CN116764616A

CN116764616A - Heavy metal resistant Y-type molecular sieve catalytic material and preparation method thereof

Info

Publication number: CN116764616A
Application number: CN202210234484.0A
Authority: CN
Inventors: 杨雪; 林伟; 王振波; 周继红; 孙敏; 刘倩倩
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2022-03-10
Filing date: 2022-03-10
Publication date: 2023-09-19

Abstract

The invention relates to a Y-type molecular sieve catalytic material containing heavy metals and a preparation method thereof, wherein the Y-type molecular sieve catalytic material is prepared by hydrothermal crystallization of zirconium-magnesium-containing reactive microspheres, and comprises 70-99.4 wt% of an alumina matrix, 0.5-15 wt% of zirconium oxide and 0.1-15 wt% of magnesium oxide based on the dry basis weight of the zirconium-magnesium-containing reactive microspheres. The molecular sieve catalytic material has lower sodium ion content, high activity after nickel-vanadium pollution and better heavy metal resistance.

Description

Heavy metal resistant Y-type molecular sieve catalytic material and preparation method thereof

Technical Field

The invention relates to a heavy metal resistant Y-type molecular sieve catalytic material and a preparation method thereof.

Background

With the world's heavy and poor quality of crude oil, heavy oils and residues have become the primary process feedstock for catalytic cracking processes. Since heavy oil contains more colloid, asphaltene and heavy metal, the FCC catalyst is required to have higher matrix activity, stronger metal pollution resistance and better catalytic activity and selectivity, wherein the FCC catalyst containing Y-type zeolite is the catalyst with the largest dosage at present.

At present, two types of Y-type molecular sieve cracking catalysts are mainly used in industry, the first type is called semi-synthetic binder type, namely, Y-type molecular sieve is subjected to exchange modification and then mixed with kaolin and a binder for spray forming. The second type is called in-situ crystallization type, namely, the kaolin spray microsphere is subjected to high-temperature roasting and then is subjected to hydrothermal crystallization in an alkaline system, so that Y-type molecular sieves are grown on the inner surface and the outer surface of the microsphere, and then the finished catalyst is obtained through exchange modification. The in-situ crystallization type semisynthetic binder catalyst has the following characteristics: (1) The Y-type molecular sieve and the matrix are generated simultaneously by in-situ crystallization and are connected in a chemical bond form, so that the Y-type molecular sieve has higher thermal and hydrothermal stability; (2) The Y-type molecular sieve is uniformly distributed on the inner and outer surfaces of the pore canal of the matrix, and the grain size is about ten times smaller than that of NaY synthesized by a gel method, so that the accessibility and cracking performance of heavy raw oil are greatly improved; (3) The kaolin microspheres baked at high temperature contain an aluminum-rich spinel structure and have excellent vanadium-nickel pollution resistance and mechanical abrasion resistance. Thus, the in-situ crystallization type cracking catalyst has advantages for processing heavy raw oil. Wherein, the precursor used by the in-situ crystallization catalyst, namely the kaolin microsphere, is the key of the preparation technology.

Engelhard corporation of the United states applied a series of patents for the preparation of cracking catalysts by crystallization of Guan Yuanwei since the sixties of the last century, which disclose the main technical features of kaolin microspheres. As in US3503990, US3506494, US3663165, US4493902, US4965233, US5023220, etc., it is disclosed in this series of patents that the precursor microspheres comprise a mixture of two different forms of chemically active calcined clay, which are metakaolin (calcined to kaolin that undergoes a strong endothermic reaction associated with dehydroxylation) and kaolin that is calcined under conditions more severe than the conditions under which normal kaolin is converted to metakaolin, i.e., kaolin that is calcined to undergo a characteristic kaolin exothermic reaction, sometimes referred to as spinel calcined kaolin. However, the technique proposed in US4493902 requires high demands on raw materials for spray forming, and requires the use of ultrafine high-earth Satone-N02 and ultrafine raw earth ASP-600, which are expensive and not easily available in the market. In addition, the method has higher energy consumption, and particularly, the spinel-type kaolin obtained by the method needs to be roasted at the temperature of about 1100 ℃, so that the catalyst cost is greatly increased.

In-situ crystallization type cracking catalysts LB-1 and LB-2 are developed by Lanzhou petrochemical company in China, and CN1232862 discloses the main technical characteristics of precursor microspheres, namely, a part of precursor particles are roasted at high temperature to obtain high-temperature roasted microspheres, and the other part of precursor particles are roasted at lower temperature to obtain metakaolin microspheres, wherein the two microspheres are mixed according to a certain proportion to be used as in-situ crystallization precursor microspheres. However, the crystallinity of the Y-type molecular sieve prepared by the method is lower, generally less than 30%, and the silicon-aluminum ratio is generally less than 5.0.

CN1778676 mentions that the addition of structural aids during spraying, including one or a mixture of starch, graphite powder, and as-methyl cellulose, mainly improves the pore structure of kaolin spray microspheres. The addition amount is 2-10% of the mass of the kaolin. The invention can also bake one part of spray microsphere containing the structural auxiliary agent with main grain diameter of 20-110 μm at high temperature to obtain high temperature baked soil, bake the other part of spray microsphere at lower temperature to obtain metakaolin, and mix the two baked kaolins for in situ crystallization.

US6942783 teaches the preparation of FCC catalysts for enhanced heavy oil conversion by in situ crystallization techniques wherein the precursor microspheres consist of metakaolin and hydrous kaolin containing microspheres which are calcined at a lower temperature prior to crystallization to avoid conversion of hydrous kaolin to metakaolin.

US20170362513A1 describes a process for the in situ preparation of an improved fluid catalytic cracking zeolite catalyst wherein the microspheres consist of a mixture of spinel kaolin, transition alumina and metakaolin.

According to analysis of the above patent technology, the technical core of the preparation of the in-situ crystallization catalyst is that firstly, a solid substance mainly composed of kaolin and derivatives thereof is prepared, then, under certain synthesis conditions, a molecular sieve is generated on the solid substance in situ through liquid-solid reaction, and further, the catalyst meeting the requirements is obtained through post-treatment. However, the composition and preparation process of the precursor kaolin microspheres are not improved greatly, the two-stage roasting method of Engelhard corporation in the early stage is basically continued, and the problems of high energy consumption and high cost are not solved.

