6 hours at 95 ℃, sequentially adding 1kg of directing agent and 0.85kg of alkali liquor, crystallizing for 5 hours at 92 ℃, adding the treated meta-soil solution, continuously crystallizing for 18 hours, filtering, washing with water, and drying to obtain the NaY molecular sieve composite material. The crystallinity of NaY molecular sieve in the composite material is 66 percent and the crystallinity of SiO is measured by an X-ray diffraction method2/Al2O3Is 5.81, the specific surface 607m2(g) total pore volume of 0.46m3Per g, medium and large pore volume of 0.17m3/g。
The NaY molecular sieve composite material prepared by the method is modified, and RE in the modified composite material2O3The content of Na is 8.28 percent2The O content was 1.18% and the crystallinity was 43%. Mixing and pulping 1.12kg of kaolin (dry basis), 0.89kg of diatomite (dry basis), 2.28kg of modified NaY molecular sieve composite material, 0.24kg of gREUSY molecular sieve, 0.21kg of ZSM-5 molecular sieve, 1.57kg of alumina sol and 7.3kg of deionized water, stirring for 1.7 hours, carrying out spray drying and forming after passing through a colloid mill, roasting, washing, filtering and drying to obtain the catalytic cracking catalyst S-3 containing the NaY molecular sieve composite material.
Example 4
The guiding agent is prepared by mixing 2.53k g water glass and 1.59k g high-alkali sodium metaaluminate and standing for 12h at 36 ℃. Roasting part of kaolin at 990 deg.C for 1.2 hr to obtain high clay, roasting the other part at 720 deg.C for 2.8 hr to obtain partial clay, mixing 3kg of partial clay with 6.85kg of 20 wt% hydrochloric acid solution, and stirring at 90.5 deg.C for 5.5 hr; mixing 1kg of high soil with 1.85kg of alkali liquor uniformly, stirring at 90.5 DEG CAnd after 5.8 hours, sequentially adding 0.8kg of directing agent and 3.5kg of alkali liquor, crystallizing at 91 ℃ for 4.2 hours, adding the treated meta-soil solution, continuously crystallizing for 31 hours, filtering, washing with water, and drying to obtain the NaY molecular sieve composite J4. The crystallinity of NaY molecular sieve in the composite material is 63 percent and the crystallinity of SiO is measured by an X-ray diffraction method2/Al2O3Is 5.61, the specific surface 602m2(g) total pore volume of 0.43m3Per g, medium and large pore volume of 0.16m3/g。
The NaY molecular sieve composite material prepared by the method is modified, and RE in the modified composite material2O3The content of Na is 3.65 percent2The O content was 1.14% and the crystallinity was 42%. Mixing and pulping 2.41kg of kaolin (dry basis), 1.51kg of modified NaY molecular sieve composite material, 0.83kg of gREY molecular sieve, 0.3kg of ZSM-5 molecular sieve, 2.78kg of alumina sol and 7.0kg of deionized water, stirring for 1.1 hours, passing through a colloid mill, spray drying and forming, roasting, washing, filtering and drying to obtain the catalytic cracking catalyst S-4 containing the NaY molecular sieve composite material.
Example 5
The guiding agent is prepared by mixing 1.46kg of water glass and 1.04kg of high-alkali sodium metaaluminate and standing for 28 hours at 33 ℃. Roasting a part of kaolin at 960 ℃ for 2.5h to obtain high soil, roasting the other part of kaolin at 780 ℃ for 2.2h to obtain partial soil, uniformly mixing 0.5kg of partial soil and 1.45kg of nitric acid solution with the concentration of 22 wt%, and stirring at 94.5 ℃ for 1 h; 3.5kg of high soil and 7.25kg of potassium hydroxide solution with the concentration of 10 weight percent are uniformly mixed, stirred for 2 hours at the temperature of 92 ℃, then sequentially added with 1.35kg of directing agent and 0.35kg of alkali liquor, crystallized for 5 hours at the temperature of 92.5 ℃, added with the treated partial soil solution, continuously crystallized for 24 hours, filtered, washed and dried to obtain the NaY molecular sieve composite material J5. The crystallinity of NaY molecular sieve in the composite material is 61 percent and the crystallinity of SiO is measured by an X-ray diffraction method2/Al2O3Is 5.86, specific surface 592m2(g) total pore volume of 0.47m3Per g, medium and large pore volume of 0.18m3/g。
The NaY molecular sieve composite material prepared by the method is modified, and RE in the modified composite material2O3The content of Na is 5.17 percent2The O content was 1.16% and the crystallinity was 44%. Mixing and pulping 1.34kg of kaolin (dry basis), 1.07kg of diatomite (dry basis), 2.74kg of modified NaY molecular sieve composite material, 0.29kg of magnesium EUSY molecular sieve, 0.24kg of ZSM-5 molecular sieve, 1.88kg of alumina sol and 8.76kg of deionized water, stirring for 1.9 hours, carrying out spray drying and forming after passing through a colloid mill, roasting, washing, filtering and drying to obtain the catalytic cracking catalyst S-5 containing the NaY molecular sieve composite material.
