CN107185586B - Catalytic cracking auxiliary agent for increasing propylene and isoamylene production, and preparation method and application thereof - Google Patents

Catalytic cracking auxiliary agent for increasing propylene and isoamylene production, and preparation method and application thereof Download PDF

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CN107185586B
CN107185586B CN201710517772.6A CN201710517772A CN107185586B CN 107185586 B CN107185586 B CN 107185586B CN 201710517772 A CN201710517772 A CN 201710517772A CN 107185586 B CN107185586 B CN 107185586B
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catalytic cracking
propylene
isoamylene
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CN107185586A (en
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李瑛�
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/38—Base treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/80—Mixtures of different zeolites
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • 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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  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to a catalytic cracking auxiliary agent for increasing propylene and isoamylene yield, and a preparation method and application thereof, wherein the catalytic cracking auxiliary agent for increasing propylene and isoamylene yield comprises 15-45 wt% of alkali modified ZSM-5 molecular sieve, 1-20 wt% of USY molecular sieve, 1-10 wt% of β zeolite and 3-25 wt% of P based on the total weight of the catalytic cracking auxiliary agent on a dry basis2O5(ii) a 3 to 25 wt% of an inorganic oxide; and the balance clay. The catalytic cracking assistant for producing more propylene and isoamylene can promote the shape selective isomerization cracking reaction of gasoline components with the carbon number of more than 8 in the catalytic cracked gasoline, can synchronously improve the yield of the propylene and the isoamylene, improve the propylene content (delta propylene/delta liquefied gas) in liquefied gas increment and produce high-octane gasoline in parallel.

Description

Catalytic cracking auxiliary agent for increasing propylene and isoamylene production, and preparation method and application thereof
Technical Field
The invention relates to a catalytic cracking auxiliary agent for producing more propylene and isoamylene, a preparation method and application thereof, which are suitable for catalytic cracking of producing more propylene and isoamylene in a catalytic cracking process and belong to the field of petroleum refining process.
Background
With the rapid development of petrochemical industry, the demand of propylene is increasing. In 2013, the domestic propylene demand is 1710 ten thousand tons per year, the yield is 1460 ten thousand tons per year, and the supply and demand gaps are large. There are many technical schemes for producing propylene in petrochemical processes, such as traditional naphtha steam cracking method, metathesis reaction technology of ethylene and butadiene, butene disproportionation reaction (CN1618512A, CN1618515A), propane dehydrogenation technology (CN 1073893A), technology of producing propylene from methanol, and catalytic cracking technology. In comparison, propylene produced by a Fluid Catalytic Cracking (FCC) process has the remarkable characteristics of low investment, wide raw material adaptability, low cost and the like, and is receiving more and more attention (US5318696A, US5997728A, US5236880A, US5472594A, CN1465527A, CN1796496A and CN 1854254A).
Methyl Tertiary Butyl Ether (MTBE) is increasingly used as a gasoline high octane blending component in the production of high grade gasoline, resulting in an increasing demand for isobutene to produce MTBE feedstock. Moreover, the catalytic cracking gasoline still accounts for about 70 percent of the domestic finished gasoline, and in various technical schemes for improving the octane value of the catalytic gasoline, the etherification treatment of the catalytic light gasoline is one of effective ways for improving the quality of the catalytic gasoline, the reaction conditions are mild, and the process is simple and environment-friendly.
The light gasoline etherification technology mainly leads tertiary carbon olefin such as isoamylene in catalytic light gasoline to carry out etherification reaction with methanol to generate high-octane ether compounds. Such as isoamylene and methanol to generate methyl tertiary amyl ether (TAME), and the octane number of the gasoline is increased from 99 to 112; isohexene reacts with methanol to produce methyl tert-hexyl ether (HXME), and the gasoline octane number increases from 90 to 100. The octane number of the gasoline is improved while the olefin of the catalytic gasoline is obviously reduced, the cheap methanol is converted into a high-value gasoline component, and the economic benefit of an enterprise is effectively increased.
Therefore, the technology of light gasoline etherification is highly regarded, and with the rapid promotion of national VI gasoline standard, the light gasoline etherification treatment capacity will rapidly increase from about 800 ten thousand tons per year to 1700 ten thousand tons per year at present. At present, one of the key factors for restricting the quality and benefit of etherification technology is that the content of tertiary carbon olefin such as isoamylene in light oil is relatively low, generally only 5-7 wt%, so that the consumption of methanol is low, approximately 7-10 wt%. Therefore, the development of a technology for effectively increasing the yield of isoamylene in light gasoline is urgent.
In the catalytic cracking reaction process, the catalyst/auxiliary agent performance is changed to achieve high yield of low-carbon olefin, so that the method has the technical advantages of flexible operation, economy, feasibility and quick response. In contrast, different types of molecular sieve modification and preparation technologies of high-yield propylene catalytic cracking catalysts/auxiliaries are developed at home and abroad, and certain application is achieved.
U.S. patent application No. 5318696A proposes a catalyst based on a large pore molecular sieve and SiO2/Al2O3A catalyst with MFI structure less than 30, and improves the existing catalytic cracking process to produce high octane gasoline and high yield of low carbon olefins, especially propylene.
US patent application US5997728A discloses a process for using a large amount of shape-selective promoter in the catalytic cracking process of heavy feedstocks. The auxiliary agent is formed by adding 12-40% of ZSM-5 molecular sieve into an amorphous matrix. The catalyst inventory includes at least 10% of a promoter such that the proportion of ZSM-5 molecular sieve in the catalyst system exceeds 3%. The method can greatly improve the low-carbon olefin without increasing the yield of aromatic hydrocarbon and losing the yield of gasoline.
The European Union patent application EP109059A1 proposes a process for the conversion of olefins from C4 to C12 to propylene. The catalyst used contains SiO2/Al2O3The molecular sieve of ZSM-5 or ZSM-11 has a molar ratio of 300 or less, a reaction temperature of 400-600 ℃ and a space velocity of more than 50 kg/h. Since ZSM-5 or ZSM-11 is not modified, the selectivity of propylene is low.
