CN112973715B - Preparation method of catalyst for preparing styrene by ethylbenzene dehydrogenation - Google Patents

Preparation method of catalyst for preparing styrene by ethylbenzene dehydrogenation Download PDF

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CN112973715B
CN112973715B CN201911290828.4A CN201911290828A CN112973715B CN 112973715 B CN112973715 B CN 112973715B CN 201911290828 A CN201911290828 A CN 201911290828A CN 112973715 B CN112973715 B CN 112973715B
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potassium
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CN112973715A (en
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杨红强
刘肖飞
刘俊涛
南洋
何崇慧
李景锋
李晓艳
蔡小霞
李燕
全民强
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Petrochina Co Ltd
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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
    • B01J23/002—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
    • 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
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • 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
    • B01J37/04—Mixing
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
    • C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method for preparing a styrene catalyst by ethylbenzene dehydrogenation, the catalyst comprising Fe, K, ce, mo and/or W, mg and/or Ca, the method comprising: (1) Mixing an iron raw material with part of Mg and Ca raw material dry powder to form a mixed material A, adding part of potassium raw material A and water to form a solution A, adding the solution A into the mixed material A, mixing and roasting to form a precursor I; grinding or crushing the precursor I, adding all Ce raw materials, mo and/or W raw materials and the rest Mg and/or Ca raw materials, carrying out dry powder mixing to form a mixture B, adding the rest potassium raw materials B into the mixture B to form a paste, granulating, forming, drying and roasting to obtain the catalyst. The method effectively improves the activity and selectivity of the catalyst after long-period operation by changing the adding mode of the cocatalyst K.

Description

Preparation method of catalyst for preparing styrene by ethylbenzene dehydrogenation
Technical Field
The invention relates to a preparation method of a dehydrogenation catalyst, in particular to a preparation method of a styrene catalyst prepared by ethylbenzene dehydrogenation, and especially relates to a preparation method for improving the activity and stability of the ethylbenzene dehydrogenation catalyst by adding potassium auxiliary step by step.
Background
With the improvement and development for many years, the ethylbenzene dehydrogenation catalyst has been gradually replaced by the zinc-based and magnesium-based catalysts used in the early stage by the iron-based catalysts with more excellent comprehensive properties. In the iron-based catalyst, fe 2 O 3 The highest content is the main active component, K, for dehydrogenation of ethylbenzene 2 The secondary O content is the main promoter. In the reaction process of preparing styrene by ethylbenzene dehydrogenation, K 2 O plays a role in transferring electrons and can improve the activity of the catalyst in geometric order. A large number of research results show that the potassium ferrate is an active phase and a structural stabilizer in a catalyst for preparing styrene by ethylbenzene dehydrogenation, and the more the phase is formed, the higher the activity of the catalyst is, and the better the stability is. At present, K is the potassium ferrate with relatively high report 2 Fe 22 O 34 The catalyst has a hexagonal structure, and each unit cell has a K atom combined with 11 Fe atoms, and plays a role in transferring electrons in the ethylbenzene dehydrogenation process. In addition, studies have found K 2 O also plays a role in promoting water gas reaction in the catalyst, can automatically remove carbon deposition on the surface of the catalyst, enhances the carbon deposition resistance and reduction resistance of the catalyst, improves the activity and stability of the catalyst, and prolongs the service life of the catalyst. Thus, the primary crystal phase structure of the catalyst, the presence of K in the catalyst, will seriously affect its co-catalytic effect.
At present, patent reports related to ethylbenzene dehydrogenation catalysts focus on the aspects of catalyst formulation design, and the influence of component proportions and auxiliary agent types on catalyst performance is mainly studied, such as patents CN101422735, CN101455968, CN1810368, CN1923364 and the like. While relatively few patent reports about the influence of the main crystal phase structure of the catalyst on the catalyst performance are reported, patent CN1765753 reports a preparation methodPotassium ferrate K 2 Fe 22 O 34 The patent successfully prepares K through the processes of mixing iron component powder and potassium component powder, extruding strips, forming, drying and high-temperature roasting 2 Fe 22 O 34 A compound; patent CN1765495 reports the addition of potassium ferrate K to cerium oxide and molybdenum oxide 2 Fe 22 O 34 And the calcium oxide or magnesium oxide component, the problem of the change of the catalyst performance after directly adding potassium ferrate into the catalyst is researched, and the research result shows that the catalyst prepared by the method has better activity and selectivity, and the water resistance and the stability of the catalyst are obviously improved.
Patent CN101602004A discloses a method for preparing a styrene catalyst by ethylbenzene dehydrogenation, and solves the problems of insufficient initial performance and long reaction induction period of the catalyst by adopting a technical scheme that a potassium oxide component is added step by step to prepare the catalyst when preparing a Fe-K-Ce-W catalyst. In the patent, firstly, part of potassium oxide and the rest of catalyst components are subjected to dry mixing, water adding and kneading, extrusion, drying and granulating, high-temperature roasting to prepare a catalyst precursor I, then the catalyst precursor I is modified by the rest of soluble potassium components to obtain a catalyst precursor II, and finally the catalyst precursor II is dried and roasted to prepare the catalyst. The catalyst prepared by the method can improve the initial performance and shorten the reaction induction period, but has low selectivity, ethylbenzene conversion rate and yield, the selectivity of the catalyst is only about 94 percent, the ethylbenzene conversion rate is about 76 percent on an isothermal reaction device at 620 ℃, the ethylbenzene conversion rate of the catalyst is about 63 percent when the catalyst is subjected to performance evaluation on a 4L adiabatic side device, and the selectivity of styrene is between 94 and 95 percent.
