CN114505091A - In-situ crystallization catalytic cracking catalyst and preparation method and application thereof - Google Patents

In-situ crystallization catalytic cracking catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN114505091A
CN114505091A CN202011282376.8A CN202011282376A CN114505091A CN 114505091 A CN114505091 A CN 114505091A CN 202011282376 A CN202011282376 A CN 202011282376A CN 114505091 A CN114505091 A CN 114505091A
Authority
CN
China
Prior art keywords
rare earth
catalytic cracking
microspheres
cracking catalyst
crystallization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011282376.8A
Other languages
Chinese (zh)
Inventor
王久江
刘涛
赵红娟
曹庚振
刘超伟
刘宏海
赵晓争
胡清勋
申宝剑
田爱珍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China University of Petroleum Beijing
Petrochina Co Ltd
Original Assignee
China University of Petroleum Beijing
Petrochina Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China University of Petroleum Beijing, Petrochina Co Ltd filed Critical China University of Petroleum Beijing
Priority to CN202011282376.8A priority Critical patent/CN114505091A/en
Publication of CN114505091A publication Critical patent/CN114505091A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
    • 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
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Abstract

The invention provides an in-situ crystallization catalytic cracking catalyst, a preparation method and an application thereof, wherein the preparation method comprises the following steps: s100, preparing a crystallization product containing the NaY molecular sieve by in-situ crystallization; s200, performing rare earth exchange on the S100 crystallization product; and S300, carrying out contact reaction on the crystallized product after the rare earth exchange in the S200 and gaseous silicon tetrachloride, wherein the space of the contact reaction is more than 2 times of the bulk volume of the crystallized product after the rare earth exchange in the reaction area, the time of the contact reaction is not more than 5 seconds, and the temperature of the contact reaction is 300-600 ℃, so as to obtain the in-situ crystallization catalytic cracking catalyst. The catalyst comprises, by 100% by weight of an in-situ crystallization catalytic cracking catalyst, less than 0.6% of sodium oxide, 0.5-5% of rare earth oxide, and a unit cell constant of 2.440-2.455 nm. The catalyst prepared by the invention has stronger heavy oil conversion activity, higher gasoline yield, light oil yield and total liquid yield, and lower coke yield.

Description

In-situ crystallization catalytic cracking catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of oil refining catalysts, and particularly relates to an in-situ crystallization catalytic cracking catalyst, and a preparation method and application thereof.
Background
Catalytic Cracking (FCC) is a main means for processing heavy oil in China, and the catalyst plays an extremely important role as the core of the technology and is divided into three types, namely, a fully-synthetic catalyst, a semi-synthetic catalyst and an in-situ crystallization catalyst. The in-situ crystallization catalyst is prepared by pulping, spraying and high-temperature roasting kaolin to obtain microspheres of a certain active silica-alumina source, and then preparing a molecular sieve and a matrix by a one-step method, the process is convenient and rapid, compared with a semi-synthetic catalyst, the in-situ crystallization catalyst has a chemical bond with strong acting force, and all in-situ crystallization catalysts have the advantages of good hydrothermal stability, high heavy oil conversion rate, strong heavy metal resistance and the like, and have an important position in an FCC catalyst.
The sodium oxide content can severely affect the activity, selectivity and stability of the catalyst and is therefore severely limited. For the in-situ crystallization catalyst, sodium oxide is simultaneously distributed in the matrix and the molecular sieve, so that the difficulty of reducing the sodium oxide is greatly increased. In industry, ammonium salt and rare earth exchange is usually carried out for many times, and sodium oxide content in the catalyst is reduced by high-temperature roasting for many times, so that a large amount of ammonia nitrogen wastewater is inevitably generated, a large amount of energy is consumed, and a serious environmental protection problem is brought.
The usage amount of ammonium salt in the modification process of Chinese patent CN1429882A is 70-145% of the weight of the catalyst; the usage amount of ammonium salt in the modification process of Chinese patent CN1204228C is 70-125% of the weight of the catalyst; the usage amount of ammonium salt in the modification process of Chinese patents CN1334314A, CN1334318A and CN1597850A is 60 to 145 percent of the weight of the catalyst; the usage amount of ammonium salt in the modification process of Chinese patent CN1232862A is 40-100% of the weight of the catalyst; the dosage of the ammonium salt in the modification process of the Chinese patent CN1683474A is 20-50% of the weight of the catalyst, but the modification steps need to be repeated for many times, so that the dosage of the ammonium salt in the above patents is very high.
In order to solve the problem of excessive use amount of ammonium salt in the modification process of the in-situ crystallization catalytic cracking catalyst, the Chinese patent CN201310219882.6 firstly stirs and mixes the crystallization product and water, adds alkali, and takes the hydroxide of the alkali as a calculation, the weight ratio of the alkali to the dry base of the crystallization product is 0.01-0.15, the reaction temperature is 70-100 ℃, the stirring time is 0.1-3 h, and after the reaction is finished, the crystallization product is filtered and washed with water to obtain the alkali-treated crystallization product; then ammonium exchange and rare earth exchange are carried out to prepare the catalyst, and the use amount of ammonium salt can be reduced to 5-15% of the weight of the catalyst. Although the amount of ammonium salt used in the patent is greatly reduced, a small amount of ammonium salt is still used, which still causes certain environmental pollution.
The method based on the hydrothermal dealumination has the obvious disadvantages of high energy consumption, complex process, large pollution, large acid loss and the like. SiCl developed in the 80 s of the 20 th century4The gas-phase dealuminization and silicon supplementation process completely improves the negative factors of the hydrothermal dealuminization process, and has the advantages of low energy consumption (the reaction temperature can be finished at 300 ℃), simple flow (only one-step reaction is needed, the ammonium exchange is not needed for the original Y-shaped molecular sieve), and large silicon-aluminum ratio range of the product (SiO)2/Al2O35 to 150) and a high crystal retention degree (C>90%) and a large amount of acid. CN1127161A discloses a method for preparing rare earth-containing silicon-rich ultrastable Y-type molecular sieve, which takes NaY as raw material and RECl as solid3In the presence of SiCl4The gas phase dealuminization silicon supplement reaction is carried out, and the method for the ultra-stabilization of NaY and the rare earth ion exchange is completed in one step. According to the methodThe prepared molecular sieve has a unit cell constant of 2.430-2.460 nm, a rare earth content of 0.15-10.0 wt%, and Na2The O content is less than 1.0 wt%, and the crystal has high crystal retention, high thermal stability and hydrothermal stability. The molecular sieve can be directly used for preparing cracking catalysts of petroleum hydrocarbons.
CN1382525A discloses a preparation method of rare earth high-silicon Y-type zeolite, which comprises the steps of drying rare earth-containing Y-type zeolite to ensure that the water content is lower than 10 wt%, introducing silicon tetrachloride gas carried by dry air according to the weight ratio of 0.1-0.9: 1 of silicon tetrachloride to Y-type zeolite, reacting for 10 minutes to 6 hours at the temperature of 150-600 ℃, and purging for 5 minutes to 2 hours by using the dry air after the reaction. The gas-phase dealuminization silicon supplementing method overcomes the defect of low retention degree of molecular sieve crystallization by a chemical dealuminization method and a hydrothermal dealuminization method.
CN108455625A discloses a preparation method of a modified Y-type molecular sieve, which comprises the steps of carrying out ion exchange reaction on a NaY molecular sieve in a rare earth solution to obtain a Y-type molecular sieve with a conventional unit cell size and reduced sodium oxide content, and then roasting at 350-480 ℃ in a 30-90 vol% steam atmosphere to obtain the Y-type molecular sieve with a reduced unit cell constant. And then carrying out contact reaction on the molecular sieve, the Y-type molecular sieve with the reduced unit cell constant and silicon tetrachloride gas according to the weight ratio of silicon tetrachloride to Y zeolite of 0.1-0.7: 1 to obtain the modified molecular sieve.
