CN113877595B - Dehydrogenation catalyst, preparation method and application thereof and method for dehydrogenating mixed diethylbenzene - Google Patents

Dehydrogenation catalyst, preparation method and application thereof and method for dehydrogenating mixed diethylbenzene Download PDF

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CN113877595B
CN113877595B CN202010628445.XA CN202010628445A CN113877595B CN 113877595 B CN113877595 B CN 113877595B CN 202010628445 A CN202010628445 A CN 202010628445A CN 113877595 B CN113877595 B CN 113877595B
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metal element
precursor
catalyst
earth metal
content
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CN113877595A (en
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危春玲
缪长喜
宋磊
陈铜
倪军平
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/67—Pore distribution monomodal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/889—Manganese, technetium or rhenium

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Abstract

The invention relates to the field of mixed divinylbenzene production, and discloses a dehydrogenation catalyst, a preparation method and application thereof, and a method for dehydrogenating mixed divinylbenzene, wherein the catalyst comprises Fe element, K element, rare earth metal element, alkaline earth metal element and auxiliary metal element; in the catalyst, based on the total amount of the catalyst, the content of Fe element is 42-59.5 wt%, the content of K element is 6-13 wt%, the content of rare earth metal element is 3-16 wt%, the content of alkaline earth metal element is 0.2-3.5 wt%, and the content of auxiliary metal element is 0.1-3.5 wt%; the auxiliary metal element is at least one selected from Mn, W, cu, zn, ti, mo, ni and Nb; the median pore diameter of the catalyst is 205-600nm. The catalyst has the characteristics of higher strength and higher inter-contrast value of the mixed divinylbenzene in the product.

Description

Dehydrogenation catalyst, preparation method and application thereof and method for dehydrogenating mixed diethylbenzene
Technical Field
The invention relates to the field of mixed divinylbenzene production, in particular to a dehydrogenation catalyst, a preparation method and application thereof and a mixed diethylbenzene dehydrogenation method.
Background
Divinylbenzene is a crosslinking agent with wide application, and is widely used in special plastics, paint, adhesive and other fields.
Industrial production methods of divinylbenzene are mainly obtained by dehydrogenation of diethylbenzene, wherein the catalyst plays a critical role, and the performance of the catalyst directly influences the economical efficiency of the production process. The zinc-based catalyst and the magnesium-based catalyst used in the initial stage of the diethylbenzene dehydrogenation catalyst are replaced with iron-based catalysts having good comprehensive properties.
In the dehydrogenation reaction process, because a large amount of water vapor exists, the catalyst is continuously flushed in long-period operation, so that the strength of the catalyst is easily reduced, and the service life of the catalyst is further influenced. According to the reports of the related literature, researchers have made some attempts to increase the strength of dehydrogenation catalysts. For example, other metal elements such as vanadium are introduced into the catalyst, however, metals similar to vanadium are toxic metals, and the preparation process of the catalyst causes environmental pollution.
The molecular dehydrogenation of diethylbenzene is carried out in two steps, wherein the first step is dehydrogenation to produce ethylvinylbenzene, and the second step is further dehydrogenation to produce the target product divinylbenzene. The reaction process was studied and found that meta-diethylbenzene remained more readily in the first step than para-diethylbenzene, resulting in a lower value for the mixed divinylbenzene product than the starting material, i.e., the mixed divinylbenzene product. However, in downstream applications of mixed divinylbenzene, such as resin synthesis, the values of the inter-product contrast must be maintained in a relatively appropriate range so that the properties of the synthesized resin are better. However, the prior art catalysts do not have significant improvement in the value of the inter-contrast ratio of the mixed divinylbenzene product.
Therefore, in view of the drawbacks of the prior art, there is a need to improve the performance of the catalyst and optimize the production process to ensure a more suitable value of the inter-product contrast, thereby meeting the demands of downstream products.
Disclosure of Invention
The invention aims to solve the problems of low strength of a mixed divinylbenzene dehydrogenation catalyst and low inter-mixed divinylbenzene in a product in the prior art, and provides a dehydrogenation catalyst, a preparation method and application thereof and a method for dehydrogenating mixed divinylbenzene.
In order to achieve the above object, a first aspect of the present invention provides a dehydrogenation catalyst comprising an Fe element, a K element, a rare earth metal element, an alkaline earth metal element, and an auxiliary metal element; in the catalyst, based on the total amount of the catalyst, the content of Fe element is 42-59.5 wt%, the content of K element is 6-13 wt%, the content of rare earth metal element is 3-16 wt%, the content of alkaline earth metal element is 0.2-3.5 wt%, and the content of auxiliary metal element is 0.1-3.5 wt%; the auxiliary metal element is at least one selected from Mn, W, cu, zn, ti, mo, ni and Nb;
The median pore diameter of the catalyst is 205-600nm.
In a second aspect, the present invention provides a process for preparing a dehydrogenation catalyst, the process comprising: mixing an iron element precursor, a potassium element precursor, a rare earth metal element precursor, an alkaline earth metal element precursor, an auxiliary metal element precursor and a pore-forming agent, and sequentially forming and roasting to obtain the catalyst;
the usage amount of the precursor of the iron element, the precursor of the potassium element, the precursor of the rare earth metal element, the precursor of the alkaline earth metal element and the precursor of the auxiliary metal element is such that in the prepared catalyst, based on the total amount of the catalyst, the content of Fe element is 42-59.5 wt%, the content of K element is 6-13 wt%, the content of the rare earth metal element is 3-16 wt%, the content of the alkaline earth metal element is 0.2-3.5 wt%, and the content of the auxiliary metal element is 0.1-3.5 wt%; the auxiliary metal element is at least one selected from Mn, W, cu, zn, ti, mo, ni and Nb;
the pore-forming agent comprises an organic matter and an inorganic matter, wherein the weight ratio of the organic matter to the inorganic matter is 1.5-10:1.
preferably, the weight ratio of the organic matters to the inorganic matters is 3-8:1.
In a third aspect the present invention provides a dehydrogenation catalyst prepared according to the second aspect.
