CN114887650A - In-situ crystallization catalyst for preparing olefin and preparation method and application thereof - Google Patents

In-situ crystallization catalyst for preparing olefin and preparation method and application thereof Download PDF

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CN114887650A
CN114887650A CN202210443936.6A CN202210443936A CN114887650A CN 114887650 A CN114887650 A CN 114887650A CN 202210443936 A CN202210443936 A CN 202210443936A CN 114887650 A CN114887650 A CN 114887650A
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molecular sieve
catalyst
naphtha
situ
aluminum
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CN114887650B (en
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张玲
郝坤
陶智超
申宝剑
李江
郭艳
樊莲莲
姜大伟
孟劭聪
杨勇
李永旺
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Synfuels China Inner Mongolia Co ltd
Zhongke Synthetic Oil Technology Co Ltd
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Synfuels China Inner Mongolia Co ltd
Zhongke Synthetic Oil Technology Co Ltd
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • 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
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
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    • 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
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    • 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
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J29/655—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • 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
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7057—Zeolite Beta
    • 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
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    • Y02P30/40—Ethylene production

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Abstract

The invention relates to an in-situ crystallization catalyst for preparing olefin, a preparation method and application thereof, wherein the catalyst comprises the following components in percentage by mass relative to the total mass of solid components in the catalyst: dehydrogenation active metal with the dry basis mass content of 0.1-25%, in-situ crystallized molecular sieve with the dry basis mass content of 9.9-84.5%, auxiliary agent with the dry basis mass content of 0-15%, residual matrix and binder with the dry basis mass content of 15.4-90%; the molecular sieve is obtained by in-situ crystallization of a molecular sieve synthesis raw material in the presence of the dehydrogenation active metal. The in-situ crystallization catalyst provided by the invention has the advantages of improved hydrothermal stability and mechanical strength, excellent catalytic performance, capability of reducing the reaction temperature of preparing olefin by coupling naphtha with low-carbon alcohol ether, inhibition of generation of low-carbon alkane such as methane and the like, improvement of the yield of low-carbon olefin, and wide raw material applicability.

Description

In-situ crystallization catalyst for preparing olefin and preparation method and application thereof
Technical Field
The invention belongs to the technical field of industrial catalysis, and particularly relates to an in-situ crystallization catalyst for preparing olefin, and an in-situ crystallization preparation method and application thereof.
Background
Low carbon olefins (olefins with carbon atoms of 2-4) are important basic organic chemical raw materials, global demand is expected to keep an average acceleration of 4% in the coming decade, and domestic low carbon olefins and aromatic hydrocarbon markets are expected to keep strong acceleration. Taking ethylene as an example, the ethylene equivalent consumption gap in 2019 of China is 2570 ten thousand tons, and the ethylene equivalent consumption gap accounts for about 50 percent of the consumption, so that the development of downstream fine chemical engineering is severely restricted.
The production of low-carbon olefin mainly adopts the technologies of steam cracking, catalytic cracking, methanol-to-olefin and the like at present. Catalytic cracking is mainly based on heavy hydrocarbons as feedstock. Naphtha is also called chemical light oil and is the light oil which is the by-product of crude oil or other processing processes. Naphtha and other light oils are mainly used for producing low-carbon olefins by a steam cracking technology, the steam cracking process has extremely high requirements on the properties of raw materials, and in order to obtain good steam cracking performance, the naphtha has the characteristics of high alkane content with the mass fraction of more than 65%, low aromatic hydrocarbon content with the mass fraction of less than 10%, olefin content with the mass fraction of less than 1% as far as possible, and the like, and only when ethane is used as the raw material, the low methane yield can be obtained, while the methane yield of steam cracking of other alkanes exceeds 10 wt%, even exceeds 20 wt%. However, due to the complex sources, the naphtha composition varies widely. The naphtha which is a byproduct in the traditional petrochemical industry, taking Daqing crude oil as an example, contains 69 wt% of alkane, 23 wt% of cyclane and about 8 wt% of arene; the naphtha as the byproduct of the coal-based Fischer-Tropsch synthesis contains 70 wt% of olefin, 26 wt% of alkane and about 4 wt% of oxygen-containing compounds. Moreover, from the energy perspective, naphtha steam cracking requires high temperature operation of 850-. In addition, the investment cost of the coal-based methanol-to-olefin process device is about twice of that of naphtha steam cracking, the carbon efficiency is low, and the carbon emission intensity is high.
The patent CN102531821B discloses a naphtha and methanol coupling reaction technology, and a lanthanum or phosphorus modified ZSM-5 molecular sieve catalyst is adopted, so that the reaction temperature can be reduced to 550-670 ℃. When naphtha is coupled with low-carbon alcohol ether to prepare olefin feed, the reaction activity of the low-carbon alcohol ether is relatively high, and the naphtha, particularly the low-carbon alkane component in the naphtha, is relatively low in activity and difficult to convert. Although the naphtha is coupled with the low-carbon alcohol ether co-feeding, the low-carbon alcohol ether can be considered to be preferentially adsorbed on the catalyst and can promote the conversion of alkane in the naphtha to a certain extent, experimental evidence for competitive adsorption inhibition of alkane conversion also exists. Therefore, the primary problem of naphtha coupled with low-carbon alcohol ether to olefin is to promote the low-temperature high-efficiency conversion of alkane components in naphtha. In addition, alkane catalytic cracking produces lower olefins and more stable, more difficult to convert lower alkanes mechanistically, which limits the yield of lower olefins. Therefore, the catalyst and the catalytic process are key for solving the problem of low-temperature high-efficiency conversion of naphtha. Patent CN101462916B discloses a method for preparing low-carbon olefins by catalytic cracking of petroleum hydrocarbons, which comprises the steps of performing catalytic dehydrogenation on petroleum hydrocarbons in the presence of a V, Cr, and Pt-based catalytic dehydrogenation catalyst under catalytic dehydrogenation conditions, and then performing catalytic cracking on catalytic dehydrogenation products in the presence of a zeolite catalytic cracking catalyst under catalytic cracking conditions. Patent CN112742456A carries out metal modification on a molecular sieve with an MFI structure, and realizes the coupling of catalytic dehydrogenation and catalytic cracking reactions of carbon tetrads. However, the alkane dehydrogenation-catalytic cracking two-stage method has complex process and high energy consumption, and the coupling method adopts post-treatment methods such as metal modification and the like, which can affect the pore canal, acidity and metal stability of the molecular sieve.
The in-situ crystallization is a kaolin type FCC catalyst synthesis method disclosed in U.S. Pat. No. 3,3647718 by Engelhard corporation of America in 1972, and has the characteristics of good molecular sieve stability, small particle size, high molecular sieve utilization rate, rich substrate inner surface, large heat capacity, low synthesis cost and the like. The in-situ crystallization method of the molecular sieve catalyst is further developed and applied from 2005 by teams represented by the china oil and gas company limited, and the in-situ crystallization preparation method of the molecular sieve material is disclosed in patent CN100450617C and the like. However, in the currently prepared catalysts, the molecular sieve therein is synthesized by in-situ crystallization, and the active metals such as Mo, Ni, Co, W and the like are introduced and prepared by post-treatment methods such as impregnation or colloid-forming mixed extrusion. The inventor finds that although the in-situ crystallization preparation method has obvious advantages in the aspects of molecular sieve content, hydrothermal stability and mechanical strength, the pore path and acidity of the molecular sieve and the stability of active metal are still influenced to a certain degree due to the introduction of metal by a post-treatment method in the preparation method of the in-situ crystallization metal-molecular sieve bifunctional catalyst reported at present.