Patent CN102039204A discloses a preparation method of catalyst for preparing styrene by ethylbenzene dehydrogenation, which comprises adding cerium as active component into catalyst by two-step method, and CeO 2 Well dispersed on the surface of the catalyst, and a large amount of CeO 2 The microcrystals are arranged on the surface of the catalyst and in the active phase KFEO 2 Fully mix with CeO 2 Has strong lattice oxygen mobility and forms masses near the boundary of two phasesThe oxygen transfer deoxidization centers are more, the activity of the catalyst is enhanced, the initial activity of the catalyst is obviously improved, and the induction period of the catalyst is shortened. The patent firstly selects a cerium source with a required amount, an iron source, a potassium source, a molybdenum source or a tungsten source with a required amount, a mixture thereof, alkaline earth metal oxide and a pore-forming agent, uniformly mixes, forms, dries and bakes the mixture to form a catalyst precursor I, adopts an impregnation method to load the rest cerium source amount on the catalyst precursor I, and finally dries and bakes the catalyst precursor I to obtain the required catalyst. The catalyst prepared by the method can improve the initial activity and shorten the induction period of the catalyst, but also has the problems of poor selectivity, low ethylbenzene conversion rate and low yield, the selectivity of the catalyst is only 94% after the catalyst activity is stable on an isothermal reaction device at 620 ℃, the ethylbenzene conversion rate is about 77%, the styrene yield is about 69%, the ethylbenzene conversion rate is about 64% on a 4L adiabatic side device, and the styrene selectivity is about 94%.
The patent CN105562023a reports a catalyst for preparing p-methylstyrene and a preparation method and application thereof, and solves the problem of low catalyst activity in the prior art by adding a potassium source step by step. The catalyst prepared by the method has the methyl ethylbenzene selectivity of 93.7% and the catalyst activity of 61% after the catalyst activity is stable on an isothermal reaction device at 620 ℃.
Patent CN105749934A reports a styrene catalyst prepared by ethylbenzene dehydrogenation with low water ratio and a preparation method thereof, and Mn-Zn-Pb oxide is added into a Fe-K-Ce-Mo-Mg-Ca system to promote the formation of main active phase potassium ferrite of the catalyst, enhance the anti-reduction capability of the catalyst and improve the activity of the catalyst; the surface acidity of the catalyst is reduced, the water absorption of the catalyst surface is enhanced, the water gas reaction rate of the catalyst surface is improved, and the stability of the catalyst under a low water ratio reaction process is improved by modifying alkali metal and light rare earth metal ions except Ce on the catalyst surface; the catalyst is suitable for a low water ratio reaction process, and the problems of low catalyst activity and stability caused by the reduction of the water vapor content in the low water ratio reaction process are effectively solved. The catalyst prepared by the method is suitable for special working conditions of low water ratio reaction, and compared with normal water ratio (usually 1.5-2.0) working conditions, the low water ratio catalyst generally has the operating water ratio of 1.0-1.2, and in order to ensure the activity and stability of the catalyst in the low water ratio working conditions, the contents of alkali metal and alkaline earth metal in the catalyst components are relatively high so as to achieve the purpose of removing coke on the surface of the catalyst, and the activity and stability of the catalyst are effectively maintained.
Patent CN108097260a discloses a catalyst for preparing styrene by ethylbenzene dehydrogenation and a preparation method thereof. The catalyst comprises the following components in percentage by mass: a) 65-75% of potassium ferrite composite oxide by K 2 Fe 10 O 16 Counting; b) 1 to 4% of K oxide, K 2 An O meter; c) 6-12% of Ce oxide, ceO 2 Counting; d) 0.6 to 4% of W oxide, WO 3 Counting; e) 2-6% of Mg or/and Ca oxide, calculated by MgO or/and CaO; f) 2-4% of at least one alkali metal oxide selected from Rb and Cs. The bonding capability between K atoms and Fe atoms is enhanced by adding Ca and Mg ions in two steps, and the main active phase K is generated to the maximum extent 2 Fe 10 O 16 The problems of carbon deposition and inactivation in the active phase potassium ferrite under the working condition of low water ratio are inhibited, so that the activity of the catalyst is improved. The bulk density and crushing resistance of the catalyst are also obviously improved, the problems of poor catalyst stability, poor selectivity and the like caused by potassium loss in the later reaction period of the high-potassium catalyst are effectively solved, and the stability and the selectivity of the catalyst in operation under the working condition of low water ratio are improved. The catalyst prepared by the method is suitable for special reaction conditions with low water ratio.
The catalyst for preparing styrene by ethylbenzene dehydrogenation is a full active component, i.e. the catalyst phase has the same structural component as the surface, and the auxiliary agent potassium salt is used for ethylbenzene dehydrogenationThe hydrogen catalyst has irreplaceable function, and many domestic and foreign scholars try to achieve the aim of optimizing the catalyst performance by changing the adding mode of potassium or improving the content of potassium. On the one hand, the prior literature reports that the potassium is added in a mode of K 2 O powder or impregnation. By K 2 The addition mode of O powder is easy to cause Fe in the mixing process 2 O 3 And K is equal to 2 The problem of uneven mixing of O density difference affects the long-period stable operation of the catalyst. The potassium salt is introduced in a dipping mode, so that alkali metals are easily distributed on the surface of the catalyst, the early water gas reaction is severe, the coke cleaning capability of the surface of the catalyst is strong, the initial activity of the catalyst is high, but the potassium salt distributed on the surface of the catalyst is continuously carried out along with the high-temperature reaction, the potassium salt is easily lost under the scouring action of high-temperature steam, excessive carbon accumulation on the surface of the catalyst is caused, and the problems of low activity, poor stability and the like of the catalyst are caused. On the other hand, the high-potassium catalyst, namely the early Fe-K-Ce-Mo/W catalyst or the ethylbenzene dehydrogenation catalyst forming potassium ferrite, is easy to cause loss of K components under a high-temperature reaction system, so that the activity of the catalyst is reduced, the stability is poor, the activity and the stability of the catalyst are reduced to a certain extent along with the reduction of the content of potassium, and particularly, the stability is obviously reduced. Therefore, the method for reducing the potassium content in the catalyst and simultaneously effectively improving the dispersity of potassium by researching the reaction mechanism of the catalyst so that the effect of the cocatalyst K is fully exerted is an important direction of ethylbenzene dehydrogenation catalyst research.