In conclusion, the molecular sieve is subjected to gaseous ultrastable treatment by silicon tetrachloride, so that the content of sodium oxide can be reduced without ammonium salt exchange, and the method has a good application prospect. However, the molecular sieve ultra-stabilized by the silicon tetrachloride gas phase has low crystallinity, and therefore, the technology related to the catalytic cracking catalyst still needs to be further improved in the field.
Disclosure of Invention
The invention mainly aims to provide an in-situ crystallization catalytic cracking catalyst, and a preparation method and application thereof, so as to overcome the defects that in the prior art, the consumption of ammonium salt is large in the modification process of the in-situ crystallization catalytic cracking catalyst, and the crystallinity of the catalyst obtained by silicon tetrachloride gas phase ultra-stable treatment is low.
In order to achieve the above object, the present invention provides a method for preparing an in-situ crystallization catalytic cracking catalyst, comprising:
s100, preparing a crystallization product containing the NaY molecular sieve by in-situ crystallization;
s200, performing rare earth exchange on the S100 crystallization product; and
s300, carrying out contact reaction on the crystallized product after the rare earth exchange of S200 and gaseous silicon tetrachloride, wherein the space of the contact reaction is more than 2 times of the bulk volume of the crystallized product after the rare earth exchange in the reaction area, the time of the contact reaction is not more than 5 seconds, and the temperature of the contact reaction is 300-600 ℃, thus obtaining the in-situ crystallization catalytic cracking catalyst.
The preparation method of the in-situ crystallization catalytic cracking catalyst comprises the following steps of (1) performing in dry basis on a crystallization product after S200 rare earth exchange, wherein the weight ratio of the crystallization product to gaseous silicon tetrachloride is: 0.05 to 0.5; and (3) the crystallized product after the S200 rare earth exchange is in countercurrent contact with the gaseous silicon tetrachloride for reaction.
The preparation method of the in-situ crystallization catalytic cracking catalyst comprises the step of carrying out contact reaction on a crystallization product after S200 rare earth exchange and gaseous silicon tetrachloride in a reactor, wherein the crystallization product after S200 rare earth exchange and the gaseous silicon tetrachloride in the reactor form a mixed state of complete mixed flow or partial complete mixed flow.
The preparation method of the in-situ crystallization catalytic cracking catalyst comprises the following steps of:
s101, preparing kaolin microspheres by taking kaolin as a raw material;
s102, mixing kaolin microspheres, a silicon source, an alkali liquor and a Y-type molecular sieve structure directing agent, and carrying out hydrothermal crystallization to prepare a crystallization product containing the NaY molecular sieve.
The preparation method of the in-situ crystallization catalytic cracking catalyst comprises the following steps of preparing kaolin, a catalyst and a catalyst, wherein the kaolin is one or more of soft kaolin, hard kaolin and coal pumice, the median diameter of the kaolin is 1.5-3.5 mu m, the mass content of the kaolin is more than 80%, the mass content of iron oxide is less than 1.7%, and the sum of the mass contents of sodium oxide and potassium oxide is less than 0.5%; and/or in the crystallized product containing the NaY molecular sieve, the mass content of the NaY molecular sieve is 20-35%.
The preparation method of the in-situ crystallization catalytic cracking catalyst comprises the following steps of S101, mixing and pulping kaolin, deionized water and a binder, spray-drying the obtained slurry to prepare microspheres, and roasting the microspheres to obtain kaolin microspheres; and/or
Si in the Y-type molecular sieve structure guiding agent is SiO2Calculated as Al2O3Calculated as Na, Na is calculated as Na2Calculated by O, the molar ratio of each component is (13-16) SiO2∶Al2O3∶(13～17)Na2O∶(300～350)H2O。
The preparation method of the in-situ crystallization catalytic cracking catalyst comprises the following steps of roasting partial microspheres in S101 at 850-1000 ℃ for 1-3 hours to obtain high-soil microspheres; roasting part of microspheres at the temperature of 600-900 ℃ for 1-3 h to obtain metasoil microspheres; the mass ratio of the high-soil microspheres to the metasoil microspheres is 9-6: 1-4.
The preparation method of the in-situ crystallization catalytic cracking catalyst comprises the step of carrying out rare earth exchange on an S100 crystallization product in S200 and a rare earth salt solution, wherein the rare earth salt is RE2O3In terms of mass ratio of the rare earth salt to the S100 crystallization product on a dry basis is 0.005-0.05, the pH value in the exchange process is 3.0-5.0, the temperature is 80-95 ℃, and the time is 0.5-3 h; and then roasting for 1-4 h at 300-700 ℃ under 20-100% of water vapor to obtain a crystallized product after rare earth exchange.
The preparation method of the in-situ crystallization catalytic cracking catalyst provided by the invention is characterized in that the water content in the crystallized product after S200 rare earth exchange is not more than 2 wt%.
In order to achieve the purpose, the invention also provides an in-situ crystallization catalytic cracking catalyst, wherein the in-situ crystallization catalytic cracking catalyst comprises, by taking the weight of 100%, less than 0.6% of sodium oxide, 0.5-5% of rare earth oxide, and the in-situ crystallization catalytic cracking catalyst has a unit cell constant of 2.440-2.455 nm.
In order to achieve the purpose, the invention further provides the application of the catalytic cracking catalyst obtained by the preparation method in heavy oil processing.
The invention has the beneficial effects that:
the catalyst prepared by the invention is used for heavy oil processing, and has stronger heavy oil conversion activity, higher gasoline yield, light oil yield and total liquid yield, and lower coke yield.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are carried out on the premise of the technical solution of the present invention, and detailed embodiments and procedures are given, but the scope of the present invention is not limited to the following examples, and the following examples are generally carried out under conventional conditions for the experimental methods not given specific conditions.
The invention provides a preparation method of an in-situ crystallization catalytic cracking catalyst, which comprises the following steps:
s100, preparing a crystallization product containing the NaY molecular sieve by in-situ crystallization;
s200, performing rare earth exchange on the S100 crystallization product; and
s300, carrying out contact reaction on the crystallized product after the rare earth exchange of S200 and gaseous silicon tetrachloride, wherein the space of the contact reaction is more than 2 times of the bulk volume of the crystallized product after the rare earth exchange in the reaction area, the time of the contact reaction is not more than 5 seconds, and the temperature of the contact reaction is 300-600 ℃, thus obtaining the in-situ crystallization catalytic cracking catalyst.
Compared with a semi-synthetic catalyst, the catalytic cracking catalyst synthesized by in-situ crystallization has a chemical bond with strong acting force, and has the advantages of good hydrothermal stability, high heavy oil conversion rate, strong heavy metal resistance and the like.
In addition, the preparation process of the catalytic cracking catalyst does not comprise an ammonium salt exchange step, and dealumination and silicon supplement can be carried out with gaseous silicon tetrachloride only after rare earth exchange, so that the steps are simplified, the generation of a large amount of ammonia nitrogen wastewater can be avoided, and the generation of an environmental protection problem is avoided.