The dehydrogenation catalyst provided by the invention has higher strength and better catalytic performance, and is particularly suitable for mixed diethylbenzene dehydrogenation reaction. Accordingly, a fourth aspect of the present invention provides the use of a catalyst as described in the first or third aspect in a mixed diethylbenzene dehydrogenation reaction.
In a fifth aspect, the present invention provides a process for the dehydrogenation of mixed diethylbenzenes, the process comprising: the dehydrogenation catalyst is contacted with the mixed divinylbenzene for reaction to obtain the mixed divinylbenzene; the dehydrogenation catalyst is the catalyst of the first aspect or the third aspect.
Through the technical scheme, the dehydrogenation catalyst provided by the invention has a specific median pore diameter, and is higher in strength and better in catalytic performance. The dehydrogenation catalyst is prepared by adopting the organic matters and the inorganic matters with specific contents as the pore-forming agent and matching with metal elements with specific compositions and contents, has higher side pressure strength, is particularly suitable for the reaction of producing the mixed divinylbenzene by dehydrogenating the mixed divinylbenzene, and has higher contrast value between the mixed divinylbenzene in the product.
In the preferred case, the molded product is aged in the preparation process, so that the performance of the dehydrogenation catalyst is further improved, and the inter-divinylbenzene contrast value in the product is further improved.
Drawings
FIG. 1 is a pore distribution diagram of the catalyst produced in example 1 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a dehydrogenation catalyst comprising an Fe element, a K element, a rare earth metal element, an alkaline earth metal element, and an auxiliary metal element; in the catalyst, based on the total amount of the catalyst, the content of Fe element is 42-59.5 wt%, the content of K element is 6-13 wt%, the content of rare earth metal element is 3-16 wt%, the content of alkaline earth metal element is 0.2-3.5 wt%, and the content of auxiliary metal element is 0.1-3.5 wt%; the auxiliary metal element is at least one selected from Mn, W, cu, zn, ti, mo, ni and Nb;
The median pore diameter of the catalyst is 205-600nm.
In the present invention, the median pore diameter (D50) is measured by mercury porosimetry.
According to the present invention, preferably, in the catalyst, the content of Fe element is 47 to 55.5 wt%, the content of K element is 7.5 to 11 wt%, the content of rare earth metal element is 6.5 to 13 wt%, the content of alkaline earth metal element is 0.5 to 2.5 wt%, and the content of auxiliary metal element is 0.5 to 2.5 wt%, based on the total amount of the catalyst, calculated as element. In this preferred case, the catalyst has better catalytic performance and is more beneficial to improving the value of the inter-contrast ratio of the mixed divinylbenzene. In the invention, the content of the elements in the catalyst is measured by adopting an X-ray fluorescence spectrometry method.
In the present invention, the range of selection of the kind of the element contained in the catalyst is wide, and preferably, the catalyst further includes at least one of an oxygen element, a silicon element, a fluorine element, and an aluminum element. The invention has wider selection range of the oxygen element, the silicon element, the fluorine element and the aluminum element content, and the invention is not particularly limited. According to the present invention, preferably, the total content of the silicon element, fluorine element and aluminum element is not more than 3% by weight, preferably not more than 1% by weight, based on the total amount of the catalyst, in terms of elements.
According to one specific embodiment of the present invention, in the catalyst, the sum of the content of Fe element, the content of K element, the content of rare earth metal element, the content of alkaline earth metal element, the content of auxiliary metal element, the content of oxygen element, the content of silicon element, the content of fluorine element and the content of aluminum element is 100% in terms of elements based on the total amount of the catalyst.
According to a preferred embodiment of the invention, the median pore diameter of the catalyst is from 280 to 500nm. In this preferred embodiment, the catalyst has better catalytic properties and is more advantageous for increasing the number of inter-catalyst comparisons of mixed divinylbenzene.
According to the present invention, preferably, the catalyst has a specific surface area of 1.5 to 5m 2 Preferably 2.1-3.6m 2 And/g. In the present invention, the specific surface area of the catalyst is measured by mercury intrusion.
According to a preferred embodiment of the present invention, the auxiliary metal element is selected from at least one of Mn, W and Mo, and further preferably Mn and/or W. In this preferred embodiment, the catalyst has better catalytic properties and is more advantageous for increasing the number of inter-catalyst comparisons of mixed divinylbenzene.
In the present invention, the rare earth metal element is selected from at least one of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y) and scandium (Sc), preferably at least one of La, ce and Pr, further preferably Ce. In this preferred case, the catalyst has better catalytic performance and is more beneficial to improving the value of the inter-contrast ratio of the mixed divinylbenzene.
According to the present invention, preferably, the alkaline earth metal element is Mg and/or Ca. In this preferred case, the catalyst has better catalytic performance and is more beneficial to improving the value of the inter-contrast ratio of the mixed divinylbenzene.
In a second aspect, the present invention provides a process for preparing a dehydrogenation catalyst, the process comprising: mixing an iron element precursor, a potassium element precursor, a rare earth metal element precursor, an alkaline earth metal element precursor, an auxiliary metal element precursor and a pore-forming agent, and sequentially forming and roasting to obtain the catalyst;
the usage amount of the precursor of the iron element, the precursor of the potassium element, the precursor of the rare earth metal element, the precursor of the alkaline earth metal element and the precursor of the auxiliary metal element is such that in the prepared catalyst, based on the total amount of the catalyst, the content of Fe element is 42-59.5 wt%, the content of K element is 6-13 wt%, the content of the rare earth metal element is 3-16 wt%, the content of the alkaline earth metal element is 0.2-3.5 wt%, and the content of the auxiliary metal element is 0.1-3.5 wt%; the auxiliary metal element is at least one selected from Mn, W, cu, zn, ti, mo, ni and Nb;
The pore-forming agent comprises an organic matter and an inorganic matter, wherein the weight ratio of the organic matter to the inorganic matter is 1.5-10:1.
in the present invention, the order of the mixing is not particularly limited, and precursors of any two elements may be mixed first and then with precursors of the remaining elements; the precursors of any three elements may be mixed first and then with the precursors of the remaining elements. Specifically, for example, the precursor of the iron element and the precursor of the potassium element may be mixed first, and then mixed with the precursor of the rare earth metal element, the precursor of the alkaline earth metal element, the precursor of the auxiliary metal element, and the pore-forming agent; or mixing the precursor of the rare earth metal element with the precursor of the potassium element, and then mixing with the precursor of the iron element, the precursor of the alkaline earth metal element, the precursor of the auxiliary metal element and the pore-forming agent; or mixing the precursor of the iron element, the precursor of the potassium element, the precursor of the alkaline earth metal element, the precursor of the auxiliary metal element and the pore-forming agent, and then mixing with the precursor of the rare earth metal element; the precursor of the iron element, the precursor of the potassium element, the precursor of the rare earth metal element, the precursor of the alkaline earth metal element, the precursor of the auxiliary metal element, and the pore-forming agent may be mixed simultaneously.