U.S. Pat. No. 4, 6566293, 1 discloses a cracking catalyst containing a phosphorus-modified ZSM-5 molecular sieve. The phosphorus-containing modified ZSM-5 molecular sieve is prepared by contacting ZSM-5 molecular sieve with aqueous solution of phosphorus-containing compound, adjusting pH of the olefin selective zeolite/phosphorus-containing compound mixture to above 4.5, and loading at least 10 wt% phosphorus-containing compound (as P) on the molecular sieve2O5And then the obtained product is pulped with matrix and other components, and is spray-dried and formed, so that the obtained catalyst has higher yield of the low-carbon olefin.
Chinese patent CN1034223C discloses a cracking catalyst for producing low-carbon olefin, which is composed of 0-70 wt% of clay, 5-99 wt% of inorganic oxide and 1-50 wt% of zeolite. Wherein the zeolite is a mixture of 1-25 wt% REY or high-silicon Y-type zeolite and 75-100 wt% pentasil zeolite containing phosphorus and rare earth. The yield of C2-C4 can be improved.
Chinese patent application CN1465527A discloses an MFI structure molecular sieve containing phosphorus and transition metal, wherein the transition metal element is one of Fe, Co and Ni. The molecular sieve is applied to the catalytic cracking process of petroleum hydrocarbon, can improve the yield and selectivity of C2-C4 olefin, and has higher liquefied gas yield.
Chinese patent CN103506155B discloses a catalytic cracking catalyst for reducing coke yield and increasing propylene yield, which comprises10-50 wt% on a dry basis of the modified Y-type molecular sieve, not more than 30 wt% on a dry basis of the molecular sieve having an MFI structure, 10-70 wt% of the clay, and 10-40 wt% on an oxide basis of the inorganic oxide binder; the modified Y-type molecular sieve has unit cell constant of 2.420-2.440nm, P in 0.05-6 wt% and RE in weight percentage2O30.03-10 wt%, alumina less than 22 wt%, and specific hydroxyl pit concentration less than 0.35 mmol/g. The catalyst can reduce coke generation, and improve the utilization rate of heavy oil and the yield of propylene.
Chinese patent application CN1796496A discloses a cracking aid for increasing propylene concentration, which comprises, on a dry basis, 10-65 wt% of a modified ZSM-5 molecular sieve, 0-60 wt% of clay, 15-60 wt% of an inorganic oxide binder, 0.5-15 wt% of one or more metal additives selected from VIIIB group metals and 2-25 wt% of a phosphorus additive, wherein the modified ZSM-5 molecular sieve is modified by phosphorus and one metal selected from Fe, Co or Ni. The cracking assistant is applied to the catalytic cracking process of petroleum hydrocarbon, and can improve the propylene concentration in liquefied gas while increasing the yield of catalytic cracking liquefied gas and improving the octane number of catalytic cracking gasoline.
Chinese patent application CN1854254A discloses a preparation method of a cracking catalyst for producing high quality gasoline and producing more propylene. The preparation method comprises the steps of uniformly mixing the prepared phosphorus-containing clay slurry, phosphorus-containing molecular sieve slurry, rare earth compound and binder slurry, and spray drying and forming, wherein the molecular sieve can be Y-type zeolite and a modified molecular sieve with an MFI structure. The prepared catalyst can produce low-olefin high-isoparaffin gasoline, and simultaneously produce more propylene and isobutane.
Chinese patent application CN1103105A discloses a catalytic cracking catalyst for high yield of isobutene and isopentene, which comprises HZSM-55-25 wt% with a silicon-aluminum ratio of 20-100, high-silicon HZSM-51-5 wt% with a silicon-aluminum ratio of 250-450, USY zeolite 5-20 wt%, β zeolite 1-5 wt%, natural clay 30-60 wt%, and inorganic oxide 15-30 wt%.
Chinese patent application CN101745413A discloses a catalytic cracking catalyst and a preparation method thereof. The catalytic cracking catalyst comprises 1-50% of modified clay based on 100% of the mass of the catalyst; 0-40% of unmodified clay; 10-60% of zeolite molecular sieve; 5-30% of a binder; 0.1 to 35 percent of alumina is added; calculated by simple substance phosphorus, the phosphorus compound is 0.1-8%; with RE2O30.1-6% of rare earth compound; wherein the modified clay is clay calcined at the temperature of 800-1100 ℃ for 0.3-10 hours. The catalytic cracking catalyst can improve the yield of propylene and the concentration of propylene in liquefied gas, and effectively reduce the yield of heavy oil.
Chinese patent CN1055105C discloses a catalytic cracking catalyst for increasing the yield of isobutene and isopentene, which comprises three zeolite components and a carrier, wherein the catalyst comprises 6-30 wt% of quinary ring high-silicon zeolite containing phosphorus and rare earth, 5-20 wt% of USY zeolite, 1-5 wt% of β zeolite, 30-60 wt% of clay and 15-30 wt% of inorganic oxide.
It can be seen that the molecular sieve catalysts/promoters prepared by the above prior art can achieve the purpose of increasing the yield of propylene to a certain extent when used in the catalytic cracking process, and thus no catalyst/promoter with high propylene and isoamylene yield and a preparation method thereof have been disclosed so far.
The reason is that the existing catalyst/auxiliary agent technology mainly cracks C5-C7 components in gasoline, and as a result, a large amount of C3-C4 components are generated, so that liquefied gas is generated while the yield of propylene and butylene is increased, the content of propylene (delta propylene/delta liquefied gas) in liquefied gas increment is low, and the isoamylene in C5 olefins is sometimes reduced.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a catalytic cracking auxiliary agent for producing more propylene and isoamylene on the basis of the prior art, which is applied to the catalytic cracking process, can synchronously improve the yield of the propylene and the isoamylene, improve the propylene content (delta propylene/delta liquefied gas) in liquefied gas increment and co-produce high-octane gasoline.