Moreover, in the process of carrying out ultrastable research on the gas phase of silicon tetrachloride, researchers of the invention find that the isomorphous replacement dealumination and silicon supplementation reaction of the silicon tetrachloride and a crystallization product (such as rare earth exchanged) containing an NaY molecular sieve is a fast reaction which is instantly finished through a large amount of basic research, and the fast reaction is an important experimental phenomenon which is not reported in the prior art. Meanwhile, researchers also find that silicon tetrachloride which is not reacted at the moment of contact does not react or does not react obviously even if the contact time of the silicon tetrachloride and the crystallization product containing the NaY molecular sieve is further increased, and the silicon tetrachloride exists in the crystallization product containing the NaY molecular sieve only in an adsorption state. Further, researchers have found that silicon tetrachloride adsorbed onto the crystallization product containing NaY molecular sieve for an extended period of time decreases the crystallinity of NaY molecular sieve. Moreover, the mixed contact and diffusion of the silicon tetrachloride and the crystallization product containing the NaY molecular sieve not only influence the silicon-aluminum distribution of the NaY molecular sieve, but also influence the reaction efficiency, the silicon-aluminum ratio of the NaY molecular sieve and the crystallinity.
Therefore, in the method for dealuminizing and supplementing silicon by using the catalytic cracking catalyst, the reaction efficiency is enhanced by controlling the contact reaction time and the reaction space of the crystallized product and the gaseous silicon tetrachloride, particularly by controlling the synergistic effect of shorter contact reaction time and larger contact reaction space, so that the catalyst has higher crystallinity, and the aim of continuously preparing the catalytic cracking catalyst with high crystallinity and low unit cell constant (high silicon-aluminum ratio) at higher efficiency is fulfilled.
Compared with hydrothermal ultrastable, the method for dealuminizing and supplementing silicon by the in-situ crystallization catalytic cracking catalyst has the advantages of short reaction time, short process flow, no ammonium exchange step, and higher relative crystallinity of the obtained product while improving the silicon-aluminum ratio; compared with the ammonium fluosilicate liquid phase ultrastable phase, the method has the advantages of short reaction time and no consideration on the discharge of fluorine compounds and ammonia nitrogen which are sensitive to the treatment environment; compared with the prior art of silicon tetrachloride gas phase ultrastable method, the modification method has the advantages of short modification time, high modification efficiency, high relative crystallinity of the modified product and low unit cell constant, and in addition, the modification process has stable operation and high efficiency and is easy to realize industrial scale-up production.
The in-situ crystallization catalytic cracking catalyst has higher thermal stability, hydrothermal stability and cracking activity. The catalyst is used for heavy oil catalytic cracking, and has stronger heavy oil conversion activity, higher gasoline yield, light oil yield and total liquid yield, and lower coke yield.
In one embodiment, S100 includes the steps of:
s101, preparing kaolin microspheres by taking kaolin as a raw material;
s102, mixing kaolin microspheres, a silicon source, an alkali liquor and a Y-type molecular sieve structure directing agent, and carrying out hydrothermal crystallization to prepare a crystallization product containing the NaY molecular sieve.
In a specific embodiment, S101 is kaolin, deionized water, and a binder, which are mixed and beaten, the obtained slurry is spray-dried to prepare microspheres, and the microspheres are calcined to obtain kaolin microspheres. Wherein the kaolin can be one or more of soft kaolin, hard kaolinite and coal kaolinite. In one embodiment, the kaolin has a median diameter of 1.5 to 3.5 μm, and the kaolin contains kaolinite in an amount of more than 80% by mass, iron oxide in an amount of less than 1.7% by mass, and the sum of the amounts of sodium oxide and potassium oxide in an amount of less than 0.5% by mass. The binder used in the present invention is not particularly limited, and may be any binder commonly used in the art, for example, water glass. The dosage proportion of the kaolin, the deionized water and the binder is not particularly limited, as long as the obtained slurry can be spray-dried into microspheres.
In another embodiment, the roasting temperature of a part of microspheres is 850-1000 ℃, and the roasting time is 1-3 h, so that the high-soil microspheres are obtained; roasting a part of microspheres at the temperature of 600-900 ℃ for 1-3 h to obtain the metasoil microspheres. Furthermore, the mass ratio of the high-soil microspheres to the metasoil microspheres is 9-6: 1-4. In other words, in this embodiment, the kaolin microspheres of the present invention are a mixture of high-soil microspheres and meta-soil microspheres, and the mixing mass ratio of the high-soil microspheres to the meta-soil microspheres is 9-6: 1-4, and the difference between the high-soil microspheres and the meta-soil microspheres in the preparation process is only the difference between the baking temperatures of the microspheres. The NaY molecular sieve prepared by adopting the mixture of the high-soil microspheres and the meta-soil microspheres has higher crystallinity.
Of course, the kaolin microspheres of the present invention may be only kaolin microspheres or only meta-clay microspheres, and the present invention is not particularly limited.
In a specific embodiment, S101 is a mixed slurry prepared from kaolin as a raw material, the solid content of the mixed slurry is 30-45%, and microspheres with the particle size of 20-110 μm are obtained by spray drying.
S102, mixing kaolin microspheres, a silicon source, an alkali liquor and a Y-type molecular sieve structure directing agent, and carrying out hydrothermal crystallization to prepare a crystallization product containing the NaY molecular sieve.
In one embodiment, the silicon source may be one or more of water glass, sodium silicate, and white carbon black, and the alkali solution may be a sodium hydroxide solution. Si in Y-type molecular sieve structure guiding agent is SiO2Calculated as Al2O3Calculated as Na, Na is calculated as Na2Calculated by O, the molar ratio of each component is (13-16) SiO2∶Al2O3∶(13～17)Na2O∶(300～350)H2O (i.e. SiO)2∶Al2O3∶Na2O∶H2O＝13～16:1:13～17:300～350)。
The invention does not specially limit the proportional relation of the kaolin microspheres, the silicon source, the alkali liquor and the Y-type molecular sieve structure directing agent, and the kaolin microspheres, the silicon source, the alkali liquor and the Y-type molecular sieve structure directing agent can be used in the conventional dosage in the field. The hydrothermal crystallization temperature is, for example, 90 to 110 ℃, and the crystallization time is, for example, 16 to 32 hours. In another embodiment, the hydrothermal crystallization further comprises the steps of filtering, washing and drying to obtain a crystallized product containing NaY molecular sieve. In one embodiment, the crystallized product containing the NaY molecular sieve contains 20 to 35% by mass of the NaY molecular sieve.
In a specific embodiment, S102 is to bake the microspheres at 600-1000 ℃ for 1-3 h, mix the microspheres with water glass, alkali liquor and guiding agent, crystallize the microspheres at 90-110 ℃ for 16-32 h, filter, wash and dry the microspheres to obtain a crystallized product containing the NaY molecular sieve.
In one embodiment, S200 is the rare earth exchange of the S100 crystallization product with a rare earth salt solution, the rare earth salt is RE2O3In terms of mass ratio of the rare earth salt to the S100 crystallization product on a dry basis is 0.005-0.05, the pH value in the exchange process is 3.0-5.0, the temperature is 80-95 ℃, and the time is 0.5-3 h; and then roasting for 1-4 h at 300-700 ℃ under 20-100% of water vapor to obtain a crystallized product after rare earth exchange.
The rare earth salt is not particularly limited in kind, and can be one or more of rare earth chloride and rare earth nitrate; the rare earth includes but is not limited to one, two or more of lanthanum, cerium, praseodymium, neodymium and ytterbium.
And S300, carrying out contact reaction on the crystallized product after the rare earth exchange of S200 and gaseous silicon tetrachloride, wherein the space of the contact reaction is more than 2 times of the bulk volume of the crystallized product after the rare earth exchange in the reaction area, the time of the contact reaction is not more than 5 seconds, and the temperature of the contact reaction is 300-600 ℃, thus obtaining the in-situ crystallization catalytic cracking catalyst. In one embodiment, after the contact reaction between the crystallized product after the S200 rare earth exchange and gaseous silicon tetrachloride, the method further comprises the steps of washing, filtering and drying, so as to obtain the in-situ crystallization catalytic cracking catalyst.