The addition of auxiliary components in the preparation of microsphere precursors, which has been described in the prior art as having a multifunctional potential, CN 105813739A provides an FCC catalyst composition that uses one or more boron oxide components to deactivate metals, particularly nickel. The effect of deleterious metals (such as nickel) on the cracking reaction is reduced or prevented by passivation of the boron component. The non-zeolite component is added in the preparation of the precursor: wherein the non-zeolitic material is selected from the group consisting of kaolinite, halloysite, montmorillonite, bentonite, attapulgite, kaolin, amorphous kaolin, metakaolin, mullite, spinel, hydrous kaolin, clay, gibbsite (blue alumina), boehmite, ferric oxide, alumina, silica alumina, silica oxide and sepiolite.

Disclosure of Invention

The invention aims to provide a heavy metal resistant Y-type molecular sieve catalytic material and a preparation method thereof.

In order to achieve the above object, according to a first aspect of the present invention, there is provided a Y-type molecular sieve catalytic material obtained by hydrothermal crystallization of zirconium-magnesium-containing reactive microspheres containing 70 to 99.4 wt% of an alumina matrix, 0.5 to 15 wt% of zirconia and 0.1 to 15 wt% of magnesia, based on the dry weight of the zirconium-magnesium-containing reactive microspheres.

Optionally, the zirconium magnesium-containing reactive microsphere comprises 81 to 98.8 weight percent of an alumina matrix, 1 to 14 weight percent of zirconium oxide and 0.2 to 10 weight percent of magnesium oxide;

the sphericity of the reactive microsphere containing zirconium and magnesium is 85-100%, the abrasion index is 0.1-3%/h, and the particle size is 20-150 μm.

Optionally, the content of the zirconia is 2-12 wt% and the content of the magnesia is 0.5-8 wt% based on the dry weight of the Y-type molecular sieve catalytic material.

Optionally, the specific surface area of the Y-type molecular sieve catalytic material is 200-700m ² Per g, the total pore volume is 0.20-0.50mL/g, the abrasion index is 0.1-2%/h, and the mesopore volume with the pore diameter of 2-50nm accounts for 20-50% of the total pore volume.

Optionally, the zirconium-magnesium-containing reactive microsphere is prepared by a method comprising the following steps:

mixing an alumina matrix raw material, zirconium sol, a first magnesium source and water to obtain slurry, and performing spray drying on the slurry to obtain a zirconium-magnesium-containing reactive microsphere precursor;

roasting the zirconium-magnesium-containing reactive microsphere precursor to obtain zirconium-magnesium-containing reactive microspheres; the conditions of the calcination treatment include: the temperature is 300-1000 ℃ and the time is 1-10 hours; preferably, the temperature is 400-850 ℃ and the time is 1.5-8 hours.

Optionally, the alumina matrix feedstock contains hydrous kaolin and/or metakaolin, optionally hydrated alumina, optionally kaolin;

preferably, the hydrated alumina is selected from one or more of boehmite, pseudoboehmite and gibbsite; more preferably, the alumina hydrate is calcined alumina hydrate or acidified alumina hydrate;

preferably, the alumina matrix material contains 0 to 100 wt.%, preferably 20 to 80 wt.% of the hydrous kaolin, 0 to 100 wt.%, preferably 10 to 80 wt.% of the metakaolin, 0 to 20 wt.%, preferably 0 to 12 wt.% of the hydrous alumina and 0 to 70 wt.%, preferably 0 to 30 wt.% of the kaolin, based on the total weight of the alumina matrix material;

The first magnesium source is selected from one or more of magnesium chloride, magnesium sulfate, magnesium nitrate, magnesium carbonate, magnesium hydroxide and magnesium oxide.

Optionally, the zirconium sol contains ZrO ₂ A stabilizer, a base cation and water;

the particle size of the colloidal particles of the zirconium sol is 5-15nm, the average particle size of the colloidal particles is 8-12nm, the concentration is more than 90%, and the ZrO ₂ The molar ratio of the stabilizer to Zr is 1-6, and the molar ratio of the basic cation to Zr is 1-8.

In a second aspect, the present invention provides a method for preparing the Y-type molecular sieve catalytic material provided in the first aspect, the method comprising: and mixing the zirconium-magnesium-containing reactive microsphere, a first silicon source, a first guiding agent, sodium hydroxide and water, and then carrying out hydrothermal crystallization treatment on the obtained mixture.

Optionally, the conditions of the hydrothermal crystallization treatment include: the temperature is 88-105 ℃ and the time is 10-78 hours;

the weight ratio of the first silicon source to the first guiding agent to the sodium hydroxide to the water is (2-15): 1: (1-7): (40-400), wherein the first silicon source is SiO ₂ The first guiding agent is Al ₂ O ₃ Calculated by Na, the sodium hydroxide is ₂ An O meter;

with Al ₂ O ₃ Reactivity of the first directing agent with the zirconium-containing magnesium on a dry weight basis The weight ratio of the microsphere dosage is (0.001-2): 1, preferably (0.01-0.5): 1, a step of;

the first silicon source is selected from one or more of sodium silicate, silica gel and organic silicon.

In a third aspect, the present invention provides a reactive microsphere containing zirconium and magnesium suitable for preparing a Y-type molecular sieve catalytic material by hydrothermal crystallization, wherein the reactive microsphere containing zirconium and magnesium contains 0.5-15 wt% of zirconium oxide, 0.1-15 wt% of magnesium oxide and 70-99.4 wt% of aluminum oxide matrix based on the dry basis weight of the reactive microsphere containing zirconium and magnesium.

Optionally, the zirconium magnesium-containing reactive microsphere comprises 76-98.8 wt% of an alumina matrix, 1-14 wt% of zirconium oxide and 0.2-10 wt% of magnesium oxide;

Alternatively, the zirconium magnesium-containing reactive microsphere comprises 10-95 wt.%, preferably 15-80 wt.%, preferably 20-50 wt.% hydrous kaolin and/or kaolin crude on a dry basis, 5-50 wt.%, preferably 10-45 wt.% metakaolin on a dry basis, 0-20 wt.%, preferably 2-15 wt.% alumina on a dry basis, 0.5-30 wt.%, preferably 5-28 wt.%, preferably 10-25 wt.% kaolin on a dry basis, 0.5-15 wt.%, preferably 1-14 wt.%, preferably 2-12 wt.%, preferably 3-10 wt.% zirconia, and 0.1-15 wt.%, preferably 0.2-10 wt.%, preferably 2-8 wt.% magnesia.

Alternatively, the zirconia is derived from a stabilizer-containing zirconium sol containing ZrO ₂ A stabilizer, a base cation and water.

According to a fourth aspect of the present invention, there is provided a method for preparing the zirconium-containing reactive microsphere according to the third aspect of the present invention, comprising the steps of:

(1) Mixing hydrous kaolin or kaolin crude, metakaolin, optionally kaolin, a zirconium magnesium sol containing a stabilizer, optionally alumina, a second magnesium source, and water to form a slurry; the slurry has a solids content of 15 to 45 wt%, preferably 25 to 40 wt%;

(2) And (3) spray drying and optionally roasting the slurry obtained in the step (1), wherein the roasting temperature is 300-1000 ℃, preferably 400-750 ℃ and the roasting time is 1-4h.

The fifth aspect of the invention provides a Y-type molecular sieve catalytic material, which is prepared by crystallizing a mixture containing the zirconium-magnesium-containing reactive microsphere of the third aspect of the invention, a second silicon source, a second directing agent, sodium hydroxide and water;

preferably, the weight ratio of the second silicon source, the second directing agent, sodium hydroxide and water is (2-15): 1: (1-7): (40-400), wherein the second silicon source is SiO ₂ The second guiding agent is calculated as Al ₂ O ₃ Calculated by Na, the sodium hydroxide is ₂ An O meter;

with Al ₂ O ₃ The weight ratio of the second directing agent to the amount of the zirconium-containing magnesium reactive microsphere on a dry basis is (0.001-2): 1, a step of;

the second silicon source is selected from one or more of sodium silicate, silica gel and organic silicon.

The invention has the following advantages:

(1) The Y-type molecular sieve catalytic material is prepared by hydrothermal crystallization of reactive microspheres containing zirconium and magnesium. Wherein, the reactive microsphere containing zirconium and magnesium has a medium-large pore structure, and can hydrothermally form a zeolite catalyst on the medium-large pore structure.

(2) According to the invention, zirconium oxide and magnesium oxide are introduced into the reactive microsphere, and the advantages of the magnesium oxide and the zirconium oxide are fully exerted through the promoting effect of zirconium magnesium metal, so that the prepared catalyst has better strength, and meanwhile, the surface area and the dispersibility of the catalyst are improved.

(3) The zirconium magnesium in the Y-type molecular sieve catalytic material is a heat stable or high temperature resistant metal compound, is used as a matrix to improve the hydrothermal stability, the wear resistance and the porosity of the catalyst, and has the capability of capturing nickel and vanadium and the capability of resisting metal pollution.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.

The invention provides a heavy metal resistant Y-type molecular sieve catalytic material, which is prepared by hydrothermal crystallization of reactive microspheres of a zirconium-containing magnesium composition, wherein the zirconium-containing magnesium reactive microspheres contain 70-99.4 wt% of an alumina matrix, 0.5-15 wt% of zirconium oxide and 0.1-15 wt% of magnesium oxide based on the dry weight of the zirconium-containing magnesium reactive microspheres.

The Y-type molecular sieve catalytic material is prepared by hydrothermal crystallization of zirconium-magnesium-containing reactive microspheres, the molecular sieve can grow on the reactive microspheres in situ, and zirconium oxide and magnesium oxide are contained in the zirconium-magnesium-containing reactive microspheres, so that the Y-type molecular sieve catalytic material has better thermal stability or high temperature resistance, the strength and the wear resistance of the microspheres are improved, and the specific surface area and the dispersibility of a synthesized catalyst can be improved. And zirconium and magnesium have the capability of capturing nickel and vanadium, are favorable for keeping the reactivity of the catalyst, and have good metal pollution resistance.

In one embodiment of the invention, the reactive microspheres comprising zirconium magnesium comprise 81 to 98.8 wt.% of an alumina matrix, 1 to 14 wt.% of zirconium oxide and 0.2 to 10 wt.% of magnesium oxide; the sphericity of the reactive microsphere containing zirconium and magnesium is 85-100%, the abrasion index is 0.1-3%/h, the particle size is 20-150 μm, preferably, the sphericity is 90-100%, and the abrasion index is 0.1-2.5%/h. Wherein "particle diameter of 20-150 μm" means that the particle diameter of the microspheres is in the range of 20-150 μm.

In one embodiment of the invention, the specific surface area of the Y-type molecular sieve catalytic material is 200-700m ² Per gram, the total pore volume is 0.2-0.5mL/g, the abrasion index is 0.1-2%/h, and the macropore volume with the pore diameter of 2-50nm accounts for 20-50% of the total pore volume; preferably, the specific surface area is 250-600m ² Per g, the total pore volume is 0.21-0.35mL/g, the abrasion index is 0.1-1%/h, and the mesopore volume with the pore diameter of 2-50nm accounts for 22-45% of the total pore volume.

In one specific embodiment of the invention, the zirconium-magnesium-containing reactive microsphere is prepared by a method comprising the following steps: mixing an alumina matrix raw material, zirconium sol, a first magnesium source and water to obtain slurry, and performing spray drying on the slurry to obtain a zirconium-magnesium-containing reactive precursor;

Spray drying is well known to those skilled in the art in accordance with the present invention, and the present invention is not described in detail herein.

In one embodiment of the invention the solids content of the slurry may vary over a wide range, in one embodiment of the invention the solids content of the slurry is from 20 to 60% by weight.

According to the present invention, the zirconium sol can be prepared by hydrolyzing zirconium salt by at least one of an alkaline method, an oxidation method and an ion exchange method, and preferably, the zirconium sol is prepared by an alkaline method. In a specific embodiment of the invention, the alumina matrix material contains hydrous kaolin and/or metakaolin, optionally hydrated alumina, optionally kaolin. Wherein the hydrous kaolin is the product of dispersing kaolin in water and removing associated sandy minerals; the metakaolin is obtained by roasting, dehydrating and converting hydrous kaolin at 500-900 ℃; the kaolin is obtained by calcining hydrous kaolin at 900-1050 ℃ and through characteristic heat release. The hydrated alumina may include, but is not limited to, one or more of boehmite, pseudoboehmite, and gibbsite, more preferably, the hydrated alumina is calcined hydrated alumina or acidified hydrated alumina, the calcined hydrated alumina being obtained by calcining hydrated alumina at 400-700 ℃; the acidified hydrated alumina is obtained by acidifying the hydrated alumina at a pH of less than 3.5.

In a specific embodiment of the present invention, the alumina base material contains 0 to 100 wt.%, preferably 20 to 80 wt.% of the hydrous kaolin, 0 to 100 wt.%, preferably 10 to 80 wt.%, preferably 15 to 45 wt.% of the metakaolin, 0 to 20 wt.%, preferably 0 to 12 wt.% of the hydrated alumina and 0 to 70 wt.%, preferably 0 to 30 wt.%, preferably 10 to 25 wt.% of the kaolin, based on the total weight of the alumina base material.

More preferably, the alumina matrix material comprises 15 to 80 wt% of the hydrous kaolin, 10 to 45 wt% of the metakaolin, 5 to 15 wt% of hydrated alumina and 5 to 25 wt% of the kaolin. Wherein hydrous kaolin is used as an inert component raw material for the catalytic material of the Y-type molecular sieve, metakaolin can provide soluble alumina for growing the molecular sieve, and kaolin is used for preparing an aluminum-rich matrix. The first magnesium source is selected from one or more of magnesium chloride, magnesium sulfate, magnesium nitrate, magnesium carbonate, magnesium oxide and magnesium hydroxide.

In a specific embodiment of the invention, the zirconium sol comprises 0.5 to 20% by weight, for example 1 to 18% by weight or 5 to 15% by weight ZrO ₂ The stabilizer, the alkali cation and the water, wherein the mole ratio of the stabilizer to Zr is 1-6, and the mole ratio of the alkali cation to Zr is 1-8.

In one specific embodiment of the invention, the colloidal particle size of the zirconium sol is 5-15nm, the average colloidal particle size is 8-12nm, and the concentration is more than 90%. The concentration degree refers to the proportion of the number of colloidal particles with the size of about 10nm in the measured colloidal particles to the total number of the measured colloidal particles in the zirconium sol sample, and the zirconium sol sample image can be obtained through TEM and is obtained through computer image analysis. The particle size of the colloidal particles refers to the diameter of the largest circumscribed circle in a projection drawing of the colloidal particles, and the average particle size of the colloidal particles is the arithmetic average value of the particle sizes of the sample colloidal particles.

In one embodiment of the invention, the zirconium sol is dried at 100 ℃ for 6 hours, calcined at 600 ℃ for 2-6 hours and subjected to heat treatment, and the obtained product is singleThe inclined phase and the tetragonal phase coexist, and the ratio of the monoclinic phase to the tetragonal phase is preferably (0.05 to 0.6): 1, a step of; in another embodiment of the present invention, the zirconium sol is dried at 100℃for 6 hours, calcined at 800℃for 2 to 6 hours, and heat treated to give ZrO in the resultant product ₂ In a monoclinic phase.

In a specific embodiment of the present invention, the stabilizer is an organic acid, and in one embodiment, the stabilizer is preferably at least one of glycolic acid, oxalic acid, acetic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, citric acid, and the like, and more preferably one or more of acetic acid, oxalic acid, or citric acid.

In one embodiment of the invention, the alkali cation is, for example, a nitrogen-containing cation, such as ammonium ion or a nitrogen-containing cation formed by aqueous organic alkali hydrolysis, such as one or more of methylamine, dimethylamine, trimethylamine, methanolamine, dimethanol amine, trimethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyl triethylammonium hydroxide, monomethyl triethanolammonium hydroxide, monomethyl tributylammonium hydroxide, and the like.

In one embodiment of the invention, the molar ratio of basic cations to Zr is preferably 1-8.

In a preferred embodiment of the invention, the zirconium sol further comprises mineral acid groups and/or alcohols in a molar ratio to Zr of from 1 to 6, for example from 1 to 4:1. mineral acid radicals such as one or more of sulfate, chloride, nitrate, and alcohols such as one or more of methanol, ethanol, propanol, butanol.

In a preferred embodiment of the present invention, the pH of the zirconium sol is preferably 1.5 to 5, more preferably 2 to 4, still more preferably 2 to 3.

According to the invention, zirconium sol can be prepared by alkaline addition, oxidation and separationAt least one of the sub-exchange methods is performed by hydrolyzing a zirconium salt, preferably by an alkaline addition method. In a preferred embodiment of the present invention, the zirconium sol is prepared by a method comprising the steps of: s1, mixing a zirconium source with a first solvent to obtain a first mixed solution, wherein the first mixed solution is prepared from ZrO ₂ The concentration is 0.5-20 wt%, preferably 1-18 wt% or 5-15 wt%; s2, enabling the first mixed solution and the stabilizer to react for 0.5-3 hours at the temperature of 20-90 ℃ to obtain a second mixed solution, wherein the molar ratio of the first mixed solution to the stabilizer is 1: (1-6) the first mixed solution is based on zirconium; s3, mixing the second mixed solution with an alkali source at 20-50 ℃ to obtain the zirconium sol, wherein the pH value of the zirconium sol is 0-10, preferably 1-7.

In one embodiment of the present invention, in step S1, the temperature of the mixing may be 15-40 ℃.

In one embodiment of the present invention, in step S3, an alkali source is slowly added to the second mixed solution to obtain a clear and transparent zirconium sol. The slow addition can be, for example, dropwise addition or a certain addition rate can be controlled, for example, the addition rate is 0.05-50 mL/min/L of the second mixed solution, for example, 0.1-30mL of the second mixed solution, 1-35mL of the second mixed solution, 0.05-10 mL/min/L of the second mixed solution or 0.1-5 mL/min/L of the second mixed solution. In one embodiment, the alkaline solution is slowly added to the second mixed solution by a pump, such as a peristaltic pump. Preferably, the amount of lye added is such that the zirconium sol has a pH of from 1.5 to 5, for example from 2 to 4, even more preferably from 2 to 3.

In one embodiment of the present invention, in step S1, the zirconium source is an inorganic zirconium salt and/or an organic zirconium salt, such as one or more of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, zirconium nitrate, zirconyl sulfate, and zirconyl carbonate; the organic zirconium salt is one or more of zirconium n-propoxide, zirconium isopropoxide, zirconium ethoxide and zirconium butoxide.

In a specific embodiment of the present invention, in step S2, the stabilizer is an organic acid capable of forming a coordination polymer with zirconium, and the stabilizer is preferably one or more of glycolic acid, acetic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid and citric acid, and more preferably one or more of acetic acid, oxalic acid and citric acid.

In a specific embodiment of the present invention, in step S3, the alkali source is selected from ammonia water or a water-soluble organic base, and the water-soluble organic base is, for example, one or more of methylamine, dimethylamine, trimethylamine, methanolamine, dimethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyl triethylammonium hydroxide, monomethyl triethanolammonium hydroxide, and monomethyl tributylammonium hydroxide.

In one embodiment of the present invention, the weight ratio of the first silicon source, the first directing agent, sodium hydroxide and water may vary within a wide range, and may be, for example, (2-15): 1: (1-7): (40-400), preferably (3-16): 1: (1.5-6.5): (42-380), wherein the first silicon source is SiO ₂ The first guiding agent is Al ₂ O ₃ Sodium hydroxide calculated as Na ₂ An O meter; with Al ₂ O ₃ The weight ratio of the amount of the first directing agent to the zirconium magnesium-containing reactive microsphere may also vary within a wide range, for example (0.001-2): 1, preferably (0.01-0.5): 1, more preferably (0.01-0.3): 1.

according to the present invention, the conditions of the hydrothermal crystallization treatment may include: the temperature is 88-105 ℃ and the time is 10-78 hours; preferably, the temperature is 90-96℃for 12-70 hours.

In one embodiment of the invention, the method further comprises: and filtering, washing and drying the product obtained by the hydrothermal crystallization treatment, and preferably washing the solid product obtained by filtering until the pH value of the washing liquid is less than 10. Drying may be performed in a constant temperature oven, and the drying conditions may include: the temperature is 100-150 ℃ and the time is 100-150 ℃.

According to the invention, the first silicon source is selected from one or more of sodium silicate, silica gel and organic silicon, preferably sodium silicate.

According to the present invention, the guiding agent may be synthesized according to conventional methods, such as the preparation method of USP3574538, USP3639099, USP3671191, USP4166099, EUP 0435625. The molar composition of the directing agent may be: (10-17) SiO ₂ ：(0.7-1.3)Al ₂ O ₃ ：(11-18)Na ₂ O：(200-350)H ₂ O. The raw materials are aged at 4-35deg.C, preferably 4-20deg.C to obtain the guiding agent.

In one embodiment of the invention, the reactive microspheres comprising zirconium magnesium comprise 76 to 98.8 wt.% alumina matrix, 1 to 14 wt.% zirconium oxide and 0.2 to 10 wt.% magnesium oxide; the sphericity of the reactive microsphere containing zirconium and magnesium is 85-100%, the abrasion index is 0.1-3%/h, and the particle size is 20-150 μm.

In a specific embodiment of the invention, the zirconium magnesium containing reactive microsphere comprises 10-95 wt. -%, preferably 15-80 wt. -%, preferably 20-50 wt. -% of hydrous kaolin and/or kaolin raw on a dry basis, 5-50 wt. -%, preferably 10-45 wt. -% of metakaolin (also referred to as metakaolin) on a dry basis, 0-20 wt. -%, preferably 2-15 wt. -% of aluminum oxide on a dry basis, 0-30 wt. -%, preferably 5-28 wt. -%, preferably 10-25 wt. -% of high clay on a dry basis, 0.5-15 wt. -%, preferably 1-14 wt. -%, preferably 2-12 wt. -%, preferably 3-10 wt. -% of zirconium oxide, and 0.1-15 wt. -%, preferably 0.2-10 wt. -%, preferably 2-8 wt. -% of magnesium oxide.

In one embodiment of the present invention, the zirconia is derived from a stabilizer-containing zirconium sol containing ZrO ₂ A stabilizer, a base cation and water.

According to a fourth aspect of the present invention, there is provided a method for preparing the reactive microsphere containing zirconium and magnesium according to the third aspect of the present invention, comprising the steps of: (1) Mixing hydrous kaolin or kaolin crude, metakaolin, optionally kaolin, a zirconium magnesium sol containing a stabilizer, optionally alumina, a second magnesium source, and water to form a slurry; the slurry has a solids content of 15 to 45 wt%, preferably 25 to 40 wt%; (2) And (3) spray drying and optionally roasting the slurry obtained in the step (1), wherein the roasting temperature is 300-1000 ℃, preferably 400-750 ℃ and the roasting time is 1-4h.

In the present invention, the alumina may include, but is not limited to, one or more of hydrated alumina, gamma-alumina, eta-alumina, kappa-alumina.

The fifth aspect of the invention provides a Y-type molecular sieve catalytic material, which is prepared by crystallizing a mixture containing the zirconium-magnesium-containing reactive microspheres provided by the third aspect of the invention, a second silicon source, a second directing agent, sodium hydroxide and water; wherein the weight ratio of the second silicon source to the second guiding agent to the sodium hydroxide to the water is (2-15): 1: (1-7): (40-400), wherein the second silicon source is SiO ₂ The second guiding agent is calculated as Al ₂ O ₃ Calculated by Na, the sodium hydroxide is ₂ An O meter; with Al ₂ O ₃ The weight ratio of the second directing agent to the amount of the zirconium-containing magnesium reactive microsphere on a dry basis is (0.001-2): 1, a step of; the second silicon source is selected from one or more of sodium silicate, silica gel and organic silicon.

The third aspect of the invention provides a catalyst comprising the Y-type molecular sieve catalytic material provided in the first aspect of the invention and a modifying component. In one embodiment of the invention, the modifying component is selected from rare earth metals, preferably one or more of lanthanum, cerium, praseodymium, neodymium and phosphorus. Preferably, the modifying component is present in an amount of 4.5 to 5.0 wt% based on the dry weight of the catalyst.

The invention is further illustrated by the following examples, which are not intended to be limiting in any way.

The molecular sieve content in the molecular sieve catalytic materials of examples and comparative examples was determined according to the RIPP146-90 standard method (RIPP standard method is described in petrochemical analysis method (RIPP test method), yang Cuiding et al, scientific Press, 1990, the same shall apply hereinafter), and was obtained from the relative crystallinity.

The content of each component in the zirconia, magnesia and alumina matrix in the molecular sieve catalytic material and the zirconium-magnesium-containing reactive microsphere is detected by an XRF method.

In the present invention, sphericity is expressed by sphericity index SPHT, which means the ratio of the surface area of a sphere of the same volume as an object to the surface area of the object. The sphericity calculation formula is as follows: sphericity index spht=4pi a ² /P ² Where A is the projected area of the particle and P is the projected perimeter of the particle. The sphericity of the catalytic cracking catalyst was tested using a CamsizerXT dynamic digital imaging particle analyzer from Leachi, germany, and falling sample particles were photographed at a photographing speed of 300 pictures per second using two digital photographing lens reference lenses CCD-B and focusing lens CCD-Z. And (3) carrying out software analysis, and carrying out statistical calculation on particle images captured by the two lenses to obtain the sphericity index SPHT of the sample. .

The attrition indexes of the molecular sieve catalytic material and the reactive microsphere containing zirconium and magnesium are detected by the NB/SH/T0943-2017 method.

The specific surface of the molecular sieve catalytic material is measured according to a nitrogen adsorption method (GB/T5816-1995), the total pore volume (Vtotal pore) and the pore volume of pores with the pore diameter of 2-50nm (pores with the pore diameter of 2-50 nm) are measured according to a nitrogen adsorption method (RIPP 151-90), and the medium macroporosity is calculated according to the following formula: macroporosity = (V total pores-pores with V pore diameters of 2-50 nm)/V total pores x 100%.

In examples and comparative examples, preparation of the directing agent: 250 kg of sodium silicate solution (containing 20.05% by weight of SiO) ₂ 6.41% by weight of Na ₂ O), 120 kg of sodium metaaluminate solution (containing 3.15% by weight of Al) was slowly added at 30℃with rapid stirring ₂ O ₃ 21.1 wt% Na ₂ O), stirring for 1 hour, and aging at 20 ℃ for 48 hours to obtain the guiding agent.

Preparation example 1 of zirconium sol

S1, adding 130g of deionized water into a beaker, then adding 125g of zirconium oxychloride, and stirring at 20 ℃ for 10min to obtain a first mixed solution;

s2, slowly adding 93g of acetic acid into the first mixed solution, stirring at 50 ℃ and reacting for 30min to obtain a second mixed solution;

s3, slowly adding concentrated ammonia water into the second mixed solution by using a pump at the temperature of 25 ℃, wherein the adding time is 30min, and the pH value is controlled to be 2.5, so that clear and transparent zirconium sol A1 is obtained, and the properties of the zirconium sol are shown in the table 1.

Preparation example 2 of zirconium sol

Zirconium sol A2 was prepared in the same manner as in preparation example 1 of zirconium sol except that 70g of oxalic acid was slowly added to the first mixed solution in step S2.

Preparation example 3 of zirconium sol

Zirconium sol A3 was prepared in the same manner as in preparation example 1 of zirconium sol except that in step S1, 170g of deionized water was added to a beaker, followed by 176g of zirconium isopropoxide; in step S2, 70g of oxalic acid is slowly added into the first mixed solution; in step S3, triethanolamine is slowly added to the second mixed solution by a pump.

TABLE 1

Zirconium sol preparation example no	Example 1	Example 2	Example 3
				Zirconium sol numbering	A1	A2	A3
ZrO ₂ Mass percent of	10.8	11.9	11.3
				pH value of	2.5	2.5	2.5
Molar ratio of basic cation to Zr	2	1.67	1.74
				Mole ratio of stabilizer to Zr	4	4	4
Average particle size, nm	10	9.8	9.7
				Colloidal particle diameter range, nm	8-10	8-10	8-10
Concentration degree, percent	95	93	92
				Proportion of monoclinic phase to tetragonal phase	0.4:1	0.35:1	0.3:1

* The sample was dried at 100deg.C for 6 hours and calcined at 600deg.C for 4 hours.

Preparation examples 1-3 and 6 of reactive microspheres containing zirconium and magnesium

The hydrous kaolin is baked in a muffle furnace at 1000 ℃ for 3 hours to obtain the high soil after characteristic heat release. The hydrous kaolin was calcined in a muffle furnace at 870 ℃ for 1 hour to obtain metakaolin. Calcining pseudoboehmite in a muffle furnace at 600 ℃ for 2 hours to obtain gamma-Al ₂ O ₃ I.e., calcined hydrated alumina.

According to the dosage ratio shown in Table 2, hydrous kaolin, metakaolin, kaolin, calcined hydrated alumina, zirconium sol, magnesium oxide solution and water are mixed and pulped, the obtained slurry with the solid content of 40 weight percent is subjected to spray drying to obtain a zirconium-magnesium-containing reactive microsphere precursor with the particle size of 20-150 mu m, and the zirconium-magnesium-containing reactive microsphere precursor is roasted for 3 hours at 800 ℃ to obtain the zirconium-magnesium-containing reactive microsphere ZQ-1. The data in the raw materials dosage portion of Table 1 shows the weight ratios of the amounts of hydrous kaolin, metakaolin, kaolin, calcined hydrated alumina, magnesia and zirconia sol. The composition of the prepared zirconium-magnesium-containing reactive microsphere is shown in Table 3 and is the same as below.

Preparation examples 4-5 and 6 of reactive microspheres containing zirconium and magnesium

The hydrous kaolin is baked in a muffle furnace at 1000 ℃ for 3 hours to obtain the high soil after characteristic heat release. The hydrous kaolin was calcined in a muffle furnace at 870 ℃ for 1 hour to obtain metakaolin. The pseudoboehmite is acidified with hydrochloric acid to a sol having a pH of 1-3, i.e., acidified hydrated alumina.

Mixing and pulping hydrous kaolin, metakaolin, high clay, calcined hydrated alumina, zirconium sol, magnesium oxide solution and water according to the dosage proportion shown in table 1, carrying out spray drying on the obtained slurry with the solid content of 40 weight percent to obtain a zirconium-magnesium-containing reactive microsphere precursor, and roasting the zirconium-magnesium-containing reactive microsphere precursor at 800 ℃ for 3 hours to obtain the zirconium-magnesium-containing reactive microsphere with the particle size of 20-150 mu m.

Preparation example 7 of reactive microspheres containing zirconium magnesium

The same method as in preparation example 1 of reactive microspheres containing zirconium magnesium was used, except that zirconium oxychloride was used instead of zirconium sol to prepare slurry.

Preparation of reactive microspheres without zirconium magnesium comparative example 1

The aqueous kaolin, metakaolin, kaolin, calcined alumina hydrate and water were mixed and slurried according to the amount ratio shown in Table 2, and the resulting slurry having a solids content of 40% by weight was spray-dried to obtain reactive microspheres DB-1 having a particle size of 20 to 150. Mu.m.

TABLE 2

TABLE 3 Table 3

Example 1 preparation of molecular sieve catalytic Material

1 kg of reactive microspheres ZQ-1 containing zirconium and magnesium was added with stirring to 6 kg of sodium silicate solution (containing 20.05% by weight of SiO) ₂ 6.41% by weight of Na ₂ O), 1.5 kg of a guiding agent and 2 kg of a sodium hydroxide solution with a concentration of 15 wt% are mixed, and then the mixture is stirred at constant temperature at 94 ℃ and a rotation speed of 400 rpm to carry out hydrothermal crystallization treatment for 24 hours. After the hydrothermal crystallization treatment is finished, the crystallization tank is quenched and filtered, and deionized water is adopted to wash the solid product obtained by filtration until the pH value of the washing liquid is less than 10. And drying at 120 ℃ for 2 hours to obtain the Y-type molecular sieve catalytic material GY-1.

Example 2 preparation of molecular sieve catalytic Material

Y-type molecular sieve catalyst GY-2 was prepared in the same manner as in example 1, except that zirconium-magnesium-containing reactive microsphere ZQ-2 was used instead of ZQ-1.

Example 3 preparation of molecular sieve catalytic Material

A Y-type molecular sieve catalyst material GY-3 was prepared in the same manner as in example 1 except that 7 kg of sodium silicate was added and that ZQ-1 was replaced with reactive microspheres ZQ-3 containing zirconium magnesium.

Example 4 preparation of molecular sieve catalytic Material

A Y-containing sieve catalyst material GY-4 was prepared in the same manner as in example 1 except that 7 kg of sodium silicate was added and that ZQ-1 was replaced with reactive microspheres ZQ-4 containing zirconium magnesium.

Example 5 preparation of molecular sieve catalytic Material

A Y-type molecular sieve catalyst material GY-5 was prepared in the same manner as in example 1 except that 7 kg of sodium silicate was added and that ZQ-1 was replaced with reactive microspheres ZQ-5 containing zirconium magnesium.

Example 6 preparation of molecular sieve catalytic Material

Y-type molecular sieve catalyst GY-6 was prepared in the same manner as in example 1, except that ZQ-1 was replaced with reactive microspheres ZQ-6 containing zirconium magnesium.

Example 7 preparation of molecular sieve catalytic Material

Y-type molecular sieve catalyst GY-7 was prepared in the same manner as in example 1, except that zirconium-containing reactive microsphere ZQ-7 was used instead of ZQ-1.

Comparative example 1 preparation of molecular sieve catalytic Material

A molecular sieve catalytic material DY-1 was prepared in the same manner as in example 1, except that reactive microsphere DB-1 was used instead of ZQ-1.

Comparative example 2 preparation of molecular sieve catalytic Material

Adding DY-1 into deionized water, adjusting the concentration to 50 weight percent, adding 5 weight percent of zirconium sol A1 and 5 weight percent of magnesium solution of DY-1, soaking for 6 hours, and drying at 120 ℃ to obtain the molecular sieve catalytic material DY-2.

TABLE 4 Table 4

Wherein, the mesoporosity refers to the proportion of the volume of macropores with the pore diameter of 2-50nm to the total pore volume.

Example 1 for preparing a catalyst

Adding deionized water into a molecular sieve catalytic material GY-1 for pulping to form slurry with the solid content of 10 weight percent; adding water into lanthanum chloride, pulping to form La ₂ O ₃ A lanthanum chloride solution having a concentration of 5 wt%; adding lanthanum chloride solution to the slurry, lanthanum chloride (in La ₂ O ₃ Calculated on a dry basis) to molecular sieve (calculated on a dry basis) of 1:19 Stirring at 70 ℃ for 1h, filtering, washing, drying at 150 ℃ for 8h, and roasting at 500 ℃ for 4h; reuse of ammonium sulfateWashing the solution, wherein the weight ratio of the ammonium sulfate to the molecular sieve catalytic material dry basis is 1:20 Stirring at 70 ℃ for 1h, filtering, washing, drying at 150 ℃ for 8h, and roasting at 500 ℃ for 2h; the resulting catalyst was designated REGY-1 and its composition is shown in Table 5.

Examples 2 to 7 for preparing the catalyst

A catalyst was prepared by the same method as in example 1 for preparing a catalyst, except that the Y-type molecular sieve catalytic materials prepared in examples 2 to 7 for preparing a molecular sieve catalytic material were used, respectively, for preparing a catalyst.

Comparative examples 1 to 2 for preparing catalysts

A catalyst was prepared by the same method as in example 1 for preparing a catalyst, except that the molecular sieve catalytic materials prepared in comparative examples 1 to 2 for preparing molecular sieve catalytic materials were used, respectively, for preparing a catalyst.

Test case

The catalysts prepared in the examples and comparative examples were treated with 800 ℃/100% steam on an aging apparatus for 17 hours, and the modified catalysts were treated with 800 ℃/100% steam on the aging apparatus for 17 hours, respectively, to perform a micro-reactive MAT test;

the catalyst was contaminated with each of the metals, calculated as 4000ppm nickel and 3000ppm vanadium, and then treated with 800 c/100% steam for 4 hours to perform the micro-reactive MAT test.

The reaction conditions for the light oil micro-reaction activity test are as follows: the light diesel oil in large harbor with the distillation range of 235-335 ℃ is used as raw material, the catalyst-oil ratio is 3.2, and the weight airspeed is 16h ^-1 The temperature was 460 ℃. The reaction product was analyzed by gas chromatography.

Wherein, light oil micro-reactivity (MAT) is calculated by the following formula:

micro-reactivity= (gas yield below C5 + gasoline yield at C5-221 ℃ + coke yield)/total feed x 100% = gas yield below C5 + gasoline yield at C5-221 ℃ + coke yield.

TABLE 5

As can be seen from Table 5, the zirconium-containing molecular sieve catalytic material of the invention has high activity after nickel-vanadium pollution and better heavy metal resistance after modification under the same conditions.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.

In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.

Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims

1. The heavy metal resistant Y-type molecular sieve catalytic material is prepared by hydrothermal crystallization of zirconium-magnesium-containing reactive microspheres, wherein the zirconium-magnesium-containing reactive microspheres contain 70-99.4 wt% of an alumina matrix, 0.5-15 wt% of zirconium oxide and 0.1-15 wt% of magnesium oxide based on the dry weight of the zirconium-magnesium-containing reactive microspheres.

2. The Y-type molecular sieve catalytic material of claim 1, wherein the zirconium magnesium-containing reactive microspheres contain 81-98.8 wt.% alumina matrix, 1-14 wt.% zirconia, and 0.2-10 wt.% magnesia;

3. The Y-type molecular sieve catalytic material of claim 1, wherein the zirconia is present in an amount of 2-12 wt% and the magnesia is present in an amount of 0.5-8 wt%, based on the dry weight of the Y-type molecular sieve catalytic material.

4. The Y-type molecular sieve catalytic material of claim 1, wherein the specific surface area of the Y-type molecular sieve catalytic material is 200-700m ² Per g, the total pore volume is 0.20-0.50mL/g, the abrasion index is 0.1-2%/h, and the mesopore volume with the pore diameter of 2-50nm accounts for 20-50% of the total pore volume.

5. The Y-type molecular sieve catalytic material of any of claims 1-4, wherein the zirconium magnesium-containing reactive microsphere is prepared by a method comprising the steps of:

6. The Y-molecular sieve catalytic material of claim 5, wherein the alumina matrix feedstock contains hydrous kaolin and/or metakaolin, optionally hydrated alumina, optionally kaolin;

7. The Y-molecular sieve catalytic material of claim 5, wherein the zirconium sol contains ZrO ₂ A stabilizer, a base cation and water;

8. A process for preparing the Y-type molecular sieve catalytic material of any of claims 1-7, the process comprising: and mixing the zirconium-magnesium-containing reactive microsphere, a first silicon source, a first guiding agent, sodium hydroxide and water, and then carrying out hydrothermal crystallization treatment on the obtained mixture.

9. The method of claim 8, wherein the conditions of the hydrothermal crystallization treatment comprise: the temperature is 88-105 ℃ and the time is 10-78 hours;

with Al ₂ O ₃ The weight ratio of the first directing agent to the amount of the zirconium-containing magnesium reactive microsphere on a dry basis is (0.001-2): 1, preferably (0.01-0.5): 1, a step of;

10. The reactive microsphere containing zirconium and magnesium is suitable for preparing Y-type molecular sieve catalytic material by hydrothermal crystallization, and contains 0.5-15 wt% of zirconium oxide, 0.1-15 wt% of magnesium oxide and 70-99.4 wt% of aluminum oxide matrix based on the dry weight of the reactive microsphere containing zirconium and magnesium.

11. The reactive zirconium magnesium microsphere according to claim 10, wherein the reactive zirconium magnesium containing microsphere comprises 76-98.8 weight percent alumina matrix, 1-14 weight percent zirconia and 0.2-10 weight percent magnesia;

12. The zirconium magnesium-containing reactive microsphere according to claim 10, wherein the zirconium magnesium-containing reactive microsphere comprises 10-95 wt. -%, preferably 15-80 wt. -%, preferably 20-50 wt. -% of hydrous kaolin and/or kaolin raw clay on a dry basis, 5-50 wt. -%, preferably 10-45 wt. -% of metakaolin on a dry basis, 0-20 wt. -%, preferably 2-15 wt. -% of aluminum oxide on a dry basis, 0-30 wt. -%, preferably 5-28 wt. -%, preferably 10-25 wt. -% of high clay on a dry basis, 0.5-15 wt. -%, preferably 1-14 wt. -%, preferably 2-12 wt. -%, preferably 3-10 wt. -% of zirconium oxide, and 0.1-15 wt. -%, preferably 0.2-10 wt. -%, preferably 2-8 wt. -% of magnesium oxide.

13. The zirconium magnesium containing reactive microsphere according to claim 10, wherein the zirconia is derived from a stabilizer containing zirconium sol containing ZrO ₂ A stabilizer, a base cation and water.

14. A method of preparing the zirconium magnesium containing reactive microsphere of any one of claims 10-13, the method comprising the steps of:

15. A Y-type molecular sieve catalytic material crystallized from a mixture comprising the zirconium-magnesium-containing reactive microsphere of any one of claims 10-13, a second silicon source, a second directing agent, sodium hydroxide, and water;