Disclosure of Invention
The invention aims to solve the technical problems of low catalytic activity, especially poor stability of low-potassium catalysts in the prior art. The invention aims to provide a method for preparing an ethylbenzene dehydrogenation catalyst with high activity and stability. The method effectively improves the activity and selectivity of the catalyst after long-period operation by changing the adding mode of the cocatalyst K.
The invention discloses a preparation method of a styrene catalyst prepared by ethylbenzene dehydrogenation, which comprises Fe, K, ce, mo and/or W, mg and/or Ca, and comprises the following steps:
(1) Mixing the iron raw material with part of the dry powder of the Mg and/or Ca raw material to form a mixed material A, wherein the adding amount of the iron raw material of the part of the Mg and/or Ca raw material is 40-70 wt% of the total adding amount of the Mg and/or Ca raw material, the potassium raw material A and water form a solution A, the solution A is added into the mixed material A, the mixed material A is continuously mixed until more than 90wt% of the raw material forms small particles with the particle size of 0.5-1mm, and then the mixture is baked for 4-8 hours at 500-900 ℃ to form a precursor I, and the adding amount of the potassium raw material A is 10-45 wt% of the total adding amount of K;
(2) Grinding or crushing the precursor I, adding all Ce raw materials, mo and/or W raw materials and the rest Mg and/or Ca raw materials, carrying out dry powder mixing to form a mixture B, adding the rest potassium raw materials B into the mixture B to form a paste, granulating, forming, drying, and roasting at 800-900 ℃ for 6-8 hours to obtain the catalyst.
The addition amount of the potassium raw material A is preferably 10-45 wt% of the total addition amount of the potassium raw material, and more preferably 30-45 wt%.
According to the preparation method disclosed by the invention, the Mg, ca and/or potassium and iron raw materials form 0.5-1mm small particles, which means that the mixture phases formed in the continuous stirring and mixing processes of the iron, potassium, magnesium and calcium raw materials are mutually wrapped.
According to the method disclosed by the invention, the solution A in the step (1) is added into the mixed material A, and the mixing is continued, wherein the mixing is carried out so that more than 90wt% of Mg and/or Ca and potassium and the iron raw material form 0.5-1mm small particles, preferably 1-5 hours, and the Mg and/or Ca and potassium and the iron raw material fully form 0.5-1mm small particles, and more preferably 1-1.5 hours.
In the method disclosed by the invention, all the steps (1) are transferred into a high-temperature resistant container and are roasted for 4-8 hours at 500-900 ℃, and the roasting process is carried out by forming potassium ferrate from an iron source and a potassium source, wherein the roasting temperature is preferably 700-900 ℃, so that the potassium source and the iron source fully react to form potassium ferrate, and the roasting temperature is more preferably 750-850 ℃.
The preparation method disclosed by the invention has the advantages that the addition amount of part of the Mg and/or Ca raw materials is 40-70 wt%, preferably 45-55 wt% of the total addition amount of the Mg and/or Ca raw materials.
The raw materials of the preparation method disclosed by the invention are well known in the art. The iron source is iron red or a mixture of iron red and iron yellow, and can be purified before use. The purification is to remove impurities and moisture by calcination. Other components may be added as oxides or precursors of oxides. The precursor of the oxide is metal nitrate, metal carbonate and oxalate; metal nitrates are preferred.
The preparation method disclosed in the invention has the addition amount of the raw materials which is equivalent to the addition amount disclosed in the technology in the field, such as CN 101455968A. The catalyst of the invention takes the mass of the catalyst as a reference, and the addition amount of each raw material is preferably as follows: iron as raw material, fe 2 O 3 66-75wt%; potassium source material of K 2 O is 6-9wt%; ce raw material, ceO 2 7-11 wt%; mo and/or W raw material in MoO 3 And/or WO 3 0.6 to 2 weight percent; and 2-12 wt% of Mg or/and Ca raw material calculated by MgO or/and CaO.
In the preparation method disclosed by the invention, preferably, one or more metal oxides or precursors thereof of light rare earth and Mn, zn, ni, cu except Ce are also added in the process of forming the mixed material B in the step (2). The precursor refers to a substance capable of forming a metal oxide in the post-firing, such as nitrate, oxalate, carbonate, etc. of a metal.
The preparation method disclosed by the invention is that the light rare earth except Ce refers to the light rare earth metal oxide of La, pr and Nd, and the mass of the catalyst is taken as the reference, and La 2 O 3 、Pr 2 O 3 、Nd 2 O 3 The addition amount of the light rare earth oxide other than Ce is preferably 2 to 5%, more preferably 2 to 3%.
The preparation method disclosed by the invention has the advantages that Mn, zn, ni, cu metal oxides are MnO respectively 2 ZnO, niO, cuO, based on the mass of the catalyst, mnO 2 The addition amount is preferably 0.3 to 2%, and more preferably 0.5 to 1%, based on ZnO, niO, cuO.
The preparation method disclosed by the invention can also preferably adopt a method of impregnating or spraying to modify the surface of the catalyst after the catalyst is prepared by roasting in the step (2) to introduce one or more of light rare earth metal oxides or precursors thereof except Ce.
The preparation method disclosed by the invention is that the light rare earth except Ce refers to the light rare earth metal oxides of La, pr and Nd, can be a mixture or a single substance, and the precursor thereof is preferably La (NO 3 ) 3 、Pr(NO 3 ) 3 、Nd(NO 3 ) 3 La (NO) 3 ) 3 。
The preparation method disclosed by the invention comprises the steps of respectively preparing La, pr and Nd light rare earth metal oxides except Ce 2 O 3 、Pr 2 O 3 、Nd 2 O 3 The amount of the additive is 2 to 5wt%, and more preferably 2 to 3wt%.
The preparation method disclosed by the invention comprises the steps that promoter metal oxides such as Mn, zn, ni, cu are MnO respectively 2 ZnO, niO, cuO, the amount of the additive is preferably 0.3 to 2wt%, and the content is more preferably 0.5 to 1wt%.
According to the preparation method disclosed by the invention, the pore-forming agent is added in the preparation process, and the addition mode is preferably as follows: in the process of adding the solution B into the mixture B to form a paste, a pore-forming agent is added. The amount and type of porogen is common knowledge in the art. For example, the amount added is 3 to 6% by weight of the catalyst; the porogen may be selected from graphite, polystyrene fiber spheres (PS), carboxymethyl cellulose (CMC), preferably carboxymethyl cellulose.
The method disclosed by the invention, the step (2) is performed at 800-900 ℃ for 6-8 hours to prepare the catalyst, and the roasting process can be performed by completely decomposing the nitrate, oxalate and carbonate of the metal in the finished catalyst into the corresponding metal oxides, and the roasting temperature is preferably 850-900 ℃.
The dehydrogenation catalyst prepared by the invention can be completely suitable for dehydrogenation of ethylbenzene and derivatives thereof under certain process conditions, wherein the ethylbenzene and derivatives thereof comprise ethylbenzene, diethylbenzene and 1-methyl ethylbenzene to prepare styrene, divinylbenzene and 1-methyl styrene.
The ethylbenzene conversion and styrene selectivity were calculated according to the following formulas:
Figure BDA0002317429670000081
Figure BDA0002317429670000082
the preparation method disclosed by the invention prepares the catalyst by adding the auxiliary agent potassium step by step, on one hand, the interaction between K atoms and Fe atoms can be effectively promoted, and the potassium ferrate K with a stable structure is formed 2 Fe 10 O 16 . On the other hand, the invention solves the problem of Fe in the traditional dry mixing process by adding the auxiliary agent potassium in the form of salt solution 2 O 3 And K is equal to 2 The density difference of O causes the problem of uneven mixing, so that active components are uniformly distributed between the surface of the catalyst and the bulk phase of the catalyst, the problem of carbon deposition deactivation of the catalyst in the catalyst under a high-temperature reaction system is restrained, and the stability of long-period operation of the catalyst is improved; meanwhile, the invention effectively solves the problem of low catalyst activity caused by potassium loss in the later reaction period of the catalyst, and inhibits excessive carbon deposition on the surface of the catalyst, thereby reducing side reaction and improving the activity and selectivity of the catalyst in a high-temperature system. The ethylbenzene dehydrogenation catalyst prepared by the invention is prepared by a 4L heat insulation negative pressure evaluation device at a primary reverse inlet 615 ℃, a secondary reverse inlet 620 ℃, a water ratio of 1.5 and a liquid space velocity of 0.42h -1 Under the conditions of 40KPa of the secondary outlet pressure, the activity of the catalyst is obviously improved, the ethylbenzene conversion rate at the initial stage of the catalytic reaction is more than or equal to 68%, the styrene selectivity is more than or equal to 97%, the ethylbenzene conversion rate of ethylbenzene which is continuously operated for more than 1000 hours (the operation is over 500 hours for a long period) on a side line device is more than or equal to 67.8%, the styrene selectivity is more than or equal to 97%, the deactivation rate is obviously reduced, and a good technical effect is obtained.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The raw material sources are as follows:
ethylbenzene, produced by China Petroleum and Lanzhou petrochemical company, has industrial grade and purity of not less than 99%;
iron oxide red, shandong Zichuan strong pigment factory, pigment grade;
potassium carbonate, industrial superior, chemical industry limited, jiande, zhejiang;
cerium oxalate, shanghai Funa rare earth materials, inc., industrial superior;
ammonium molybdate, zhejiang Qingqing Tian Jian petrochemical Co., ltd., industrial superior;
light magnesia, dunhuang chemical plant in Shanghai, chemical purity;
calcium oxide, shanghai voxiancheng reagent factory, analytically pure;
sodium carboxymethylcellulose, shanghai long-distance optical enterprises development Co., ltd, IH9-1;
zinc oxide, manganese dioxide, nickel oxide, lanthanum oxide were all purchased from the Tianjin chemical reagent company, miou chemical Co., ltd.
Evaluation method
The ethylbenzene dehydrogenation catalyst prepared by the method of the invention is subjected to activity stability evaluation in a 4L adiabatic negative pressure side device, and the reaction process is as follows: the primary inlet temperature is 615 ℃, the secondary inlet temperature is 620 ℃, the water ratio (the mass ratio of water vapor to ethylbenzene) is 1.5, and the ethylbenzene liquid space velocity is 0.42h -1 The two-way outlet pressure was 40KPa (absolute), and the process was briefly described as follows: the 4L heat-insulating negative pressure side line device comprises 2 sections of reactors, each reactor is filled with 2L of catalyst, the heat-insulating layer is externally divided into three sections and heated by heating wires, so that the temperature of the heat-insulating layer is close to the temperature of the reactor bed layer to ensure the heat-insulating effect, heating iron blocks are arranged at the upper part and the lower part of the reactor, and the iron blocks play roles in regulating the temperature of reaction raw materials and preventing the axial heat lossIs effective in (1). A mixer is arranged in front of the inlet of the first stage reactor to ensure that two feeds of water and ethylbenzene can be fully mixed before reaction, so as to meet the reaction requirement. The first reactor outlet and the second reactor outlet are respectively provided with a sampler, and the liquid of the two samplers is taken every 8 hours and sent to a gas chromatograph for analysis. The composition of the reaction product was analyzed by means of a Shimadzu GC-14C gas chromatograph (by means of a calibrated area normalization method).
Example 1
335g of iron oxide red, 66.06g of potassium carbonate, 79g of cerium oxalate, 20g of ammonium molybdate, 30g of magnesium oxide, 30g of calcium oxide and 25g of carboxymethyl cellulose are respectively weighed, and the preparation steps of the catalyst are as follows: firstly roasting 335g of iron oxide red at 750 ℃ for 4 hours, secondly adding 6.6g of potassium carbonate into deionized water to form 70ml of potassium carbonate aqueous solution A, finally adding 335g of iron oxide red, 15g of magnesium oxide and 15g of calcium oxide into the prepared potassium carbonate aqueous solution A after dry mixing for 1 hour, completely transferring the mixture into a high-temperature resistant container after Mg, ca and potassium form 0.5-1mm small particles with more than 90% of iron raw materials, and roasting the mixture at 750 ℃ for 4 hours to obtain a precursor I; adding the rest potassium raw material into deionized water to form 85mL of potassium carbonate aqueous solution B, grinding the precursor I to 80 meshes, adding the rest magnesium oxide, calcium oxide, cerium oxalate, ammonium molybdate and carboxymethyl cellulose, dry-mixing for 0.5h, adding 85mL of potassium carbonate aqueous solution B, kneading into a paste which is sticky and suitable for extrusion, extruding and granulating into particles with the diameter of about 3 mm and the length of 6-8 mm, drying at 120 ℃ for 4 hours, and roasting at 850 ℃ for 4 hours to obtain a catalyst finished product.
Example 2
Respectively weighing 350g of iron oxide red, 44g of potassium carbonate, 63.2g of cerium oxalate, 10g of ammonium molybdate, 25g of magnesium oxide, 25g of calcium oxide, 66g of lanthanum nitrate and 28g of carboxymethyl cellulose, wherein the preparation steps of the catalyst are as follows: firstly roasting 350g of iron oxide red at 750 ℃ for 4 hours, secondly adding 17.6g of potassium carbonate into deionized water to form 75ml of potassium carbonate aqueous solution A, finally dry-mixing 350g of iron oxide red, 10g of magnesium oxide and 10g of calcium oxide for 1 hour, adding the prepared potassium carbonate aqueous solution A, completely transferring the mixture into a high-temperature resistant container after Mg, ca and more than 90% of potassium and iron raw materials form small particles with the size of 0.5-1mm, and roasting the mixture at 730 ℃ for 4 hours to obtain a precursor I; adding the rest potassium raw material into deionized water to form 90mL of potassium carbonate aqueous solution B, grinding the precursor I to 80 meshes, adding the rest magnesium oxide, calcium oxide, cerium oxalate, ammonium molybdate and carboxymethyl cellulose, dry-mixing for 0.5h, adding 90mL of potassium carbonate aqueous solution B, kneading into a paste which is sticky and suitable for extrusion, extruding and granulating into particles with the diameter of about 3 mm and the length of 6-8 mm, drying at 120 ℃ for 4 hours, and roasting at 900 ℃ for 4 hours to obtain a precursor II; preparing lanthanum nitrate into 100mL solution, uniformly spraying the solution on the surface of a precursor II by adopting a spraying method, and then drying at 100 ℃ for 4 hours and roasting at 750 ℃ for 4 hours to obtain a catalyst finished product.
Example 3
375g of iron oxide red, 58.7g of potassium carbonate, 55g of cerium oxalate, 6g of ammonium molybdate, 17g of magnesium oxide, 20g of calcium oxide, 10.0g of zinc oxide and 30g of carboxymethyl cellulose are respectively weighed, and the preparation steps of the catalyst are as follows: firstly, 375g of iron oxide red is roasted for 4 hours at 700 ℃, secondly, 17.6g of potassium carbonate is added into deionized water to form 75ml of potassium carbonate aqueous solution A, finally 375g of iron oxide red, 10.2g of magnesium oxide and 12g of calcium oxide are dry-mixed for 1 hour, then the prepared potassium carbonate aqueous solution A is added, after more than 90% of Mg, ca and potassium and iron raw materials form small particles with the size of 0.5-1mm, all the small particles are transferred into a high-temperature resistant container, and roasting is carried out for 4 hours at 780 ℃ to obtain a precursor I; adding the rest potassium raw material into deionized water to form 80mL of potassium carbonate aqueous solution B, grinding the precursor I to 80 meshes, adding the rest magnesium oxide, calcium oxide, cerium oxalate, ammonium molybdate, zinc oxide and carboxymethyl cellulose, dry-mixing for 0.5h, adding 80mL of potassium carbonate aqueous solution B, kneading into a sticky paste suitable for extrusion, extruding and granulating into granules with the diameter of about 3 mm and the length of 6-8 mm, drying at 120 ℃ for 4 hours, and roasting at 850 ℃ for 4 hours to obtain a catalyst finished product.
Example 4
355g of iron oxide red, 51.4g of potassium carbonate, 71.6g of cerium oxalate, 11g of ammonium molybdate, 30g of magnesium oxide, 25.0g of calcium oxide, 5g of manganese dioxide and 27g of carboxymethyl cellulose are respectively weighed, and the preparation steps of the catalyst are as follows: firstly, 355g of iron oxide red is roasted for 4 hours at 750 ℃, secondly, 10.3g of potassium carbonate is added into deionized water to form 75ml of potassium carbonate aqueous solution A, finally, 355g of iron oxide red, 13.5g of magnesium oxide and 11.25g of calcium oxide are dry-mixed for 1 hour, then, the prepared potassium carbonate aqueous solution A is added, after more than 90% of Mg, ca and potassium and iron raw materials form small particles with the particle size of 0.5-1mm, all the small particles are transferred into a high-temperature resistant container, and roasting is carried out for 4 hours at 780 ℃ to obtain a precursor I; adding the rest potassium raw material into deionized water to form 90mL of potassium carbonate aqueous solution B, grinding the precursor I to 80 meshes, adding the rest magnesium oxide, calcium oxide, cerium oxalate, manganese dioxide, ammonium molybdate and carboxymethyl cellulose, dry-mixing for 0.5h, adding 90mL of potassium carbonate aqueous solution B, kneading into a paste which is sticky and suitable for extrusion, extruding, granulating into particles with the diameter of about 3 mm and the length of 6-8 mm, drying at 120 ℃ for 4 hours, and roasting at 850 ℃ for 4 hours to obtain a catalyst finished product.
Example 5
345g of iron oxide red, 66.06g of potassium carbonate, 71.6g of cerium oxalate, 15g of ammonium molybdate, 27.5g of calcium oxide, 12.5g of magnesium oxide, 59.4g of lanthanum nitrate and 29g of carboxymethyl cellulose are respectively weighed, and the preparation steps of the catalyst are as follows: firstly roasting 345g of iron oxide red at 750 ℃ for 4 hours, secondly adding 16.51g of potassium carbonate into deionized water to form 80ml of potassium carbonate aqueous solution A, finally dry-mixing 345g of iron oxide red, 8.75g of magnesium oxide and 19.25g of calcium oxide for 1 hour, then adding the prepared potassium carbonate aqueous solution A, completely transferring the mixture into a high-temperature resistant container after more than 90% of Mg, ca and potassium and iron raw materials form small particles with the particle size of 0.5-1mm, and roasting the mixture at 730 ℃ for 4 hours to obtain a precursor I; adding the rest potassium raw material into deionized water to form 90mL of potassium carbonate aqueous solution B, grinding the precursor I to 80 meshes, adding the rest calcium oxide, magnesium oxide, cerium oxalate, ammonium molybdate and carboxymethyl cellulose, dry-mixing for 0.5h, adding 90mL of potassium carbonate aqueous solution B, kneading into a paste which is sticky and suitable for extrusion, extruding and granulating into particles with the diameter of about 3 mm and the length of 6-8 mm, drying at 120 ℃ for 4 hours, and roasting at 850 ℃ for 4 hours to obtain a precursor II; preparing lanthanum nitrate into 100mL solution, uniformly spraying the solution on the surface of a precursor II by adopting a spraying method, and then drying at 100 ℃ for 4 hours and roasting at 750 ℃ for 4 hours to obtain a catalyst finished product.
Example 6
340g of iron oxide red, 62.4g of potassium carbonate, 75.6g of cerium oxalate, 20g of ammonium molybdate, 22.5g of magnesium oxide, 27.5g of calcium oxide, 10.0g of nickel oxide and 30g of carboxymethyl cellulose are respectively weighed, and the preparation steps of the catalyst are as follows: firstly, roasting 340g of iron oxide red at 750 ℃ for 4 hours, secondly, adding 21.8g of potassium carbonate into deionized water to form 85ml of potassium carbonate aqueous solution A, finally, dry-mixing 340g of iron oxide red, 12.4g of magnesium oxide and 15g of calcium oxide for 1 hour, then adding the prepared potassium carbonate aqueous solution A, completely transferring the mixture into a high-temperature resistant container after more than 90% of Mg, ca and potassium and iron raw materials form small particles with the particle size of 0.5-1mm, and roasting the mixture at 730 ℃ for 4 hours to obtain a precursor I; adding the rest potassium raw material into deionized water to form 90mL of potassium carbonate aqueous solution B, grinding the precursor I to 80 meshes, adding the rest magnesium oxide, calcium oxide, cerium oxalate, nickel oxide, ammonium molybdate and carboxymethyl cellulose, dry-mixing for 0.5h, adding 90mL of potassium carbonate aqueous solution B, kneading into a sticky paste suitable for extrusion, extruding and granulating into granules with the diameter of about 3 mm and the length of 6-8 mm, drying at 120 ℃ for 4 hours, and roasting at 850 ℃ for 4 hours to obtain a catalyst finished product.
Example 7
346g of iron oxide red, 55g of potassium carbonate, 87g of cerium oxalate, 10g of ammonium molybdate, 20g of calcium oxide, 27.5g of magnesium oxide, 3.0g of zinc oxide, 3.0g of manganese dioxide, 3.0g of nickel oxide and 28g of carboxymethyl cellulose are respectively weighed, and the preparation steps of the catalyst are as follows: firstly, roasting 346g of iron oxide red at 750 ℃ for 4 hours, secondly, adding 8.25g of potassium carbonate into deionized water to form 82ml of potassium carbonate aqueous solution A, finally, dry-mixing 346g of iron oxide red, 13g of calcium oxide and 17.8g of magnesium oxide for 1 hour, then adding the prepared potassium carbonate aqueous solution A, completely transferring the mixture into a high-temperature resistant container after more than 90% of Mg, ca and potassium and iron raw materials form small particles of 0.5-1mm, and roasting the mixture at 750 ℃ for 4 hours to obtain a precursor I; adding the rest potassium raw materials into deionized water to form 95mL of potassium carbonate aqueous solution B, grinding the precursor I to 80 meshes, adding the rest magnesium oxide, calcium oxide, cerium oxalate, zinc oxide, manganese dioxide, nickel oxide, ammonium molybdate and carboxymethyl cellulose, dry-mixing for 0.5h, adding 95mL of potassium carbonate aqueous solution B, kneading into a sticky paste suitable for extrusion, extruding and granulating into granules with the diameter of about 3 mm and the length of 6-8 mm, drying at 120 ℃ for 4 hours, and roasting at 900 ℃ for 4 hours to obtain a catalyst finished product.
Comparative example 1
335g of iron oxide red, 6.60g of potassium carbonate, 79g of cerium oxalate, 20g of ammonium molybdate, 30g of calcium oxide, 30g of magnesium oxide and 25g of carboxymethyl cellulose are weighed, and the preparation steps of the catalyst are as follows: firstly roasting 335g of iron oxide red at 750 ℃ for 4 hours, secondly stirring the weighed raw materials in a kneader for 1 hour, adding 85ml of deionized water, stirring for half an hour, extruding, granulating into particles with the diameter of about 3 mm and the length of 5-10 mm, putting into a baking oven, baking at 80 ℃ for 4 hours, putting into a muffle furnace, roasting at 750 ℃ for 4 hours to obtain a catalyst precursor, dissolving 59.46g of potassium carbonate into 70ml of water, soaking the solution on the catalyst precursor at room temperature, drying at 100 ℃ for 5 hours after 2 hours, and roasting at 850 ℃ for 4 hours to obtain a catalyst finished product.
Comparative example 2
375g of iron oxide red, 29.4g of potassium carbonate, 55g of cerium oxalate, 6g of ammonium molybdate, 17g of magnesium oxide, 20g of calcium oxide, 10g of zinc oxide and 30g of carboxymethyl cellulose are stirred in a kneader for 1 hour, 90ml of deionized water is added, and the mixture is stirred for half an hour, extruded and pelletized into particles with the diameter of about 3 mm and the length of 5 to 6 mm, and then the particles are put in an oven, dried for 2 hours at 50 ℃, dried for 10 hours at 100 ℃, then put in a muffle furnace and baked for 4 hours at 780 ℃ to obtain a catalyst precursor. 29.4g of potassium carbonate is dissolved in 55.0ml of water, the solution is immersed on the catalyst precursor under the condition of room temperature, and the catalyst is baked for 12 hours at 80 ℃, and then baked for 4 hours at 850 ℃ to obtain the finished catalyst.
Comparative example 3
Respectively weighing 355g of iron oxide red, 51.4g of potassium carbonate and 5g of manganese dioxide, dry-mixing for 1 hour, roasting at 600 ℃ for 2 hours, adding 71.6g of cerium oxalate, 11g of ammonium molybdate, 30g of magnesium oxide, 25g of calcium oxide and 27g of carboxymethyl cellulose into the roasted product, mixing the dry powder for 2 hours, adding 130mL of deionized water, kneading for about 1 hour, forming a dough suitable for extruding, extruding and granulating into granules with the diameter of about 3 mm and the length of 6-8 mm; aging at room temperature for 12h, drying at 120 ℃ for 4h, and roasting in a muffle furnace at a high temperature of 780 ℃ for 6 h to obtain a catalyst precursor; preparing a mixed solution which consists of 10g of lanthanum nitrate and has the same volume as the catalyst precursor, loading the mixed salt solution on the catalyst precursor by adopting an equal volume impregnation method, and drying at 120 ℃ for 6 hours and roasting at 850 ℃ for 4 hours to prepare a catalyst finished product.
Comparative example 4
335g of iron oxide red, 60.06g of potassium carbonate, 79g of cerium oxalate, 20g of ammonium molybdate, 30g of magnesium oxide, 30g of calcium oxide and 25g of carboxymethyl cellulose are respectively weighed, and the preparation steps of the catalyst are as follows: firstly roasting 335g of iron oxide red at 750 ℃ for 4 hours, secondly dry-mixing 335g of iron oxide red, 6.6g of potassium carbonate, 15g of magnesium oxide and 15g of calcium oxide for about 1 hour, fully mixing Mg, ca and potassium with iron raw materials, then fully transferring the mixture into a high-temperature resistant container, and roasting at 750 ℃ for 4 hours to obtain a precursor I; grinding the precursor I to 80 meshes, adding the rest potassium carbonate, magnesium oxide, calcium oxide, cerium oxalate, ammonium molybdate and carboxymethyl cellulose, dry-mixing for 0.5h, adding 85mL of deionized water, kneading into paste which is sticky and suitable for extrusion, extruding, granulating into particles with the diameter of about 3 mm and the length of 6-8 mm, drying at 120 ℃ for 4 hours, and roasting at 850 ℃ for 4 hours to obtain a catalyst finished product.
Comparative example 5
The catalyst composition was the same as in example 7, and the preparation method was dry-blending. After 346g of iron oxide red is roasted for 4 hours at 700 ℃, 55g of potassium carbonate, 87g of cerium oxalate, 10g of ammonium molybdate, 27.5g of magnesium oxide, 20g of calcium oxide, 3.0g of zinc oxide, 3.0g of manganese dioxide, 3.0g of nickel oxide and 28g of carboxymethyl cellulose are respectively added, after mixing for 2 hours, 130mL of deionized water is added, kneading is carried out for about 1 hour, a dough suitable for extrusion is formed, and the extrusion and the pelletization are carried out, so that the granules with the diameter of about 3 mm and the length of 6-8 mm are formed; aging at room temperature for 12h, drying at 120 ℃ for 4h, and roasting in a muffle furnace at high temperature of 900 ℃ for 6 h to obtain the catalyst finished product.
Catalyst physical property detection items include bulk density and radial crush resistance; the catalyst performance evaluations of the comparative examples and examples were carried out on a 4L adiabatic negative pressure evaluation apparatus. The physical property data of the catalyst are shown in table 1, the initial activity evaluation result (48 h evaluation result) of the catalyst is shown in table 2, and the 1000h stability evaluation result of the catalyst is shown in table 3.
Table 1 lists the bulk density and radial crush resistance test data for the catalysts prepared in the comparative examples and examples. As can be seen from Table 1, the bulk density and radial crush resistance of the catalyst were both significantly improved by the two-stage method of preparing precursor I, II by adding the auxiliary potassium in the form of a salt solution.
TABLE 1 comparison of bulk Density with radial crushing force data
Figure BDA0002317429670000161
Figure BDA0002317429670000171
TABLE 2 evaluation results of initial Activity of catalysts
Figure BDA0002317429670000172
TABLE 3 evaluation results of catalyst stability
Figure BDA0002317429670000173
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Figure BDA0002317429670000181
The results of the activity and stability investigation of the catalysts prepared in the comparative examples and the examples are shown in tables 2 and 3, respectively, and it can be seen from the tables that the catalyst has the activity of above 68.0% and the catalyst has high activity under the normal water ratio working condition by the method of adding auxiliary potassium step by step in the form of salt solution; after 1000 hours of reaction, the ethylbenzene conversion rate is basically unchanged, and is still kept at about 68%, the catalyst deactivation rate is low, and the stability is good. The catalysts prepared in comparative examples 1 to 5 were poor in activity, and after 1000 hours of reaction, the activity was significantly reduced and the stability was poor.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.

Claims (13)

1. A method for preparing a styrene catalyst by ethylbenzene dehydrogenation, which comprises Fe, K, ce, mo and/or W and Mg and/or Ca, characterized in that the method comprises the following steps:
(1) Mixing the iron raw material with part of dry powder of the Mg and/or Ca raw material to form a mixed material A, wherein the adding amount of the part of the Mg and/or Ca raw material is 40-70 wt% of the total adding amount of the Mg and/or Ca raw material, the potassium raw material A and water form a solution A, the solution A is added into the mixed material A, and after 90-wt% of the solution A forms small particles with the size of 0.5-1mm, the solution A is continuously mixed and baked for 4-8 hours at 500-900 ℃ to form a precursor I, and the adding amount of the potassium raw material A is 10-45-wt% of the total adding amount of the potassium raw material;
(2) Grinding or crushing the precursor I, adding all Ce raw materials, mo and/or W raw materials and the rest Mg and/or Ca raw materials, carrying out dry powder mixing to form a mixture B, adding the rest potassium raw materials B into the mixture B to form a paste, granulating, forming, drying, and roasting at 800-900 ℃ for 6-8 hours to obtain the catalyst.
2. The process according to claim 1, wherein the calcination temperature in step (1) is 700 to 900 ℃.
3. The preparation method according to claim 1, wherein the addition amount of the potassium raw material A is 30-45 wt% of the total addition amount of the potassium raw material.
4. The method of claim 1, wherein in step (1), the solution a is added to the mixture a for a mixing time of 1 to 5 hours.
5. The method of claim 1, wherein in step (1), the solution a is added to the mixture a for a mixing time of 1 to 1.5 hours.
6. The process according to any one of claims 1 to 5, wherein the amount of the Mg and/or Ca raw material added is 45 to 55% wt% of the total amount of Mg and/or Ca raw material added.
7. The method according to any one of claims 1 to 5, wherein the catalyst comprises the following components in the following amounts based on the mass of the catalyst: iron as raw material, fe 2 O 3 66-75 wt%; potassium source material of K 2 O meter, 6-9 wt%; ce raw material, ceO 2 7-11 wt%; mo and/or W raw material in MoO 3 And/or WO 3 0.6 to 2 percent wt percent; mg or/and Ca raw material, calculated by MgO or/and CaO, 2-12 wt%.
8. The method according to any one of claims 1 to 5, wherein a metal oxide of one or more of light rare earth other than Ce, mn, zn, ni, or a precursor thereof is further added during the formation of the mixture B in step (2).
9. The preparation method according to claim 8, wherein the addition amount of the light rare earth other than Ce is 2 to 5% based on the mass of the metal oxide of the corresponding light rare earth; mn, zn and Ni metals are added in an amount of 0.3-2% based on the mass of the metal oxide.
10. The process according to any one of claims 1 to 5, wherein after the catalyst is prepared by calcination in step (2), one or more of light rare earth metal oxides other than Ce or precursors thereof are introduced into the surface of the catalyst by dipping or spraying.
11. The preparation method according to claim 10, wherein the addition amount of the light rare earth other than Ce is 2 to 5% based on the mass of the metal oxide of the light rare earth.
12. The preparation method according to claim 11, wherein the addition amount of the light rare earth other than Ce is 2 to 3% based on the mass of the metal oxide of the light rare earth.
13. The method of any one of claims 1 to 5, wherein in step (2), a porogen is added during the addition of solution B to blend B to form a paste.
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