In one embodiment, the weight ratio of the crystallized product after S200 rare earth exchange to gaseous silicon tetrachloride is 1: 0.05 to 0.5. In another embodiment, the contact reaction of the crystallized product after S200 rare earth exchange and gaseous silicon tetrachloride is performed in a reactor, such as a vertical gas phase ultra-stable reactor, wherein the crystallized product after S200 rare earth exchange and gaseous silicon tetrachloride form a mixed state of complete flow or partial complete flow, so that the crystallized product containing NaY molecular sieve is fully subjected to modification reaction. In another embodiment, the crystallized product after S200 rare earth exchange is contacted with the gaseous silicon tetrachloride in a countercurrent way for reaction, and the countercurrent contact can ensure SiCl in a short time in comparison with the cocurrent contact way4And the reaction with the NaY molecular sieve is fully carried out, and the reaction heat can be taken away in time, so that the molecular sieve structure is prevented from collapsing.
The reaction time of the contact reaction between the crystallized product after the exchange of the S200 rare earth and the gaseous silicon tetrachloride is, for example, the time of the actual contact between the crystallized product after the exchange of the S200 rare earth and the gaseous silicon tetrachloride, and the space of the contact reaction is, for example, the space occupied by the crystallized product after the exchange of the S200 rare earth and the gaseous silicon tetrachloride. In one embodiment, the reaction time of the contact reaction of the crystallized product after the rare earth exchange of S200 and gaseous silicon tetrachloride is the time from the entering of the crystallized product to the leaving of the reactor, and the space of the contact reaction is the volume of the reactor.
In one embodiment, the water content of the crystallized product after S200 rare earth exchange is ensured not to exceed 2 wt% before the crystallized product after S200 rare earth exchange is subjected to contact reaction with gaseous silicon tetrachloride. The water content of the crystallized product after S200 rare earth exchange can be controlled by heating, drying and the like.
In one embodiment, the washing condition of the mixture obtained by the contact reaction of the S300 crystallization product and the gaseous silicon tetrachloride is that the mixture is H2O is 1: 3-25, the pH value is 2.5-8.5, the washing temperature is 30-95 ℃, and the washing time is 0.5-2 h.
In summary, the invention provides a preparation method of an in-situ crystallization catalytic cracking catalyst, comprising the steps of mixing and pulping kaolin and deionized water, and adding a binder; spray drying the obtained slurry to prepare microspheres, and roasting the microspheres at high temperature to obtain roasted kaolin microspheres; mixing the roasted kaolin microspheres with a silicon source, an alkali liquor and a guiding agent, and then carrying out hydrothermal crystallization, filtering, washing and drying to obtain a crystallized product with the NaY molecular sieve content of 20-35%; and performing rare earth exchange, roasting, vertical gas phase ultra-stable reactor treatment and washing on the crystallized product to obtain the in-situ crystallization catalytic cracking catalyst, wherein the content of sodium oxide is less than 0.6 percent, the content of rare earth oxide is 0.5-5 percent and the unit cell constant is 2.440-2.455 nm based on 100 percent of the weight of the in-situ crystallization catalytic cracking catalyst. The catalyst prepared by the invention is used for heavy oil processing, and has stronger heavy oil conversion activity, higher gasoline yield, light oil yield and total liquid yield, and lower coke yield.
The technical scheme of the invention is further explained in detail by the following specific examples, and the test methods in the following examples are all conventional methods unless otherwise specified; the reagents used are commercially available, unless otherwise specified. Preferred embodiments are given below, for example, "the volume of the reactor is 10 times of the bulk volume of the rare earth-modified in-situ crystallized product entering the reactor during the reaction time", but the present invention is not limited thereto, and for example, the volume of the reactor is 5 times, 15 times, etc. of the bulk volume of the rare earth-modified in-situ crystallized product entering the reactor during the reaction time, and the present invention can be realized.
In the preparation of the kaolin microspheres in the examples, the adding amount of the water glass is calculated by the content of silicon dioxide and sodium oxide respectively, and the adding amount of other substances is calculated by a dry basis.
(1) The specification of main raw materials is as follows:
kaolin: suzhou S-1 kaolin, produced by Chinese Kaolin corporation, has a median particle size of 3.1 μm, a kaolinite content of 84%, an iron oxide content of 0.58%, and a sum of potassium oxide and sodium oxide content of 0.35%.
Water glass: SiO 22 250g/L，Na2O88 g/L, produced by Lanzhou petrochemical company.
Sodium metaaluminate solution: al (Al)2O343g/L，Na2O282 g/L, produced by landification corporation.
Rare earth chloride solution: RE2O3300g/L, produced by Lanzhou petrochemical company.
Ammonium sulfate: chemical purity, 500g, Tianjin, Kemiou Chemicals, Inc.
Hydrochloric acid: chemical purity, density of 1.19g/L and mass concentration of 36 percent.
A guiding agent: the mixture ratio is as follows: 15SiO2:Al2O3:16Na2O:320H2O (molar ratio).
(2) Analytical method
TABLE 1 Main analytical methods to which the invention relates
Item Method Standard code number
Degree of crystallization of NaY Powder X-ray diffraction method Q/SYLS 0596-2002
NaY unit cell Powder X-ray diffraction method Q/SYLS 0573-2002
Particle size Laser granulometer method Q/SYLS 0519-2002
RE2O3，m％ XRF method /
Na2O，m％ XRF method /
Specific surface area, m2/g Nitrogen adsorption and desorption process ASTM D4365-95
Pore volume, cm3/g Nitrogen adsorption and desorption process ASTM D4365-95
(3) Evaluation of catalyst:
the micro-reaction activity evaluation adopts a micro-reaction evaluation device produced by Beijing Huayang company, the raw oil adopts Hongkong light diesel, and the properties of the raw oil are shown in a table 2. The evaluation conditions were: the catalyst is aged for 17 hours by 100 percent of water vapor at the temperature of 800 ℃, the reaction temperature is 460 ℃, and the oil inlet time is 70 seconds.
TABLE 2 Properties of the Hongkong light diesel
Figure BDA0002779549350000101
The reaction performance is evaluated by a small fixed fluidized bed, the used raw oil is Xinjiang reduced pressure wide-cut wax oil and Xinjiang reduced pressure residual oil, the slag mixing ratio is 30%, and the properties of the raw oil are shown in Table 3.
TABLE 3 evaluation of the Properties of the raw oils used for the catalyst Selectivity evaluation
Figure BDA0002779549350000111
Example 1:
2000g (dry basis) of kaolin, 2% of water glass and a certain amount of deionized water are prepared into slurry with the solid content of 32%, and kaolin microspheres with the particle size of 20-110 microns are obtained by spraying. Roasting a part of kaolin microspheres at 960 ℃ for 2h to obtain high-soil spheres, and roasting the other part of kaolin microspheres at 860 ℃ for 2h to obtain meta-soil spheres. Mixing 80g of high-soil microspheres, 20g of meta-soil microspheres, 180mL of water glass, 50mL of 14 wt% sodium hydroxide solution and 30mL of guiding agent, uniformly stirring, putting into a plastic bottle, heating to 96 ℃, standing and crystallizing for 24 hours at constant temperature. And after crystallization is finished, settling for many times to remove the white powder, and then filtering, washing and drying to obtain an in-situ crystallization product. The content of NaY molecular sieve is 31% by X-ray diffraction method. 200g of in-situ crystallization product (calculated on a dry basis) is added into 2L of deionized water and stirred, and then 15ml of RECl is added3Stirring the solution, heating to 90-95 ℃, adjusting the pH to 4.0, exchanging for 1.5h, filtering, washing with water, and 5Roasting for 2.5 hours at 50 ℃ under 100 percent of water vapor to obtain an in-situ crystallization product with reduced sodium oxide content and modified rare earth, and drying to ensure that the water content is less than 1 percent. According to SiCl4The rare earth modified in-situ crystallization product and silicon tetrachloride gas are subjected to countercurrent contact reaction in a vertical gas phase ultra-stable reactor according to the weight ratio of 0.4:1 on a dry basis, the feeding speed of the rare earth modified in-situ crystallization product is controlled so that the volume of the reactor is 10 times of the bulk volume of the rare earth modified in-situ crystallization product entering the reactor within the reaction time, the reaction temperature is 450 ℃, and the contact reaction is carried out for 4 seconds. The washing condition is in-situ crystallization catalytic cracking catalyst H2And (3) O is 1:6, the pH value is 4.5, the washing temperature is 90 ℃, the washing time is 1h, and the in-situ crystallization catalytic cracking CAT-1 is obtained by filtering and drying.