In the present invention, the above mixing order is merely illustrative. In the present invention, the mixing may or may not contain a solvent, as long as the precursor of each element can be mixed with the pore-forming agent to obtain a mixture that is advantageous for molding. In the present invention, the solvent of the mixing process is water and/or an organic solvent, preferably water.
According to a preferred embodiment of the present invention, the precursor of the iron element, the precursor of the potassium element, the precursor of the alkaline earth metal element, the precursor of the auxiliary metal element, the pore-forming agent and a part of the precursor of the rare earth metal element are mixed first, and then mixed with the solution of the remaining precursor of the rare earth metal element. In the invention, the precursor of the part of rare earth metal element is used in an amount of 10-90 wt% of the total precursor of the rare earth metal element based on the total precursor of the rare earth metal element.
The molding method is not particularly limited in the present invention, and the molding may be performed according to any molding method known in the art, and the molding is preferably extrusion molding. The shape after molding can be at least one of trilobal, butterfly, cylindrical, solid cylindrical, hollow cylindrical, diamond, quincuncial, honeycomb, quadrulobal, pentalobal and spherical.
The present invention is not particularly limited in terms of the diameter and length of the molded product, and preferably the molded product has a diameter of 3 to 5mm and a length of 5 to 10mm. The diameter represents the equivalent diameter of the cross section of the molded product.
In one specific embodiment, the molded product is a quincuncial type with a diameter of 3-5mm and a length of 5-10mm, and the invention is not limited thereto.
According to the invention, the shaping process is preferably carried out in the presence of a solvent, preferably water. In the present invention, the manner of introducing the solvent is not particularly limited, and the solvent may be introduced alone or together with a solution of a precursor of the element, as long as the environment for molding can be provided. Specifically, for example, the solvent may be introduced together with the precursor solution of the rare earth metal element. The solvent is used in a wide selection range, so long as the requirement of forming can be met, and the man skilled in the art can select the additive according to the actual requirement according to the precursor of the iron element, the precursor of the potassium element, the precursor of the alkaline earth metal element, the precursor of the auxiliary metal element, the precursor of the rare earth metal element and the dosage of the pore-forming agent. In the present invention, the requirement of molding is that the weight ratio of the solvent to the powder (in the present invention, the solid material before molding) in the material obtained by mixing is suitable, for example, the weight ratio of the solvent to the powder may be 0.05-0.35:1, preferably 0.1 to 0.25:1.
According to the present invention, preferably, the auxiliary metal element is selected from at least one of Mn, W, and Mo, and further preferably Mn and/or W. In this preferred case, the catalyst has better catalytic performance and is more beneficial to improving the value of the inter-contrast ratio of the mixed divinylbenzene.
The selection range of the rare earth metal element is as described above, and the invention is not described herein. In the present invention, the selection range of the alkaline earth metal element is as described above, and the present invention is not described herein.
According to a preferred embodiment of the present invention, the precursor of iron element, the precursor of potassium element, the precursor of rare earth metal element, the precursor of alkaline earth metal element and the precursor of auxiliary metal element are used in such amounts that the catalyst is produced, based on the total amount of the catalyst, in terms of the elements, the content of Fe element is 47 to 55.5% by weight, the content of K element is 7.5 to 11% by weight, the content of rare earth metal element is 6.5 to 13% by weight, the content of alkaline earth metal element is 0.5 to 2.5% by weight, and the content of auxiliary metal element is 0.5 to 2.5% by weight. In this preferred embodiment, the catalyst has better catalytic properties and is more advantageous for increasing the number of inter-catalyst comparisons of mixed divinylbenzene.
The invention has wide selection range of the precursor of the iron element, wherein the precursor of the iron element refers to an iron-containing compound, and the iron-containing compound can be soluble or insoluble. By soluble is meant capable of being dissolved directly in a solvent (preferably water) or in a solvent under co-solvent.
According to the present invention, preferably, the precursor of the iron element is selected from at least one of iron oxide red, iron oxide yellow, iron oxide black, iron nitrate, iron hydroxide, and iron oxide green, and more preferably, iron oxide red and/or iron oxide yellow. In this preferred case, the catalyst has better catalytic performance and is more beneficial to improving the value of the inter-contrast ratio of the mixed divinylbenzene.
The invention has wider selection range of the precursor of the potassium element, wherein the precursor of the potassium element refers to a potassium-containing compound, and the potassium-containing compound can be soluble or insoluble.
According to the present invention, preferably, the precursor of potassium element is selected from at least one of potassium hydroxide, potassium carbonate, potassium sulfate, potassium chloride, potassium bicarbonate, and potassium nitrate, preferably at least one of potassium hydroxide, potassium carbonate, and potassium nitrate.
The invention has wider selection range for the precursor of the rare earth metal element, wherein the precursor of the rare earth metal element refers to a rare earth metal element-containing compound, and the rare earth metal element-containing compound can be soluble or insoluble.
According to the present invention, preferably, the precursor of the rare earth metal element is selected from at least one of oxalate, nitrate, and carbonate of the rare earth metal element. The rare earth metal element is exemplified by Ce, and the Ce element-containing compound is preferably at least one of cerium oxalate, cerium nitrate, and cerium carbonate.
The precursor of the alkaline earth metal element is a compound containing the alkaline earth metal element, and the compound containing the alkaline earth metal element can be soluble or insoluble.
