CN112570017B - Five-membered ring zeolite catalytic cracking catalyst - Google Patents
Five-membered ring zeolite catalytic cracking catalyst Download PDFInfo
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- CN112570017B CN112570017B CN201910933501.8A CN201910933501A CN112570017B CN 112570017 B CN112570017 B CN 112570017B CN 201910933501 A CN201910933501 A CN 201910933501A CN 112570017 B CN112570017 B CN 112570017B
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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
- B01J29/80—Mixtures of different zeolites
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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
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—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 containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention belongs to the technical field of catalysts containing pentasil zeolite, and discloses a pentasil zeolite catalytic cracking catalyst, which comprises pentasil zeolite, optional faujasite, zirconium-aluminum composite sol, other inorganic oxide binders and natural minerals; in the XRD spectrum of the solid obtained by drying the zirconium-aluminum composite sol at 100 ℃ for 6 hours and roasting at 600 ℃ for 6 hours, diffraction peaks are found at positions of 2 theta of 30 degrees+/-0.5 degrees, 35 degrees+/-0.5 degrees, 46 degrees+/-0.5 degrees and 51 degrees+/-0.5 degrees, and no peaks are detected at positions of 2 theta of 28 degrees+/-0.5 degrees and 31.4 degrees+/-0.5 degrees. The catalytic cracking catalyst is used for hydrocarbon oil conversion, and has higher ethylene and propylene hydrocarbon selectivity.
Description
Technical Field
The present invention belongs to the field of five-membered ring containing zeolite catalyst technology.
Background
Pentasil zeolite can be used in a catalytic cracking catalyst as an active component, for example, it can be used as an active component for catalytically cracking gasoline octane number additive, as a catalytic component for reducing the olefin content of gasoline, and as a catalytic cracking catalyst or additive for increasing propylene yield.
Ethylene, propylene and butene low-carbon olefin are indispensable chemical raw materials, and can be used for synthesizing resins, fibers, rubber and the like. Propylene is an important raw material for manufacturing petrochemical products, and is mainly used for producing chemical products such as polypropylene, acrylonitrile, propylene oxide and the like. At present, propylene is mainly derived from byproducts of ethylene production by thermal cracking at home and abroad, the second largest source of propylene is an FCC unit, which provides about 30% of the demand, and in the United states, half of the demand for propylene by petrochemical products. Thus, the substantial production of propylene by FCC is an effective and efficient way to meet the growing demand. With the weight of crude oil becoming heavier, heavy oil conversion is increasingly utilized to produce low-carbon olefins, but due to the smaller pore size of pentasil, the existing catalytic cracking catalyst using pentasil is not ideal in propylene yield when used for heavy oil conversion, especially for heavier oil conversion.
Disclosure of Invention
The invention aims to solve the technical problems of providing a catalytic cracking catalyst containing five-membered ring zeolite, and the preparation method and the application method of the catalytic cracking catalyst.
The invention provides a catalytic cracking catalyst, which comprises the following components in terms of dry basis by taking the dry basis weight of the catalytic cracking catalyst as the reference, wherein the catalyst comprises the following components in percentage by weight:
(a) 5-75 wt% of a pentasil zeolite having a major pore size of less than 0.57nm;
(b) 0-70 wt% faujasite;
(c) 10-65 wt% natural minerals;
(d) 10-60 wt% of zirconium-aluminum composite sol; and
(e) 3 wt% to 20 wt% of other inorganic oxide binders;
the zirconium-aluminum composite sol has an aluminum content of 1-10 wt%, a zirconium content of 0.5-10 wt%, a chloride ion content of not more than 0.8 wt%, for example, 0.1-0.8 wt%, a pH value of 2-5, a corrosion rate of preferably not more than 10mm/a, for example, 0.5-10mm/a, and is dried at 100 ℃ for 6 hours, and then calcined at 600 ℃ for 6 hours to obtain a solid in which zirconium exists mainly in the form of tetragonal zirconia, diffraction peaks are detected at 2 theta of 30 DEG + -0.5 DEG, 35 DEG + -0.5 DEG, 51 DEG + -0.5 DEG, and 61 DEG + -0.5 DEG, and no diffraction peak is detected at 2 theta of 28 DEG + -0.5 DEG, 31.4 DEG + -0.5 DEG.
The other inorganic oxide binders are those used in the art other than the zirconium aluminum composite sol.
The invention also provides a preparation method of the catalytic cracking catalyst, which comprises the following steps: mixing five-membered ring zeolite, optional faujasite, natural minerals, zirconium aluminum composite sol and other inorganic oxide binders, pulping, and spray drying.
The invention provides a catalytic cracking method for producing propylene, which comprises the step of carrying out contact reaction on hydrocarbon oil and a catalytic cracking catalyst under the condition of catalytic cracking; wherein, the catalytic cracking catalyst comprises, on a dry basis: 5 to 75 weight percent of five-membered ring zeolite, 0 to 70 weight percent of faujasite, 10 to 60 weight percent of zirconium aluminum composite sol, 3 to 20 weight percent of other inorganic oxide binder and 10 to 65 weight percent of natural mineral; in the zirconium-aluminum composite sol, the content of zirconium element is 0.5-10 wt%, the content of aluminum element is 1-10 wt%, the content of chloride ion is not more than 0.8 wt%, the pH value of the sol is 2-5, the zirconium-aluminum composite sol is dried at 100 ℃ for 6 hours and then baked at 600 ℃ for 6 hours to obtain a solid, diffraction peaks are arranged at positions of 30 DEG + -0.5 DEG, 35 DEG + -0.5 DEG, 51 DEG + -0.5 DEG and 61 DEG + -0.5 DEG in an XRD pattern of the solid, and no XRD peak is detected at positions of 28 DEG + -0.5 DEG, 31.4 DEG + -0.5 DEG in the 2 theta.
The catalytic cracking method for producing propylene provided by the invention comprises the following steps: the reaction temperature is 500-650 ℃, the reaction time is 0.5-10 seconds, the weight ratio of the catalyst to the fuel oil is 5-40, the diluent gas is introduced in the reaction process, and the weight ratio of the diluent gas to the raw materials is 0.1-1:1. Such as one or more of steam, catalytically cracked dry gas, nitrogen.
The invention provides a catalytic cracking method for producing propylene, wherein hydrocarbon oil comprises the following steps: one or more of vacuum residuum, atmospheric residuum, vacuum gas oil, atmospheric gas oil, coker gas oil and hydro-modified oil.
The catalytic cracking catalyst provided by the invention is prepared by using the zirconium-aluminum composite sol, is used for catalytic cracking of hydrocarbon oil, especially heavy oil, can improve the cracking of macromolecular hydrocarbon in a matrix, and has a good catalytic cracking effect when being matched with the five-membered ring zeolite and other components.
The catalytic cracking catalyst provided by the invention has good strength, is used for heavy oil catalytic cracking, can have higher cracking activity and higher ethylene and propylene selectivity than the existing five-membered ring zeolite cracking catalyst, and can also have higher liquefied gas yield and/or higher propylene yield.
The catalytic cracking method provided by the invention can have at least one of the following effects, and preferably has a plurality of effects thereof: (1) has higher conversion rate, (2) has higher propylene yield, (3) has higher liquefied gas yield, (4) has higher propylene selectivity, (5) has higher low-carbon olefin selectivity, and (6) has higher ethylene yield.
The specific embodiment is as follows:
according to the catalytic cracking catalyst provided by the invention, the content of chloride ions in the zirconium-aluminum composite sol is 0-0.8 wt%, for example, 0-0.5 wt%, or 0.1-0.8 wt%, or 0.3-0.5 wt%.
The element content in the zirconium-aluminum composite sol can be measured by ICP-OES inductively coupled plasma-atomic emission spectrometry, see GB/T30902-2014.