Therefore, in order to solve the problem that the catalyst adopted in the process of producing olefins by coupling naphtha with lower alcohol ether in the prior art is unsatisfactory, it is necessary to develop a catalyst capable of catalyzing naphtha and lower alcohol ether more efficiently and stably to produce lower olefins.
Disclosure of Invention
The inventor discovers that in the process of developing a catalyst for catalyzing naphtha coupled low-carbon alcohol ether to olefin, after an in-situ crystallization preparation method of the conventional bifunctional catalyst is improved (metal components, matrixes and the like are introduced in the pulping process to be jointly pulped with a molecular sieve and spray-dried to prepare microspheres, so that in-situ crystallization synthesis is carried out in the presence of the metal components to generate the molecular sieve components and obtain the bifunctional catalyst), in-situ crystallization of the molecular sieve is carried out after the metal components and the molecular sieve synthesis raw materials are uniformly mixed, part of metal can enter a molecular sieve framework, the molecular sieve framework is effectively utilized to stabilize the metal components, the distance between the metal and an acid center is effectively shortened, rich mesopores penetrating through the catalyst are provided, and the high hydrothermal stability and high mechanical strength of the obtained microspherical catalyst can be ensured, so that the obtained catalyst well solves the problems of low-temperature conversion activity of alkane components in naphtha raw materials and low-temperature conversion of products The yield of the low-carbon olefin is limited. Based on this finding, the present inventors prepared a bifunctional catalyst comprising a dehydrogenation center and an acid center by in-situ crystallization after preparing microspheres by co-beating an active metal, a matrix, a binder, and the like and spray-drying. The bifunctional catalyst has the advantages of effectively shortened metal-acid center distance, abundant mesopores penetrating through the bifunctional catalyst and improved hydrothermal stability and mechanical strength of the microspherical catalyst, and has excellent performance in catalytic dehydrogenation and cracking reaction of naphtha coupled low-carbon alcohol ether, strong raw material universality, low reaction temperature, high yield of low-carbon olefin and remarkable social benefit and economic benefit.
In one aspect, the present invention provides an in situ crystallization catalyst for the production of olefins, wherein the catalyst comprises, relative to the total mass of solid components in the catalyst: dehydrogenation active metal with the dry mass content of 0.1-25%, in-situ crystallized molecular sieve with the dry mass content of 9.9-84.5%, auxiliary agent with the dry mass content of 0-15%, residual matrix with the dry mass content of 15.4-90% and adhesive; the dehydrogenation active metal is one or more selected from Pt, Ag, Au, Fe, Co, Cu, Ni, Rh, Cr, Ga and Zn, the in-situ crystallized molecular sieve is one or more selected from eight-membered ring, ten-membered ring, twelve-membered ring silicon-aluminum molecular sieve or eight-membered ring, ten-membered ring and twelve-membered ring silicon-phosphorus-aluminum molecular sieve, and the molecular sieve is obtained by in-situ crystallization of molecular sieve synthetic raw materials in the presence of the dehydrogenation active metal.
In another aspect, the present invention provides a method for preparing the in-situ crystallization catalyst for preparing olefin, wherein the method comprises:
(1) mixing and pulping dehydrogenation active metal, a substrate, a binder and deionized water to prepare slurry with the solid content of 20-55 wt%, and spray-drying the slurry to obtain microspheres with the particle size of 20-150 microns;
the dehydrogenation active metal is one or more selected from Pt, Ag, Au, Fe, Co, Cu, Ni, Rh, Cr, Ga and Zn; the matrix is one or more selected from hard kaolin, soft kaolin, coal pumice, natural clay, pseudo-boehmite, perlite, diatomite, halloysite, rectorite, montmorillonite, sepiolite, bentonite, sodium silicate, boehmite, amorphous silicon, amorphous aluminum and amorphous silicon aluminum, and the binder is one or more selected from silica sol, alumina sol, water glass and phosphor-aluminum gel;
(2) adding a silicon-aluminum-phosphorus source and a pH value regulator into the microspheres, mixing, crystallizing at 90-200 ℃ for 0.5-5 days to obtain a crystallization mother solution, separating in-situ crystallized microspheres from the crystallization mother solution, washing, filtering and drying the in-situ crystallized microspheres to obtain an in-situ crystallized product;
the silicon-aluminum-phosphorus source is one or more selected from water glass, silica sol, sodium silicate, solid silica gel, silicic acid, white carbon black, aluminum sulfate, aluminum nitrate, aluminum chloride, pseudo-boehmite, sodium aluminate, aluminum isopropoxide, aluminum hydroxide, phosphoric acid and ammonium hydrogen phosphate, and the pH value regulator is one or more selected from sodium hydroxide, potassium hydroxide, sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid and aqueous solution thereof;
(3) and (3) performing ammonia exchange or acid exchange on the in-situ crystallization product, and roasting at the temperature of 500-700 ℃ to prepare the catalyst.
In another aspect, the invention provides an application of the in-situ crystallization catalyst in catalyzing raw materials naphtha to be coupled with low-carbon alcohol ether to prepare olefin.
The catalyst, its preparation and use provided by the present invention may have, but are not limited to, the following features and advantages:
1. the dehydrogenation center and acid center bifunctional catalyst provided by the invention adopts metal components to provide dehydrogenation active centers, effectively promotes dehydrogenation and activation of alkane components in naphtha, and inhibits generation of low-carbon alkane.
2. In the preparation method of the catalyst, the coupling of the active metal to the molecular sieve component is realized by carrying out in-situ crystallization on the microsphere containing the metal component.
3. The in-situ crystallization preparation method of the catalyst can stabilize the metal component through the molecular sieve framework, effectively shorten the distance between the metal and the acid center, provide rich penetrating mesopores, and improve the stability and the mechanical strength of the microsphere catalyst.
4. The catalyst can catalyze naphtha from various sources to be coupled with the low-carbon alcohol ether to prepare olefin, has no limit on the content of alkane, olefin, cycloparaffin, aromatic hydrocarbon and oxygen-containing compounds in naphtha raw materials, and has wide raw material applicability.
5. The catalyst can realize the high-efficiency conversion of naphtha and low-carbon alcohol ether at the low temperature of 450-650 ℃, and has high selectivity of low-carbon olefin and low yield of methane.
6. The catalyst provided by the invention has the advantages of low raw material cost, simple preparation process, good repeatability and excellent catalytic reaction performance, and can be used for large-scale industrial production and application.
Drawings
Fig. 1 shows XRD patterns of the respective catalysts prepared in examples 1 to 5 (subfigures A, B, C, D and E show the catalysts prepared in examples 1 to 5, respectively).
FIG. 2 shows H on bifunctional catalysts prepared in example 1 and comparative examples 1 and 2 2 The TPR characterization result shows that the molecular sieve framework is effectively utilized to stabilize the metal component in the catalyst, so that the stability of the catalyst is improved.
Detailed Description
The following exemplary embodiments are further illustrative of the in situ crystallization catalyst for producing olefins according to the present invention, and the preparation method and application thereof, but do not limit the scope of the present invention.
In one embodiment, the present invention relates to an in situ crystallization catalyst for the production of olefins, wherein the catalyst comprises, relative to the total mass of the solid components in the catalyst: dehydrogenation active metal with the dry mass content of 0.1-25%, in-situ crystallized molecular sieve with the dry mass content of 9.9-84.5%, auxiliary agent with the dry mass content of 0-15%, residual matrix with the dry mass content of 15.4-90% and adhesive; the dehydrogenation active metal is one or more selected from Pt, Ag, Au, Fe, Co, Cu, Ni, Rh, Cr, Ga and Zn, the in-situ crystallized molecular sieve is one or more selected from eight-membered ring, ten-membered ring, twelve-membered ring silicon-aluminum molecular sieve or eight-membered ring, ten-membered ring and twelve-membered ring silicon-phosphorus-aluminum molecular sieve, and the molecular sieve is obtained by in-situ crystallization of molecular sieve synthetic raw materials in the presence of the dehydrogenation active metal.