Means for solving the problems
The invention provides a catalytic cracking auxiliary agent for producing more propylene and isoamylene, wherein the catalytic cracking auxiliary agent comprises the following components in percentage by dry basis based on the total weight of the catalytic cracking auxiliary agent:
15-45 wt% of an alkali-modified ZSM-5 molecular sieve;
1-20 wt% of a USY molecular sieve;
β zeolite in an amount of 1 to 10 wt%;
3 to 25% by weight of P2O5；
3 to 25 wt% of an inorganic oxide; and
the balance being clay.
The catalytic cracking auxiliary for producing propylene and isoamylene in high yield comprises, on a dry basis, based on the total weight of the catalytic cracking auxiliary, 20-40 wt% of the alkali-modified ZSM-5 molecular sieve, 3-15 wt% of the USY molecular sieve, 2-8 wt% of the β zeolite, and P2O5The content of (a) is 5-20 wt%, the content of the inorganic oxide is 4-20 wt%, and the balance is clay.
The catalytic cracking auxiliary agent for producing more propylene and isoamylene, provided by the invention, is characterized in that the external specific surface area of the alkali modified ZSM-5 molecular sieve is 90-160 m2Preferably 100 to 150 m/g2(ii)/g; the total specific surface area of the alkali modified ZSM-5 molecular sieve is 300-360 m2Per g, preferably 310 to 350m2(ii)/g; the pore volume of the alkali modified ZSM-5 molecular sieve is 0.35-0.55 mL/g, preferably 0.36-0.45 mL/g.
According to the catalytic cracking auxiliary agent for producing propylene and isoamylene in high yield, the alkali modified ZSM-5 molecular sieve is obtained by treating the ZSM-5 molecular sieve with an alkaline substance; preferably, the alkaline substance is selected from the group consisting of Na2CO3、NaHCO3NaOH and ammonia.
The catalytic cracking assistant for high yield of propylene and isoamylene according to the invention, wherein the alkaline substance is selected from Na2CO3、NaHCO3And NaOH, the preparation method of the alkali modified ZSM-5 molecular sieve comprises the following steps: after the ZSM-5 molecular sieve reacts with alkaline substances, ammonium salt is used for ion exchange, and the reaction product is obtained by roasting; or
Under the condition that the alkaline substance is ammonia water, the preparation method of the alkali modified ZSM-5 molecular sieve comprises the following steps: the ZSM-5 molecular sieve is reacted with ammonia water and then roasted to obtain the catalyst.
The catalytic cracking assistant for high yield of propylene and isoamylene, provided by the invention, wherein the inorganic oxide is derived from an inorganic binder and/or pseudo-boehmite;
preferably, the inorganic binder is selected from the group consisting of an aluminum sol, a silica sol, a silicon aluminum composite sol, and an aluminum phosphate sol.
The catalytic cracking assistant for high yield of propylene and isoamylene according to the invention, wherein, the P2O5Derived from a phosphorus-containing compound, preferably selected from the group consisting of phosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
The catalytic cracking auxiliary agent for producing more propylene and isoamylene, disclosed by the invention, is characterized in that the unit cell parameter of the USY molecular sieve is 2.410-2.460 nm.
The catalytic cracking aid for increasing propylene and isoamylene production according to the present invention, wherein said clay is selected from the group consisting of kaolin, halloysite, montmorillonite and rectorite.
The invention also provides a preparation method of the catalytic cracking auxiliary agent for producing more propylene and isoamylene, which comprises the following steps: uniformly mixing the materials, then drying and molding, and roasting and solidifying.
The preparation method comprises the following steps of uniformly mixing the materials:
mixing clay, optional pseudo-boehmite and water, adding a phosphorus-containing compound, and pulping to obtain carrier slurry; wherein the content of the phosphorus-containing compound is represented by P based on the total weight of the catalytic cracking assistant2O53-25 wt%;
mixing an alkali modified ZSM-5 molecular sieve, a USY molecular sieve and β zeolite, and adding water for pulping to obtain molecular sieve pulp, wherein the solid content of the molecular sieve pulp is not lower than 30 wt%;
mixing the molecular sieve slurry with the carrier slurry, and adding an inorganic binder.
The invention also provides a catalytic cracking catalyst system, which comprises the catalytic cracking auxiliary agent for producing more propylene and isoamylene; preferably, the content of the catalytic cracking aid for increasing the yield of propylene and isoamylene is 2-20 wt%, preferably 3-15 wt%, based on the total weight of the catalytic cracking catalyst system.
The invention also provides application of the catalytic cracking assistant for increasing yield of propylene and isoamylene in raw material processing, wherein the raw material comprises paraffin-based wax oil, naphthenic-based wax oil, intermediate-based wax oil or blended residual oil.
ADVANTAGEOUS EFFECTS OF INVENTION
The catalytic cracking assistant for producing more propylene and isoamylene can promote the shape selective isomerization cracking reaction of gasoline components with the content of C8 and above in catalytic cracking gasoline, can synchronously improve the yield of propylene and isoamylene, greatly reduce the gasoline loss, improve the propylene content (delta propylene/delta liquefied gas) in liquefied gas increment and produce high-octane gasoline in parallel.
Detailed Description
Various exemplary embodiments, features and aspects of the invention will be described in detail below. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
< first embodiment >
A first embodiment of the present invention provides a catalytic cracking promoter for high yield of propylene and isoamylene, wherein the catalytic cracking promoter comprises, on a dry basis, based on the total weight of the catalytic cracking promoter:
15-45 wt% of an alkali-modified ZSM-5 molecular sieve;
1-20 wt% of a USY molecular sieve;
β zeolite in an amount of 1 to 10 wt%;
3 to 25% by weight of P2O5；
3 to 25 wt% of an inorganic oxide; and the balance clay.
In the invention, the ZSM-5 molecular sieve has higher silica-alumina ratio. Before modifying the ZSM-5 molecular sieve, the silica-alumina ratio of the ZSM-5 molecular sieve can be 15-400. In the invention, based on the total weight of the catalytic cracking assistant, the content of the alkali modified ZSM-5 molecular sieve is 15-45 wt%, preferably 20-40 wt% on a dry basis.
The alkali-modified ZSM-5 molecular sieve has an external specific surface area of 90-160 m2Preferably 100 to 150 m/g2(ii)/g; the total specific surface area of the alkali modified ZSM-5 molecular sieve is 300-360 m2Per g, preferably 310 to 350m2(ii)/g; the pore volume of the alkali modified ZSM-5 molecular sieve is 0.35-0.55 mL/g, preferably 0.36-0.45 mL/g.
The alkali modified ZSM-5 molecular sieve can be obtained by treating the ZSM-5 molecular sieve with an alkaline substance. After ZSM-5 molecular sieve is treated by alkaline substance, part of amorphous oxygen can be removedThe silicon oxide and partial framework silicon oxide improve the specific surface area and pore volume, improve the pore structure and create conditions for catalyzing the cracking of components above C8 in the light gasoline. In particular, the alkaline substance may be selected from the group consisting of Na2CO3、NaHCO3NaOH and ammonia.
The catalytic cracking assistant for high yield of propylene and isoamylene according to the invention is characterized in that the alkaline substance is selected from Na2CO3、NaHCO3And NaOH, the preparation method of the alkali modified ZSM-5 molecular sieve comprises the following steps: reacting a ZSM-5 molecular sieve with an alkaline substance in an aqueous solution, performing ion exchange by using ammonium salt, and roasting to obtain the ZSM-5 molecular sieve; or
Under the condition that the alkaline substance is ammonia water, the preparation method of the alkali modified ZSM-5 molecular sieve comprises the following steps: the ZSM-5 molecular sieve and ammonia water react in water solution and are roasted to obtain the catalyst.
In the invention, according to different alkaline substances, reaction conditions are different when the alkali modified ZSM-5 molecular sieve is prepared.
For example, in the case where the basic substance is selected from Na2CO3、NaHCO3And NaOH, the reaction conditions for preparing the alkali-modified ZSM-5 molecular sieve are: according to ZSM-5 molecular sieve: na (Na)2O: the water is reacted for 0.5 to 3 hours at a weight ratio of 1:0.2 to 1.5:3 to 10 at a temperature of 30 to 95 ℃.
Specifically, the alkaline substance is selected from Na2CO3、NaHCO3And NaOH, the preparation method of the alkali modified ZSM-5 molecular sieve comprises the following steps:
according to ZSM-5 molecular sieve: na (Na)2O: reacting water at a weight ratio of 1: 0.2-1.5: 3-10 at a temperature of 30-95 ℃ for 0.5-3 hours; and then filtering, adding ammonium salt for ion exchange, filtering, washing with water, and roasting to prepare the alkali modified ZSM-5 molecular sieve. Preferably, the ion exchange is carried out in an aqueous solution of an ammonium salt.
Preferably, the reaction temperature during ion exchange is 70-90 ℃, the ion exchange time is 20-50 min, and the mass ratio of the ammonium salt to the water is 1: 30-1: 20.
Preferably, the pH value can be adjusted to be between 3.5 and 4.5 after the ion exchange is carried out.
For another example, in the case where the basic substance is ammonia, the reaction conditions for preparing the alkali-modified ZSM-5 molecular sieve are as follows: according to the ZSM-5 molecular sieve: the ammonia water is reacted for 1 to 48 hours at a weight ratio of 1:3 to 9 at a temperature of 25 to 60 ℃.
Specifically, in the case that the alkaline substance is ammonia water, the preparation method of the alkali modified ZSM-5 molecular sieve is as follows: according to the ZSM-5 molecular sieve: reacting ammonia water at a weight ratio of 1: 3-9 at a temperature of 25-60 ℃ for 1-48 hours; and then filtering, washing with water, drying and roasting to prepare the alkali modified ZSM-5 molecular sieve. Preferably, the concentration of the ammonia water is 10-28 wt%.
The USY molecular sieve contains aluminum and silicon atoms and has SiO2/Al2O3The skeleton structure of (1). The USY molecular sieve can be prepared by methods such as high-temperature hydrothermal method, organic complexation, high-temperature gas phase reaction, ammonium fluosilicate liquid phase reaction and the like, and the preparation of the USY molecular sieve by the high-temperature hydrothermal method can be preferably considered in industry. The unit cell parameters of the USY molecular sieve in the invention can be 2.410-2.460 nm. In the invention, the content of the USY molecular sieve may be 1 to 20 wt%, preferably 3 to 15 wt%, based on the total weight of the catalytic cracking assistant, on a dry basis.
The catalytic cracking assistant also contains β zeolite, wherein the content of β zeolite is 1-10 wt%, preferably 2-8 wt% on a dry basis based on the total weight of the catalytic cracking assistant.
The catalytic cracking assistant for producing more propylene and isoamylene also contains inorganic oxide. The inorganic oxide may be alumina, silica, or the like. The inorganic oxide in the present invention is obtained by conversion of an inorganic binder and/or pseudo-boehmite. In the present invention, the content of the inorganic oxide may be 3 to 25 wt%, preferably 4 to 20 wt%, on a dry basis, based on the total weight of the catalytic cracking assistant.
The inorganic oxide is derived from an inorganic binder and/or pseudo-boehmite; preferably, the inorganic binder is selected from the group consisting of an aluminum sol, a silica sol, a silicon aluminum composite sol, an aluminum phosphate sol, and the like; more preferably, the pseudo-boehmite is added in an amount of 0 to 15 wt% on a dry basis based on the total weight of the catalytic cracking assistant.
In the present invention, the inorganic binder and/or the pseudo-boehmite may be referred to as a precursor of the inorganic oxide.
P of the invention2O5The alkali modified ZSM-5 molecular sieve, the USY molecular sieve and the β zeolite can be modified, so that the yield of the catalytic cracking liquefied gas and the octane value of the catalytic cracking gasoline can be increased, and the yield of propylene and isoamylene can be synchronously increased2O5The content of (b) may be 3 to 25% by weight, preferably 5 to 20% by weight.
P of the invention2O5May be derived from a phosphorus-containing compound, preferably selected from the group consisting of phosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and the like.
The clay in the present invention may be selected from the group consisting of kaolin, halloysite, montmorillonite, rectorite, and the like. Preferably, the clay in the present invention may be selected from kaolin and/or halloysite.
In the additive provided by the invention, the ZSM-5 molecular sieve is subjected to alkali modification treatment, so that the pore structure is optimized, the additive is compounded with the USY molecular sieve and β zeolite, and the shape selective isomerization cracking reaction of gasoline components with the carbon number of more than 8 in the catalytic cracking gasoline is promoted by modification treatment of phosphorus-containing compounds, so that the yield of propylene and isoamylene can be synchronously improved, the propylene content (delta propylene/delta liquefied gas) in liquefied gas increment is improved, and high-octane gasoline is produced.
< second embodiment >
The second embodiment of the invention provides a preparation method of a catalytic cracking assistant for increasing the yield of propylene and isoamylene, which comprises the following steps: uniformly mixing the materials, then drying and molding, and roasting and curing.
Specifically, the step of uniformly mixing the materials comprises the following steps:
mixing clay, optional pseudo-boehmite and water, adding a phosphorus-containing compound, and pulping to obtain carrier slurry, wherein the preferable pulping time is 0.5-3 hours; wherein the content of the phosphorus-containing compound is represented by P based on the total weight of the catalytic cracking assistant2O53-25 wt%;
mixing an alkali modified ZSM-5 molecular sieve, a USY molecular sieve and β zeolite, and adding water for pulping to obtain molecular sieve pulp, wherein the solid content of the molecular sieve pulp is not lower than 30 wt%;
and mixing the molecular sieve slurry and the carrier slurry, adding an inorganic binder, and uniformly mixing by pulping, preferably, the pulping time is 5-30 min.
< third embodiment >
The third embodiment of the present invention provides a catalytic cracking catalyst system, which comprises the catalytic cracking assistant for increasing the yield of propylene and isoamylene according to the first embodiment of the present invention or the catalytic cracking assistant for increasing the yield of propylene and isoamylene obtained by the preparation method according to the second embodiment.
When the auxiliary agent provided by the invention is used in the catalytic cracking process, the auxiliary agent can be independently added into a catalytic cracking reactor, and can also be mixed with a catalytic cracking catalyst for use. When the catalyst is mixed with a catalytic cracking catalyst for use, the content of the catalytic cracking auxiliary agent for increasing the yield of propylene and isoamylene is 2-20 wt%, preferably 3-15 wt%, based on the total weight of the catalytic cracking catalyst system.
< fourth embodiment >
A fourth embodiment of the present invention provides a catalytic cracking assistant with high propylene and isoamylene yield according to the first embodiment of the present invention or the catalytic cracking assistant with high propylene and isoamylene yield obtained by the preparation method of the second embodiment.
The raw material can be paraffin-based wax oil, naphthenic-based wax oil, intermediate-based wax oil or blended residual oil.
In addition, in the raw material processing, the reaction temperature of the catalytic cracking reaction can be 400-600 ℃, preferably 450-550 ℃, and the catalyst-oil ratio can be 2-15, preferably 3-12.
Hereinafter, examples are shown for further explaining the present invention in detail, and the present invention is not limited to the examples.
Examples
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The analytical test method used in the embodiment of the invention comprises the following steps:
1. kaolinite and halloysite: x-ray diffraction method
2. Relative crystallinity, unit cell parameters: x-ray diffraction method
3. Silicon to aluminum ratio (molar ratio of silicon oxide to aluminum oxide): elemental analysis method
4. Average particle size: laser granulometer method
5. Specific surface area (external specific surface area and total specific surface area) and pore volume: nitrogen adsorption process
6. Microreflective Activity (MA) assay: wherein the micro-reverse activity test conditions are that the raw oil is the Hongkong light diesel oil, the catalyst loading is 5.0 g, the catalyst-oil ratio is 3.2, the reaction temperature is 460 ℃, the reaction time is 70 seconds, and MA (gasoline, gas and coke which are lower than 200 ℃ in the product)/the total oil inlet amount is multiplied by 100 percent.
Reagents, raw materials, specifications, manufacturers and the like used in the application include:
1. kaolin: 86 weight percent of kaolinite, 84.9 percent of solid content and 3.2 mu m of average particle size; halloysite 81 wt%, solid content 83.2%, average particle size 2.5 μm; china kaolin corporation.
2. Phosphoric acid, concentration 80 wt%; phosphorous acid, chemically pure; hydrochloric acid, analytically pure; sodium carbonate, sodium hydroxide, ferric chloride (FeCl)3·6H2O), chemically pure; diammonium phosphate, ammonium chloride, ammonia water, all are industrial products.
3. Pseudo-boehmite with a solid content of 60.0 wt%; alumina sol containing 23.0 wt% alumina; silica sol containing 23.8% by weight of silica was an industrially acceptable product.
4. The molecular sieve of No. 1 USY has a unit cell parameter of 2.425nm and a solid content of 96.0 percent, the molecular sieve of No. 2 USY has a unit cell parameter of 2.445nm and a solid content of 97.0 percent, the zeolite of No. 1 β has a silicon-aluminum ratio of 25 and a solid content of 95.0 percent, the zeolite of No. 2 β has a silicon-aluminum ratio of 80 and a solid content of 95.5 percent, the ZSM-5 of No. 1 has a silicon-aluminum ratio of 40 and a relative crystallinity of 92 weight percent, and the solid content of 96.0 percent, which are all provided by Tianjin Shen.
5. 2# ZSM-5, a silica-alumina ratio of 100, a relative crystallinity of 89 wt%, a solid content of 95.5%; 3# ZSM-5, a silica-alumina ratio of 250, a relative crystallinity of 87 wt%, a solid content of 95.6%; provided by Shanghai Zhuoyue chemical technology Limited.
6. ZRP Zeolite, silica to alumina ratio 30, RE2O3The content is 2.2 weight percent, the solid content is 94.5 percent, and the catalyst is produced by Qilu Branch of China Shinetization catalyst.
Example 1
521g of 1# ZSM-5 molecular sieve and 427g of Na2CO3And 150g of NaOH, adding 3500g of deionized water, stirring uniformly, and reacting at 90 ℃ for 1.0 hour. Then, the mixture was filtered, washed, ion-exchanged by adding 150g of ammonium chloride and 3500g of deionized water, adjusted to pH 3.5 to 4.5 with 1:1 hydrochloric acid, and exchanged at 80 ℃ for 30 minutes. Filtering, washing with water, drying, and calcining at 550 deg.C for 1.5 hr to obtain alkali modified ZSM-5 molecular sieve designated as MZ-1.
Example 2
521g of 2# ZSM-5 molecular sieve and 705gNa2CO3And 65g of NaOH, adding 4500g of deionized water, uniformly stirring, and reacting at 65 ℃ for 1.5 hours. Then filtering, washing, adding 150g ammonium chloride and 3500g deionized water for ion exchange, and adjusting the pH of the system with 1:1 hydrochloric acidTo 3.5-4.5, exchange at 85 ℃ for 40 minutes. Filtering, washing, drying, and calcining at 530 deg.C for 1.0 hr to obtain the alkali modified ZSM-5 molecular sieve designated as MZ-2.
Example 3
521g of the No. 1 ZSM-5 molecular sieve and 4000g of 17 wt% ammonia water are uniformly mixed in a closed reactor, the mixture reacts for 30 hours at 60 ℃, and then the mixture is filtered, washed with water, dried and roasted for 1.0 hour at 520 ℃ to obtain the modified alkali modified ZSM-5 molecular sieve marked as MZ-3.
Example 4
521g of the 3# ZSM-5 molecular sieve and 2000g of ammonia water with the concentration of 27 weight percent are uniformly mixed in a closed reactor, reacted for 10 hours at 35 ℃, filtered, washed with water, dried and roasted for 1.5 hours at 550 ℃, and the alkali modified ZSM-5 molecular sieve marked as MZ-4 is obtained.
The relative crystallinity, total specific surface area, external specific surface area, pore volume and solid content of the base-modified ZSM-5 molecular sieves MZ-1-MZ-4 prepared in examples 1-4 were determined as shown in Table 1 below:
TABLE 1
Item 1#ZSM-5 2#ZSM-5 3#ZSM-5 MZ-1 MZ-2 MZ-3 MZ-4
Relative degree of crystallinity,% by weight 92 89 87 85 84 90 89
Total specific surface area, m2/g 285 288 280 320 325 347 329
External specific surface area, m2/g 65 67 62 125 133 110 121
Pore volume, mL/g 0.30 0.32 0.33 0.38 0.41 0.44 0.42
Solids content% 96.0 95.5 95.6 98.8 97.9 98.3 98.5
As shown in Table 1, the relative crystallinity of the ZSM-5 molecular sieve is not changed much after the molecular sieve is subjected to alkali modification; however, the total specific surface area, the external specific surface area and the pore volume are obviously increased, and the pore structure of the ZSM-5 molecular sieve is improved.
Example 5
Mixing 441g of deionized water, 358g of kaolin and 174g of pseudo-boehmite, pulping for 15 minutes, adding 176g of phosphoric acid, pulping for 1.5 hours to obtain carrier slurry, uniformly mixing 344gMZ-3 molecular sieve, 16g of 1# β zeolite and 55g of 1# USY molecular sieve, adding 685g of deionized water, pulping and homogenizing to obtain molecular sieve slurry, adding the molecular sieve slurry into the carrier slurry, adding 400g of silica sol, pulping uniformly, spray-drying and forming, and roasting at 550 ℃ for 0.5-1.0 hour to obtain the catalytic cracking assistant A-1.
Example 6
Mixing 441g of deionized water, 362g of halloysite and 121g of pseudo-boehmite, pulping for 15 minutes, adding 163g of phosphorous acid, pulping for 1.5 hours to obtain carrier slurry, uniformly mixing 131gMZ-1 molecular sieve, 131gMZ-2 molecular sieve, 46g of 2# β zeolite and 107g of 2# USY molecular sieve, adding 685g of deionized water, pulping and homogenizing to obtain molecular sieve slurry, adding the molecular sieve slurry into the carrier slurry, adding 280g of silica sol, pulping uniformly, spray-drying and forming, and roasting at 550 ℃ for 0.5-1.0 hour to obtain the catalytic cracking assistant A-2.
Example 7
Mixing 441g of deionized water, 394g of kaolin and 83g of pseudo-boehmite, pulping for 15 minutes, adding 311g of phosphoric acid, pulping for 1.5 hours to obtain carrier slurry, uniformly mixing 311gMZ-1 molecular sieve, 21g of 2# β zeolite and 78g of 1# USY molecular sieve, adding 685g of deionized water, pulping and homogenizing to obtain molecular sieve slurry, adding the molecular sieve slurry into the carrier slurry, adding 175g of alumina sol, pulping uniformly, spray-drying and forming, and roasting at 550 ℃ for 0.5-1.0 hour to obtain the catalytic cracking assistant A-3.
Example 8
Mixing 441g of deionized water and 485g of kaolin, pulping for 15 minutes, adding 222g of phosphoric acid, pulping for 1.5 hours to obtain carrier slurry, uniformly mixing 295gMZ-1 molecular sieve, 37g of 2# β zeolite and 85g of 2# USY molecular sieve, adding 685g of deionized water, pulping and homogenizing to obtain molecular sieve slurry, adding the molecular sieve slurry into the carrier slurry, adding 237g of alumina sol, pulping uniformly, spray-drying and forming, and roasting at 550 ℃ for 0.5-1.0 hour to obtain the catalytic cracking assistant A-4.
Comparative example 1
Mixing 441g of deionized water, 358g of kaolin and 174g of pseudo-boehmite, pulping for 15 minutes, adding 232g of phosphoric acid, pulping for 1.5 hours to prepare carrier slurry, uniformly mixing 375g of 1# ZSM-5 molecular sieve and 16g of 1# β zeolite, adding 685g of deionized water, pulping and homogenizing to prepare molecular sieve slurry, adding the molecular sieve slurry into the carrier slurry, adding 314g of silica sol, pulping uniformly, spray-drying and molding, and roasting at 550 ℃ for 0.5-1.0 hour to obtain the comparative auxiliary agent C-1.
Comparative example 2
The phosphorus and rare earth containing pentasil zeolite P-ZRP was prepared according to the procedure used in the example disclosed in CN 1055105C.
3530g of deionized water and 560g of halloysite are taken, pulped for 1 hour, added with 75g of industrial hydrochloric acid for acidification, stirred for 0.5 hour, added with 500g of pseudo-boehmite and stirred evenly, heated to 55 ℃, and aged for 1 hour to prepare carrier slurry.
202g of P-ZRP, 100g of 1# USY molecular sieve and 30g of 1# β zeolite are uniformly mixed, 600g of deionized water is added and pulped to prepare molecular sieve slurry, and the molecular sieve slurry is added into carrier slurry, and then the carrier slurry is pulped, filtered, spray-dried and formed to prepare the contrast aid C-2.
Comparative example 3
Sample A in CN1796496A was prepared by modifying ZSM-5 zeolite according to the method disclosed in CN1465527A1。
Comparative adjuvant C-3 was prepared according to CN1796496A, example 2. The method specifically comprises the following steps: sample A was taken at 1.84kg (dry basis)11.33kg (dry basis) of kaolin and 0.98kg (dry basis) of pseudo-boehmite, 7.2kg of deionized water and 2.61kg of alumina sol were added and the mixture was slurried for 2 hours, 1 liter of FeCl was added with stirring3·6H2O in water (containing 250 g Fe)2O3) Adjusting the pH value of the pulp to 3.0, and continuing pulping for 45 minutes. The slurry was spray-dried to obtain microspheres having an average particle size of 65 μm. And roasting the microspheres at 500 ℃ for 1 hour to obtain the Fe additive. Wherein the Fe additive contained 36.8 wt.% of sample A126.6% by weight of kaolin and 31.6% by weight of Al2O3And 5.0 wt.% Fe2O3。
Taking 1kg (dry basis) of the Fe additive, adding 10 liters of deionized water and 100g of diammonium phosphate, heating to 60 ℃ under stirring, reacting for 20 minutes at the temperature, filtering and drying the slurry in vacuum, and roasting at 500 ℃ for 2 hours to obtain a comparative auxiliary agent C-3. Wherein comparative auxiliary C-3 contained 35.0% by weight of sample A125.3% by weight of kaolin, 30.0% by weight of Al2O34.7% by weight of Fe2O3And 5.0% by weight of P2O5。
Comparative example 4
P/ZSM-5 and thus the comparative auxiliary C-4 were prepared according to the method disclosed in US 5472594A.
P/ZSM-5 was prepared according to the method of example 1 of US5472594A, with the following specific steps: 500g of 1# ZSM-5 (dry basis) was taken, 1160g of deionized water was added, the mixture was stirred uniformly, 79g of phosphoric acid (so that P/ZSM-5 contained 4 wt% of phosphorus) was added, the mixture was stirred for 30 minutes, dried, and then calcined at 500 ℃ for 1 hour to obtain P/ZSM-5. The phosphorus content was 4% by weight and the solids content was 97.5%.
Mixing 920g of deionized water, 635g of kaolin and 175g of pseudo-boehmite, and pulping for 1.5 hours to obtain carrier slurry; mixing 293g of P/ZSM-5 molecular sieve and 660g of deionized water, pulping and homogenizing to prepare molecular sieve slurry; adding the molecular sieve slurry into the carrier slurry, adding 297g of silica sol, pulping uniformly, spray-drying and forming, and roasting at 550 ℃ for 0.5-1.0 hour to obtain the comparative auxiliary agent C-4.
The material compositions of examples 5 to 8 and comparative examples 1 to 4 are shown in Table 2 below.
TABLE 2
Figure BDA0001337007140000181
Application examples and comparative application examples
The following application examples and comparative application examples illustrate the reaction effect of the catalytic cracking assistant provided by the present invention in a fixed fluidized bed reactor.
Application examples
100g of A-1 to A-4 samples were treated at 800 ℃ under 100% steam for 8 hours, and the aged A-1 to A-4 samples were mixed with an industrial balance agent (an industrial CC-20D catalyst-based device balance agent, see Table 3 for main properties, the same below). Cracking reaction is carried out in a fixed fluidized bed reactor under the reaction conditions of 150g of catalyst loading, 5.5 of catalyst-oil ratio, 500 ℃ of reaction temperature and 16 hours of weight space velocity-1The properties of the raw oil are shown in table 4, the industrial equilibrium agent (main catalyst) and the sample compounded with the A-1-A-4 auxiliary agents of the invention are compared and evaluated, the compositions of cracked gas, gasoline, diesel oil, heavy oil and the like of the reaction products are analyzed by HP6890 gas chromatography, simulated distillation software is used for calculation, the gasoline composition and the gasoline octane number are analyzed by multidimensional gas chromatography, and the results are shown in table 5.
TABLE 3
Figure BDA0001337007140000191
TABLE 4
Figure BDA0001337007140000192
TABLE 5
Figure BDA0001337007140000201
Note: propylene concentration refers to: propylene yield/liquefied gas yield × 100% total liquid yield means: liquefied gas, gasoline and diesel oil
Comparative application
The samples C-1 to C-4 were aged according to the method of the above application example, and the industrial balance agent (main catalyst) and the samples compounded with the comparative aids C-1 to C-4 were evaluated under the same reaction conditions, and the product analysis method was the same as that of the application example, and the results are shown in Table 6.
TABLE 6
Figure BDA0001337007140000211
Note: propylene concentration refers to: propylene yield/liquefied gas yield × 100% total liquid yield means: liquefied gas, gasoline and diesel oil
It is seen from tables 5 and 6 that the catalytic cracking assistant for increasing yield of propylene and isoamylene provided by the invention can synchronously improve yield of propylene and isoamylene in catalytic cracking reaction, greatly reduce gasoline loss, obviously improve propylene content (delta propylene/delta liquefied gas) in liquefied gas increment and co-produce high-octane gasoline.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (18)

1. A catalytic cracking promoter for increasing the yield of propylene and isoamylene, which is characterized by comprising the following components in percentage by dry basis based on the total weight of the catalytic cracking promoter:
15-45 wt% of an alkali-modified ZSM-5 molecular sieve;
1-20 wt% of a USY molecular sieve;
β zeolite in an amount of 1 to 10 wt%;
3 to 25% by weight of P2O5；
3 to 25 wt% of an inorganic oxide; and
the balance clay;
the external specific surface area of the alkali modified ZSM-5 molecular sieve is 90-160 m2(ii)/g; the total specific surface area of the alkali modified ZSM-5 molecular sieve is 300-360 m2(ii)/g; the pore volume of the alkali modified ZSM-5 molecular sieve is 0.35-0.55 mL/g;
the alkali modified ZSM-5 molecular sieve is obtained by treating the ZSM-5 molecular sieve with an alkaline substance.
2. The catalytic cracking assistant for high yield of propylene and isoamylene according to claim 1, wherein the content of the alkali modified ZSM-5 molecular sieve is 20-40 wt%, the content of the USY molecular sieve is 3-15 wt%, the content of the β zeolite is 2-8 wt%, and the P content is P, based on the total weight of the catalytic cracking assistant on a dry basis2O5The content of (a) is 5-20 wt%, the content of the inorganic oxide is 4-20 wt%, and the balance is clay.
3. The catalytic cracking assistant for high yield of propylene and isoamylene according to claim 1, wherein the alkali-modified ZSM-5 molecular sieve has an external specific surface area of 100-150 m2(ii)/g; the total specific surface area of the alkali modified ZSM-5 molecular sieve is 310-350 m2(ii)/g; the pore volume of the alkali modified ZSM-5 molecular sieve is 0.36-0.45 mL/g.
4. The catalytic cracking assistant for high yield of propylene and isoamylene according to any one of claims 1 to 3, wherein the alkaline substance is selected from Na2CO3、NaHCO3NaOH and ammonia.
5. The catalytic cracking promoter with high propylene and isoamylene production according to claim 4, wherein the alkaline substance is selected from Na2CO3、NaHCO3And NaOH, the preparation method of the alkali modified ZSM-5 molecular sieve comprises the following steps: after the ZSM-5 molecular sieve reacts with alkaline substances, ammonium salt is used for ion exchange, and the reaction product is obtained by roasting; or
Under the condition that the alkaline substance is ammonia water, the preparation method of the alkali modified ZSM-5 molecular sieve comprises the following steps: the ZSM-5 molecular sieve is reacted with ammonia water and then roasted to obtain the catalyst.
6. The catalytic cracking promoter with high propylene and isoamylene production according to any one of claims 1 to 3, wherein the inorganic oxide is derived from an inorganic binder.
7. The catalytic cracking promoter with high propylene and isoamylene production according to claim 6, wherein the inorganic oxide is derived from pseudo-boehmite.
8. The catalytic cracking promoter for the production of propylene and isopentene of claim 6, wherein the inorganic binder is selected from the group consisting of aluminum sol, silica-alumina composite sol, and aluminum phosphate sol.
9. The catalytic cracking assistant for high yield of propylene and isoamylene according to any one of claims 1 to 3, wherein P is2O5Derived from a phosphorus-containing compound.
10. The catalytic cracking promoter for high yield of propylene and isoamylene according to claim 9, wherein said phosphorus-containing compound is selected from the group consisting of phosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
11. The catalytic cracking assistant for high yield of propylene and isoamylene according to any one of claims 1 to 3, wherein the USY molecular sieve has a unit cell parameter of 2.410-2.460 nm.
12. The catalytic cracking promoter with high propylene and isoamylene production according to any one of claims 1 to 3, wherein the clay is selected from the group consisting of kaolin, halloysite, montmorillonite and rectorite.
13. The preparation method of the catalytic cracking assistant for high yield of propylene and isoamylene according to any one of claims 1 to 12, comprising: uniformly mixing the materials, then drying and molding, and roasting and curing.
14. The method of claim 13, wherein the step of uniformly mixing the materials comprises:
mixing clay, optional pseudo-boehmite and water, adding a phosphorus-containing compound, and pulping to obtain carrier slurry; wherein the content of the phosphorus-containing compound is represented by P based on the total weight of the catalytic cracking assistant2O53-25 wt%;
mixing an alkali modified ZSM-5 molecular sieve, a USY molecular sieve and β zeolite, and adding water for pulping to obtain molecular sieve slurry, wherein the solid content of the molecular sieve slurry is not lower than 30 wt%;
mixing the molecular sieve slurry with the carrier slurry, and adding an inorganic binder.
15. A catalytic cracking catalyst system, characterized by comprising the catalytic cracking promoter for increasing propylene and isoamylene according to any one of claims 1 to 12.
16. The catalytic cracking catalyst system of claim 15, wherein the catalytic cracking promoter for increasing propylene and isoamylene content is 2 to 20 wt% based on the total weight of the catalytic cracking catalyst system.
17. The catalytic cracking catalyst system of claim 16, wherein the catalytic cracking promoter for increasing propylene and isoamylene content is 3 to 15 wt% based on the total weight of the catalytic cracking catalyst system.
18. The application of the catalytic cracking assistant for increasing the yield of propylene and isoamylene according to any one of claims 1 to 12 in raw material processing, wherein the raw material comprises paraffin-based wax oil, naphthenic-based wax oil, intermediate-based wax oil or blending residual oil.
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