Example 6
The guiding agent is prepared by mixing 2.28k g water glass and 1.35k g high-alkali sodium metaaluminate and standing at 38 ℃ for 19 h. Roasting a part of kaolin at 975 ℃ for 1.3 hours to obtain high soil, roasting the other part of kaolin at 835 ℃ for 1.7 hours to obtain partial soil, uniformly mixing 1.2kg of partial soil and 2.7kg of sulfuric acid solution with the concentration of 18 weight percent, and stirring at 93.5 ℃ for 1.4 hours; uniformly mixing 2.8kg of kaolin with 5.2kg of alkali liquor, stirring for 1.2 hours at the temperature of 92 ℃, sequentially adding 1.05kg of directing agent and 1.9kg of alkali liquor, crystallizing for 5.7 hours at the temperature of 93.7 ℃, adding the treated meta-soil solution, continuously crystallizing for 27 hours, filtering, washing with water, and drying to obtain the NaY molecular sieve composite material. The crystallinity of NaY molecular sieve in the composite material is 69 percent and the crystallinity of SiO is measured by an X-ray diffraction method2/Al2O3Is 5.65, the specific surface is 620m2(g) total pore volume of 0.41m3Per g, medium and large pore volume of 0.15m3/g。
The NaY molecular sieve composite material prepared by the method is modified, and RE in the modified composite material2O3The content of Na is 2.81%2The O content was 1.22% and the crystallinity was 43%. Mixing and pulping 2.47kg of diatomite (dry basis), 1.16kg of modified NaY molecular sieve composite material, 0.53kg of gREY molecular sieve, 2.37kg of alumina sol, 0.53kg of pseudo-boehmite and 7.1kg of deionized water, stirring for 1.3 hours, passing through a colloid mill, spray drying and forming, roasting, washing, filtering and drying to obtain the catalytic cracking catalyst S-6 containing the NaY molecular sieve composite material.
Comparative example 1
The guiding agent is prepared by mixing 1.54kg of water glass and 0.945kg of high-alkali sodium metaaluminate and standing for 15 hours at 35 ℃. Part of kaolin is at 940 deg.CRoasting for 2.4 hours to obtain high soil, roasting the other part of the high soil for 2.8 hours at 800 ℃ to obtain partial soil, uniformly mixing 2kg of partial soil, 2kg of high soil, 1.4kg of directing agent and 5.3kg of alkali liquor, crystallizing for 24 hours at 92 ℃, filtering, washing and drying to obtain the NaY molecular sieve composite material. The crystallinity of NaY molecular sieve in the composite material is 65 percent and the crystallinity of SiO is measured by an X-ray diffraction method2/Al2O3Is 4.83, the specific surface 603m2(g) total pore volume of 0.38m3Per g, medium and large pore volume of 0.11m3/g。
The NaY molecular sieve composite material prepared by the method is modified, the modification process is the same as that of the example 1, and RE in the modified composite material2O3The content of Na is 4.02%2The O content was 1.19% and the crystallinity was 39%. The catalyst preparation procedure was also the same as in example 1 to obtain comparative catalyst D1.