Example 2:
2000g (dry basis) of kaolin, 2% of water glass and a certain amount of deionized water are prepared into slurry with the solid content of 32%, and kaolin microspheres with the particle size of 20-110 microns are obtained through spraying. Roasting a part of kaolin microspheres at 960 ℃ for 2h to obtain high-soil spheres, and roasting the other part of kaolin microspheres at 860 ℃ for 2h to obtain meta-soil spheres. Mixing 80g of high-soil microspheres, 20g of meta-soil microspheres, 180mL of water glass, 50mL of 14 wt% sodium hydroxide solution and 30mL of guiding agent, uniformly stirring, putting into a plastic bottle, heating to 96 ℃, standing and crystallizing for 24 hours at constant temperature. And after crystallization is finished, settling for many times to remove the white powder, and then filtering, washing and drying to obtain an in-situ crystallization product. The content of NaY molecular sieve is 31% by X-ray diffraction method. 200g of in-situ crystallization product (calculated on a dry basis) is added into 2L of deionized water and stirred, and then 22ml of RECl is added3Stirring the solution, heating to 90-95 ℃, adjusting the pH value to 4.0, exchanging for 2h, filtering, washing, roasting at 600 ℃ for 2.5h under 80% of water vapor to obtain an in-situ crystallization product with reduced sodium oxide content and modified rare earth, and drying to ensure that the water content is lower than 1%. According to SiCl4The rare earth modified in-situ crystallization product and silicon tetrachloride gas are subjected to countercurrent contact reaction in a vertical gas phase ultra-stable reactor according to the weight ratio of 0.3:1 on a dry basis, the reaction temperature is 400 ℃, and the rare earth modified in-situ crystallization product is controlledThe feeding speed of the crystallization product is set to ensure that the volume of the reactor is 10 times of the bulk volume of the rare earth modified in-situ crystallization product entering the reactor in the reaction time, and the contact reaction is carried out for 3 seconds. The washing condition is in-situ crystallization catalytic cracking catalyst H2And (3) O is 1:9, the pH value is 3.5, the washing temperature is 90 ℃, the washing time is 1h, and the in-situ crystallization catalytic cracking CAT-2 is obtained by filtering and drying.
Example 3:
2000g (dry basis) of kaolin, 2% of water glass and a certain amount of deionized water are prepared into slurry with the solid content of 32%, and kaolin microspheres with the particle size of 20-110 microns are obtained by spraying. Roasting a part of kaolin microspheres at 960 ℃ for 2h to obtain high-soil spheres, and roasting the other part of kaolin microspheres at 860 ℃ for 2h to obtain meta-soil spheres. 80g of high-soil microspheres, 20g of meta-soil microspheres, 180mL of water glass, 50mL of 14 wt% sodium hydroxide solution and 30mL of guiding agent are mixed, stirred uniformly and then put into a plastic bottle, heated to 96 ℃, kept at constant temperature and crystallized for 24 hours. And after crystallization is finished, settling for many times to remove the white powder, and then filtering, washing and drying to obtain an in-situ crystallization product. The content of NaY molecular sieve is 31% by X-ray diffraction method. 200g of in-situ crystallization product (calculated on a dry basis) is added into 2L of deionized water and stirred, and then 30ml of RECl is added3Stirring the solution, heating to 90-95 ℃, adjusting the pH value to 4.0, exchanging for 2h, filtering, washing, roasting at 550 ℃ under 90% of water vapor for 2.5h to obtain an in-situ crystallization product with reduced sodium oxide content and modified rare earth, and drying to ensure that the water content is lower than 1%. According to SiCl4The method comprises the steps of carrying out countercurrent contact reaction on a rare earth modified in-situ crystallization product and silicon tetrachloride gas in a vertical gas phase ultra-stable reactor according to the weight ratio of 0.4:1 on a dry basis, controlling the feeding speed of the rare earth modified in-situ crystallization product at 500 ℃, enabling the volume of the reactor to be 10 times of the loose bulk volume of the rare earth modified in-situ crystallization product entering the reactor in the reaction time, and carrying out contact reaction for 1 second. The washing condition is in-situ crystallization catalytic cracking catalyst H2O is 1:12, the pH value is 4.5, the washing temperature is 90 ℃, the washing time is 1h, and the in-situ crystallization catalytic cracking CAT-3 is obtained by filtering and drying.
Example 4:
2000g (dry basis) of kaolin, 2% of water glass and a certain amount of deionized water are prepared into slurry with the solid content of 32%, and kaolin microspheres with the particle size of 20-110 microns are obtained by spraying. Roasting a part of kaolin microspheres at 960 ℃ for 2h to obtain high-soil spheres, and roasting the other part of kaolin microspheres at 860 ℃ for 2h to obtain meta-soil spheres. Mixing 80g of high-soil microspheres, 20g of meta-soil microspheres, 180mL of water glass, 60mL of 14 wt% sodium hydroxide solution and 30mL of guiding agent, uniformly stirring, putting into a plastic bottle, heating to 96 ℃, standing and crystallizing for 24 hours at constant temperature. And after crystallization is finished, settling for many times to remove the white powder, and then filtering, washing and drying to obtain an in-situ crystallization product. The content of NaY molecular sieve is 32% by X-ray diffraction method. 200g of in-situ crystallization product (calculated on a dry basis) is added into 2L of deionized water and stirred, and then 15ml of RECl is added3Stirring the solution, heating to 90-95 ℃, adjusting the pH value to 4.0, exchanging for 1.5h, filtering, washing, roasting at 550 ℃ under 100% of water vapor for 2.5h to obtain an in-situ crystallization product with reduced sodium oxide content and modified rare earth, and drying to ensure that the water content is lower than 1%. According to SiCl4The rare earth modified in-situ crystallization product and silicon tetrachloride gas are subjected to countercurrent contact reaction in a vertical gas phase ultra-stable reactor according to the weight ratio of 0.4:1 on a dry basis, the feeding speed of the rare earth modified in-situ crystallization product is controlled so that the volume of the reactor is 10 times of the bulk volume of the rare earth modified in-situ crystallization product entering the reactor within the reaction time, the reaction temperature is 400 ℃, and the contact reaction is carried out for 2 seconds. The washing condition is in-situ crystallization catalytic cracking catalyst H2O is 1:15, the pH value is 4.5, the washing temperature is 90 ℃, the washing time is 1h, and the in-situ crystallization catalytic cracking CAT-4 is obtained by filtering and drying.