According to the present invention, preferably, the precursor of the alkaline earth metal element is an oxide and/or a salt of the alkaline earth metal element. Further preferably, the precursor of the alkaline earth metal element is selected from at least one of an oxide of the alkaline earth metal element, a hydroxide of the alkaline earth metal element, and a carbonate of the alkaline earth metal element. Taking Ca element as an example, preferably, the alkaline earth metal element compound is selected from at least one of calcium oxide, calcium hydroxide, calcium bicarbonate, and calcium carbonate.
The invention has wider selection range for the precursor of the auxiliary metal element, wherein the precursor of the auxiliary metal element refers to an auxiliary metal element-containing compound, and the auxiliary metal element-containing compound can be soluble or insoluble.
According to the present invention, preferably, the precursor of the auxiliary metal element is selected from the group consisting of oxides and salts of the auxiliary metal element, and further preferably at least one selected from the group consisting of oxides, hydroxides of the auxiliary metal element, nitrates of the auxiliary metal element, and carbonates of the auxiliary metal element. The auxiliary metal element is exemplified by Mn, and the precursor of the auxiliary metal element is preferably manganese oxide. Taking W as an example, preferably, the precursor of the auxiliary metal element is ammonium tungstate and/or tungstic acid.
The amount of the pore-forming agent used in the present invention is preferably 2 to 16 parts by weight, preferably 4 to 9 parts by weight, based on 100 parts by weight of the total amount of the precursor of the iron element, the precursor of the potassium element, the precursor of the rare earth metal element, the precursor of the alkaline earth metal element, and the precursor of the auxiliary metal element. In this preferred case, the catalyst has better performance and is more advantageous in increasing the overall conversion of mixed divinylbenzene and the number of comparisons between mixed divinylbenzene.
According to a preferred embodiment of the present invention, the weight ratio of the organic matter to the inorganic matter is 3-8:1. in this preferred embodiment, it is further advantageous to increase the performance of the catalyst, and thus the overall conversion of mixed diethylbenzene and the number of comparisons between mixed divinylbenzene.
According to the present invention, preferably, the organic matter is selected from at least one of starch, synthetic cellulose, and polymeric alcohol. In the present invention, the synthetic cellulose is preferably at least one of methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylmethyl cellulose; the polymeric alcohol is preferably at least one of dimer glycerol, trimer glycerol, triethanolamine (TEA), polyethylene glycol and polyvinyl alcohol. Preferably, the organic matter is selected from at least one of sesbania powder, polyethylene glycol, methylcellulose, carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl methylcellulose, and more preferably hydroxyethyl cellulose. In this preferred case, it is more advantageous to increase the performance of the catalyst and to increase the overall conversion of mixed divinylbenzene and the value of the inter-contrast of mixed divinylbenzene.
According to a preferred embodiment of the invention, the mineral is selected from at least one of dicalcium silicate, tricalcium aluminate, tetracalcium aluminoferrite and cement, preferably cement. In this preferred embodiment, it is further advantageous to increase the performance of the catalyst, and thus the overall conversion of mixed diethylbenzene and the number of comparisons between mixed divinylbenzene.
In the present invention, the cement is selected from a wide range, and preferably the cement is at least one selected from the group consisting of silicate cement, aluminate cement, aluminoferrite cement and sulfoaluminate cement, and preferably silicate cement. The cement is commercially available.
According to the present invention, preferably, the conditions of the firing include: the temperature is 350-900 ℃, preferably 400-850 ℃; the time is 1-24 hours, preferably 10-20 hours.
In the present invention, the firing atmosphere is widely selected, and preferably, the firing is performed under an oxygen-containing atmosphere. The oxygen content in the oxygen-containing atmosphere of the present invention may be selected within a wide range, and specifically, for example, the oxygen content may be not less than 1% by volume, 5% by volume, 10% by volume, 20% by volume, 30% by volume, and a value therebetween.
According to the present invention, preferably, the firing is performed in air. The flow rate of the gas during the calcination is not particularly limited in the present invention, and may be selected as needed by those skilled in the art according to actual needs.
According to a preferred embodiment of the present invention, the firing process comprises: roasting at 350-650 deg.c, preferably 400-600 deg.c, in oxygen containing atmosphere for 6-12 hr; and then calcined at 750-900 c, preferably 800-850 c, for 4-7 hours. In this preferred embodiment, it is further advantageous to increase the performance of the catalyst, and thus the overall conversion of mixed diethylbenzene and the number of comparisons between mixed divinylbenzene.
Further preferably, the roasting process comprises: heating to 350-650deg.C at 0.5-5deg.C/min, preferably 2-4deg.C/min, preferably 400-600deg.C under oxygen-containing atmosphere, and roasting for 6-12 hr; then heating to 750-900 ℃ at 0.5-5 ℃/min, preferably 1.5-2.5 ℃/min, and roasting for 4-7h at 800-850 ℃. In this preferred embodiment, further improvement in the performance of the catalyst and thus further improvement in the overall conversion of mixed divinylbenzene and the numerical value of the contrast between mixed divinylbenzene is further facilitated.
According to the invention, preferably, the method further comprises ageing and/or drying the shaped product before said firing. In this preferred case, it is further advantageous to further increase the performance of the catalyst and thus the value of the inter-contrast of the mixed divinylbenzene.
According to a preferred embodiment of the present invention, the method further comprises aging and drying the molded product in sequence before the firing. In this preferred embodiment, further improvement in the performance of the catalyst and thus further improvement in the overall conversion of mixed divinylbenzene and the numerical value of the contrast between mixed divinylbenzene is further facilitated.
According to the present invention, preferably, the aging conditions include: the temperature is 20-60 ℃, preferably 20-40 ℃; the time is 0.5-12h, preferably 2-8h. The inventors of the present invention found that in this preferred case, the prepared catalyst had better performance and higher strength, which was more advantageous for improving the total conversion of mixed divinylbenzene and the value of the inter-mixed divinylbenzene.
