CN111054362A - Catalyst for producing divinylbenzene and preparation method thereof - Google Patents

Catalyst for producing divinylbenzene and preparation method thereof Download PDF

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CN111054362A
CN111054362A CN201811201445.0A CN201811201445A CN111054362A CN 111054362 A CN111054362 A CN 111054362A CN 201811201445 A CN201811201445 A CN 201811201445A CN 111054362 A CN111054362 A CN 111054362A
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catalyst
parts
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divinylbenzene
particles
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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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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8474—Niobium
    • 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
    • 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
    • C07C2523/847—Vanadium, niobium or tantalum
    • 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

Abstract

The invention relates to a catalyst for producing divinylbenzene and a preparation method thereof, and mainly solves the problem of poor stability of the catalyst divinylbenzene in the prior art. The invention adopts a diethylbenzene dehydrogenation catalyst, which comprises the following components in percentage by weight: (a) 66-80% Fe2O3(ii) a (b)6 to 16% of K2O; (c) 6-14% of CeO2(ii) a (d)0.5 to 5% of MgO; (e)0.5 to 4% of Nb2O5(ii) a (f) Selected from SnO2、PbO2Or GeO2The content of at least one or more than one of the above technical scheme is 0.1-5%, the technical problem is well solved, the stability of the catalyst divinylbenzene can be effectively improved when the catalyst is used for preparing divinylbenzene by diethylbenzene dehydrogenation, and the catalyst can be used for preparing divinylbenzene by the diethylbenzene dehydrogenationIn industrial production.

Description

Catalyst for producing divinylbenzene and preparation method thereof
Technical Field
The invention relates to a catalyst for producing divinylbenzene and a preparation method thereof.
Background
Divinylbenzene is a very useful crosslinking agent and is widely used in ion exchange resins, ion exchange membranes, ABS resins, polystyrene resins, unsaturated polyester resins, synthetic rubbers, special plastics, coatings, adhesives and other fields.
There are many methods for preparing divinylbenzene, but the most suitable method for industrial production is by dehydrogenation of diethylbenzene over a catalyst. For the chemical catalytic process of preparing divinylbenzene by dehydrogenating diethylbenzene, the catalyst plays a critical role, and the economic efficiency of the dehydrogenation process is determined by the quality of the catalyst. The diethylbenzene dehydrogenation catalyst is similar to an ethylbenzene dehydrogenation catalyst system, and a zinc-series catalyst and a magnesium-series catalyst used in the initial stage are quickly replaced by an iron-series catalyst with good comprehensive performance. The early catalyst is an Fe-K-Cr system, and although the catalyst has good activity and stability, the catalyst contains Cr oxide, so that the catalyst causes certain pollution to the environment and is gradually eliminated. Then, the catalyst is developed into Fe-K-Ce-Mo series, and Ce is used for replacing Cr, so that the activity and the stability of the catalyst can be better improved, and the defects of high toxicity and environmental pollution of Cr are overcome. As disclosed in U.S. patent 3360579 and british patent 1100088, although the catalyst has good activity and stability, the catalyst contains Cr oxide, which causes environmental pollution. The diethylbenzene molecule is larger than the ethylbenzene molecule, so that the ethylbenzene dehydrogenation catalyst is not suitable for the diethylbenzene dehydrogenation reaction simply, and the stability of the divinylbenzene is lower when the conventional catalyst is used for the diethylbenzene dehydrogenation reaction. For this reason, the search for suitable catalysts to improve the stability of divinylbenzene is a goal of the researchers' efforts.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a new catalyst for producing divinylbenzene, which is a problem of poor divinylbenzene stability existing in the prior art. When the catalyst is used for producing divinylbenzene, the divinylbenzene has the characteristic of good stability.
The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst for producing divinylbenzene corresponding to the first technical problem.
The present invention is also directed to a method for producing a divinylbenzene catalyst, which is used to solve one of the above problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a catalyst for the production of divinylbenzene comprising the following composition in weight percent:
(a) 66-80% Fe2O3；
(b)6 to 16% of K2O；
(c) 6-14% of CeO2；
(d)0.5 to 5% of MgO;
(e)0.5 to 4% of Nb2O5；
(f) Selected from SnO2、PbO2Or GeO2At least one or more of (a), the content of which is 0.1-5%.
In the above technical solution, the Nb2O5The source of (A) is selected from niobic acid or niobium hydroxide; the Nb2O5The content is preferably 1-2.5%; the content of the component (f) is preferably 0.5-2.5%.
In the technical scheme, in the aspect of improving the stability of the divinylbenzene, Nb is contained in the auxiliary agent2O5And (f) component, such as but not limited to Nb and Sn.
In the above technical solution, the component (f) preferably comprises SnO at the same time2And PbO2Or SnO2And GeO2Or PbO2And GeO2The two oxides have a binary synergistic effect in improving the stability of divinylbenzene.
To solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the catalyst in the technical scheme of one of the technical problems comprises the following steps: the catalyst for producing divinyl benzene is prepared by uniformly mixing the components with required amount and the pore-forming agent in percentage by weight, adding water to prepare a sticky dough-like substance suitable for extrusion, extruding, forming, drying and roasting.
The amount of water added is not particularly limited, and one skilled in the art can reasonably control the dry humidity for extrusion, for example, but not limited to, the amount of water added is 18-30% of the total weight of the catalyst raw material.
In the above technical scheme, Fe2O3Adding the iron oxide red and the iron oxide yellow; the K is added in the form of potassium carbonate or hydroxide; the Ce used is added in the form of its salt or hydroxide; the Mg is added in the form of oxide, salt or hydroxide; nb is added in the form of niobic acid or hydroxide thereof; the rest of the elements are added in the form of salts or oxides thereof; in the preparation process of the invention, besides the main components of the catalyst, a pore-forming agent is added, wherein the pore-forming agent is selected from graphite, sesbania powder, polystyrene microspheres and sodium carboxymethylcellulose, and the addition amount of the pore-forming agent is 2.5-5.5% of the total weight of the catalyst.
In the technical scheme, the roasting temperature is 120-380 ℃ for 3-10 hours, and then the roasting temperature is 650-900 ℃ for 3-10 hours; the drying temperature is 30-120 ℃; the drying time is 4-16 hours.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the application of the catalyst for producing divinylbenzene in preparing divinylbenzene by dehydrogenating diethylbenzene.
The above-mentioned applications are not particularly limited, and can be utilized according to the existing process conditions. The activity evaluation of the prepared catalyst in an isothermal fixed bed is used for the activity evaluation of the catalyst for producing divinylbenzene, and the process is briefly described as follows:
the reaction raw materials are respectively input into a preheating mixer through a metering pump, preheated and mixed into a gas state, and then the gas state enters a reactor, and the reactor is heated by adopting an electric heating wire to reach a preset temperature. The reactor was a 1 "internal diameter stainless steel tube filled with 100 ml of catalyst. The composition of the reactants exiting the reactor was analyzed by gas chromatography after condensation of water.
The conversion rate and activity reduction rate of diethylbenzene are calculated according to the following formulas:
Figure BDA0001830100680000031
Figure BDA0001830100680000032
the greater the rate of activity decrease, the more unstable the catalyst and vice versa. When this value is negative, it indicates that the activity does not decrease or increase inversely, this is a more favorable result.
The invention adds a proper amount of Nb into an iron-potassium-cerium-magnesium catalytic system2O5And is selected from SnO2、PbO2Or GeO2The prepared catalyst has the characteristic of good stability when used for producing divinyl benzene, can stably run for 450 hours under the conditions of the temperature of 630 ℃ and the water ratio of 2.5, and achieves better technical effect.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Will correspond to 46.79 parts of Fe2O3Iron oxide red of (1), corresponding to 24.49 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.06 parts of K2Potassium carbonate of O, corresponding to 10.28 parts of CeO2Cerium oxalate, 1.50 parts of MgO, corresponding to 2.50 parts of Nb2O5Niobium hydroxide, 1.38 parts SnO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, and then the particles are placed into a muffle furnace and baked for 6 hours at the temperature of 250 ℃ and then baked for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1At 630 ℃ and a water ratio (by weight) of 2.5The activity was evaluated, and the evaluation results are shown in Table 2.
[ COMPARATIVE EXAMPLE 1 ]
Except that no Nb is added2O5And SnO2In addition, the catalyst preparation method and the catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 48.68 parts of Fe2O3Iron oxide red of (5), corresponding to 25.48 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.59 parts of K2Potassium carbonate of O, corresponding to 10.69 parts of CeO2Stirring cerium oxalate, 1.56 parts of MgO and 5.8 parts of graphite in a kneader for 1.5 hours, adding deionized water accounting for 25.3 percent of the total weight of the catalyst raw materials, stirring for 0.8 hour, taking out extruded strips, extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, drying for 1.5 hours at 50 ℃, drying for 12 hours at 95 ℃, then putting the particles into a muffle furnace, roasting for 6 hours at 250 ℃, and then roasting for 5 hours at 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ COMPARATIVE EXAMPLE 2 ]
Except that no Nb is added2O5In addition, the catalyst preparation method and the catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 47.99 parts of Fe2O3Iron oxide red of (5), corresponding to 25.12 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.39 parts of K2Potassium carbonate of O, corresponding to 10.54 parts of CeO2Cerium oxalate, 1.54 parts of MgO, 1.42 parts of SnO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, and then the particles are placed into a muffle furnace and baked for 6 hours at the temperature of 250 ℃ and then baked for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst was chargedThe reactor is used for reacting at normal pressure and the space velocity of the diethylbenzene liquid volume of 1.0 hour－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ COMPARATIVE EXAMPLE 3 ]
Except for using MoO3Replacing Nb2O5And SnO2In addition, the catalyst preparation method and the catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 46.79 parts of Fe2O3Iron oxide red of (1), corresponding to 24.49 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.06 parts of K2Potassium carbonate of O, corresponding to 10.28 parts of CeO2Cerium oxalate, 1.50 parts MgO, equivalent to 3.88 parts MoO3Stirring ammonium molybdate and 5.8 parts of graphite in a kneader for 1.5 hours, adding deionized water accounting for 25.3 percent of the total weight of the catalyst raw materials, stirring for 0.8 hour, taking out an extruded strip, extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, baking for 1.5 hours at 50 ℃, baking for 12 hours at 95 ℃, then putting the particles into a muffle furnace, baking for 6 hours at 250 ℃, and then baking for 5 hours at 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 2 ]
Except for using PbO2Replacement SnO2In addition, the catalyst preparation method and the catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 46.79 parts of Fe2O3Iron oxide red of (1), corresponding to 24.49 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.06 parts of K2Potassium carbonate of O, corresponding to 10.28 parts of CeO2Cerium oxalate, 1.50 parts of MgO, corresponding to 2.50 parts of Nb2O5Niobium hydroxide, 1.38 parts of PbO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the catalyst raw materials is added, stirred for 0.8 hour, taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters,putting the mixture into an oven, baking the mixture for 1.5 hours at the temperature of 50 ℃, baking the mixture for 12 hours at the temperature of 95 ℃, then putting the mixture into a muffle furnace, baking the mixture for 6 hours at the temperature of 250 ℃, and then baking the mixture for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 3 ]
Except using GeO2Replacement SnO2In addition, the catalyst preparation method and the catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 46.79 parts of Fe2O3Iron oxide red of (1), corresponding to 24.49 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.06 parts of K2Potassium carbonate of O, corresponding to 10.28 parts of CeO2Cerium oxalate, 1.50 parts of MgO, corresponding to 2.50 parts of Nb2O5Niobium hydroxide, 1.38 parts of GeO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, and then the particles are placed into a muffle furnace and baked for 6 hours at the temperature of 250 ℃ and then baked for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 4 ]
A catalyst was prepared and the catalyst was evaluated as in example 1, except that 0.69 parts of SnO was used2And 0.69 part of PbO2Replacement of 1.38 parts SnO2. The method specifically comprises the following steps:
will correspond to 46.79 parts of Fe2O3Iron oxide red of (1), corresponding to 24.49 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.06 parts of K2Potassium carbonate of O, corresponding to 10.28 parts of CeO2Cerium oxalate, 1.50 parts of MgO, corresponding to 2.50 parts of Nb2O50.69 part of SnO20.69 part of PbO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, and then the particles are placed into a muffle furnace and baked for 6 hours at the temperature of 250 ℃ and then baked for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 5 ]
A catalyst was prepared and the catalyst was evaluated as in example 1, except that 0.69 parts of SnO was used2And 0.69 parts of GeO2Replacement of 1.38 parts SnO2. The method specifically comprises the following steps:
will correspond to 46.79 parts of Fe2O3Iron oxide red of (1), corresponding to 24.49 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.06 parts of K2Potassium carbonate of O, corresponding to 10.28 parts of CeO2Cerium oxalate, 1.50 parts of MgO, corresponding to 2.50 parts of Nb2O50.69 part of SnO20.69 parts of GeO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, and then the particles are placed into a muffle furnace and baked for 6 hours at the temperature of 250 ℃ and then baked for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 6 ]
A catalyst was prepared and evaluated by the same procedures as in example 1, except that 0.69 parts of PbO was used2And 0.69 parts of GeO2Replacement of 1.38 parts SnO2. The method specifically comprises the following steps:
will correspond to 46.79 parts of Fe2O3Iron oxide red of (1), corresponding to 24.49 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.06 parts of K2Potassium carbonate of O, corresponding to 10.28 parts of CeO2Cerium oxalate, 1.50 parts of MgO, corresponding to 2.50 parts of Nb2O5Niobium hydroxide, 0.69 part of PbO20.69 parts of GeO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, and then the particles are placed into a muffle furnace and baked for 6 hours at the temperature of 250 ℃ and then baked for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 7 ]
A catalyst was prepared and the catalyst was evaluated as in example 1, except that 0.46 part of SnO was used20.46 part of PbO2And 0.46 part of GeO2Replacement of 1.38 parts SnO2. The method specifically comprises the following steps:
will correspond to 46.79 parts of Fe2O3Iron oxide red of (1), corresponding to 24.49 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.06 parts of K2Potassium carbonate of O, corresponding to 10.28 parts of CeO2Cerium oxalate, 1.50 parts of MgO, corresponding to 2.50 parts of Nb2O50.46 part of SnO20.46 part of PbO20.46 part of GeO2Stirring 5.8 parts of graphite in a kneader for 1.5 hours, adding deionized water accounting for 25.3 percent of the total weight of the catalyst raw materials, stirring for 0.8 hour, taking out the extruded strips, extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, drying for 1.5 hours at 50 ℃, and drying for 12 hours at 95 DEGThen placing the mixture into a muffle furnace, roasting the mixture for 6 hours at 250 ℃, and then roasting the mixture for 5 hours at 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 8 ]
A catalyst was prepared and the catalyst was evaluated as in example 7, except that Nb was used2O5With SnO2、PbO2And GeO2In different proportions. The method specifically comprises the following steps:
will correspond to 46.79 parts of Fe2O3Iron oxide red of (1), corresponding to 24.49 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.06 parts of K2Potassium carbonate of O, corresponding to 10.28 parts of CeO2Cerium oxalate, 1.50 parts of MgO, corresponding to 3.10 parts of Nb2O50.26 part of SnO20.26 part of PbO20.26 part of GeO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, and then the particles are placed into a muffle furnace and baked for 6 hours at the temperature of 250 ℃ and then baked for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 9 ]
A catalyst was prepared and the catalyst was evaluated as in example 7, except that Nb was used2O5With SnO2、PbO2And GeO2In different proportions. The method specifically comprises the following steps:
will correspond to 46.79 parts of Fe2O3Iron oxide red of (1), corresponding to 24.49 parts of Fe2O3Oxygen of (2)Iron oxide yellow, equivalent to 13.06 parts of K2Potassium carbonate of O, corresponding to 10.28 parts of CeO2Cerium oxalate, 1.50 parts of MgO, corresponding to 0.78 part of Nb2O5Niobium hydroxide, 1.04 parts SnO21.03 part of PbO21.03 parts of GeO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, and then the particles are placed into a muffle furnace and baked for 6 hours at the temperature of 250 ℃ and then baked for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 10 ]
A catalyst was prepared and the catalyst was evaluated as in example 7, except that SnO2、PbO2And GeO2The amount of the compound is different. The method specifically comprises the following steps:
will correspond to 46.79 parts of Fe2O3Iron oxide red of (1), corresponding to 24.49 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.06 parts of K2Potassium carbonate of O, corresponding to 10.28 parts of CeO2Cerium oxalate, 1.50 parts of MgO, corresponding to 2.50 parts of Nb2O50.69 part of SnO20.34 part of PbO20.35 part of GeO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, and then the particles are placed into a muffle furnace and baked for 6 hours at the temperature of 250 ℃ and then baked for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1Activity evaluation was performed at 630 ℃ under the condition that the water ratio (by weight) was 2.5The evaluation results are shown in Table 2.
[ example 11 ]
A catalyst was prepared and the catalyst was evaluated as in example 7, except that SnO2、PbO2And GeO2The amount of the compound is different. The method specifically comprises the following steps:
will correspond to 46.79 parts of Fe2O3Iron oxide red of (1), corresponding to 24.49 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.06 parts of K2Potassium carbonate of O, corresponding to 10.28 parts of CeO2Cerium oxalate, 1.50 parts of MgO, corresponding to 2.50 parts of Nb2O50.34 part of SnO20.35 part of PbO20.69 parts of GeO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, and then the particles are placed into a muffle furnace and baked for 6 hours at the temperature of 250 ℃ and then baked for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 12 ]
Will correspond to 51.91 parts Fe2O3Iron oxide red of (1), corresponding to 22.75 parts of Fe2O3Iron oxide yellow of (1), corresponding to 11.81 parts of K2Potassium carbonate of O, corresponding to 9.32 parts of CeO2Cerium oxalate, 1.04 parts of MgO, corresponding to 1.16 parts of Nb2O5Niobium hydroxide, 1.32 parts SnO20.68 part of PbO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, and then the particles are placed into a muffle furnace and baked for 6 hours at the temperature of 250 ℃ and then baked for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. Catalyst compositionAre shown in Table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 13 ]
Will correspond to 50.77 parts of Fe2O319.17 parts of Fe2O3Iron oxide yellow of (1), corresponding to 9.29 parts of K2Potassium carbonate of O, equivalent to 13.91 parts of CeO2Cerium oxalate, 4.31 parts of MgO, corresponding to 1.03 parts of Nb2O5Niobium hydroxide, 0.99 part of SnO20.54 portion of ZnO and 6.1 portions of graphite are stirred in a kneader for 1.7 hours, deionized water accounting for 20.8 percent of the total weight of the catalyst raw materials is added, stirred for 0.8 hour, taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven, baked for 1.7 hours at 65 ℃ and 12 hours at 105 ℃, then the particles are put into a muffle furnace, baked for 5 hours at 270 ℃ and then baked for 6 hours at 800 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 14 ]
Will correspond to 54.95 parts Fe2O3Iron oxide red of (1), corresponding to 24.65 parts of Fe2O3Iron oxide yellow of (1), corresponding to 6.85 parts of K2Potassium carbonate of O, corresponding to 10.23 parts of CeO2Cerium oxalate, 0.61 part of MgO, corresponding to 0.62 part of Nb2O50.65 part of SnO20.61 part of PbO20.82 part of ZnO and 6.5 parts of graphite are stirred in a kneader for 1.6 hours, deionized water accounting for 26.5 percent of the total weight of the catalyst raw materials is added, stirred for 0.8 hour, taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven, dried for 5.5 hours at the temperature of 30 ℃ and dried for 10 hours at the temperature of 85 ℃, then the particles are put into a muffle furnace, roasted for 4 hours at the temperature of 350 ℃, and then roasted for 4 hours at the temperature of 875 ℃ to obtain the finished catalyst. The catalyst composition is listed inTable 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 15 ]
Will correspond to 50.61 parts Fe2O3Iron oxide red of (1), corresponding to 15.40 parts of Fe2O3Iron oxide yellow of (1), corresponding to 14.21 parts of K2Potassium carbonate of O, corresponding to 7.58 parts of CeO2Cerium oxalate, 1.32 parts of MgO, corresponding to 3.52 parts of Nb2O50.80 part of SnO21.13 parts of PbO20.56 part of ZnO and 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.8 hour, extruded strips are taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, then the particles are put into a muffle furnace and baked for 6 hours at the temperature of 250 ℃, and then the particles are baked for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 16 ]
Will correspond to 49.28 parts Fe2O3Iron oxide red of (1), corresponding to 17.87 parts of Fe2O3Iron oxide yellow of (1), corresponding to 15.98 parts of K2Potassium carbonate of O, corresponding to 11.53 parts of CeO2Cerium oxalate, 2.58 parts of MgO, corresponding to 1.82 parts of Nb2O5Niobium hydroxide, 1.24 parts of SnO20.84 part of PbO2And 5.9 parts of graphite are stirred in a kneader for 1.6 hours, deionized water accounting for 24.9 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.75 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 45 ℃ and 14 hours at the temperature of 98 ℃, and then the particles are put into a muffle furnace and baked for 6 hours at the temperature of 250 ℃ and then baked for 5 hours at the temperature of 825 ℃ to obtain the finished catalyst. Catalyst compositionAre shown in Table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 17 ]
Will correspond to 47.36 parts of Fe2O3Iron oxide red of (1), corresponding to 19.79 parts of Fe2O3Iron oxide yellow of (1), corresponding to 11.57 parts of K2Potassium carbonate of O, corresponding to 6.08 parts of CeO2Cerium oxalate, 4.98 parts of MgO, corresponding to 3.97 parts of Nb2O5Niobium hydroxide, 4.89 parts SnO20.11 part of PbO2Stirring 1.25 parts of ZnO and 6.2 parts of graphite in a kneader for 1.5 hours, adding deionized water accounting for 25.5 percent of the total weight of the catalyst raw materials, stirring for 0.8 hour, taking out an extruded strip, extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, baking for 1.5 hours at 50 ℃, baking for 12 hours at 95 ℃, then putting the particles into a muffle furnace, baking for 6 hours at 250 ℃, and then baking for 5 hours at 805 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 18 ]
Will correspond to 54.01 parts of Fe2O3Iron oxide red of (1), corresponding to 18.00 parts of Fe2O3Iron oxide yellow of (1), corresponding to 12.31 parts of K2Potassium carbonate of O, corresponding to 10.41 parts of CeO2Cerium oxalate, 0.89 part of MgO, equivalent to 2.01 parts of Nb2O5Niobium hydroxide, 1.10 parts SnO20.75 part of PbO20.52 part of ZnO and 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 23.6 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.8 hour, an extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and dried at 30 ℃ for 8 hours and 98 ℃ for 8 hours, then the particles are put into a muffle furnace and calcined at 290 ℃ for 6 hours, and then the particles are calcined at 820 ℃ for 5 hours to obtain the finished catalyst.The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 19 ]
Will correspond to 50.08 parts Fe2O3Iron oxide red of (5), corresponding to 25.04 parts of Fe2O3Iron oxide yellow of (1), corresponding to 10.25 parts of K2Potassium carbonate of O, corresponding to 8.12 parts of CeO2Cerium oxalate, 3.08 parts of MgO, corresponding to 1.16 parts of Nb2O5Niobium hydroxide, 0.91 part of SnO20.61 part of PbO20.75 portion of GeO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.3 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, and then the particles are placed into a muffle furnace and baked for 4 hours at the temperature of 350 ℃ and then baked for 4 hours at the temperature of 845 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 20 ]
Will correspond to 49.10 parts of Fe2O3Iron oxide red of (1), corresponding to 24.52 parts of Fe2O3Iron oxide yellow of (1), corresponding to 8.24 parts of K2Potassium carbonate of O, corresponding to 12.83 parts of CeO2Cerium oxalate, 0.92 parts MgO, corresponding to 1.56 parts Nb2O5Niobium hydroxide, 1.05 part SnO21.21 parts of PbO20.54 part of GeO2Stirring 5.8 parts of graphite in a kneader for 1.5 hours, adding deionized water accounting for 25.3 percent of the total weight of the raw materials of the catalyst, stirring for 0.8 hour, taking out an extruded strip, extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, baking for 1.5 hours at 50 ℃, baking for 12 hours at 95 ℃, then putting the particles into a muffle furnace, baking for 6 hours at 365 ℃, and then baking at 8 ℃ for 6 hoursRoasting for 4 hours at 30 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 21 ]
Will correspond to 56.38 parts of Fe2O3Iron oxide red (equivalent to 14.10 parts of Fe)2O3Iron oxide yellow of (1), corresponding to 12.86 parts of K2Potassium carbonate of O, corresponding to 11.76 parts of CeO2Cerium oxalate, 0.97 parts of MgO, corresponding to 1.07 parts of Nb2O5Niobium hydroxide, 0.63 part of SnO21.42 parts of PbO20.81 part of GeO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 24.5 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 55 ℃, baked for 12 hours at the temperature of 105 ℃, then the particles are put into a muffle furnace and baked for 7 hours at the temperature of 370 ℃, and then baked for 7 hours at the temperature of 820 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 22 ]
Will correspond to 52.12 parts of Fe2O3Iron oxide red of (1), corresponding to 17.37 parts of Fe2O3Iron oxide yellow of (1), corresponding to 11.73 parts of K2Potassium carbonate of O, corresponding to 12.85 parts of CeO2Cerium oxalate, 1.47 parts of MgO, corresponding to 2.16 parts of Nb2O50.76 part of SnO21.03 part of PbO20.51 part of GeO2Stirring 5.8 parts of graphite in a kneader for 1.5 hours, adding deionized water accounting for 26.1 percent of the total weight of the catalyst raw materials, stirring for 0.8 hour, taking out an extruded strip, extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, baking for 8 hours at the temperature of 35 ℃, baking for 2 hours at the temperature of 120 ℃, and then putting the particles into a muffle furnaceAnd roasting at 315 deg.C for 6 hr, and then at 810 deg.C for 7.5 hr to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 23 ]
Will correspond to 52.92 parts Fe2O3Iron oxide red of (1), corresponding to 17.64 parts of Fe2O3Iron oxide yellow of (1), corresponding to 12.91 parts of K2Potassium carbonate of O, corresponding to 11.01 parts of CeO2Cerium oxalate, 1.51 parts of MgO, corresponding to 1.15 parts of Nb2O50.85 part of SnO21.46 parts of PbO20.55 part of GeO2And 5.8 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.0 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.8 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are put into an oven and baked for 1.5 hours at the temperature of 50 ℃ and 12 hours at the temperature of 95 ℃, and then the particles are placed into a muffle furnace and baked for 6 hours at the temperature of 250 ℃ and then baked for 5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 24 ]
Will correspond to 54.77 parts of Fe2O3Iron oxide red of (1), corresponding to 17.84 parts of Fe2O3Iron oxide yellow of (1), corresponding to 11.86 parts of K2Potassium carbonate of O, corresponding to 11.72 parts of CeO2Cerium oxalate, 0.95 parts of MgO, corresponding to 0.91 part of Nb2O50.56 part of SnO20.72 part of PbO20.67 part of GeO2Stirring 5.8 parts of graphite in a kneader for 1.5 hours, adding deionized water accounting for 24.8 percent of the total weight of the catalyst raw materials, stirring for 0.8 hour, taking out the extruded strips, extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, and drying for 1.5 hours at the temperature of 50 DEG CBaking at 95 ℃ for 12 hours, then placing in a muffle furnace, baking at 320 ℃ for 8 hours, and then baking at 820 ℃ for 4 hours to obtain the finished catalyst. The catalyst composition is listed in table 1.
100 ml of catalyst is loaded into a reactor, and the space velocity of the diethylbenzene liquid volume is 1.0 hour under normal pressure－1The activity was evaluated at 630 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
TABLE 1
Figure BDA0001830100680000131
Figure BDA0001830100680000141
TABLE 2
Figure BDA0001830100680000151

Claims (10)

1. A catalyst for the production of divinylbenzene comprising the following composition in weight percent of the total catalyst:
(a) 66-80% Fe2O3；
(b)6 to 16% of K2O；
(c) 6-14% of CeO2；
(d)0.5 to 5% of MgO;
(e)0.5 to 4% of Nb2O5；
(f) Selected from SnO2、PbO2Or GeO2At least one or more of (a), the content of which is 0.1-5%.
2. The catalyst for the production of divinylbenzene according to claim 1, characterized in that said Nb2O5The source of (b) is selected from niobic acid or niobium hydroxide.
3. Catalyst for the production of divinylbenzene according to claim 1A catalyst characterized in that said Nb2O5The content is 1-2.5%.
4. The catalyst for producing divinylbenzene according to claim 1, wherein said component (f) is contained in an amount of 0.5 to 2.5%.
5. The catalyst for the production of divinylbenzene as claimed in claim 1, wherein said component (f) comprises simultaneously SnO2And PbO2Or SnO2And GeO2Or PbO2And GeO2。
6. The method of any one of claims 1 to 5 for preparing a divinylbenzene catalyst, comprising the steps of: the catalyst for producing divinyl benzene is prepared by uniformly mixing the components with required amount and a pore-forming agent in percentage by weight, adding water to prepare a sticky dough-like substance suitable for extrusion, extruding, forming, drying and roasting.
7. The method of claim 6, wherein the calcination temperature is 120 to 380 ℃ for 3 to 10 hours, and then 650 to 900 ℃ for 3 to 10 hours.
8. The preparation method for producing a divinylbenzene catalyst according to claim 6, wherein the drying temperature is 30 to 120 ℃.
9. The preparation method for producing a divinylbenzene catalyst according to claim 6, wherein the drying time is 4 to 16 hours.
10. The use of a catalyst as claimed in any one of claims 1 to 5 for the production of divinylbenzene by dehydrogenation of diethylbenzene.
CN201811201445.0A 2018-10-16 2018-10-16 Catalyst for producing divinylbenzene and preparation method thereof Pending CN111054362A (en)

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