Comparative example 2
The guiding agent is prepared by mixing 0.624kg of water glass and 0.416kg of high-alkali sodium metaaluminate and standing for 20 hours at 33 ℃. Roasting one part of kaolin at 970 ℃ for 1.5 hours to obtain high soil, roasting the other part of kaolin at 830 ℃ for 2.0 hours to obtain partial soil, uniformly mixing 2.5kg of partial soil, 1.5kg of high soil, 0.8kg of directing agent and 5.2kg of alkali liquor, crystallizing at 93 ℃ for 34 hours, filtering, washing and drying to obtain the NaY molecular sieve composite material. The crystallinity of NaY molecular sieve in the composite material is measured by X-ray diffraction method to be 62 percent, and the crystallinity of SiO molecular sieve in the composite material is measured by X-ray diffraction method to be 62 percent2/Al2O3Is 5.01, the specific surface area is 597m2(g) total pore volume of 0.39m3(g), the pore volume of the medium and large pores is 0.13m3/g。
The NaY molecular sieve composite material prepared by the method is modified, the modification process is the same as that in example 2, and RE in the modified composite material2O3The content of Na is 1.98 percent2The O content was 1.31% and the crystallinity was 39%. The catalyst preparation procedure was also the same as in example 2, to obtain comparative catalyst D2.
Comparative example 3
The guiding agent is prepared by mixing 1.53k g water glass and 0.98kg high-alkali sodium metaaluminate and standing at 34 ℃ for 32 h. Roasting a part of kaolin at 950 deg.C for 2.0 hr to obtain high clay, and roasting the other partAnd roasting part of the mixture at 900 ℃ for 1.5 hours to obtain partial soil, uniformly mixing 1.0kg of partial soil, 3.0kg of high soil, 1.0kg of directing agent and 5.4kg of alkali liquor, crystallizing at 92 ℃ for 22.5 hours, filtering, washing and drying to obtain the NaY molecular sieve composite material. The crystallinity of NaY molecular sieve in the composite material is 69 percent and the crystallinity of SiO is measured by an X-ray diffraction method2/Al2O3Is 4.73, specific surface 643m2(g) total pore volume of 0.35m3Per g, medium and large pore volume of 0.10m3/g。
The NaY molecular sieve composite material prepared by the method is modified, the modification process is the same as that in example 3, and RE in the modified composite material2O3The content of Na is 8.16 percent2The O content was 1.21% and the crystallinity was 43%. The catalyst preparation procedure was also the same as in example 3, to obtain comparative catalyst D3.
The reaction performances of the catalytic cracking catalysts S-1 to S-3 of the invention and the comparative catalysts D1 to 3 were measured by an ACE device, and the measurement results are shown in Table 1.
TABLE 1 ACE assay data
Figure BDA0001671207590000151
Figure BDA0001671207590000161
As seen from table 1, the catalytic cracking catalyst prepared according to the present invention has high gasoline yield and low heavy oil yield, while having good coke selectivity, as compared to the comparative catalyst.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (14)

1. A preparation method of a catalytic cracking catalyst containing a NaY molecular sieve composite material is characterized in thatThe preparation method comprises the following steps: (1) roasting a part of kaolin at 940-1000 ℃ for 1-3 hours to obtain high soil, and roasting the other part of kaolin at 700-900 ℃ for 1-3 hours to form partial soil; (2) mixing partial soil and inorganic acid solution, and treating at 90-95 deg.C for 1-6 hr, wherein the partial soil is dried and inorganic acid H+The mass ratio is 80-160: 1, the mass ratio of partial soil dry basis to high soil dry basis is 0.1-10: 1; (3) mixing high soil with alkali solution, and treating at 90-95 deg.C for 1-6 hr, wherein high soil dry basis is alkali solution OH-The mass ratio is 4-11: 1, then the guiding agent and the alkali liquor are added to prepare the Na with the raw material molar ratio of (5-10)2O∶Al2O3∶(8-25)SiO2∶(80-380)H2Crystallizing the mixture of O, adding the treated meta-soil in the step (2) after crystallizing for 4-6 hours, continuously crystallizing for 16-32 hours, filtering, washing with water, and drying to obtain a composite material containing the NaY molecular sieve; (4) modifying the composite material obtained in the step (3) according to a commonly used industrial two-way two-baking process to obtain a modified NaY molecular sieve composite material; (5) mixing and pulping the modified NaY molecular sieve composite material, clay, other molecular sieves and a binder, and spray-drying to obtain the catalytic cracking catalyst containing the NaY molecular sieve composite material.