In the present invention, the conditions for drying are wide in limitation, and preferably, the conditions for drying include: the temperature is 40-180deg.C, preferably 50-100deg.C; the time is 3-24 hours, preferably 6-20 hours. The drying mode is not particularly limited in the present invention, and for example, the drying may be at least one of drying, forced air drying, spray drying and flash drying. In the present invention, the drying atmosphere is not particularly limited, and may be performed in at least one of air, oxygen and nitrogen, and air is preferable in order to reduce the production cost.
In a third aspect, the present invention provides a dehydrogenation catalyst prepared by the above method. The dehydrogenation catalyst provided by the invention has better catalytic performance and higher strength, is particularly suitable for producing mixed divinylbenzene by dehydrogenation of mixed divinylbenzene, and has higher inter-contrast value of the mixed divinylbenzene in the product.
Accordingly, a fourth aspect of the present invention provides the use of a dehydrogenation catalyst as described above in the dehydrogenation of mixed diethylbenzenes.
In a fifth aspect, the present invention provides a process for the dehydrogenation of mixed diethylbenzenes, the process comprising: the dehydrogenation catalyst is contacted with the mixed divinylbenzene for reaction to obtain the mixed divinylbenzene; the dehydrogenation catalyst is the catalyst provided by the invention.
According to the invention, the mixed diethylbenzene contains m-diethylbenzene, p-diethylbenzene and optionally o-diethylbenzene, preferably the total content of m-diethylbenzene and p-diethylbenzene in the mixed diethylbenzene is more than 90 wt%, preferably more than 95 wt%, for example 95-99.9 wt%. The optional representation may or may not be present.
According to the present invention, preferably, in the mixed diethylbenzene, the molar ratio of m-diethylbenzene to p-diethylbenzene is 0.5 to 9:1, preferably 1.8-4:1.
According to the method for dehydrogenating the mixed diethylbenzene provided by the invention, the reaction conditions are selected in a wide range, and preferably, the reaction conditions comprise: the temperature is 580-680 ℃, preferably 610-640 ℃, and further preferably 625-640 ℃; the pressure is 1 to 101kPa, preferably 20 to 50kPa; the liquid hourly space velocity is 0.3 to 1h -1 Preferably 0.3-0.5h -1 。
According to a preferred embodiment of the present invention, the reaction conditions further comprise: the weight ratio of the water vapor to the mixed diethylbenzene is 2.5-10:1, preferably 3.5-5:1. in this preferred case, it is advantageous to increase the value of the inter-contrast of the mixed divinylbenzene in the product.
According to the invention, preferably, before said contacting, the method further comprises: the dehydrogenation catalyst is purged with an inert gas for 1 to 6 hours, preferably 2 to 3.5 hours. In the present invention, the inert gas may be selected from a wide range, and may be, for example, at least one of nitrogen, argon, helium and neon, and preferably nitrogen.
According to a preferred embodiment of the invention, after said purging, before said reacting, the method further comprises: heating the dehydrogenation catalyst to 250-350 ℃, preferably 280-330 ℃, under an inert atmosphere; then, the temperature is continuously increased to 580-680 ℃, preferably 610-640 ℃, further preferably 625-640 ℃ under the water vapor condition, and the temperature is kept for 1-8 hours, preferably 2-4 hours.
The numerical value of the contrast between the mixed divinylbenzene products obtained by the method for dehydrogenating the mixed divinylbenzene is higher, so that the method is more suitable for the requirements of downstream products, and the production economy is further improved.
The present invention will be described in detail by examples.
In the examples below, room temperature represents 25 ℃, unless otherwise specified; atmospheric pressure means one atmosphere;
the side pressure strength of the catalyst is measured by a DL-II type intelligent particle strength meter according to a standard HG/T2782-1996, wherein the length of a sample is 5 mm, 40 samples are taken as a group, the arithmetic average value of the measurement results is taken as a final mechanical strength value, and the unit of mechanical strength is Newton (N);
the specific surface area and the median pore diameter of the catalyst are measured by adopting a mercury intrusion method, and an adopted instrument is a Pascal-140+240 pore diameter analyzer of Thermo company, and the testing range is 7.4nm-116 mu m;
the composition and content of the reaction product were analyzed by gas chromatograph.
Example 1
The method provided by the invention is used for preparing the catalyst, and comprises the following specific steps:
(1) In parts by weight, 38.31 parts of iron oxide red corresponding to Fe, 12.77 parts of iron oxide yellow corresponding to Fe, 9.68 parts of potassium carbonate corresponding to K, 7.65 parts of cerium oxalate corresponding to Ce, 1.01 parts of ammonium tungstate corresponding to W, 0.78 part of calcium hydroxide corresponding to Ca, 0.58 part of magnesium hydroxide corresponding to Mg, 0.05 part of manganese oxide corresponding to Mn, 5 parts of hydroxyethyl cellulose and 1 part of cement are mixed in a kneader, and then a cerium nitrate aqueous solution corresponding to 1.91 parts of Ce is added for wet kneading, and then extrusion is carried out to obtain a quincuncial shaped formed article with the diameter of 3mm and the length of 5-10 mm;
(2) Aging the molded article at room temperature for 6 hours; then drying at 85 ℃ for 12 hours; roasting the dried product at 400 ℃ for 10 hours under the air condition, and roasting the product at 850 ℃ for 5 hours to obtain a catalyst C1, wherein the physical and chemical properties are shown in Table 1;
the pore distribution of catalyst C1, as measured by mercury intrusion, is shown in FIG. 1, with a median pore diameter of 443.7nm.
Example 2
The method provided by the invention is used for preparing the catalyst, and comprises the following specific steps:
(1) In parts by weight, 47.51 parts of iron oxide red corresponding to Fe, 9.21 parts of potassium carbonate corresponding to K, 1.77 parts of potassium hydroxide corresponding to K, 8.17 parts of cerium carbonate corresponding to Ce, 1.56 parts of ammonium tungstate corresponding to W, 1.23 parts of calcium carbonate corresponding to Ca, 0.51 part of magnesium oxide corresponding to Mg, 0.50 part of manganese oxide corresponding to Mn, 4 parts of hydroxyethyl cellulose and 2 parts of cement are mixed in a kneader, and then a cerium nitrate aqueous solution corresponding to 2.72 parts of Ce is added for wet kneading, and then extrusion is carried out to obtain a quincuncial shaped formed article with the diameter of 3mm and the length of 5-10 mm;
(2) Aging the molded article at room temperature for 6 hours; then drying at 85 ℃ for 12 hours; the dried product was calcined at 400℃for 10 hours and then at 800℃for 6 hours under air conditions to give catalyst C2, the physicochemical properties of which are shown in Table 1.