According to the catalytic cracking catalyst provided by the invention, the zirconium-aluminum composite sol has lower corrosiveness, wherein the corrosion rate of the zirconium-aluminum composite sol is 0.5-10mm/a, for example, 1-8mm/a or 2-6mm/a or 2.5-4.5mm/a or 1-9mm/a or 2-8mm/a or 3-5mm/a or 2.5-5mm/a or 3-4mm/a. The corrosion rate can be measured by the following method:
experimental equipment: spin etching apparatus, 20# carbon steel coupon (type I, size 50 mm. Times.25 mm. Times.2 mm) experimental medicine: absolute ethanol, hydrochloric acid (10 wt%), hexamethylenetetramine (0.5 wt%), 5N sodium hydroxide;
The experimental steps are as follows:
(1) Firstly, washing a sample of a test piece with absolute ethyl alcohol to remove grease on the surface of the test piece; after being dried by cold air, the test piece is wrapped by filter paper, placed in a dryer for preservation, weighed after 24 hours, and the weight of the test piece is recorded as W1.
(2) On a rotary corrosion device, a test piece is hung on a rotary rod, and the test piece is placed in a beaker containing sol for reaction for 1h at the temperature of 60 ℃.
(3) After the reaction is finished, firstly, 10 weight percent of hydrochloric acid and 0.5 weight percent of hexamethylenetetramine mixture are used for cleaning to remove black corrosion products on hanging pieces, and the cleaned hanging pieces are immediately immersed into 5N sodium hydroxide solution for passivation for 1min; taking out, soaking in clean absolute ethyl alcohol for 1min, wiping with filter paper, drying with cold air, wrapping with filter paper, placing in a dryer for preservation, weighing after 24h, and recording the weight as W2.
(4) The corrosion rate is calculated as the average corrosion depth of the metal material over a year < mm/a, millimeters per year > as follows:
v in formula-corrosion rate, mm/a;
rho-density of hanging tablet, carbon steel 7.85g/cm 3
DeltaW-weight loss before and after hanging tablet reaction, g
T-time of hanging tablet, h
A- -the area of the hanging tablet (type I- -28 cm) 2 )
According to the catalytic cracking catalyst provided by the invention, preferably, the pH value of the zirconium aluminum composite sol is 2-5, such as 2.2-4.5 or 2.5-4, more preferably 2.6-4.5, still more preferably 2.8-4, such as 2.7-3.8 or 3-3.5 or 3.2-3.4 or 3-4.
The catalytic cracking catalyst provided by the invention comprises the zirconium-aluminum composite sol, wherein the zirconium-aluminum composite sol is dried at 100 ℃ for 6 hours and then baked at 600 ℃ for 6 hours to obtain a solid, diffraction peaks are arranged at positions of 30 DEG + -0.5 DEG, 35 DEG + -0.5 DEG, 51 DEG + -0.5 DEG and 61 DEG + -0.5 DEG in the XRD spectrum of the solid, and no peaks are detected at positions of 28 DEG + -0.5 DEG and 31.4 DEG + -0.5 DEG in the XRD spectrum of the solid, so that zirconium mainly exists in a tetragonal phase zirconium dioxide form in the solid. Preferably, the solid has diffraction peaks at 46 ° ± 0.5 ° and 67 ° ± 0.5 ° 2θ. Diffraction peaks at 46 DEG + -0.5 DEG and 67 DEG + -0.5 DEG are attributed to gamma-alumina, peaks at 28 DEG + -0.5 DEG and 31.4 DEG + -0.5 DEG are attributed to monoclinic phase zirconium dioxide, and diffraction peaks at about 30 DEG + -0.5 DEG, 35 DEG + -0.5 DEG, 51 DEG + -0.5 DEG and 61 DEG + -0.5 DEG are characteristic diffraction peaks of tetragonal phase zirconium dioxide.
Preferably, the zirconium-aluminum composite sol is dried at 100 ℃ for 6 hours and then baked at 600 ℃ for 6 hours to obtain a solid, wherein zirconium in the solid mainly exists in a tetragonal phase zirconium dioxide form. Preferably, the solids have a pore volume of 0.3 to 0.7cc/g, for example 0.3 to 0.6cc/g g or 0.40 to 0.55cc/g or 0.35 to 0.557cc/g or 0.4 to 0.57cc/g.
Preferably, the average pore diameter of the solid is from 5 to 15nm, for example from 6 to 12nm or from 7.8 to 9nm or from 7.9 to 8.6nm or from 7 to 10nm.
The catalytic cracking catalyst provided by the invention comprises 1-10 wt% of zirconium-aluminum composite sol, 0.5-10 wt% of zirconium element, preferably 2-6 wt% of aluminum element and 1-6 wt% of zirconium element; it is further preferred that the content of the aluminum element is 3 to 5 wt% or 4 to 5 wt% or 4.5 to 6 wt%, and the content of the zirconium element is 0.6 to 6 wt%, for example, 0.7 to 2.2 wt% or 1.4 to 2.2 wt% or 1.8 to 2.2 wt% or 1.2 to 2.2 wt%.
According to the catalytic cracking catalyst provided by the invention, in the zirconium-aluminum composite sol, preferably, the weight ratio of aluminum element to zirconium element is (0.3-6.5): 1 is, for example, 2-6.5:1 or (0.5-6): 1, more preferably (0.5 to 5): 1, more preferably (1-4): 1 or 2-3.2:1, for example (2.2-3.1): 1.
according to the catalytic cracking catalyst provided by the invention, preferably, the zirconium aluminum composite sol further contains a surfactant, wherein the content of the surfactant is 0.5-10 wt% of the content of aluminum element, for example, 0.5-2 wt% or 1-2 wt%, and further preferably, 0.5-1.5 wt% or 1-1.5 wt% of the content of aluminum element. The surfactant may be an ionic surfactant or a nonionic surfactant, and is not particularly limited in the present invention, and is preferably selected from the group consisting of nonionic surfactants, more preferably at least one selected from the group consisting of polyoxyethylene-8-octylphenyl ether, fatty alcohol polyoxyethylene ether, fatty acid methyl polyoxyethylene ether, polyethylene glycol, hydroxypropyl cellulose, fatty acid polyoxyethylene ester, fatty acid glyceride, fatty acid sorbitan, polysorbate, sucrose triethanolamine soap ester and sucrose polyol ester, still more preferably at least one selected from the group consisting of polyoxyethylene-8-octylphenyl ether, fatty alcohol polyoxyethylene ether and polysorbate, and most preferably polyoxyethylene-8-octylphenyl ether. The preferable implementation mode of the surfactant is more favorable for improving the dispersibility of the zirconium-aluminum composite sol, and the application of the zirconium-aluminum composite sol in a catalytic cracking catalyst is more favorable for improving the hydrothermal stability and the abrasion strength of the catalyst.
According to the invention, the zirconium-aluminum composite sol also contains water. The water content is an equilibrium amount and may be, for example, 60 to 99% by weight or 70 to 95% by weight or 75 to 89% by weight or 80 to 92% by weight.
The weight ratio of the faujasite to the pentasil is 0-14:1, preferably 1:10-10:1, for example 0.1:1-4:1 or 1:5-2:1 or 1:4 to 4:1 is preferably 0.3:1-4:1 or 1:3-3:1 or 1:2-2:1 or 0.3:1-0.8:1. for example, it may be 1:10-2:1 or greater than 2:1 and less than 3:1 (noted as greater than 2:1 to less than 3:1) or greater than 3:1-5:1 or greater than 5:1-8:1 or greater than 8:1-10:1 or 2:10-9:1 or 2.5: 10-less than 3:1 or greater than 3:1-10:1 or 3.5:10-7:1. in one embodiment, the weight ratio of the faujasite to the pentasil is 0.2:1-2.9:1 or 0.25-2.9:1 or 0.3:1-2.8:1 or 1:3-2.8:1 or 0.3:1-2:1 or 1:3-3:2, in this way, higher propylene yields and higher propylene selectivities are possible.