2. The method for preparing a catalytic cracking catalyst containing NaY molecular sieve composite material according to claim 1, wherein the step (2) is to mix the partial soil with the inorganic acid solution for 1-3 hours, wherein the partial soil is inorganic acid H on a dry basis+The mass ratio is 100-120: 1, and the mass ratio of the partial soil dry basis to the high soil dry basis is preferably 0.5-2: 1.
3. The preparation method of the catalytic cracking catalyst containing the NaY molecular sieve composite material according to claim 1, wherein the crystallinity of the NaY molecular sieve composite material in the step (3) is 60-70%, the ratio of silicon to aluminum is more than 5.5, and the volume of medium and large pores accounts for more than 35% of the total pore volume.
4. The preparation method of the catalytic cracking catalyst containing the NaY molecular sieve composite material according to claim 1The preparation method is characterized in that the kaolin and the alkali liquor in the step (3) are mixed and treated for 1 to 3 hours at the temperature of between 90 and 95 ℃, wherein the dry basis of the kaolin is OH-The mass ratio is 6-8: 1.
5. The method of claim 1, wherein the partial soil and the high soil are mixed with inorganic acid and alkali solution, respectively, wherein the liquid-solid ratio of the inorganic acid to the partial soil dry basis and the liquid-solid ratio of the alkali solution to the high soil dry basis are 3-1.5: 1.
6. The method for preparing a catalytic cracking catalyst containing NaY molecular sieve composite material according to claim 1, wherein the inorganic acid in the step (2) is selected from one of hydrochloric acid, sulfuric acid and nitric acid; the alkali liquor in the step (3) is selected from one of sodium hydroxide solution and potassium hydroxide solution.
7. The preparation method of the catalytic cracking catalyst containing the NaY molecular sieve composite material according to claim 1, wherein the kaolin in the step (1) comprises soft kaolin and hard kaolin, wherein the particle size is 2.5-3.5 μm, the content of crystalline kaolinite is higher than 80%, the content of iron oxide is lower than 1.7%, and the sum of sodium oxide and potassium oxide is lower than 0.5%.
8. The preparation method of the catalytic cracking catalyst containing the NaY molecular sieve composite material as claimed in claim 1, wherein the mass molar ratio of the guiding agent is as follows: (14-16) SiO2:(0.7～1.3)Al2O3:(14～16)Na2O:(300～330)H2O, the addition amount of the guiding agent is 1 to 10 percent of the weight of the synthetic material.
9. The method of claim 1, wherein the clay is selected from one or more of kaolin, halloysite, acid-extracted kaolin, alkali-extracted kaolin, montmorillonite, diatomaceous earth, rectorite, halloysite, sepiolite, and bentonite.
10. The process of claim 1, wherein the other molecular sieves comprise one or more of REY, REUSY and ZSM-5.
11. The method for preparing a catalytic cracking catalyst containing NaY molecular sieve composite according to claim 1, wherein the binder is one or more selected from silica sol, aluminum sol, modified silica sol, modified aluminum sol, amorphous silica-alumina gel, and pseudo-boehmite.
12. The method for preparing a catalytic cracking catalyst containing NaY molecular sieve composite material according to claim 1, wherein the binder is pseudo-boehmite and/or alumina sol.
13. The catalyst prepared by the preparation method of the catalytic cracking catalyst containing the NaY molecular sieve composite material according to any one of claims 1 to 12, wherein the catalyst composition comprises, by mass of the catalyst, 100%, 30 to 70% of the modified NaY molecular sieve composite material on a dry basis, 10 to 80% of clay on a dry basis, 0 to 30% of one or more other molecular sieves on a dry basis, and 5 to 40% of a binder on an oxide basis.
14. The catalyst of claim 13, wherein the catalyst composition comprises, based on 100% of the catalyst mass, 35 to 60% of the modified NaY molecular sieve composite material on a dry basis, 20 to 65% of the clay on a dry basis, 0 to 15% of one or more other molecular sieves on a dry basis, and 5 to 30% of the binder on an oxide basis.
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