Example 5:
2000g (dry basis) of kaolin, 2% of water glass and a certain amount of deionized water are prepared into slurry with the solid content of 32%, and kaolin microspheres with the particle size of 20-110 microns are obtained by spraying. Roasting a part of kaolin microspheres at 960 ℃ for 2h to obtain high-soil spheres, and roasting the other part of kaolin microspheres at 860 ℃ for 2h to obtain meta-soil spheres. 80g of high-soil microspheres, 20g of meta-soil microspheres, 180mL of water glass and 60mL of 14 wt% sodium hydroxide solutionMixing with 30ml guiding agent, stirring, placing into plastic bottle, heating to 96 deg.C, standing, and crystallizing for 24 hr. And after crystallization is finished, settling for many times to remove the white powder, and then filtering, washing and drying to obtain an in-situ crystallization product. The content of NaY molecular sieve is 32% by X-ray diffraction method. 200g of in-situ crystallization product (calculated on a dry basis) is added into 2L of deionized water and stirred, and then 22ml of RECl is added3Stirring the solution, heating to 90-95 ℃, adjusting the pH value to 4.0, exchanging for 2h, filtering, washing, roasting at 600 ℃ for 2.5h under 80% of water vapor to obtain an in-situ crystallization product with reduced sodium oxide content and modified rare earth, and drying to ensure that the water content is lower than 1%. According to SiCl4The rare earth modified in-situ crystallization product and silicon tetrachloride gas are subjected to countercurrent contact reaction in a vertical gas phase ultra-stable reactor according to the weight ratio of 0.2:1 on a dry basis, the feeding speed of the rare earth modified in-situ crystallization product is controlled so that the volume of the reactor is 10 times of the bulk volume of the rare earth modified in-situ crystallization product entering the reactor within the reaction time, the reaction temperature is 450 ℃, and the contact reaction is carried out for 1 second. The washing condition is in-situ crystallization catalytic cracking catalyst H2And (3) O is 1:6, the pH value is 4.5, the washing temperature is 90 ℃, the washing time is 1h, and the in-situ crystallization catalytic cracking CAT-5 is obtained by filtering and drying.
Example 6:
2000g (dry basis) of kaolin, 2% of water glass and a certain amount of deionized water are prepared into slurry with the solid content of 32%, and kaolin microspheres with the particle size of 20-110 microns are obtained by spraying. Roasting a part of kaolin microspheres at 960 ℃ for 2h to obtain high-soil spheres, and roasting the other part of kaolin microspheres at 860 ℃ for 2h to obtain meta-soil spheres. Mixing 80g of high-soil microspheres, 20g of meta-soil microspheres, 180mL of water glass, 60mL of 14 wt% sodium hydroxide solution and 30mL of guiding agent, uniformly stirring, putting into a plastic bottle, heating to 96 ℃, standing and crystallizing for 24 hours at constant temperature. And after crystallization is finished, settling for many times to remove the white powder, and then filtering, washing and drying to obtain an in-situ crystallization product. The content of NaY molecular sieve is 32% by X-ray diffraction method. 200g of in-situ crystallization product (calculated on a dry basis) is added into 2L of deionized water and stirred, and then 30ml of RECl is added3Stirring the solution, heating to 90-95 DEG CAdjusting pH to 4.0, exchanging for 2h, filtering, washing with water, calcining at 550 deg.C under 90% water vapor for 2.5h to obtain in-situ crystallized product with reduced sodium oxide content and modified rare earth, and drying to make water content lower than 1%. According to SiCl4The rare earth modified in-situ crystallization product and silicon tetrachloride gas are subjected to countercurrent contact reaction in a vertical gas phase ultra-stable reactor according to the weight ratio of 0.4:1 on a dry basis, the feeding speed of the rare earth modified in-situ crystallization product is controlled so that the volume of the reactor is 10 times of the bulk volume of the rare earth modified in-situ crystallization product entering the reactor within the reaction time, the reaction temperature is 450 ℃, and the contact reaction is carried out for 2 seconds. The washing condition is in-situ crystallization catalytic cracking catalyst H2And (3) O is 1:9, the pH value is 4.0, the washing temperature is 90 ℃, the washing time is 1h, and the in-situ crystallization catalytic cracking CAT-6 is obtained by filtering and drying.
Comparative example 1:
2000g (dry basis) of kaolin, 2% of water glass and a certain amount of deionized water are prepared into slurry with the solid content of 32%, and kaolin microspheres with the particle size of 20-110 microns are obtained by spraying. Roasting a part of kaolin microspheres at 960 ℃ for 2h to obtain high-soil spheres, and roasting the other part of kaolin microspheres at 860 ℃ for 2h to obtain meta-soil spheres. Mixing 80g of high-soil microspheres, 20g of meta-soil microspheres, 180mL of water glass, 50mL of 14 wt% sodium hydroxide solution and 30mL of guiding agent, uniformly stirring, putting into a plastic bottle, heating to 96 ℃, standing and crystallizing for 24 hours at constant temperature. And after crystallization is finished, settling for many times to remove the white powder, and then filtering, washing and drying to obtain an in-situ crystallization product. The content of NaY molecular sieve is 31% by X-ray diffraction method. Taking 200g of crystallized product, ammonium sulfate and deionized water, wherein the ammonium sulfate and the crystallized product are 0.35:1, exchanging for 1h under the conditions that the pH value is 3.3 and the temperature is 90 ℃, filtering to remove filtrate, washing a filter cake with the deionized water, and drying to obtain a first-handed material; exchanging the first mixed material with rare earth chloride once, wherein the rare earth is 0.02:1, the pH is 3.9, the temperature is 90 ℃, the time is 1h, and filtering, washing and drying the exchanged material to obtain a second mixed material; roasting the secondary cross-linked material for 2 hours at 550 ℃ under the condition of 100 percent of water vapor to obtain a primary roasted material; exchanging the primary baked material once with ammonium sulfate at a pH of 0.2:1 and 3.8 at 90 deg.C for 1 hr, filtering, washing, and drying to obtain tertiary-exchange material; roasting the tertiary mixed material for 2 hours at 600 ℃ under the condition of 100 percent of water vapor to obtain secondary roasted material; exchanging the secondary material with hydrochloric acid once again, adjusting the pH value to 3.4, the temperature to 90 ℃, and the time to 1h, filtering, washing and drying the exchanged product to obtain the in-situ crystallization catalytic cracking CAT-7.
Comparative example 2:
2000g (dry basis) of kaolin, 2% of water glass and a certain amount of deionized water are prepared into slurry with the solid content of 32%, and kaolin microspheres with the particle size of 20-110 microns are obtained by spraying. Roasting a part of kaolin microspheres at 960 ℃ for 2h to obtain high-soil spheres, and roasting the other part of kaolin microspheres at 860 ℃ for 2h to obtain meta-soil spheres. 80g of high-soil microspheres, 20g of meta-soil microspheres, 180mL of water glass, 60mL of 14 wt% sodium hydroxide solution and 30mL of guiding agent are mixed, stirred uniformly and then put into a plastic bottle, heated to 96 ℃, kept at constant temperature and crystallized for 24 hours. And after crystallization is finished, settling for many times to remove the white powder, and then filtering, washing and drying to obtain an in-situ crystallization product. The content of NaY molecular sieve is 32% by X-ray diffraction method. Taking 200g of crystallized product, ammonium sulfate and deionized water, wherein the ammonium sulfate and the crystallized product are 0.35:1, exchanging for 1h under the conditions that the pH value is 3.3 and the temperature is 90 ℃, filtering to remove filtrate, washing a filter cake with the deionized water, and drying to obtain a first-handed material; exchanging the first mixed material with rare earth chloride once, wherein the rare earth is 0.03:1, the pH is 3.9, the temperature is 90 ℃, the time is 1h, and filtering, washing and drying the exchanged material to obtain a second mixed material; roasting the secondary cross-linked material for 2 hours at 550 ℃ under the condition of 100 percent of water vapor to obtain a primary roasted material; exchanging the first baked material with ammonium sulfate at a ratio of 0.2:1 and pH of 3.8 at 90 deg.C for 1 hr, filtering, washing, and drying to obtain a third-exchange material; roasting the tertiary mixed material for 2 hours at 600 ℃ under the condition of 100 percent of water vapor to obtain secondary roasted material; exchanging the secondary baked material with hydrochloric acid once again, adjusting the pH value to 3.4, the temperature to 90 ℃, and the time to 1 hour, and filtering, washing and drying the exchanged product to obtain the in-situ crystallization catalytic cracking CAT-8.