Example 3
The method provided by the invention is used for preparing the catalyst, and comprises the following specific steps:
(1) According to parts by weight, 45.15 parts of Fe iron oxide red, 9.03 parts of Fe iron oxide yellow, 8.62 parts of K potassium carbonate, 5.87 parts of Ce cerium oxalate, 1.47 parts of cerium carbonate, 0.86 part of W ammonium tungstate, 0.98 part of Ca calcium hydroxide, 0.21 part of Mg magnesium hydroxide, 0.16 part of Mn manganese oxide, 9 parts of methylcellulose and 1.5 parts of cement are mixed in a kneader, water is added for wet kneading, and extrusion is carried out to obtain a quincuncial shaped formed product with the diameter of 3mm and the length of 5-10 mm;
(2) Aging the molded article at room temperature for 6 hours; then drying at 80 ℃ for 10 hours; the dried product was calcined at 450℃for 11 hours and then at 850℃for 5 hours under air conditions to give catalyst C3, the physicochemical properties of which are shown in Table 1.
Example 4
The same procedure as in example 1 was followed except that in step (1), 5 parts of hydroxyethyl cellulose and 1 part of cement were replaced with 2.5 parts of hydroxyethyl cellulose and 0.5 part of cement;
Step (2) was carried out in the same manner as in example 1 to obtain catalyst C4, and the physicochemical properties thereof are shown in Table 1.
Example 5
The same procedure as in example 1 was followed except that in step (2), the dried product was baked at 400℃for 10 hours and then at 850℃for 5 hours instead of baking the dried product at 850℃for 15 hours;
catalyst C5 was obtained and the physicochemical properties are shown in Table 1.
Example 6
According to the same method as that of example 1, except that in the step (2), the molded article obtained in the step (1) is directly dried and baked in order without aging;
catalyst C6 was obtained and the physicochemical properties are shown in Table 1.
Example 7
The same procedure as in example 1 was followed except that in step (1), the following steps were carried out:
(1) In parts by weight, iron oxide red corresponding to 41.81 parts of Fe, iron oxide yellow corresponding to 15.27 parts of Fe, potassium carbonate corresponding to 9.68 parts of K, cerium oxalate corresponding to 1.65 parts of Ce, ammonium tungstate corresponding to 1.01 parts of W, calcium hydroxide corresponding to 0.78 part of Ca, magnesium hydroxide corresponding to 0.58 part of Mg, manganese oxide corresponding to 0.05 part of Mn, 5 parts of hydroxyethyl cellulose and 1 part of cement are mixed in a kneader, and then cerium nitrate aqueous solution corresponding to 1.91 parts of Ce is added for wet kneading, and then extrusion is carried out to obtain a trilobate shaped molded article with a diameter of 4mm and a length of 5-10 mm;
Step (2) was carried out in the same manner as in example 1 to obtain a catalyst C7, and the physicochemical properties thereof are shown in Table 1.
Example 8
The same procedure as in example 1 was followed except that in step (1), the following steps were carried out:
(1) In parts by weight, 38.31 parts of iron oxide red corresponding to Fe, 12.77 parts of iron oxide yellow corresponding to Fe, 9.68 parts of potassium carbonate corresponding to K, 7.65 parts of cerium oxalate corresponding to Ce, 1.01 parts of ammonium tungstate corresponding to W, 1.36 parts of calcium hydroxide corresponding to Ca, 0.05 part of manganese oxide corresponding to Mn, 5 parts of hydroxyethyl cellulose and 1 part of cement are mixed in a kneader, and then cerium nitrate aqueous solution corresponding to 1.91 parts of Ce is added for wet kneading, and then extrusion is carried out to obtain a tetraleaf-shaped formed product with a diameter of 5mm and a length of 5-10 mm;
step (2) was carried out in the same manner as in example 1 to obtain catalyst C8, and the physicochemical properties thereof are shown in Table 1.
Example 9
The same procedure as in example 1 was followed except that in step (1), 5 parts of hydroxyethyl cellulose and 1 part of cement were replaced with 5.45 parts of hydroxyethyl cellulose and 0.55 part of cement;
step (2) was carried out in the same manner as in example 1 to obtain catalyst C9, and the physicochemical properties thereof are shown in Table 1.
Example 10
The same procedure as in example 1 was followed except that in step (1), 5 parts of hydroxyethyl cellulose and 1 part of cement were replaced with 3.6 parts of hydroxyethyl cellulose and 2.4 parts of cement;
step (2) was carried out in the same manner as in example 1 to obtain catalyst C10, and the physicochemical properties thereof are shown in Table 1.
Comparative example 1
The same procedure as in example 1 was followed except that in step (1), 5 parts of hydroxyethyl cellulose and 1 part of cement were replaced with 6 parts of hydroxyethyl cellulose;
step (2) was carried out in the same manner as in example 1 to obtain a catalyst D1, and the physicochemical properties thereof are shown in Table 1.
Comparative example 2
The same procedure as in example 1 was followed except that in step (1), 5 parts of hydroxyethylcellulose and 1 part of cement were replaced with 6 parts of cement;
step (2) was carried out in the same manner as in example 1 to obtain catalyst D2, and the physicochemical properties thereof are shown in Table 1.
Test example 1
The catalysts prepared in the examples were evaluated using an isothermal fixed bed reactor:
the raw materials are mixed diethylbenzene, wherein the content of the m-diethylbenzene is 67.98 wt%, the content of the p-diethylbenzene is 30.90 wt%, and the rest components comprise benzene, toluene, ethylbenzene and o-diethylbenzene; before the catalyst is contacted with the mixed diethylbenzene, nitrogen is used for purging for 3 hours, then the temperature is raised to 300 ℃ under nitrogen, then the temperature is raised to 630 ℃ under water vapor, and the temperature is kept for 3 hours;
After the mixed diethylbenzene is contacted with saturated water vapor, the mixed diethylbenzene and the saturated water vapor are sent into a preheating mixer together, the preheating temperature is 400 ℃, and the mixed diethylbenzene enters a reactor to be contacted with a catalyst for reaction after being preheated to a gaseous state, wherein a stainless steel pipe with the inner diameter of 1 inch of the reactor is filled with 100 milliliters of catalyst; the reaction conditions include: the temperature is 630 ℃, the pressure is normal pressure, and the liquid hourly space velocity is 0.5h -1 The weight ratio of the water vapor to the mixed diethylbenzene is 3.5; the composition of the resultant reaction product was analyzed by gas chromatograph after condensation, and the results are shown in Table 2;
wherein the element content in the catalyst in table 2 is based on the total amount of Fe, K, ce, ca, mg, W, mn and O;
total olefin selectivity = ethyl vinyl benzene selectivity + divinylbenzene selectivity
Inter-contrast value r= (M/P) of mixed divinylbenzene DVB /(M/P) DEB 。
TABLE 1
Note that: element content of 0 indicates no detectable content;
"organics: the term "inorganic" means the weight ratio of organic to inorganic.
TABLE 2
Note that: total diethylbenzene conversion represents total mixed diethylbenzene conversion;
meta-position represents the weight content of m-diethylbenzene or m-divinylbenzene;
para-position indicates the weight content of p-diethylbenzene or p-divinylbenzene.
As can be seen from the results in Table 1, the dehydrogenation catalyst prepared by the method has the characteristics of larger specific surface area and median pore diameter, higher side pressure strength and higher strength.
As can be seen from the results in Table 2, when the dehydrogenation catalyst provided by the invention is applied to the reaction for producing the mixed divinylbenzene by dehydrogenation of the mixed divinylbenzene, the total conversion rate of the mixed divinylbenzene is higher, the total selectivity of olefin is higher, the inter-comparison value of the mixed divinylbenzene in the product is higher, and the effect is remarkable.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (41)

1. A dehydrogenation catalyst comprising an Fe element, a K element, a rare earth metal element, an alkaline earth metal element, and an auxiliary metal element; in the catalyst, based on the total amount of the catalyst, the content of Fe element is 42-59.5 wt%, the content of K element is 6-13 wt%, the content of rare earth metal element is 3-16 wt%, the content of alkaline earth metal element is 0.2-3.5 wt%, and the content of auxiliary metal element is 0.1-3.5 wt%; the auxiliary metal element is at least one selected from Mn, W, cu, zn, ti, mo, ni and Nb;
The median pore diameter of the catalyst is 205-600nm;
the preparation method of the dehydrogenation catalyst comprises the following steps: mixing an iron element precursor, a potassium element precursor, a rare earth metal element precursor, an alkaline earth metal element precursor, an auxiliary metal element precursor and a pore-forming agent, and sequentially forming and roasting to obtain the catalyst;
the pore-forming agent comprises an organic matter and an inorganic matter, wherein the weight ratio of the organic matter to the inorganic matter is 3-8:1, a step of;
the organic matter is at least one selected from starch, synthetic cellulose and polymeric alcohol;
the inorganic matters are at least one selected from dicalcium silicate, tricalcium aluminate, tetracalcium aluminoferrite and cement.
2. The catalyst according to claim 1, wherein the catalyst contains, in terms of elements, 47 to 55.5% by weight of Fe element, 7.5 to 11% by weight of K element, 6.5 to 13% by weight of rare earth metal element, 0.5 to 2.5% by weight of alkaline earth metal element and 0.5 to 2.5% by weight of auxiliary metal element, based on the total amount of the catalyst.
3. The catalyst according to claim 1, wherein,
the median pore diameter of the catalyst is 280-500nm.
4. The catalyst according to claim 1, wherein the specific surface area of the catalyst is 1.5-5m 2 /g。
5. The catalyst according to claim 4, wherein the specific surface area of the catalyst is 2.1-3.6m 2 /g。
6. The catalyst according to any one of claims 1 to 5, wherein the promoter metal element is selected from at least one of Mn, W and Mo.
7. The catalyst according to claim 6, wherein the promoter metal element is Mn and/or W.
8. The catalyst according to any one of claims 1 to 5, wherein,
the rare earth metal element is selected from at least one of La, ce and Pr.
9. The catalyst according to claim 8, wherein,
the rare earth metal element is Ce.
10. The catalyst according to any one of claims 1 to 5, wherein,
the alkaline earth metal element is Mg and/or Ca.
11. A method of preparing a dehydrogenation catalyst, the method comprising: mixing an iron element precursor, a potassium element precursor, a rare earth metal element precursor, an alkaline earth metal element precursor, an auxiliary metal element precursor and a pore-forming agent, and sequentially forming and roasting to obtain the catalyst;
The usage amount of the precursor of the iron element, the precursor of the potassium element, the precursor of the rare earth metal element, the precursor of the alkaline earth metal element and the precursor of the auxiliary metal element is such that in the prepared catalyst, based on the total amount of the catalyst, the content of Fe element is 42-59.5 wt%, the content of K element is 6-13 wt%, the content of the rare earth metal element is 3-16 wt%, the content of the alkaline earth metal element is 0.2-3.5 wt%, and the content of the auxiliary metal element is 0.1-3.5 wt%; the auxiliary metal element is at least one selected from Mn, W, mo, cu, zn, ti, ni and Nb;
the pore-forming agent comprises an organic matter and an inorganic matter, wherein the weight ratio of the organic matter to the inorganic matter is 3-8:1, a step of;
the organic matter is at least one selected from starch, synthetic cellulose and polymeric alcohol;
the inorganic matters are at least one selected from dicalcium silicate, tricalcium aluminate, tetracalcium aluminoferrite and cement;
the median pore diameter of the catalyst prepared by the preparation method is 205-600nm.
12. The method of claim 11, wherein the promoter metal element is selected from at least one of Mn, W, and Mo.
13. The method of claim 12, wherein the promoter metal element is Mn and/or W.
14. The method of claim 11, wherein,
the rare earth metal element is selected from at least one of La, ce and Pr.