In the catalyst cracking catalyst provided by the invention, the faujasite is preferably a Y-type molecular sieve. The Y-type molecular sieve is, for example, HY, REY, REHY, USY molecular sieve, and is prepared by gas phase chemical method (SiCl) 4 Al-removing and Si-supplementing method), liquid phase chemical method ((NH) 4 ) 2 SiF 6 Aluminum extraction and silicon compensation) or other methods (such as acid dealumination, complexation dealumination) or a mixture of various modified Y zeolite or the Y zeolite. The Y-type molecular sieve can be a hydrogen-type Y-type molecular sieve or a Y-type molecular sieve containing phosphorus and/or transition metal. The faujasite is preferably a USY molecular sieve, such as one or more of hydrogen form USY, REUSY molecular sieve containing rare earth, USY molecular sieve containing phosphorus and rare earth. In one embodiment, the USY molecular sieve is a DASY molecular sieve.
In the catalyst cracking catalyst provided by the invention, the pentasil zeolite is a molecular sieve with a main pore diameter smaller than 0.57nm, and comprises at least one of rare earth-containing pentasil zeolite, phosphorus-containing pentasil zeolite, iron-containing pentasil zeolite and phosphorus-containing and transition metal-containing pentasil zeolite, and one or more transition metals in RE, fe, cu, zn, mn, co, ni, sn, ti are preferably RE or Fe. Preferably, the pentasil is a rare earth-containing molecular sieve and/or a phosphorus-and rare earth-containing pentasil and/or a phosphorus-and iron-containing pentasil. More preferably, the pentasil zeolite is a rare earth-containing pentasil zeolite and/or a phosphorus-and rare earth-containing pentasil zeolite. The Y-type molecular sieve is preferably a USY molecular sieve, for example, a DASY molecular sieve, which may or may not contain rare earth elements. The five-membered ring zeolite is, for example, a ZSM-5 molecular sieve. Preferably, the pentasil zeolite is one or more of a ZSM-5 molecular sieve containing phosphorus and iron, a ZSM-5 molecular sieve containing phosphorus and/or rare earth, such as a ZRP molecular sieve. A ZSM-5 molecular sieve containing phosphorus and iron, such as one or more of a ZSP-2 molecular sieve, a ZSP-3 molecular sieve.
In the catalytic cracking catalyst provided by the invention, the pentasil zeolite and the faujasite are in the same particle or in different particles.
In the catalytic cracking catalyst provided by the invention, the other inorganic oxide binders are one or more of inorganic oxides or composite oxides with binding functions, such as silica sol, alumina sol, silica-alumina gel, acidified pseudo-boehmite, phosphoalumina gel and the like.
In the catalyst cracking catalyst provided by the invention, the natural mineral substances are one or more of kaolin, halloysite, montmorillonite, kieselguhr, attapulgite, sepiolite, hydrotalcite, bentonite and rectorite.
In one embodiment, the catalytic cracking catalyst provided by the invention comprises:
a) 25 wt% to 60 wt%, e.g., 20 wt% to 50 wt% or 25 wt% to 45 wt% faujasites and pentasils on a dry basis; the weight ratio of faujasite to pentasil is preferably 1:4-4:1, for example, 0.3:1-2.9:1 or 1:3-2.8:1 or 0.3:1-2:1 or 1:3-3:2;
b) 10-40 wt%, e.g., 15-35 wt%, or 10-30 wt%, or 20-30 wt%, of the zirconium-aluminum composite sol on a dry basis;
C) 15-60 wt%, e.g. 20-50 wt% or 25-55 wt% natural minerals on a dry basis; and
d) 3 wt% to 20 wt%, e.g., 5 wt% to 15 wt%, of other inorganic oxide binders on a dry basis.
In one embodiment, the catalytic cracking catalyst provided by the invention comprises:
a) 10 wt% to 60 wt%, e.g., 15 to 55 wt% or 20 wt% to 50 wt% or 25 wt% to 45 wt% five membered ring zeolite on a dry basis; no faujasite;
b) 10-40 wt%, e.g., 15-35 wt%, or 10-30 wt%, or 20-30 wt%, of the zirconium-aluminum composite sol on a dry basis;
c) 15-60 wt%, e.g. 20-50 wt% or 25-55 wt% natural minerals on a dry basis; and
d) 3 wt% to 20 wt%, e.g., 5 wt% to 15 wt%, of other inorganic oxide binders on a dry basis.
In this embodiment, the catalyst does not contain faujasite, and may be used alone or as an auxiliary agent in combination with other catalysts, for example, a catalyst containing Y zeolite and not containing pentasil, for increasing propylene yield.
In one embodiment, the catalytic cracking catalyst provided by the invention has pentasil zeolite and faujasite in different particles. Preferably, the pentasil-containing particles have the following composition:
a) 10 wt% to 60 wt%, e.g., 15 to 55 wt% or 20 wt% to 50 wt% or 25 wt% to 45 wt% five membered ring zeolite on a dry basis; no faujasite;
b) 10-40 wt%, e.g., 15-35 wt%, or 10-30 wt%, or 20-30 wt%, of the zirconium-aluminum composite sol on a dry basis;
c) 15-60 wt%, e.g. 20-50 wt% or 25-55 wt% natural minerals on a dry basis; and
d) 3 wt% to 20 wt%, e.g., 5 wt% to 15 wt%, of other inorganic oxide binders on a dry basis.
The faujasite-containing particles have the following composition:
a) 2-60 wt%, e.g., 5-60 wt% or 10-60 wt% or 15-55 wt% or 20-50 wt% or 25-45 wt% faujasite, on a dry basis; no five membered ring zeolite;
b) 10-40 wt%, e.g., 15-35 wt%, or 10-30 wt%, or 20-30 wt%, of the zirconium-aluminum composite sol on a dry basis;
C) 15-60 wt%, e.g. 20-50 wt% or 25-55 wt% natural minerals on a dry basis; and
d) 3 wt% to 20 wt%, e.g., 5 wt% to 15 wt%, of other inorganic oxide binders on a dry basis.
In the mixture of particles comprising faujasite and particles comprising pentasil, the particles comprising pentasil comprise 10 to 90% by weight, for example 20 to 85% by weight or 30 to 70% by weight.
According to the preparation method of the catalyst provided by the invention, in one embodiment, the preparation method of the zirconium-aluminum composite sol comprises the following steps:
(1) Mixing zirconium dioxide precursor with water, and exchanging with anion exchange resin to obtain a first mixture, wherein the pH value of the first mixture is 2-5;
(2) Contacting the alumina precursor, optionally water, and the first mixture to form a second mixture having a pH preferably in the range of 2 to 5; and
optionally, (3) mixing the second mixture with a surfactant to obtain the zirconium-aluminum composite sol provided by the invention.
According to the preparation method of the catalyst provided by the invention, in the preparation method of the zirconium-aluminum composite sol, the mixture of the zirconium oxide precursor and water is subjected to pH value adjustment by using anion exchange resin to form a first mixture with the pH value of 2-5. Preferably, the pH of the first mixture is from 2.2 to 4.5, preferably from 2.5 to 4. Preferably, the zirconium content of the first mixture is from 0.5 to 20% by weight, for example from 1 to 15% by weight or from 2 to 10% by weight or from 5 to 20% by weight. The pH of the mixture can be adjusted by adjusting the amount of anion exchange resin and the exchange time. There is no special requirement on the amount of anion exchange resin and the exchange time, so long as the pH value after the exchange can be ensured to be 2-5. The zirconium dioxide precursor and the anion exchange resin can be used in an amount of, for example, 1: (1-20) (mass ratio) and the exchange time is 0.01-2h, such as 1min-60min. Preferably, the operating temperature of the exchange: 0℃to 50℃e.g.5℃to 40 ℃. In one embodiment, the zirconium dioxide precursor is mixed with water and, after addition to the anion exchange resin, filtered to obtain a first mixture, preferably, the exchange is such that the pH of the first mixture is from 2 to 5, such as from 2 to 4 or from 2.5 to 3.5 or from 2.2 to 4.5 or from 2.5 to 4. In one embodiment, after the addition of the anion exchange resin, the zirconium dioxide precursor is exchanged with the anion exchange resin by a residence time of greater than 0 to 2 hours, such as 1min to 1 hour or 5 to 50min, at 0 ℃ to 50 ℃, such as 5 to 40 ℃ or 25 ℃. In another embodiment, a mixture of zirconium dioxide precursor and water is passed through an anion exchange resin for ion exchange.
According to the preparation method of the catalyst, in the preparation method of the zirconium-aluminum composite sol, a first mixture, an alumina precursor and optional water form a second mixture, and acid is added to adjust the pH value of the mixture, so that the pH value of the mixture is 2-5, and the second mixture with the pH value of 2-5 is obtained after a period of reaction; preferably, the reaction temperature at which the alumina precursor, water, acid and first mixture are reacted is from 0 ℃ to 50 ℃, e.g. from 5 ℃ to 40 ℃, for a reaction time of from 0.01 to 2 hours or from 0.5 to 2 hours, e.g. from 1min to 1 hour, e.g. from 5 to 50min. In one embodiment, the alumina precursor is first mixed with water to form an alumina precursor-containing water mixture (referred to as a third mixture), and then mixed with the first mixture, and acid is added while mixing, wherein the pH of the mixture is controlled to be 2-5 throughout the mixing process to obtain a second mixture. In another embodiment, the alumina precursor is first mixed with water to form a mixture, the pH of the mixture is adjusted to 2-5 by adding acid to obtain a third mixture, and then the third mixture is mixed with the first mixture to obtain a second mixture, wherein the pH of the second mixture is 2-5. The alumina precursor is mixed with water to form a mixture, and the mixture may be stirred for 0.1 to 5 hours at a temperature of 0 to 50 ℃, and the solid content of the mixture is preferably 5 to 20% by weight. The acid may be selected from at least one of an inorganic acid and an organic acid dissolved in water, preferably at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid, and most preferably hydrochloric acid.
According to the catalyst preparation method provided by the invention, the second mixture can be directly used for catalyst preparation as zirconium-aluminum composite sol. Preferably, according to the preparation method of the zirconium-aluminum composite sol, the surfactant is added into the second mixture, and the mixture is stirred uniformly, for example, for 0.2-5h, so as to obtain a fourth mixture. The fourth mixture is used as the zirconium aluminum composite solution, and the pH of the fourth mixture, namely the zirconium aluminum composite sol, is preferably 2-5.
According to the method for preparing the zirconium-aluminum composite sol provided by the invention, preferably, the aluminum oxide precursor and the zirconium dioxide precursor are used in an amount such that the content of aluminum element in the prepared zirconium-aluminum composite sol is 1-10 wt%, further preferably, the content of aluminum element is 2-6 wt%, for example, 3-5 wt% or 4-5 wt%, still further preferably, the content of aluminum element is 4.5-6 wt%; the content of the zirconium element is 0.5 to 10% by weight, more preferably, the content of the zirconium element is 0.6 to 6% by weight, for example, 1 to 6% by weight or 0.7 to 2.2% by weight, still more preferably, the content of the zirconium element is 1.4 to 2.2% by weight.
According to the preparation method of the zirconium-aluminum composite sol provided by the invention, preferably, the surfactant is used in an amount such that the content of the surfactant in the prepared zirconium-aluminum composite sol is 0.5-10 wt%, for example 0.5-2 wt% or 1-2 wt%, and more preferably 0.5-1.5 wt% or 0.8-1.5 wt% of the content of aluminum element.
According to the present invention, the zirconia precursor solution is contacted with an anion exchange resin, which may be strongly basic or weakly basic, and the present invention is not particularly limited thereto, and preferably the anion exchange resin is at least one selected from the group consisting of strong base type #201, strong base type 201×7, weak base 330, weak base type 301, amerlite XE-98, dowex2, amerlite IR-4B, dowex 3, lewatit MII; further preferably at least one of strong base type #201, strong base type 201×7, amerlite XE-98, lewatit MII; most preferred is the strong base 201X 7. The adoption of the preferred embodiment of the invention is more beneficial to adjusting the pH value of the zirconium solution to form the zirconium-aluminum composite sol.
According to the invention, the alumina precursor is an aluminium-containing substance capable of forming aluminium oxide by calcination after the treatment to form the second mixture. Preferably, the alumina precursor is selected from at least one of SB powder, pseudo-boehmite, alumina trihydrate, boehmite, alumina sol and amorphous aluminum hydroxide, more preferably SB powder and/or pseudo-boehmite.
According to the invention, the zirconium dioxide precursor is a zirconium-containing substance which is able to form zirconium dioxide by calcination after the treatment to form the second mixture. Preferably, the zirconium dioxide precursor is at least one selected from zirconium tetrachloride, zirconium oxychloride, zirconium acetate, zirconium sulfate, hydrous zirconium oxide and amorphous zirconium dioxide, more preferably zirconium tetrachloride and/or zirconium oxychloride.
According to the method for preparing the catalyst provided by the invention, in the method for preparing the zirconium aluminum composite sol, the acid in the step (2) can be at least one selected from inorganic acid and organic acid which are dissolved in water, preferably at least one selected from hydrochloric acid, nitric acid, phosphoric acid and acetic acid, and most preferably hydrochloric acid.
According to the preparation method of the catalyst provided by the invention, in the preparation method of the zirconium-aluminum composite sol, the types of the surfactant are as described above, and are not described in detail herein. Preferably, the surfactant is selected from nonionic surfactants, more preferably from at least one of polyoxyethylene-8-octylphenyl ether, fatty alcohol polyoxyethylene ether, fatty acid methyl polyoxyethylene ether, polyethylene glycol, hydroxypropyl cellulose, fatty acid polyoxyethylene ester, fatty acid glyceride, fatty acid sorbitan, polysorbate, triethanolamine soap sucrose ester and polyol sucrose ester, still more preferably from at least one of polyoxyethylene-8-octylphenyl ether, fatty alcohol polyoxyethylene ether and polysorbate, and most preferably from polyoxyethylene-8-octylphenyl ether.
The preparation method of the catalytic cracking catalyst provided by the invention comprises the steps of mixing and pulping pentasil, optional faujasite, natural minerals, water, zirconium-aluminum composite sol and other inorganic oxide binders to form catalyst slurry, and then spray drying.
The preparation method of the catalytic cracking catalyst provided by the invention comprises the following steps of taking the sum of the dry basis weight of pentasil zeolite, faujasite, natural mineral substances, zirconium-aluminum composite sol and other inorganic oxide binders as 100 parts by weight, wherein the weight ratio of the faujasite to the pentasil zeolite is preferably 1:10-4:1, and the weight ratio of the faujasite to the pentasil zeolite is 5-60 parts by weight, the weight ratio of the natural mineral substances is 10-65 parts by weight, and the weight ratio of the other inorganic oxide binders is preferably 1:10-4:1. Preferably, the natural minerals comprise 20 to 55 parts by weight, the zirconium aluminum composite sol comprises 10 to 40 parts by weight, for example 15 to 35 parts by weight, the faujasite and the pentasil comprise 25 to 60 parts by weight, for example 25 to 50 parts by weight, the other inorganic oxide binder comprises 3 to 20 parts by weight, for example 5 to 15 parts by weight, and the weight ratio of the faujasite to the pentasil is 0.3:1 to 2:0.1.
The natural minerals of the present invention are clay raw materials well known to those skilled in the art, and common clay types may be used in the present invention, and for the present invention, it is preferable that the clay is one or more of kaolin, montmorillonite, diatomaceous earth, halloysite, quasi-halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. For the present invention, the clay is preferably one or more of sepiolite, kaolin and halloysite, and further preferably kaolin. The other inorganic oxide binder is one or more of aluminum sol, silica sol, acidified pseudo-boehmite, silica alumina sol, and phosphoalumina sol, and preferably aluminum sol.
In the preparation method of the catalytic cracking catalyst provided by the invention, the molecular sieve is a molecular sieve raw material well known in the art, and the molecular sieve types commonly used in the art can be used in the invention, and aiming at the invention, the faujasite is preferably YMolecular sieves of the type Y, preferably REY, REHY, REUSY, USY, are prepared by gas phase chemical methods (SiCl 4 Al-removing and Si-supplementing method), liquid phase chemical method ((NH) 4 ) 2 SiF 6 Aluminum extraction and silicon compensation) and other methods, the faujasite is preferably a USY molecular sieve such as a DASY molecular sieve, and the USY molecular sieve can be one or more of a hydrogen type USY molecular sieve, a phosphorus and rare earth-containing USY molecular sieve, a phosphorus-containing USY molecular sieve and a rare earth-containing USY molecular sieve.
The pentasil zeolite comprises at least one of rare earth-containing pentasil zeolite, phosphorus-containing pentasil zeolite, iron-containing pentasil zeolite and phosphorus-containing and transition metal-containing pentasil zeolite, wherein the transition metal is one or more of RE, fe, cu, zn, mn, co, ni, sn, ti, and the transition metal is preferably RE and/or Fe. Preferably, the pentasil is a rare earth-containing pentasil and/or a phosphorus-and iron-containing pentasil. More preferably, the pentasil zeolite is a pentasil zeolite containing phosphorus and rare earth and/or iron and/or a pentasil zeolite containing rare earth, and the Y-type molecular sieve is a DASY molecular sieve. The pentasil zeolite is, for example, ZSM-5 zeolite.
The phosphorus-and/or transition metal-containing pentasil zeolite may be commercially available or prepared according to a conventional method, for example, the transition metal-containing pentasil zeolite such as rare earth may be obtained by subjecting a hydrogen-type pentasil zeolite or a sodium-type pentasil zeolite to ion exchange with a salt of a transition metal such as a rare earth salt solution or a solution of a transition metal-containing salt such as a rare earth salt with an inorganic ammonium salt, followed by filtration, washing, and calcination under a 0-100% steam atmosphere at 300-700 c, and the sodium oxide content in the obtained rare earth-modified pentasil zeolite is preferably not higher than 0.5% by weight, for example not higher than 0.2% by weight. The phosphorus may be introduced by impregnation.
According to the method for producing a catalytic cracking catalyst of the present invention, the solid content of the catalyst slurry is preferably 20% by weight or more, and more preferably 20 to 40% by weight.
According to a preferred embodiment of the present invention, the total content of faujasite and pentasil in the catalyst slurry is 20-55 wt%, preferably 25-45 wt%, on a dry basis, based on the weight of the catalyst slurry; the clay content is 10-50 wt%, preferably 35-45 wt%, on a dry basis; the content of the zirconium-aluminum composite sol is 6-50 wt%, preferably 10-40 wt%, or 10-25 wt%, or 15-35 wt%, on a dry basis, and the content of the aluminum sol is 3-20 wt%, preferably 5-15 wt%, on a dry basis.
In the invention, the dry basis content, the solid content and the burning basis content refer to the ratio of the weight of a sample after being roasted at 800 ℃ for 1 hour to the weight of the sample before being roasted.
According to the preparation method of the catalytic cracking catalyst, catalyst slurry is spray-dried to obtain catalyst microspheres, and preferably, the catalyst microspheres are roasted to obtain the catalytic cracking catalyst. The calcination method is an existing method, for example, the calcination temperature is 400-600 ℃ and the calcination time is 0.5-4 hours, preferably 1-3 hours.
The preparation method of the catalytic cracking catalyst provided by the invention comprises the following steps: pulping natural minerals and water, adding part of other inorganic oxide binders, and stirring to obtain slurry A; the faujasite such as Y-type molecular sieve and pentasil is pulped with water to obtain molecular sieve slurry, slurry A is mixed with molecular sieve slurry, and finally the rest of other inorganic oxide binder and zirconium-aluminum composite sol are added, pulped and stirred to obtain catalyst slurry, the catalyst slurry is spray-dried, and the obtained catalyst microsphere is roasted for 1-3 hours such as 500 ℃ at 450-550 ℃ to obtain the catalytic cracking catalyst. Wherein in one manner, the amount of other inorganic oxide binder added to slurry a is from 10 to 30 wt%, e.g., from 20 to 30 wt%, on a dry basis, of the total amount of other inorganic oxide binder added.
The present invention will be described in detail by examples.
The raw materials used in the catalyst preparation were as follows:
SB powder: commercially available from Sasol, germany, 75% by weight solids;
pseudo-boehmite: commercially available from Shandong aluminum company, 74% by weight solids;
zirconium oxychloride: commercially available from Aldrich company, analytically pure, 98.5%;
triton X-100: polyoxyethylene-8-octylphenyl ether, commercially available from the dow company, usa, analytically pure, 99%;
kaolin: the solid content was 75% by weight, produced by chinese kaolin limited (su zhou);
DASY molecular sieves: qilu catalyst division, rare earth content of 2.3 wt%, silicon-aluminum ratio (SiO 2 /Al 2 O 3 ) 6, crystallinity 65%; a solids content of 85% by weight;
ZSP-3 molecular sieve: qilu catalyst division, P 2 O 5 The content of (C) is 3.02 wt%, fe 2 O 3 Content 1.5 wt%; solids content 75 wt%
Aluminum sol: produced by Shandong aluminum factory, the solid content is 21 weight percent.
Hydrochloric acid: chemically pure, produced by beijing chemical plant, at a concentration of 37 wt%;
nitric acid: chemically pure, produced by beijing chemical plant at a concentration of 69.2% by weight;
fatty alcohol polyoxyethylene ether: MOA-3, purchased from Jiangsu province sea-An petrochemical plant, analytical purity;
Strong base 201 x 7 anion exchange resin: gallery sennater chemical company, inc.
The element content in the zirconium-aluminum composite sol is determined by ICP-OES inductively coupled plasma-atomic emission spectrometry GB/T30902-2014.
Preparation of zirconium aluminum composite sol example 1
(1) 100g of water was added to a beaker, followed by 33g of zirconium oxychloride, a strong base type 201X 7 anion exchange resin was added, the pH value was controlled to 3, and then a first mixture was obtained by filtration; 432g of deionized water is added into another beaker, 5.3g of hydrochloric acid is slowly added, 71g of SB powder is then added, and the mixture is dispersed in a homogenizer for 30 minutes to obtain a third mixture; mixing the two materials (the first mixture and the third mixture), and dispersing in a homogenizer for 20min to obtain a second mixture; to the second mixture was added 0.3g of the surfactant triton X-100 and stirred at 20℃for 30min. The zirconium aluminum composite sol A1 is obtained, and the pH value is 3.13.
The resultant zirconium-aluminum composite sol A1 was subjected to ICP-OES analysis, and the results are shown in Table 1.
Drying the obtained zirconium-aluminum composite sol A1 at 100 ℃ for 6 hours, roasting at 600 ℃ for 6 hours to obtain a solid, and carrying out XRD analysis on the solid, wherein diffraction peaks exist at positions of 30 degrees+/-0.5 degrees, 36 degrees+/-0.5 degrees, 46 degrees+/-0.5 degrees, 51 degrees+/-0.5 degrees, 61 degrees+/-0.5 degrees and 67 degrees+/-0.5 degrees in an XRD spectrogram. Wherein 2 theta is 30 DEG + -0.5, 36 DEG + -0.5 DEG, 51 DEG + -0.5 DEG, 61 DEG + -0.5 DEG, the diffraction peak at which corresponds to tetragonal phase zirconium dioxide; diffraction peaks are present at a 2 theta of 46 DEG + -0.5 DEG and 67 DEG + -0.5 DEG, corresponding to gamma-Al 2 O 3 Is a diffraction peak of (2). No diffraction peak was detected at 28 ° ± 0.5 °, 31.4 ° ± 0.5 °. The corrosion rate of the zirconium aluminum composite sol and the pore volume, average pore size of the solid were analyzed and the results are shown in table 1.
Preparation example 2 of zirconium aluminum composite sol
This example illustrates the zirconium aluminum composite sol and the preparation method thereof.
Adding 100g of water into a beaker, then adding 33g of zirconium oxychloride, adding a strong base type 201X 7 anion exchange resin, reacting for 15min at 20 ℃, and then filtering to obtain a first mixture with the pH value of 3; adding 262g of deionized water into another beaker, adding 50g of SB powder, pulping and stirring for 10min, slowly adding into the first mixture, adding hydrochloric acid while adding 4g of hydrochloric acid, and dispersing in a homogenizer for 30min to obtain a second mixture; to the second mixture was added 0.2g of the surfactant triton X-100 and stirred at 20℃for 30min. The zirconium aluminum composite sol A2 is obtained, and the pH value is 3.25.
The resultant zirconium-aluminum composite sol A2 was subjected to ICP-OES analysis, and the results are shown in Table 1.
Drying the obtained zirconium-aluminum composite sol A2 at 100 ℃ for 6 hours, and then roasting at 600 ℃ for 6 hours to obtain a solid, and carrying out the treatment on the solidXRD analysis is carried out, the XRD spectrum is similar to that of A1, and diffraction peaks exist at positions of 30 degrees+/-0.5 degrees, 36 degrees+/-0.5 degrees, 46 degrees+/-0.5 degrees, 51 degrees+/-0.5 degrees, 61 degrees+/-0.5 degrees and 67 degrees+/-0.5 degrees on the XRD spectrum. Wherein 2 theta is 30 DEG + -0.5, 36 DEG + -0.5 DEG, 51 DEG + -0.5 DEG, 61 DEG + -0.5 DEG, the diffraction peak at which corresponds to tetragonal phase zirconium dioxide; diffraction peaks are present at a2 theta of 46 DEG + -0.5 DEG and 67 DEG + -0.5 DEG, corresponding to gamma-Al 2 O 3 Is a diffraction peak of (2). No diffraction peak was detected at 28 ° ± 0.5 °, 31.4 ° ± 0.5 °. A2 corrosion rate and pore volume, average pore size of the solid are shown in Table 1.
Preparation example 3 of zirconium aluminum composite sol
100g of water was added to a beaker, then 16g of zirconium oxychloride was added, a strong base type 201X 7 anion exchange resin was added, the pH value was controlled to 4, and then a first mixture was obtained by filtration; 432g of deionized water is added into another beaker, 5.3g of hydrochloric acid is slowly added, 71g of SB powder is then added, and the mixture is dispersed in a homogenizer for 30 minutes to obtain a third mixture; mixing the first mixture and the third mixture, and dispersing in a homogenizer for 20min to obtain a second mixture; to the second mixture was added 0.3g of triamcinolone acetonide X-100 as a surfactant, and the mixture was stirred at 45℃for 30 minutes to obtain a zirconium aluminum composite sol A3 having a pH of 3.86, and the results of the ICP-OES analysis are shown in Table 1.
Drying the obtained zirconium-aluminum composite sol A3 at 100 ℃ for 6 hours, roasting at 600 ℃ for 6 hours to obtain a solid, and carrying out XRD analysis on the solid, wherein the XRD spectrum of the solid is similar to that of A1, and diffraction peaks exist at positions of 30 degrees+/-0.5 degrees and 2 theta of 36 degrees+/-0.5 degrees, 46 degrees+/-0.5 degrees, 51 degrees+/-0.5 degrees, 61 degrees+/-0.5 degrees and 67 degrees+/-0.5 degrees on the XRD spectrum. Wherein 2 theta is 30 DEG + -0.5, 36 DEG + -0.5 DEG, 51 DEG + -0.5 DEG, 61 DEG + -0.5 DEG, the diffraction peak at which corresponds to tetragonal phase zirconium dioxide; diffraction peaks are present at a2 theta of 46 DEG + -0.5 DEG and 67 DEG + -0.5 DEG, corresponding to gamma-Al 2 O 3 Is a diffraction peak of (2). No diffraction peak was detected at 28℃0.5℃31.4℃0.5℃for 2. Theta. Indicating that Zr was mainly tetragonal ZrO 2 Exists. A3 corrosion rates and pore volumes of the solids, average pore diameters are shown in Table 1.
Substrate preparation comparative example 1
Alumina sol: 772g of deionized water was added to the beaker, 167g of SB powder was then added, dispersed in a homogenizer for 30min, and 21g of hydrochloric acid was added for acidification to obtain alumina sol D1.
Substrate preparation comparative example 2
The procedure of matrix preparation example 1 was followed except that no anion exchange resin was added to the second mixture to obtain zirconium aluminum composite sol D2.
The resultant zirconium-aluminum composite sol D2 was subjected to ICP-OES analysis, and the results are shown in Table 1.
Comparative example 3
(1) 440g of deionized water is added into a beaker, 140g of SB powder is then added, 21g of hydrochloric acid is slowly added, and the mixture is dispersed in a homogenizer for 30min; to another beaker was added 337g of water followed by 52g of zirconium oxychloride; mixing the materials in the two beakers, and dispersing in a homogenizer for 20min to obtain a first mixture; to the first mixture was added 0.8g of the surfactant triton X-100, and the mixture was stirred at 20℃for 30min at a rotational speed of 150r/min.
(2) And (3) placing the reaction product in the step (1) into an ultrasonic water bath, and reacting for 120min at the reaction temperature of 30 ℃ under the frequency of 50KHz and the power of 280W to obtain the zirconium-aluminum composite sol D3.
(3) The zirconium aluminum composite sol D3 is dried at 100 ℃ for 6 hours, and then is baked at 600 ℃ for 6 hours to obtain a solid with diffraction peaks at 28 degrees and 31 degrees of 2 theta and 30 degrees, 35 degrees, 50 degrees, 60 degrees, 46 degrees and 67 degrees of 2 theta; peaks at 28 DEG + -0.5 DEG and 31.4 DEG + -0.5 DEG for 2 theta correspond to ZrO 2 The peaks at 2 theta of 30.3 DEG + -0.5, 35 DEG + -0.5 DEG, 50 DEG + -0.5 DEG, 60 DEG + -0.5 DEG correspond to ZrO 2 Tetragonal phase(s); diffraction peaks are present at 46 DEG + -0.5 DEG and 66.6 DEG + -0.5 DEG for 2 theta, corresponding to gamma-Al 2 O 3 Is a diffraction peak of (2).
Preparation example 4 of zirconium aluminum composite sol
The procedure of example 1 was followed except that hydrochloric acid was replaced with dilute nitric acid (69% by weight) of the same molar concentration, to obtain zirconium aluminum composite sol A4.
The resultant zirconium-aluminum composite sol A4 was subjected to ICP-OES analysis, and the results are shown in Table 1.
Drying the obtained zirconium-aluminum composite sol A4 at 100 ℃ for 6 hours, roasting at 600 ℃ for 6 hours to obtain a solid, carrying out XRD analysis on the solid, wherein diffraction peaks exist at positions of 30 degrees+/-0.5 degrees, 36 degrees+/-0.5 degrees, 46 degrees+/-0.5 degrees, 51 degrees+/-0.5 degrees, 61 degrees+/-0.5 degrees and 67 degrees+/-0.5 degrees on an XRD spectrogram. Wherein 2 theta is 30 DEG + -0.5, 36 DEG + -0.5 DEG, 51 DEG + -0.5 DEG, 61 DEG + -0.5 DEG, the diffraction peak at which corresponds to tetragonal phase zirconium dioxide; diffraction peaks are present at a 2 theta of 46 DEG + -0.5 DEG and 67 DEG + -0.5 DEG, corresponding to gamma-Al 2 O 3 Is a diffraction peak of (2). No diffraction peak was detected at 28 ° ± 0.5 °, 31.4 ° ± 0.5 °. A4 and the pore volume of the solid, and the average pore size are shown in table 1.
TABLE 1
Catalyst preparation example 1:
and (3) preparing a catalyst: firstly, pulping 200g of kaolin to obtain slurry with the solid content of 40 wt%, and adding 74g of aluminum sol for pulping; 88g of DASY molecular sieve and 133g of ZSP-3 molecular sieve are taken, added with water for pulping, and dispersed by a homogenizer to obtain molecular sieve slurry with the solid content of 35 weight percent; mixing and stirring kaolin slurry and molecular sieve slurry, adding zirconium-aluminum composite sol A1, finally adding 164g of aluminum sol, and stirring for 30min. And (3) spray drying the catalyst slurry, and roasting the obtained catalyst microsphere at 500 ℃ for 2 hours to obtain the catalytic cracking catalyst C1. The catalyst attrition index and relative crystallinity characterization results are shown in table 2. The composition of C1 weight percent on a dry basis was calculated from the feed amounts and is shown in Table 2.
Catalyst preparation examples 2-7,
the catalyst was prepared as in example 1: pulping kaolin to prepare slurry with the solid content of 40 wt%, and adding alumina sol (called alumina sol 1) to pulp to obtain kaolin slurry; adding water into DASY molecular sieve and ZSP-3 molecular sieve to pulp, and dispersing by using a homogenizer to obtain molecular sieve slurry with the solid content of 35 wt%; mixing and stirring kaolin slurry and molecular sieve slurry, adding zirconium-aluminum composite sol, finally adding aluminum sol (called aluminum sol 2), stirring for 30min to obtain catalyst slurry, spray-drying the catalyst slurry, and roasting the obtained catalyst microsphere at 500 ℃ for 2 hours to obtain the catalytic cracking catalyst.
In each example, the catalyst C2-C7 was obtained by using A1, A2, A3 or A4 zirconium aluminum composite sol, and the DASY molecular sieve and the ZSP-3 molecular sieve were different in proportion, and the compositions thereof are shown in Table 2 (the compositions of Table 2 are weight percent compositions in terms of dry basis, and are calculated according to the feeding amount).
TABLE 2
Catalyst preparation comparative examples 1 to 4
Catalyst preparation A catalyst was prepared according to the procedure of catalyst preparation example 1, the composition of which is shown in Table 2.
The relative crystallinity and attrition index of the catalyst were measured by the methods RIPP146-90 and RIPP29-90 in petrochemical analysis methods, RIPP test methods (Yang Cui, scientific Press, 1990). The results are shown in Table 2.
Catalyst evaluation:
the catalyst was subjected to a 100% steam aging deactivation treatment at 800℃for 17 hours. The evaluation was carried out on the fixed fluidized bed micro-reverse ACE, wherein the raw oil was a hydrogenated modified oil (composition and physical properties are shown in Table 3), and the evaluation conditions were: the reaction temperature is 560 ℃, the catalyst-to-oil ratio (weight) is 10, and the weight hourly space velocity is 16h -1 . The results are shown in Table 4.
Wherein conversion = gasoline yield + liquefied gas yield + dry gas yield + coke yield
C3 olefin selectivity = C3 olefin yield/LPG yield x 100%
Low olefin yield = propylene yield + ethylene yield
TABLE 3 Table 3
| Project | Raw oil |
| Density (20 ℃), g/cm 3 | 0.9334 |
| Refraction (70 ℃ C.) | 1.5061 |
| Four components, m% | |
| Saturated hydrocarbons | 55.6 |
| Aromatic hydrocarbons | 30 |
| Colloid | 14.4 |
| Asphaltenes | <0.1 |
| Freezing point, DEG C | 34 |
| Metal content, ppm | |
| Ca | 3.9 |
| Fe | 1.1 |
| Mg | <0.1 |
| Na | 0.9 |
| Ni | 3.1 |
| Pb | <0.1 |
| V | 0.5 |
| C m％ | 86.88 |
| H m％ | 11.94 |
| S m％ | 0.7 |
| Carbon residue m% | 1.77 |
| H m％ | 11.94 |
TABLE 4 Table 4
As can be seen from Table 4, the catalytic cracking catalyst provided by the invention has better abrasion strength and higher relative crystallinity. In the catalytic cracking reaction, the catalyst has higher hydrocarbon oil conversion rate, higher ethylene yield, obviously higher propylene yield, higher liquefied gas yield, higher low-carbon olefin yield and higher propylene selectivity.
Claims (33)
1. A catalytic cracking catalyst comprising, on a dry weight basis, the catalyst:
a) 5-75 wt% five-membered ring zeolite, on a dry basis, said five-membered ring zeolite having a major pore size of less than 0.57nm;
b) 0-70 wt% faujasite zeolite on a dry basis;
c) 10-65 wt% natural minerals on a dry basis;
d) 10-60 wt% of a zirconium-aluminum composite sol on a dry basis; in the zirconium-aluminum composite sol, the content of zirconium element is 0.5-10 wt%, the content of aluminum element is 1-10 wt%, the content of chloride ion is not more than 0.8 wt%, and the pH value of the sol is 2-5; drying the composite sol at 100 ℃ for 6 hours, and then roasting at 600 ℃ for 6 hours to obtain a solid, wherein in the XRD spectrum of the solid, diffraction peaks are detected at positions of 30 DEG+/-0.5 DEG, 35 DEG+/-0.5 DEG, 51 DEG+/-0.5 DEG and 61 DEG+/-0.5 DEG, no diffraction peaks are detected at positions of 28 DEG+/-0.5 DEG and 31.4 DEG+/-0.5 DEG, the zirconium-aluminum composite sol contains a surfactant, and the surfactant is at least one selected from polyoxyethylene-8-octylphenyl ether, fatty alcohol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, polyethylene glycol, hydroxypropyl cellulose, fatty acid polyoxyethylene ester, fatty acid glyceride, fatty acid sorbitan, polysorbate, triethanolamine soap sucrose ester and polyol sucrose ester, the content of the surfactant is 0.5-10 wt% of aluminum element content, and the corrosion rate of the zirconium-aluminum composite sol is 0.5-10mm/a;
And E) 3% to 20% by weight, on a dry basis, of other inorganic oxide binders.
2. The catalytic cracking catalyst of claim 1, wherein the zirconium aluminum composite sol has a corrosion rate of 3-5mm/a.
3. The catalytic cracking catalyst of claim 1, wherein the pH of the zirconium aluminum composite sol is 2.2-4.5.
4. The catalytic cracking catalyst according to claim 1, wherein the content of aluminum element in the zirconium-aluminum composite sol is 2 to 6 wt%, and the content of zirconium element is 1 to 6 wt%; the content of chloride ion is 0.1-0.8 wt%; the weight ratio of the aluminum element to the zirconium element is (0.3-6.5): 1.
5. the catalytic cracking catalyst of claim 1, wherein;
the content of the surfactant is 0.5-2 wt% of the content of aluminum element.
6. The catalytic cracking catalyst of claim 1, wherein the solid has an XRD pattern with diffraction peaks at 46 ° ± 0.5 °, 67 ° ± 0.5 ° 2Θ; zirconium in the solid is present predominantly as tetragonal phase zirconium dioxide.
7. The catalytic cracking catalyst of any one of claims 1-6, wherein the solids have a pore volume of 0.3-0.7cc/g and an average pore diameter of 5-15nm.
8. The catalytic cracking catalyst according to claim 1, wherein the catalyst contains faujasite, and the total content of faujasite and pentasil is 22-75 wt% on a dry basis.
9. The catalytic cracking catalyst of claim 8, wherein the weight ratio of faujasite to pentasil is 0-14:1.
10. The catalytic cracking catalyst of claim 4, wherein the pentasil zeolite comprises at least one of rare earth-containing pentasil zeolite, phosphorus-containing pentasil zeolite, iron-containing pentasil zeolite, and phosphorus-and transition metal-containing pentasil zeolite, the transition metal being one or more of RE, fe, cu, zn, mn, co, ni, sn, ti, and the faujasite being one or more of REY, REHY, REUSY, USY; the other inorganic oxide binder comprises one or more of silica sol, alumina sol, acidified pseudo-boehmite, silica-alumina gel and phosphoalumina gel; the natural mineral substances comprise one or more of kaolin, diatomite, montmorillonite, attapulgite, hydrotalcite, sepiolite, rectorite and bentonite.
11. The catalytic cracking catalyst of claim 1, wherein the catalytic cracking catalyst is:
A) The total content of faujasite and pentasil is 25-60 wt% on a dry basis;
b) The content of the zirconium-aluminum composite sol is 10-40 percent based on dry basis;
c) The content of other inorganic oxide binders is 3% -20% on a dry basis; and
d) The natural mineral content is 20 wt% to 55 wt% on a dry basis.
12. A catalytic cracking catalyst according to claim 3, wherein the pH of the zirconium aluminium composite sol is 3-4.
13. The catalytic cracking catalyst according to claim 4, wherein the weight ratio of aluminum element to zirconium element is (2-3.2): 1.
14. the catalytic cracking catalyst according to claim 5, wherein the surfactant is contained in an amount of 1 to 1.5% by weight based on the aluminum element.
15. The catalytic cracking catalyst of claim 7, wherein the solids have a pore volume of 0.4-0.57cc/g and an average pore diameter of 7-10nm.
16. The catalytic cracking catalyst of claim 9, wherein the weight ratio of faujasite to pentasil is 0.1:1-4:1.
17. the catalytic cracking catalyst of claim 9, wherein the weight ratio of faujasite to pentasil is 1:5-2:1.
18. The catalytic cracking catalyst of claim 10, wherein the pentasil zeolite is a ZSM-5 zeolite.
19. A method of preparing the catalytic cracking catalyst of claim 1, comprising: mixing five-membered ring zeolite, optional faujasite, natural minerals, zirconium-aluminum composite sol and other inorganic oxide binders, pulping, and spray drying; the preparation method of the zirconium-aluminum composite sol comprises the following steps:
(1) Mixing zirconium dioxide precursor with water, and exchanging with anion exchange resin to obtain a first mixture, wherein the pH value of the first mixture is 2-5;
(2) Reacting the alumina precursor, optionally water, acid, and the first mixture to form a second mixture, the second mixture having a pH of 2 to 5; and
(3) The second mixture is mixed with a surfactant.
20. The preparation method of claim 19, wherein the anion exchange resin is at least one selected from the group consisting of strong base #201, strong base 201 x 7, weak base 330, weak base #301, amerlite XE-98, dowex2, amerlite IR-4B, dowex 3, lewatit MII.
21. The method of claim 19, wherein the exchanging results in a first mixture having a pH of 2.2-4.5;
The zirconium dioxide precursor is at least one selected from zirconium acetate, zirconium tetrachloride, zirconium oxychloride, hydrous zirconium oxide and amorphous zirconium dioxide.
22. The method of claim 19, wherein the exchange is at a temperature of 0 ℃ to 50 ℃ for a time period of greater than 0 and no more than 2 hours.
23. The process according to claim 19, wherein the second mixture has a pH of 2 to 4 and the mixture obtained in step (3) has a pH of 2 to 5.
24. The process according to claim 23, wherein the pH of the mixture obtained in step (3) is 2 to 4.
25. The process according to claim 19, wherein the pH of the second mixture is adjusted to 2-5 by adding an acid in the step (2); the reaction temperature of the alumina precursor, optionally water, and the first mixture is from 0 ℃ to 50 ℃ and the reaction time is from 0.01 to 2 hours.
26. The process of claim 25, wherein the reaction temperature for reacting the alumina precursor, the optional water, and the first mixture is from 5 to 40 ℃ for a reaction time of from 10 to 50 minutes.
27. The method of claim 25, wherein the acid is at least one of hydrochloric acid, nitric acid, phosphoric acid, and acetic acid.
28. The method of claim 19, wherein the reacting the alumina precursor, the optional water, and the first mixture is performed as follows: firstly, mixing an alumina precursor with water to form a mixture, then mixing the mixture with the first mixture, regulating the pH value in the mixing process by adding acid, controlling the pH value in the mixing process to be 2-5 and the temperature to be 0-50 ℃ to obtain a second mixture, wherein the temperature of the second mixture is 0-50 ℃; or firstly forming a mixture of the alumina precursor and water, adding acid to adjust the pH value to 2-5, and then mixing with the first mixture to obtain a second mixture; the alumina precursor is at least one of boehmite, pseudo-boehmite, alumina trihydrate, alumina sol and amorphous aluminum hydroxide.
29. The production method according to claim 19, wherein the alumina precursor and the zirconia precursor are used in such an amount that the content of the aluminum element in the produced zirconium-aluminum composite sol is 1 to 10% by weight and the content of the zirconium element is 0.5 to 10% by weight;
the amount of the surfactant is such that the content of the surfactant in the prepared zirconium-aluminum composite sol is 0.5-10 wt% of the content of aluminum element; the surfactant is at least one of polyoxyethylene-8-octyl phenyl ether, fatty alcohol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, polyethylene glycol, hydroxypropyl cellulose, fatty acid polyoxyethylene ester, fatty acid glyceride, fatty acid sorbitan, polysorbate, triethanolamine soap sucrose ester and polyol sucrose ester.
30. The production method according to claim 29, wherein the content of the aluminum element in the zirconium-aluminum composite sol is 2 to 6% by weight, and the content of the zirconium element in the zirconium-aluminum composite sol is 0.6 to 6% by weight.
31. The production method according to claim 30, wherein the content of the aluminum element in the zirconium-aluminum composite sol is 4 to 5% by weight, and the content of the zirconium element in the zirconium-aluminum composite sol is 0.7 to 2.2% by weight.
32. A catalytic cracking process for producing propylene comprising the step of contacting a hydrocarbon oil with a catalytic cracking catalyst under catalytic cracking conditions, wherein the catalytic cracking catalyst comprises the catalytic cracking catalyst of any one of claims 1-18, and wherein the catalytic cracking conditions comprise: the reaction temperature is 500-650 ℃, and the reaction time is 0.5-10 seconds.
33. The catalytic cracking process according to claim 32, wherein the weight ratio of catalytic cracking catalyst to hydrocarbon oil is 5-40, and dilution gas is introduced during the reaction, the weight ratio of dilution gas to raw material is 0.1-1:1; the hydrocarbon oil is one or more of vacuum residuum, atmospheric residuum, vacuum gas oil, atmospheric gas oil, coker wax oil and hydro-modified oil.
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