Comparative example 3:
2000g (dry basis) of kaolin, 2% of water glass and a certain amount of deionized water are prepared into slurry with the solid content of 32%, and kaolin microspheres with the particle size of 20-110 microns are obtained by spraying. Roasting a part of kaolin microspheres at 960 ℃ for 2h to obtain high-soil spheres, and roasting the other part of kaolin microspheres at 860 ℃ for 2h to obtain meta-soil spheres. Mixing 80g of high-soil microspheres, 20g of meta-soil microspheres, 180mL of water glass, 50mL of 14 wt% sodium hydroxide solution and 30mL of guiding agent, uniformly stirring, putting into a plastic bottle, heating to 96 ℃, standing and crystallizing for 24 hours at constant temperature. And after crystallization is finished, settling for many times to remove the white powder, and then filtering, washing and drying to obtain an in-situ crystallization product. The content of NaY molecular sieve is 31% by X-ray diffraction method. Taking 200g of crystallized product, ammonium sulfate and deionized water, wherein the ammonium sulfate and the crystallized product are 0.35:1, exchanging for 1h under the conditions that the pH value is 3.3 and the temperature is 90 ℃, filtering to remove filtrate, washing a filter cake with the deionized water, and drying to obtain a first-handed material; exchanging the first mixed material with rare earth chloride once, wherein the rare earth is 0.04:1, the pH is 3.9, the temperature is 90 ℃, the time is 1h, and filtering, washing and drying the exchanged material to obtain a second mixed material; roasting the secondary cross-linked material for 2 hours at 550 ℃ under the condition of 100 percent of water vapor to obtain a primary roasted material; exchanging the first baked material with ammonium sulfate at a ratio of 0.3:1, pH of 3.8, temperature of 90 deg.C for 1 hr, filtering, washing, and drying to obtain a third-exchange material; roasting the tertiary mixed material for 2 hours at 600 ℃ under the condition of 100 percent of water vapor to obtain secondary roasted material; exchanging the secondary material with hydrochloric acid once again, adjusting the pH value to 3.4, the temperature to 90 ℃, and the time to 1h, filtering, washing and drying the exchanged product to obtain the in-situ crystallization catalytic cracking CAT-9.
Comparative example 4:
2000g (dry basis) of kaolin, 2% of water glass and a certain amount of deionized water are prepared into slurry with the solid content of 32%, and kaolin microspheres with the particle size of 20-110 microns are obtained by spraying. Roasting a part of kaolin microspheres at 960 ℃ for 2h to obtain high-soil spheres, and roasting the other part of kaolin microspheres at 860 ℃ for 2h to obtain meta-soil spheres. Mixing 80g of high-soil microspheres, 20g of meta-soil microspheres, 180mL of water glass, 60mL of 14 wt% sodium hydroxide solution and 30mL of guiding agent, uniformly stirring, putting into a plastic bottle, heating to 96 ℃, standing and crystallizing for 24 hours at constant temperature. And after crystallization is finished, settling for many times to remove the white powder, and then filtering, washing and drying to obtain an in-situ crystallization product. Measured by X-ray diffraction method, contains32% of NaY molecular sieve. 200g of in-situ crystallization product (calculated on a dry basis) is added into 2L of deionized water and stirred, and then 30ml of RECl is added3Stirring the solution, heating to 90-95 ℃, adjusting the pH value to 4.0, exchanging for 2h, filtering, washing, roasting at 550 ℃ under 90% of water vapor for 2.5h to obtain an in-situ crystallization product with reduced sodium oxide content and modified rare earth, and drying to ensure that the water content is lower than 1%. According to SiCl4Reacting the rare earth modified in-situ crystallization product with silicon tetrachloride gas in a weight ratio of 0.3:1 on a dry basis in a horizontal gas-phase ultra-stable reactor at the reaction temperature of 450 ℃ for 30 minutes. The washing condition is in-situ crystallization catalytic cracking catalyst H2And (3) O is 1:8, the pH value is 4.0, the washing temperature is 90 ℃, the washing time is 1h, and the in-situ crystallization catalytic cracking CAT-10 is obtained by filtering and drying.
The catalysts CAT-1 to CAT-6 prepared in examples 1 to 6 and the catalysts CAT-7 to CAT-10 prepared in comparative examples 1 to 4 were subjected to micro-inversion evaluation, and the results of the evaluation of the physical and chemical properties and the micro-inversion of the catalysts are shown in Table 4.
TABLE 4 evaluation results of physical and chemical properties and microreflective activity of CAT-1 to CAT-6 and CAT-7 to CAT-10
Figure BDA0002779549350000181
800 ℃ and 17 hours, 100% water vapor aging.
As can be seen from the comparison of the data in Table 4, the in-situ crystallization catalyst prepared by the present invention has higher crystallinity retention, lower unit cell constant, larger specific surface area and larger pore volume than the comparative example.
The catalysts CAT-1 to CAT-6 prepared in examples 1 to 6 and the catalysts CAT-7 to CAT-10 prepared in comparative examples 1 to 4 were subjected to the evaluation of reaction properties, and the results are shown in Table 5. As shown by the data in table 5, the catalyst of the present invention shows higher activity and excellent reaction performance in catalytic cracking of heavy oil compared to the catalysts prepared by the conventional processes in comparative examples 1 to 4, and the catalysts obtained in examples 1 to 6 of the present invention have higher conversion rate, higher total liquid yield and higher light yield (gasoline + diesel oil yield) when used for catalytic cracking of heavy oil feedstock.
TABLE 5 evaluation of the reactivity of the different catalysts
Figure BDA0002779549350000191
800 ℃ for 10 hours, 100% moisture aging.
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 (11)

1. The preparation method of the in-situ crystallization catalytic cracking catalyst is characterized by comprising the following steps:
s100, preparing a crystallization product containing the NaY molecular sieve by in-situ crystallization;
s200, performing rare earth exchange on the S100 crystallization product; and
s300, carrying out contact reaction on the crystallized product after the rare earth exchange of S200 and gaseous silicon tetrachloride, wherein the space of the contact reaction is more than 2 times of the bulk volume of the crystallized product after the rare earth exchange in the reaction area, the time of the contact reaction is not more than 5 seconds, and the temperature of the contact reaction is 300-600 ℃, thus obtaining the in-situ crystallization catalytic cracking catalyst.
2. The method for preparing the in-situ crystallization catalytic cracking catalyst according to claim 1, wherein the weight ratio of the S200 rare earth exchanged crystallization product to gaseous silicon tetrachloride is 1: 0.05 to 0.5; and (3) the crystallized product after the S200 rare earth exchange is in countercurrent contact with the gaseous silicon tetrachloride for reaction.
3. The method for preparing an in-situ crystallized catalytic cracking catalyst according to claim 1, wherein the contact reaction of the S200 crystallized product after rare earth exchange and gaseous silicon tetrachloride is carried out in a reactor, and the crystallized product after rare earth exchange and gaseous silicon tetrachloride in the reactor form a mixed state of a fully mixed flow or a partially fully mixed flow.
4. The method for preparing an in-situ crystallized catalytic cracking catalyst according to claim 1, wherein the step S100 comprises the steps of:
s101, preparing kaolin microspheres by taking kaolin as a raw material;
s102, mixing kaolin microspheres, a silicon source, an alkali liquor and a Y-type molecular sieve structure directing agent, and carrying out hydrothermal crystallization to prepare a crystallization product containing the NaY molecular sieve.