15. The method of claim 14, wherein,
the rare earth metal element is Ce.
16. The method of claim 11, wherein,
the alkaline earth metal element is Mg and/or Ca.
17. The method according to claim 11, wherein the precursor of iron element, the precursor of potassium element, the precursor of rare earth metal element, the precursor of alkaline earth metal element and the precursor of auxiliary metal element are used in such an amount that the catalyst is obtained, based on the total amount of the catalyst, in terms of element, the content of Fe element is 47 to 55.5 wt%, the content of K element is 7.5 to 11 wt%, the content of rare earth metal element is 6.5 to 13 wt%, the content of alkaline earth metal element is 0.5 to 2.5 wt%, and the content of auxiliary metal element is 0.5 to 2.5 wt%.
18. The method of claim 11, wherein,
the precursor of the iron element is at least one selected from iron oxide red, iron oxide yellow, iron oxide black, ferric nitrate, ferric hydroxide and ferric oxide green;
the precursor of the potassium element is at least one selected from potassium hydroxide, potassium carbonate, potassium sulfate, potassium chloride, potassium bicarbonate and potassium nitrate;
The precursor of the rare earth metal element is at least one selected from oxalate, nitrate and carbonate of the rare earth metal element;
the precursor of the alkaline earth metal element is selected from at least one of an oxide of the alkaline earth metal element, a hydroxide of the alkaline earth metal element and a carbonate of the alkaline earth metal element;
the precursor of the auxiliary metal element is selected from at least one of an oxide of the auxiliary metal element, a hydroxide of the auxiliary metal element, a nitrate of the auxiliary metal element and a carbonate of the auxiliary metal element.
19. The method of claim 18, wherein,
the precursor of the potassium element is at least one selected from potassium hydroxide, potassium carbonate and potassium nitrate.
20. The method according to any one of claims 11 to 19, wherein the pore-forming agent is used in an amount of 2 to 16 parts by weight relative to 100 parts by weight of the total amount of the precursor of the iron element in terms of the iron element, the precursor of the potassium element in terms of the potassium element, the precursor of the rare earth metal element in terms of the rare earth metal element, the precursor of the alkaline earth metal element in terms of the alkaline earth metal element, and the precursor of the auxiliary metal element in terms of the auxiliary metal element.
21. The method according to claim 20, wherein the pore-forming agent is used in an amount of 4 to 9 parts by weight relative to 100 parts by weight of the total of the precursor of the iron element in terms of the iron element, the precursor of the potassium element in terms of the potassium element, the precursor of the rare earth metal element in terms of the rare earth metal element, the precursor of the alkaline earth metal element in terms of the alkaline earth metal element, and the precursor of the auxiliary metal element in terms of the auxiliary metal element.
22. The method according to any one of claims 11-19, wherein,
the organic matter is at least one selected from sesbania powder, polyethylene glycol, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose.
23. The method of any of claims 11-19, wherein the firing conditions include: the temperature is 350-900 ℃ and the time is 1-24h.
24. The method of claim 23, wherein the firing conditions include: the temperature is 400-850 ℃ and the time is 10-20h.
25. The method of claim 23, wherein,
the roasting process comprises the following steps: roasting for 6-12h at 350-650 ℃ in an oxygen-containing atmosphere; then roasting for 4-7h at 750-900 ℃.
26. The method of claim 24, wherein,
the roasting process comprises the following steps: roasting for 6-12h at 400-600 ℃ in an oxygen-containing atmosphere; then roasting for 4-7h at 800-850 ℃.
27. The method of any one of claims 11-19, wherein prior to the firing, the method further comprises aging and/or drying the shaped product.
28. The method of claim 27, wherein prior to firing, the method further comprises sequentially aging and drying the shaped product.
29. The method of claim 28, wherein,
the aging conditions include: the temperature is 20-60 ℃ and the time is 0.5-12h.
30. The method of claim 29, wherein,
the aging conditions include: the temperature is 20-40 ℃; the time is 2-8h.
31. The method of claim 28, wherein,
the drying conditions include: the temperature is 40-180 ℃ and the time is 3-24h.
32. The method of claim 31, wherein,
the drying conditions include: the temperature is 50-100 ℃; the time is 6-20h.
33. A dehydrogenation catalyst prepared by the process of claims 11-32.
34. Use of the catalyst of any one of claims 1-10 and 33 in a mixed diethylbenzene dehydrogenation reaction.
35. A process for the dehydrogenation of mixed diethylbenzenes, the process comprising: the dehydrogenation catalyst is contacted with the mixed divinylbenzene for reaction to obtain the mixed divinylbenzene; the dehydrogenation catalyst is the catalyst of any one of claims 1-10 and 33.
36. The method of claim 35, wherein the reaction conditions comprise: the temperature is 580-680 ℃; the pressure is 1-101kPa; the liquid hourly space velocity is 0.3 to 1h -1 The method comprises the steps of carrying out a first treatment on the surface of the The weight ratio of the water vapor to the mixed diethylbenzene is 2.5-10:1.
37. the method of claim 36, wherein the reaction conditions comprise: the temperature is 625-640 ℃; the pressure is 20-50kPa; the liquid hourly space velocity is 0.3 to 0.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the The weight ratio of the water vapor to the mixed diethylbenzene is 3.5-5:1.
38. the method of claim 35, wherein,
prior to said contacting, the method further comprises: the dehydrogenation catalyst is purged with an inert gas for 1-6 hours.
39. The method of claim 38, wherein,
prior to said contacting, the method further comprises: the dehydrogenation catalyst is purged with an inert gas for 2-3.5 hours.
40. The method of claim 35, wherein,
after the purging, and prior to the reacting, the method further comprises: heating the dehydrogenation catalyst to 250-350 ℃ in an inert atmosphere; then heating to 580-680 deg.C under steam condition, and keeping at constant temperature for 1-8h.
41. The method of claim 40, wherein,
after the purging, and prior to the reacting, the method further comprises: heating the dehydrogenation catalyst to 280-330 ℃ in an inert atmosphere; then heating to 625-640 deg.c under water vapor condition, and maintaining at constant temperature for 2-4 hr.
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