In the catalyst, the dehydrogenation active metal and the in-situ crystallized molecular sieve respectively form a dehydrogenation center and an acid center of the catalyst, so that the catalyst simultaneously has the catalytic functions of catalytic dehydrogenation reaction, cracking, aromatization, isomerization and the like.
In some preferred embodiments, in the catalyst, the dehydrogenation-active metal is in the form of an inorganic salt, oxide, sulfide, nitride, carbide, or reduced metal.
In some preferred embodiments, the in situ crystallized molecular sieve (also referred to as "solid acid") may be a mixed crystal and co-crystal of one or more selected from, but not limited to, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-35, Beta, Y, MOR, MCM-22, IM-5, SSZ-13, SAPO-18, SAPO-11, SAPO-34, SAPO-5, and the like. In a further preferred embodiment, the in-situ crystallized molecular sieve may be a mixed crystal and co-crystal of one or more selected from ZSM-5, ZSM-11, ZSM-35, Beta, SAPO-18, SAPO-34, Y, MOR, and the like.
In some preferred embodiments, the adjuvant may be selected from one or more of, but not limited to, Ca, Mg, K, P, Sn, Mn, La, Ce, and the like.
In some preferred embodiments, the matrix is one or more selected from the group consisting of hard kaolin, soft kaolin, halloysite, natural clay, pseudo-boehmite, perlite, diatomaceous earth, halloysite, rectorite, montmorillonite, sepiolite, bentonite, sodium silicate, boehmite, amorphous silica, amorphous alumina, and amorphous silica-alumina, and the binder is one or more selected from the group consisting of silica sol, alumina sol, water glass, and phosphoalumina gel.
In one embodiment, the present invention relates to a method for preparing the above in situ crystallization catalyst for olefin production, wherein the method comprises:
(1) mixing and pulping dehydrogenation active metal, a substrate, a binder and deionized water to prepare slurry with the solid content of 20-55 wt%, and spray-drying the slurry to obtain microspheres with the particle size of 20-150 microns;
the dehydrogenation active metal is one or more selected from Pt, Ag, Au, Fe, Co, Cu, Ni, Rh, Cr, Ga and Zn; the matrix is one or more selected from hard kaolin, soft kaolin, coal pumice, natural clay, pseudo-boehmite, perlite, diatomite, halloysite, rectorite, montmorillonite, sepiolite, bentonite, sodium silicate, boehmite, amorphous silicon, amorphous aluminum and amorphous silicon aluminum, and the binder is one or more selected from silica sol, alumina sol, water glass and phosphor-aluminum gel;
(2) adding a silicon-aluminum-phosphorus source and a pH value regulator into the microspheres, mixing, crystallizing at 90-200 ℃ (for example, 95-180 ℃) for 0.5-5 days (preferably 20h-4 days) to obtain a crystallization mother liquor, separating in-situ crystallization microspheres from the crystallization mother liquor, washing, filtering and drying the in-situ crystallization microspheres to obtain an in-situ crystallization product;
the silicon-aluminum-phosphorus source is one or more selected from water glass, silica sol, sodium silicate, solid silica gel, silicic acid, white carbon black, aluminum sulfate, aluminum nitrate, aluminum chloride, pseudo-boehmite, sodium aluminate, aluminum isopropoxide, aluminum hydroxide, phosphoric acid and ammonium hydrogen phosphate, and the pH value regulator is one or more selected from sodium hydroxide, potassium hydroxide, sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid and aqueous solution thereof;
(3) and (3) performing ammonia exchange or acid exchange on the in-situ crystallization product, and roasting at the temperature of 500-700 ℃ to prepare the catalyst.
In some preferred embodiments, in step (1), the binder is added in an amount of 2% to 30% by mass of the matrix on a dry basis.
In some preferred embodiments, in step (1), during the pulping process, molecular sieve seed crystals are further added to facilitate the subsequent in situ crystallization. In a further preferred embodiment, the molecular sieve seeds may be solid phase or liquid phase molecular sieve seeds. In a further preferred embodiment, the molecular sieve seeds may be added in an amount of 0% to 10% of the mass of the matrix on a dry mass basis.
In some preferred embodiments, in step (1), one or both of an auxiliary and a pore-enlarging additive are further added during the beating.
In a further preferred embodiment, the auxiliary agent may be, but is not limited to, one or more of Ca, Mg, K, P, Sn, Mn, La, Ce, and the like. In a further preferred embodiment, the addition amount of the auxiliary agent is 0% to 20% by mass of the above-mentioned substrate.
In yet further preferred embodiments, the pore enlarging additive may be, but is not limited to, one or more of ethanol, propanol, pentane, hexane, propylamine, butylamine, ammonium bicarbonate, ammonium oxalate and urea. In a still further preferred embodiment, the pore-enlarging additive is added in an amount of 0-10% by mass of the matrix.
In this context, the microspheres obtained by spray drying may be used after calcination or may be used as such without calcination. In some preferred embodiments, prior to step (2), the spray-dried microspheres are calcined at 600-1000 ℃ for 0-7 hours.
In some preferred embodiments, in step (2), a structure directing agent is further added to the crystallization mother liquor during the crystallization. In a further preferred embodiment, the structure directing agent may be, but is not limited to, one or more of the following: quaternary or quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltriethylammonium hydroxide, dimethyldiethylamine hydroxide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, dimethyldiethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, methyltriethylammonium bromide, dimethyldiethylammonium bromide, etc.; monoamines such as cyclohexylamine, triethylamine and the like; and dibasic organic amines such as ethylenediamine, 1, 6-hexamethylenediamine, and the like. In a further preferred embodiment, the structure directing agent may be added in an amount of 0-15 wt% of the total mass of the crystallization mother liquor.
In some preferred embodiments, in step (3), the in situ crystallized product is subjected to ammonia exchange with one or more selected from ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium hydroxide solution, and the like.
In some preferred embodiments, in step (3), the in situ crystallized product is acid exchanged with one or more selected from dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid, dilute acetic acid, and the like.
In one embodiment, the invention relates to application of the in-situ crystallization catalyst in catalyzing raw material naphtha to be coupled with low-carbon alcohol ether to prepare olefin.
In some preferred embodiments, the raw naphtha may be, but is not limited to, naphtha by-produced from coal chemical industry (e.g., naphtha by-produced from coal-to-olefins, hydrogenated naphtha by-produced from coal-to-oils, straight-run naphtha by-produced from coal-to-oils), naphtha by-produced from petrochemical industry (also referred to as "petroleum-based naphtha"), and shale gas, natural gas, or natural gas oil associated with oil fields, etc.
In some preferred embodiments, the lower alcohol ether may be, but is not limited to, one or more of methanol, ethanol, propanol, butanol, dimethyl ether, a light mixed alcohol by-product of fischer-tropsch synthesis, a light mixed alcohol by-product of methanol from syngas, and the like.
In some preferred embodiments, the mass ratio of the lower alcohol ether to the raw naphtha may be 0.1% to 500%.
In some preferred embodiments, the olefin may be, for example, a lower olefin such as ethylene, propylene, butene, and the like.
In some preferred embodiments, gasoline components may be by-produced in the catalytic feedstock naphtha coupled with the lower alcohol ethers to olefins.
In some preferred embodiments, the reaction to produce olefins may be carried out in the following apparatus: riser reactor, stationary fluidized bed or circulating fluidized bed.
In some preferred embodiments, the reaction conditions for producing olefins are: the temperature is 450 ℃ and 650 ℃, and the reaction pressure is 30-300 kPa.
In some preferred embodiments, the following may be employed as atomizing media for the feed naphtha and lower alcohol ethers: steam, dry gas, hydrogen, synthesis gas, and fischer-tropsch synthesis tail gas, but is not limited thereto.
Exemplary aspects of the present invention may be illustrated by the following numbered paragraphs, but the scope of the present invention is not limited thereto:
1. an in-situ crystallization catalyst for the production of olefins, wherein the catalyst comprises, relative to the total mass of the solid components in the catalyst: dehydrogenation active metal with the dry mass content of 0.1-25%, in-situ crystallized molecular sieve with the dry mass content of 9.9-84.5%, auxiliary agent with the dry mass content of 0-15%, residual matrix with the dry mass content of 15.4-90% and adhesive; the dehydrogenation active metal is one or more selected from Pt, Ag, Au, Fe, Co, Cu, Ni, Rh, Cr, Ga and Zn, the in-situ crystallized molecular sieve is one or more selected from eight-membered ring, ten-membered ring, twelve-membered ring silicon-aluminum molecular sieve or eight-membered ring, ten-membered ring and twelve-membered ring silicon-phosphorus-aluminum molecular sieve, and the molecular sieve is obtained by in-situ crystallization of molecular sieve synthetic raw materials in the presence of the dehydrogenation active metal.
2. The catalyst of paragraph 1 wherein the dehydrogenation-active metal is in the form of an inorganic salt, oxide, sulfide, nitride, carbide, or reduced metal.
3. The catalyst of paragraph 1 or 2 wherein the in situ crystallized molecular sieve is a mixed crystal and co-crystal of one or more selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-35, Beta, Y, MOR, MCM-22, IM-5, SSZ-13, SAPO-18, SAPO-11, SAPO-34, SAPO-5.
4. The catalyst of any of paragraphs 1-3, wherein said in situ crystallized molecular sieve is a mixed crystal and co-crystal of one or more selected from the group consisting of ZSM-5, ZSM-11, ZSM-35, Beta, SAPO-18, SAPO-34, Y, MOR.
5. The catalyst of any of paragraphs 1-4, wherein the promoter is one or more selected from the group consisting of Ca, Mg, K, P, Sn, Mn, La, Ce.
6. The catalyst of any of paragraphs 1-5, wherein the matrix is one or more selected from the group consisting of hard kaolin, soft kaolin, halloysite, natural clay, pseudo-boehmite, perlite, diatomaceous earth, halloysite, rectorite, montmorillonite, sepiolite, bentonite, sodium silicate, boehmite, amorphous silica, amorphous alumina, and amorphous silica-alumina, and the binder is one or more selected from the group consisting of silica sol, alumina sol, water glass, and phosphoalumina gel.
7. A method of preparing the in situ crystallization catalyst for olefin production of any of paragraphs 1-6, wherein the method comprises:
(1) mixing and pulping dehydrogenation active metal, a substrate, a binder and deionized water to prepare slurry with the solid content of 20-55 wt%, and spray-drying the slurry to obtain microspheres with the particle size of 20-150 microns;
the dehydrogenation active metal is one or more selected from Pt, Ag, Au, Fe, Co, Cu, Ni, Rh, Cr, Ga and Zn; the matrix is one or more selected from hard kaolin, soft kaolin, coal pumice, natural clay, pseudo-boehmite, perlite, diatomite, halloysite, rectorite, montmorillonite, sepiolite, bentonite, sodium silicate, boehmite, amorphous silicon, amorphous aluminum and amorphous silicon aluminum, and the binder is one or more selected from silica sol, alumina sol, water glass and phosphor-aluminum gel;
(2) adding a silicon-aluminum-phosphorus source and a pH value regulator into the microspheres, mixing, crystallizing at 90-200 ℃ for 0.5-5 days to obtain a crystallized mother liquor, separating in-situ crystallized microspheres from the crystallized mother liquor, washing, filtering and drying the in-situ crystallized microspheres to obtain an in-situ crystallized product;
the silicon-aluminum-phosphorus source is one or more selected from water glass, silica sol, sodium silicate, solid silica gel, silicic acid, white carbon black, aluminum sulfate, aluminum nitrate, aluminum chloride, pseudo-boehmite, sodium aluminate, aluminum isopropoxide, aluminum hydroxide, phosphoric acid and ammonium hydrogen phosphate, and the pH value regulator is one or more selected from sodium hydroxide, potassium hydroxide, sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid and aqueous solution thereof;
(3) and (3) performing ammonia exchange or acid exchange on the in-situ crystallization product, and roasting at the temperature of 500-700 ℃ to prepare the catalyst.
8. The method of paragraph 7, wherein in step (1) the binder is added in an amount of 2% to 30% by mass of the matrix on a dry basis.
9. The method of paragraph 7 or 8, in step (1), during said slurrying, further adding molecular sieve seeds.
10. The method of paragraph 9 wherein the molecular sieve seeds are solid phase or liquid phase molecular sieve seeds.
11. The method of paragraph 9 or 10, wherein the molecular sieve seeds are added in an amount of 0% to 10% of the mass of the matrix on a dry mass basis.
12. The method as set forth in any of paragraphs 7-11, wherein in step (1), one or both of an aid and a pore-enlarging additive are further added during the beating.
13. The method of paragraph 12 wherein the promoter is one or more of Ca, Mg, K, P, Sn, Mn, La, Ce.
14. The method of paragraph 12 or 13 wherein the adjuvant is added in an amount of 0% to 20% by mass of the matrix.
15. The method of any of paragraphs 12-14, wherein the pore-enlarging additive is one or more of ethanol, propanol, pentane, hexane, propylamine, butylamine, ammonium bicarbonate, ammonium oxalate and urea.
16. The method of any of paragraphs 12-15, wherein the pore-enlarging additive is added in an amount of 0-10% by mass of the matrix.
17. The method as described in any of paragraphs 7-16, wherein, prior to step (2), the spray dried microspheres are calcined at 600-1000 ℃ for 0-7 hours.
18. The method of any one of paragraphs 7-17, wherein in step (2), a structure directing agent is further added to the crystallization mother liquor during the crystallization.
19. The method of paragraph 18, wherein the structure directing agent is one or more of: quaternary amine or quaternary ammonium salt, monoamine, binary organic amine.
20. The method of paragraphs 18 or 19 wherein the quaternary or quaternary ammonium salt is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltriethylammonium hydroxide, dimethyldiethylamine hydroxide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, dimethyldiethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, methyltriethylammonium bromide, or dimethyldiethylammonium bromide; the monoamine is one or two of cyclohexylamine and triethylamine; the binary organic amine is one or two of ethylenediamine and 1, 6-hexamethylenediamine.
21. The method of any of paragraphs 18-20, wherein the structure directing agent is added in an amount of 0-15 wt% of the total mass of the crystallization mother liquor.
22. The method of any of paragraphs 7-21, wherein in step (3) the in situ crystallized product is subjected to ammonia exchange with one or more selected from the group consisting of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium hydroxide solution.
23. The method of any of paragraphs 7-22, wherein in step (3), the in situ crystallized product is acid exchanged with one or more selected from the group consisting of dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid, and dilute acetic acid.
24. The use of the in situ crystallization catalyst for the production of olefins as described in any of paragraphs 1-6 in the production of olefins by the coupling of a catalytic feedstock naphtha with a low carbon alcohol ether.
25. The use of paragraph 24 wherein the raw naphtha is selected from the group consisting of coal chemical by-product naphtha, petrochemical by-product naphtha, and shale gas, natural gas, or oil field associated natural gas oil.
26. The use as set forth in paragraph 24 or 25, wherein the naphtha as a by-product of the coal chemical industry is selected from the group consisting of naphtha as a by-product of coal-to-olefins, hydrogenated naphtha as a by-product of coal-to-liquids, and straight-run naphtha as a by-product of coal-to-liquids.
27. The use of any of paragraphs 24-26, wherein the lower alcohol ether is one or more of methanol, ethanol, propanol, butanol, dimethyl ether, a fischer-tropsch synthesis by-product light mixed alcohol, and a syngas to methanol by-product light mixed alcohol.
28. The use as in any of paragraphs 24-27, wherein the mass ratio of the lower alcohol ether to the raw naphtha is between 0.1% and 500%.
29. The use of any of paragraphs 24-28, wherein the olefin is ethylene, propylene, or butene.
30. The use as set forth in any of paragraphs 24-29 wherein a gasoline component is by-produced in the catalytic feedstock naphtha coupled with the lower alcohol ether to olefins.
31. The use of any of paragraphs 24-30, wherein the reaction to produce olefins is carried out in the following apparatus: riser reactors, fixed fluidized beds or circulating fluidized beds.
32. The use of any of paragraphs 24-31, wherein the reaction conditions for the production of olefins are: the temperature is 450 ℃ and 650 ℃, and the reaction pressure is 30-300 kPa.
33. The use as in any of paragraphs 24-32, wherein the following is employed as the atomizing medium for the feed naphtha and lower alcohol ethers: steam, dry gas, hydrogen, synthesis gas and fischer-tropsch synthesis tail gas.
Examples
Reagents, materials and equipment used in the following examples are all commercially available reagents, materials and equipment unless otherwise specified.
Example 1
Preparation of the catalyst: (1) 2135g of cobalt nitrate hexahydrate with the purity of 99 percent, 4486g of hard kaolin, 6086g of amorphous silica-alumina and 30 weight percent of SiO 2 1468g of water glass, 734g of ZSM-5 molecular sieve seed crystal, 1038g of pore-expanding additive hexane and 11100g of deionized water, mixing and pulping, and spray-drying the pulp (with solid content of 50 wt%) to obtain kaolin microspheres with particle size of 20-150 micrometers; (2) roasting the kaolin microspheres for 2 hours at 950 ℃ to obtain roasted kaolin microspheres; (3) mixing the above calcined kaolin microspheres 40g with SiO content of 30 wt% 2 135g of water glass and 120g of distilled water were mixed at 90 ℃ and stirred overnight, and 3M sulfuric acid solution was added thereto20g of liquid and 14g of 3M nitric acid solution, uniformly mixing, crystallizing at 170 ℃ for 30 hours to obtain crystallized mother liquor, separating the crystallized mother liquor into in-situ crystallized microspheres and ex-situ crystallized powder products by a water separation method, washing the in-situ crystallized microspheres with water, filtering and naturally drying to obtain in-situ crystallized products, wherein the ex-situ crystallized molecular sieve powder can be subsequently used as mixed pulping seed crystals; (4) and (3) performing ammonia exchange on the in-situ crystallization product twice by adopting 1M ammonium chloride solution at 90 ℃ for 1 hour each time, then washing with water, filtering, naturally drying, and roasting at 650 ℃ for 2 hours to obtain the metal-acid bifunctional catalyst CAT-1. The product has a ZSM-5 molecular sieve characteristic diffraction peak through XRD analysis, and the content of the molecular sieve is about 83 wt%. The cobalt content was 1.9 wt% by XRF analysis.
Evaluation of catalyst reactivity: the reaction was carried out in a fixed fluidized bed reactor unit with a catalyst loading of 300g, using steam as the feedstock atomizing medium. The raw materials are coal-to-liquid byproduct hydrogenated naphtha and methanol, and the mass ratio of the methanol in the raw materials to the coal-to-liquid byproduct hydrogenated naphtha is 475%. The reaction temperature is 625 ℃, and the space velocity is 18h -1 And the pressure is 50 kPa. The composition of the raw material naphtha is shown in Table 1, and the reaction results are shown in Table 2.
Example 2
Preparation of the catalyst: (1) 54g of tetramine platinum nitrate with the purity of 99.5 percent, 144g of stannous chloride with the purity of 99 percent, 8396g of rectorite, 8375g of phosphor-aluminum glue (30 wt percent of dry basis and 18.3wt percent of aluminum content based on the total dry basis of aluminum/adhesive) and 8452g of deionized water are mixed and pulped, and slurry (43 wt percent of solid content) is sprayed and dried to obtain microspheres with the particle size of 20-150 micrometers; (2) roasting the microspheres at 1000 ℃ for 5 hours to obtain roasted microspheres; (3) taking 13.8g of the above-mentioned calcined microsphere and mixing it with SiO content of 30 wt% 2 16.2g of acidic silica sol, 23.3g of orthophosphoric acid with the purity of 85%, 22.8g of triethylamine and 75g of distilled water are fully mixed and then put into a 200ml reaction kettle to be crystallized for 96 hours at the temperature of 150 ℃ to obtain crystallized mother liquor, the crystallized mother liquor is separated into in-situ crystallized microspheres by a water separation method, and the in-situ crystallized microspheres are washed by water, filtered and naturally dried to obtain in-situ crystallized products; (4) performing acid exchange on the in-situ crystallization product for 2 times at 85 ℃ by using 0.1M dilute nitric acid,each time for 2 hours, then washing with water, filtering and naturally drying, and roasting at 540 ℃ for 4 hours to obtain the metal-acid bifunctional catalyst CAT-2. XRD analysis shows that the product has characteristic diffraction peaks of two molecular sieves SAPO-34/SAPO-18, and the molecular sieve content is about 11 wt%. XRF analysis shows that the platinum content is 0.2 wt% and the auxiliary agent content is 1.2 wt%.
Evaluation of catalyst reaction Performance: the reaction is carried out on a circulating fluidized bed device, the reaction temperature is 600 ℃, the pressure is 150kPa, the catalyst inventory is 3000g, and the space velocity is 1.5h -1 The catalyst circulation amount is 200g/min, and synthetic gas is used as a raw material atomizing medium. The raw materials are petroleum-based naphtha and light mixed alcohol of Fischer-Tropsch synthesis byproducts, and the mass ratio of the light mixed alcohol of the Fischer-Tropsch synthesis byproducts in the raw materials to the petroleum-based naphtha is 100%. The composition of the raw material naphtha is shown in Table 1, and the reaction results are shown in Table 2.
Example 3
Preparation of the catalyst: (1) 9441g of ferric chloride hexahydrate with the purity of 99 percent, 306g of lanthanum nitrate hexahydrate with the purity of 99 percent, 2042g of amorphous silicon, 285g of diatomite and Al 2 O 3 Mixing and pulping 310g of alumina sol with the content of 15 wt%, 195g of ZSM-11 seed crystal, 99g of pore-expanding additive urea and 12997g of deionized water, and spray-drying the pulp (with the solid content of 32 wt%) to obtain microspheres with the particle size of 20-150 microns; (2) taking 15.0g of the microspheres, 12.5g of white carbon black, 29.2g of 2M sodium hydroxide solution, 7.8g of 2M potassium hydroxide solution, 21.2g of tetrabutyl ammonium hydroxide with the concentration of 40%, 3.1g of 1, 6-hexamethylene diamine and 68.2g of distilled water, fully mixing, then putting into a 200ml reaction kettle, crystallizing for 48 hours at 164 ℃ to obtain a crystallization mother liquor, separating the in-situ crystallization microspheres from the crystallization mother liquor by a water separation method, washing the in-situ crystallization microspheres with water, filtering and naturally drying to obtain an in-situ crystallization product; (3) and (3) carrying out acid exchange on the in-situ crystallization product for 2 times and 1 hour at 95 ℃ by using mixed acid (wherein the concentration of hydrochloric acid is 0.05M, and the concentration of sulfuric acid is 0.02M), then washing with water, filtering, naturally drying, and roasting at 500 ℃ for 6 hours to obtain the metal-acid bifunctional catalyst CAT-3. XRD analysis shows that the product has ZSM-11/MOR composite molecular sieve characteristic diffraction peak and small amount of iron oxide characteristic diffraction peak, the molecular sieve content is about 32 wt%, XRF analysis shows that the iron content is 23.8 wt%,the content of the auxiliary agent is 0.8 wt%.
Evaluation of catalyst reactivity: the reaction is carried out on a fixed fluidized bed reactor device, the loading of the catalyst is 250g, the reaction temperature is 550 ℃, the pressure is 275kPa, and the space velocity is 10h -1 Dry gas is used as a raw material atomizing medium. The raw materials are oilfield associated natural gas oil and ethanol, and the mass ratio of the ethanol in the raw materials to the oilfield associated natural gas oil is 30%. The composition of the raw material naphtha is shown in Table 1, and the reaction results are shown in Table 2.
Example 4
Preparation of the catalyst: (1) 2511g of nonahydrate gallium nitrate with the purity of 99%, 2065g of anhydrous magnesium chloride with the purity of 98%, 10047g of soft kaolin, 281g of pseudo-boehmite and 30 wt% SiO in the mixture 2 405g of silica sol containing 15 wt% of Al 2 O 3 252g of alumina sol, 205g of NaY molecular sieve seed crystal, 363g of ammonium bicarbonate, 179g of butylamine, 198g of pentane and 11375g of deionized water are mixed and pulped, and slurry (solid content is 55 wt%) is spray-dried to obtain kaolin microspheres with the particle size of 20-150 microns; (2) roasting one part of the kaolin microspheres at 900 ℃ for 3 hours to obtain high-soil microspheres, and roasting the other part of the kaolin microspheres at 750 ℃ for 2 hours to obtain meta-soil microspheres; (3) taking 27.5g of high-soil microspheres, 7g of partial soil microspheres and 30 wt% of SiO 2 92.8g of sodium silicate, 1.3g of aluminum nitrate nonahydrate, 0.5g of anhydrous aluminum chloride and 32.7g of 3.5M sodium hydroxide solution are mixed and stirred for 30min, the mixture is fully mixed and then put into a 200ml reaction kettle to be crystallized for 24 hours at 95 ℃ to obtain crystallized mother liquor, the crystallized mother liquor is separated out in-situ crystallized microspheres by a water separation method, and the in-situ crystallized microspheres are washed by water, filtered and naturally dried to obtain in-situ crystallized products; (4) and (3) performing 80-degree ammonia exchange on the in-situ crystallization product for 2 times by adopting 0.08M ammonium nitrate solution, wherein each time lasts for 2 hours, then washing with water, filtering, naturally drying, and roasting at 500 ℃ for 6 hours to obtain the metal-acid bifunctional catalyst CAT-4. XRD analysis shows that the product has Y-type molecular sieve characteristic diffraction peak and molecular sieve content of about 51 wt%, and XRF analysis shows that the product has gallium content of 4.3 wt% and assistant content of 14 wt%.
Evaluation of catalyst reactivity: the reaction is carried out on a riser reactor device, the catalyst loading is 5000g, the catalyst-oil ratio is 25, and the hydrogen-rich Fischer-Tropsch synthesis tail gas is used as a raw material atomization medium. The raw materials are coal indirect liquefied straight-run naphtha and propanol, the mass ratio of the propanol in the raw materials to the coal indirect liquefied straight-run naphtha is 10%, the reaction temperature is 650 ℃, and the pressure is 175 kPa. The composition of the raw material naphtha is shown in Table 1, and the reaction results are shown in Table 2.
Example 5
Preparation of the catalyst: (1) the method disclosed in the patent US3639009 is used for preparing the SiO with the molar ratio of 15 2 :Al 2 O 3 :16Na 2 O:320H 2 Liquid phase molecular sieve seed crystal of O; (2) 5057g of zinc nitrate hexahydrate with the purity of 99%, 1141g of coal xuanyao stone, 296g of natural clay, 214g of montmorillonite, 692g of the liquid-phase molecular sieve seed crystal and SiO 2 492g of water glass with the content of 30 wt% and 17879g of deionized water are mixed and beaten to obtain slurry (the solid content is 20 wt%), and the slurry is spray-dried to obtain kaolin microspheres with the particle size of 20-150 microns; (3) roasting the kaolin microspheres at 650 ℃ for 7 hours to obtain roasted microspheres; (4) mixing and stirring 18g of the roasted microspheres, 68.3g of sodium silicate solution with the concentration of 40 wt%, 3.2g of solid silica gel, 4.2g of aluminum sulfate octadecahydrate solution with the concentration of 50 wt% and 35g of deionized water for 30min, fully mixing, then loading into a 200ml reaction kettle, aging at 120 ℃ for 20 hours, cooling, adding 1.9g of tetraethylammonium chloride and 3.1g of cyclohexylamine, stirring, adding 30 wt% hydrochloric acid solution, adjusting the pH value to 10.15, crystallizing at 165 ℃ for 24 hours to obtain crystallized mother liquor, separating the crystallized mother liquor into in-situ crystallized microspheres by a water separation method, washing the in-situ crystallized microspheres with water, filtering and naturally drying to obtain in-situ crystallized products; (5) and (3) performing ammonia exchange on the in-situ crystallization product for 1 time and 2 hours at 75 ℃ by adopting a 1.2M ammonium sulfate solution, then washing with water, filtering, naturally drying, and roasting at 700 ℃ for 3 hours to obtain the metal-acid bifunctional catalyst CAT-5. The product has characteristic diffraction peaks for XRD analysis of 23 wt% beta type molecular sieve and 12 wt% ZSM-35 molecular sieve, and has a zinc content of 2.9 wt% by XRF analysis.
Evaluation of reaction Performance: the reaction is carried out on a fixed fluidized bed reactor device, the catalyst loading is 350g, the reaction temperature is 450 ℃, the pressure is 100kPa, and the space velocity is 30h -1 The hydrogen-rich Fischer-Tropsch synthesis tail gas is used as the raw material for atomizationA medium. The raw materials are naphtha and dimethyl ether which are byproducts of the coal-to-olefin, the mass ratio of the dimethyl ether in the raw materials to the naphtha which is a byproduct of the coal-to-olefin is 0.1%, the reaction temperature is 450 ℃, and the pressure is 125 kPa. The composition of the raw material naphtha is shown in Table 1, and the reaction results are shown in Table 2.
Comparative example 1
Preparation of ex-situ crystallization catalyst and evaluation of reaction performance: 1270g of cobalt nitrate hexahydrate with the purity of 99 percent, 1426g of hard kaolin, 1934g of amorphous silica-alumina and 30 weight percent of SiO 2 459g of sodium silicate, 10484g of ex-situ crystallized H-type ZSM-5 molecular sieve, 325g of pore-enlarging additive hexane and 9510g of deionized water are mixed and pulped, microspheres with the particle size of 20-150 microns are obtained by spraying slurry (solid content), and the microspheres are roasted for 2 hours at 650 ℃ to obtain the ex-situ crystallized metal-acid bifunctional catalyst CAT-6. The product has diffraction peaks similar to those of ZSM-5 molecular sieve, wherein the content of the molecular sieve is about 84 wt%. The cobalt content was 1.9 wt% by XRF analysis. The same raw materials, the same device and the same working conditions in example 1 were used to perform the reaction of coupling the coal-to-liquid byproduct hydrogenated naphtha with methanol to produce low-carbon olefins, and the reaction results are shown in table 2. As can be seen from the table, the catalyst CAT-1 of example 1 exhibits higher mechanical strength and olefin yield than the CAT-6 of comparative example 1.
Comparative example 2
Preparing a catalyst with active metal added after in-situ crystallization of the molecular sieve and evaluating the reaction performance: the method of example 1 is adopted, but cobalt nitrate is not added in the preparation process of kaolin microspheres, but the in-situ crystallization product is subjected to ammonia exchange twice by using 1M ammonium chloride solution at 90 ℃ in the step (4), each time is 1 hour, then the product is washed by water, filtered and naturally dried, and after being roasted at 650 ℃ for 2 hours, the cobalt nitrate is soaked in the same volume and roasted at 650 ℃ for 2 hours to prepare the metal-acid bifunctional in-situ crystallization catalyst CAT-7 with metal added later. XRD analysis shows that the product has diffraction peaks similar to those of ZSM-5 molecular sieve, wherein the content of the molecular sieve is about 82 wt%; the cobalt content was 2.0 wt% by XRF analysis. The same raw materials, the same device and the same working conditions in example 1 are adopted to carry out the reaction of preparing low-carbon olefin from the coal-to-liquid byproduct hydrogenated naphtha coupled with methanol, and the reaction results are shown in table 2. As can be seen in the table, catalyst CAT-1 of example 1 exhibited a higher olefin yield and a lower methane yield than CAT-7 of comparative example 2.
Examples of the experiments
The bifunctional catalysts prepared in example 1 and comparative examples 1 and 2 were subjected to H 2 TPR characterization, experimental conditions: by H 2 And Ar gas mixture (containing 5 vol% of H) 2 ) Passing through each catalyst sample of 0.14g and 20-40 mesh, the gas flow rate was about 20ml/min, the temperature rise rate was 10 ℃/min, and the TPR spectrum was obtained from the thermal conductivity cell in response to the hydrogen consumption signal, and the results are shown in FIG. 2. Comparison of H for three catalyst samples 2 It can be seen from the position of the reduction peak that the bifunctional catalyst prepared by in-situ crystallization synthesis in the presence of the metal component in example 1 can effectively utilize the molecular sieve framework to stabilize the metal component.
TABLE 1 Mass composition of the feed naphtha
Figure BDA0003615786960000171
Note: the content of alkane or olefin in the coal indirect liquefied hydrogenated naphtha and the coal-to-olefin by-product naphtha can slightly and dynamically change along with the corresponding process.
TABLE 2 yield by mass of each product obtained by the olefin production reaction of examples 1 to 5 and comparative examples 1 to 2
Catalyst and process for preparing same CAT-1 CAT-2 CAT-3 CAT-4 CAT-5 CAT-6 CAT-7
Wear index% 2.8 0.5 1.2 2.0 1.4 6.2 2.9
Methane% 3 5 4 2 1 5 7
Ethylene content% 29 36 34 30 24 21 19
Propylene content% 33 27 31 35 32 23 27
Butene% 10 5 9 12 13 5 7
C5+,％ 14 10 15 17 25 12 11
RON 94 92 99 95 103 83 89
Having described embodiments of the present invention in detail, it will be apparent to those skilled in the art that many modifications and variations can be made without departing from the basic spirit of the invention, and all such changes and modifications are intended to be within the scope of the invention.

Claims (10)

1. An in-situ crystallization catalyst for the production of olefins, wherein the catalyst comprises, relative to the total mass of the solid components in the catalyst: dehydrogenation active metal with the dry mass content of 0.1-25%, in-situ crystallized molecular sieve with the dry mass content of 9.9-84.5%, auxiliary agent with the dry mass content of 0-15%, residual matrix with the dry mass content of 15.4-90% and adhesive; the dehydrogenation active metal is one or more selected from Pt, Ag, Au, Fe, Co, Cu, Ni, Rh, Cr, Ga and Zn, the in-situ crystallized molecular sieve is one or more selected from eight-membered ring, ten-membered ring, twelve-membered ring silicon-aluminum molecular sieve or eight-membered ring, ten-membered ring and twelve-membered ring silicon-phosphorus-aluminum molecular sieve, and the molecular sieve is obtained by in-situ crystallization of molecular sieve synthetic raw materials in the presence of the dehydrogenation active metal.
2. The catalyst of claim 1, wherein the dehydrogenation-active metal is in the form of an inorganic salt, oxide, sulfide, nitride, carbide, or reduced metal;
preferably, the in-situ crystallized molecular sieve is mixed crystal and cocrystallization of one or more selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-35, Beta, Y, MOR, MCM-22, IM-5, SSZ-13, SAPO-18, SAPO-11, SAPO-34 and SAPO-5; more preferably, the in-situ crystallized molecular sieve is a mixed crystal and a co-crystal of one or more selected from ZSM-5, ZSM-11, ZSM-35, Beta, SAPO-18, SAPO-34 and Y, MOR;
preferably, the auxiliary agent is one or more selected from Ca, Mg, K, P, Sn, Mn, La and Ce;
preferably, the matrix is one or more selected from hard kaolin, soft kaolin, halloysite, natural clay, pseudo-boehmite, perlite, diatomite, halloysite, rectorite, montmorillonite, sepiolite, bentonite, sodium silicate, boehmite, amorphous silica, amorphous alumina and amorphous silica-alumina, and the binder is one or more selected from silica sol, alumina sol, water glass and phosphor-alumina gel.
3. A method of preparing the in-situ crystallization catalyst for the preparation of olefins according to claim 1 or 2, wherein the method comprises:
(1) mixing and pulping dehydrogenation active metal, a substrate, a binder and deionized water to prepare slurry with the solid content of 20-55 wt%, and spray-drying the slurry to obtain microspheres with the particle size of 20-150 microns;
the dehydrogenation active metal is one or more selected from Pt, Ag, Au, Fe, Co, Cu, Ni, Rh, Cr, Ga and Zn; the matrix is one or more selected from hard kaolin, soft kaolin, coal pumice, natural clay, pseudo-boehmite, perlite, diatomite, halloysite, rectorite, montmorillonite, sepiolite, bentonite, sodium silicate, boehmite, amorphous silicon, amorphous aluminum and amorphous silicon aluminum, and the binder is one or more selected from silica sol, alumina sol, water glass and phosphor-aluminum gel;
(2) adding a silicon-aluminum-phosphorus source and a pH value regulator into the microspheres, mixing, crystallizing at 90-200 ℃ for 0.5-5 days to obtain a crystallized mother liquor, separating in-situ crystallized microspheres from the crystallized mother liquor, washing, filtering and drying the in-situ crystallized microspheres to obtain an in-situ crystallized product;
the silicon-aluminum-phosphorus source is one or more selected from water glass, silica sol, sodium silicate, solid silica gel, silicic acid, white carbon black, aluminum sulfate, aluminum nitrate, aluminum chloride, pseudo-boehmite, sodium aluminate, aluminum isopropoxide, aluminum hydroxide, phosphoric acid and ammonium hydrogen phosphate, and the pH value regulator is one or more selected from sodium hydroxide, potassium hydroxide, sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid and aqueous solution thereof;
(3) and (3) performing ammonia exchange or acid exchange on the in-situ crystallization product, and roasting at the temperature of 500-700 ℃ to prepare the catalyst.
4. The method of claim 3, in step (1), the binder is added in an amount of 2-30% by mass of the matrix on a dry basis;
preferably, in the step (1), during the pulping, molecular sieve seed crystals are further added; more preferably, the molecular sieve seeds are solid phase or liquid phase molecular sieve seeds; further preferably, the addition amount of the molecular sieve seed crystal is 0-10% of the mass of the matrix on a dry basis;
preferably, in the step (1), during the pulping, one or two of an auxiliary agent and a pore-expanding additive are further added; more preferably, the auxiliary agent is one or more of Ca, Mg, K, P, Sn, Mn, La and Ce; further preferably, the addition amount of the auxiliary agent is 0-20% of the mass of the matrix; or more preferably, the pore-enlarging additive is one or more of ethanol, propanol, pentane, hexane, propylamine, butylamine, ammonium bicarbonate, ammonium oxalate and urea; further preferably, the pore-enlarging additive is added in an amount of 0 to 10% by mass of the matrix.
5. The method as claimed in claim 3 or 4, wherein, before step (2), the microspheres obtained by spray drying are calcined at 600-1000 ℃ for 0-7 hours;
preferably, in the step (2), during the crystallization, a structure directing agent is further added to the crystallization mother liquor; more preferably, the structure directing agent is one or more of: quaternary amine or quaternary ammonium salt, monoamine, binary organic amine; further preferably, the quaternary amine or quaternary ammonium salt is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltriethylammonium hydroxide, dimethyldiethylammonium hydroxide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, dimethyldiethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, methyltriethylammonium bromide, or dimethyldiethylammonium bromide; the monoamine is one or two of cyclohexylamine and triethylamine; the binary organic amine is one or two of ethylenediamine and 1, 6-hexanediamine;
preferably, the addition amount of the structure directing agent is 0-15 wt% of the total mass of the crystallization mother liquor.
6. The process of any one of claims 3-5, wherein in step (3), the in situ crystallized product is subjected to ammonia exchange with one or more selected from ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium hydroxide solution;
preferably, in step (3), the in-situ crystallized product is subjected to acid exchange with one or more selected from dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid, and dilute acetic acid.
7. The use of the in-situ crystallization catalyst for olefin production according to claim 1 or 2 in catalyzing a feedstock naphtha to couple with a low carbon alcohol ether to produce olefins.
8. The use of claim 7, wherein the raw naphtha is selected from the group consisting of coal chemical by-product naphtha, petrochemical by-product naphtha, and shale gas, natural gas, or oil field associated natural gas oil; preferably, the naphtha by-produced in the coal chemical industry is selected from the group consisting of a naphtha by-produced in the coal-to-olefins process, a hydrogenated naphtha by-produced in the coal-to-liquids process, and a straight-run naphtha by-produced in the coal-to-liquids process;
preferably, the low-carbon alcohol ether is one or more of methanol, ethanol, propanol, butanol, dimethyl ether, light mixed alcohol of a Fischer-Tropsch synthesis byproduct and light mixed alcohol of a methanol preparation byproduct from synthesis gas;
preferably, the mass ratio of the low carbon alcohol ether to the raw material naphtha is 0.1-500%.
9. Use according to claim 7 or 8, wherein the olefin is ethylene, propylene or butene;
preferably, gasoline components are by-produced in the process of preparing olefins by coupling catalytic raw material naphtha with low carbon alcohol ether.
10. Use according to any one of claims 7 to 9, wherein the reaction to produce olefins is carried out in an apparatus comprising: riser reactor, stationary fluidized bed or circulating fluidized bed;
preferably, the reaction conditions for producing olefins are: the temperature is 450 ℃ and 650 ℃, and the reaction pressure is 30-300 kPa;
preferably, the following are used as atomization media for the raw naphtha and lower alcohol ether: steam, dry gas, hydrogen, synthesis gas and Fischer-Tropsch synthesis tail gas.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116351459A (en) * 2023-06-02 2023-06-30 潍坊正轩稀土催化材料有限公司 Methanol aromatization catalyst and preparation method thereof
CN116371456A (en) * 2023-06-02 2023-07-04 潍坊正轩稀土催化材料有限公司 Liquefied gas aromatization catalyst and preparation method thereof
CN116408137A (en) * 2023-03-07 2023-07-11 中国石油大学(华东) Catalyst for preparing olefin from naphtha, preparation method and application thereof
CN118080000A (en) * 2024-03-19 2024-05-28 山西腾茂科技股份有限公司 Composite modified molecular sieve, catalytic cracking catalyst, and preparation and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1232862A (en) * 1998-04-21 1999-10-27 中国石化兰州炼油化工总厂 All-white clay catalyst for fluid catalytic cracking and its preparation
CN103253684A (en) * 2012-02-16 2013-08-21 中国石油天然气股份有限公司 Method for synthesizing small-grain ZSM-5 molecular sieve by direct method in-situ crystallization
CN104275205A (en) * 2013-07-12 2015-01-14 中国石油天然气股份有限公司 Preparation method of catalyst for improving yield of catalytic cracking diesel oil
CN106607089A (en) * 2015-10-21 2017-05-03 中国石油化工股份有限公司 Catalyst for coupling catalytic pyrolysis of methanol and naphtha, preparation method and application
CN107971008A (en) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 A kind of catalytic cracking catalyst and preparation method thereof and petroleum hydrocarbon catalytic pyrolysis method
CN113289671A (en) * 2021-06-23 2021-08-24 中国第一汽车股份有限公司 Zinc-based molecular sieve catalyst and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1232862A (en) * 1998-04-21 1999-10-27 中国石化兰州炼油化工总厂 All-white clay catalyst for fluid catalytic cracking and its preparation
CN103253684A (en) * 2012-02-16 2013-08-21 中国石油天然气股份有限公司 Method for synthesizing small-grain ZSM-5 molecular sieve by direct method in-situ crystallization
CN104275205A (en) * 2013-07-12 2015-01-14 中国石油天然气股份有限公司 Preparation method of catalyst for improving yield of catalytic cracking diesel oil
CN106607089A (en) * 2015-10-21 2017-05-03 中国石油化工股份有限公司 Catalyst for coupling catalytic pyrolysis of methanol and naphtha, preparation method and application
CN107971008A (en) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 A kind of catalytic cracking catalyst and preparation method thereof and petroleum hydrocarbon catalytic pyrolysis method
CN113289671A (en) * 2021-06-23 2021-08-24 中国第一汽车股份有限公司 Zinc-based molecular sieve catalyst and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈希强等: ""ZSM-5沸石的原位晶化及其石脑油催化裂解性能"", 化学反应工程与工艺, vol. 27, no. 6, pages 481 - 487 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116408137A (en) * 2023-03-07 2023-07-11 中国石油大学(华东) Catalyst for preparing olefin from naphtha, preparation method and application thereof
CN116351459A (en) * 2023-06-02 2023-06-30 潍坊正轩稀土催化材料有限公司 Methanol aromatization catalyst and preparation method thereof
CN116371456A (en) * 2023-06-02 2023-07-04 潍坊正轩稀土催化材料有限公司 Liquefied gas aromatization catalyst and preparation method thereof
CN116351459B (en) * 2023-06-02 2023-09-15 潍坊正轩稀土催化材料有限公司 Methanol aromatization catalyst and preparation method thereof
CN116371456B (en) * 2023-06-02 2023-09-15 潍坊正轩稀土催化材料有限公司 Liquefied gas aromatization catalyst and preparation method thereof
CN118080000A (en) * 2024-03-19 2024-05-28 山西腾茂科技股份有限公司 Composite modified molecular sieve, catalytic cracking catalyst, and preparation and application thereof

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