5. The preparation method of the in-situ crystallization catalytic cracking catalyst according to claim 4, wherein the kaolin is one or more of soft kaolin, hard kaolinite and coal pumice, the median diameter of the kaolin is 1.5-3.5 μm, the mass content of the kaolinite in the kaolin is more than 80%, the mass content of the iron oxide is less than 1.7%, and the sum of the mass contents of the sodium oxide and the potassium oxide is less than 0.5%; and/or the NaY molecular sieve accounts for 20-35% of the crystallized product containing the NaY molecular sieve.
6. The method for preparing the in-situ crystallization catalytic cracking catalyst according to claim 4, wherein S101 is prepared by mixing and pulping kaolin, deionized water and a binder, spray-drying the obtained slurry to prepare microspheres, and roasting the microspheres to obtain kaolin microspheres; and/or
Si in the Y-type molecular sieve structure guiding agent is SiO2Calculated as Al2O3Calculated as Na, Na is calculated as Na2Calculated by O, the molar ratio of each component is (13-16) SiO2∶Al2O3∶(13～17)Na2O∶(300～350)H2O。
7. The preparation method of the in-situ crystallization catalytic cracking catalyst according to claim 6, wherein the roasting temperature of the partial microspheres in S101 is 850-1000 ℃, and the roasting time is 1-3 h, so as to obtain the high-soil microspheres; roasting part of microspheres at the temperature of 600-900 ℃ for 1-3 h to obtain metasoil microspheres; the mass ratio of the high-soil microspheres to the metasoil microspheres is 9-6: 1-4.
8. The method for preparing in-situ crystallized catalytic cracking catalyst according to claim 1, wherein the S100 crystallized product in S200 is subjected to rare earth exchange with rare earth salt solution, and the rare earth salt is RE2O3In terms of mass ratio of the rare earth salt to the S100 crystallization product on a dry basis is 0.005-0.05, the pH value in the exchange process is 3.0-5.0, the temperature is 80-95 ℃, and the time is 0.5-3 h; and then roasting for 1-4 h at 300-700 ℃ under 20-100% of water vapor to obtain a crystallized product after rare earth exchange.
9. The method of claim 1, wherein the water content of the crystallized product after S200 rare earth exchange is not more than 2 wt%.
10. The in-situ crystallization catalytic cracking catalyst is characterized in that the in-situ crystallization catalytic cracking catalyst contains 22-28% of NaY molecular sieve, less than 0.6% of sodium oxide, 0.5-5% of rare earth oxide, and the unit cell constant of the in-situ crystallization catalytic cracking catalyst is 2.440-2.455 nm, wherein the weight of the in-situ crystallization catalytic cracking catalyst is 100%.
11. Use of the catalytic cracking catalyst obtained by the production method according to any one of claims 1 to 9 in heavy oil processing.
CN202011282376.8A 2020-11-16 2020-11-16 In-situ crystallization catalytic cracking catalyst and preparation method and application thereof Pending CN114505091A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011282376.8A CN114505091A (en) 2020-11-16 2020-11-16 In-situ crystallization catalytic cracking catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011282376.8A CN114505091A (en) 2020-11-16 2020-11-16 In-situ crystallization catalytic cracking catalyst and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN114505091A true CN114505091A (en) 2022-05-17

Family

ID=81547263

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011282376.8A Pending CN114505091A (en) 2020-11-16 2020-11-16 In-situ crystallization catalytic cracking catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114505091A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0100544A2 (en) * 1982-08-02 1984-02-15 Union Carbide Corporation Modification of molecular sieves by treatment with a silicon tetrafluoride gas mixture
US4684511A (en) * 1984-08-29 1987-08-04 Union Carbide Corporation Process for the halogen modification of aluminophosphate molecular sieves and a product so produced
CA2503898A1 (en) * 2002-10-28 2004-05-06 China Petroleum & Chemical Corporation A rare-earth y-zeolite-containing catalyst for cracking hydrocarbons and a method for preparing the same
CN102553630A (en) * 2010-12-16 2012-07-11 华东理工大学 High- silica alumina ratio small- crystal grain Y zeolite catalytic cracking catalyst and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0100544A2 (en) * 1982-08-02 1984-02-15 Union Carbide Corporation Modification of molecular sieves by treatment with a silicon tetrafluoride gas mixture
US4684511A (en) * 1984-08-29 1987-08-04 Union Carbide Corporation Process for the halogen modification of aluminophosphate molecular sieves and a product so produced
CA2503898A1 (en) * 2002-10-28 2004-05-06 China Petroleum & Chemical Corporation A rare-earth y-zeolite-containing catalyst for cracking hydrocarbons and a method for preparing the same
CN102553630A (en) * 2010-12-16 2012-07-11 华东理工大学 High- silica alumina ratio small- crystal grain Y zeolite catalytic cracking catalyst and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YUAN, DL，ET AL.: "Creation of mesostructured hollow Y zeolite by selective demetallation of an artificial heterogeneous Al distributed zeolite crystal", 《CATALYSIS SCIENCE & TECHNOLOGY》, pages 8364 - 8374 *
张德奇等: "水汽和空气焙烧制备LaY 沸石的SiCl4气相超稳研究", 《分子催化》, pages 209 - 218 *

Similar Documents

Publication Publication Date Title
EP0726807B1 (en) Modified microsphere fcc catalysts
CN101108734B (en) Beta type molecular sieve and method of manufacturing the same
CN101767028B (en) Preparation method of fluid catalytic cracking catalyst
CN101767027B (en) Preparation method of cracking catalyst containing ultrastable molecular sieve
CN1225311C (en) Structurally enhanced cracking catalysts
CN101491772B (en) Catalyst for naphtha catalytic cracking
CN106268919B (en) A kind of Modified Zeolite Y catalyst containing rare earth and phosphorus
CN107971001B (en) It is a kind of to contain the assistant for calalytic cracking and preparation method thereof for being rich in mesoporous Beta molecular sieve
CN102019196B (en) Method for improving pore structure of kaolin microsphere in-situ crystallization product
US6991774B2 (en) Rare earth zeolite Y and the preparation process thereof
CN102553630B (en) High- silica alumina ratio small- crystal grain Y zeolite catalytic cracking catalyst and preparation method thereof
CN109304223B (en) Low-coking type catalytic cracking catalyst and preparation method thereof
CN103301870A (en) Preparation method for catalytic cracking cocatalyst
CN108745409B (en) Catalytic cracking catalyst for improving gasoline yield and preparation method thereof
CN116265108A (en) Preparation method of catalytic cracking catalyst for producing more gasoline
CN109046445A (en) A kind of preparation method of H β/MCM-22 composite molecular sieves and the method for preparing tert-butyl phenol
CN114505091A (en) In-situ crystallization catalytic cracking catalyst and preparation method and application thereof
CN114433252B (en) Catalytic cracking catalyst and preparation method thereof
CN114212800A (en) Novel high-silicon Y-type zeolite and preparation method and application thereof
CN116265106A (en) Preparation method of catalytic cracking catalyst for high yield of low carbon olefin
CN116265107A (en) Preparation method of catalytic cracking catalyst for producing diesel oil in large quantity
CN105854927A (en) Catalytic cracking catalyst and preparation method thereof
CN103100401B (en) Preparation method of hydrocracking catalyst containing in-situ Y zeolite
CN101664691B (en) Method for preparing catalytic cracking bottom oil converting additive
CN101279285B (en) Naphtha catalytic pyrolysis catalyst for preparing ethylene propylene

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination