CN111054370A - High strength catalyst for preparing styrene - Google Patents

High strength catalyst for preparing styrene Download PDF

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Publication number
CN111054370A
CN111054370A CN201811201567.XA CN201811201567A CN111054370A CN 111054370 A CN111054370 A CN 111054370A CN 201811201567 A CN201811201567 A CN 201811201567A CN 111054370 A CN111054370 A CN 111054370A
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catalyst
parts
hours
cao
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
    • B01J23/85—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
    • 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

Abstract

The invention relates to a high-strength catalyst for preparing styrene, which mainly solves the technical problem that the mechanical strength of the catalyst is not high enough under the condition of not adding ordinary calcium silicate cement in the prior art, so that the long-period operation capability of the catalyst is not enough. The invention adopts a high-strength catalyst for ethylbenzene dehydrogenation, and comprises the following components in percentage by weight: 61-84% Fe2O3(ii) a 7 to 14% of K2O; 6-14% of CeO2(ii) a 0.5-5% MoO3(ii) a 0.25-4.8% of CaO; 0.1-2% of Na2O; wherein, CaO: na (Na)2The weight ratio of O is 1-9: the technical scheme 1 can better solve the technical problems and can be used in the industrial production of preparing styrene by ethylbenzene dehydrogenation.

Description

High strength catalyst for preparing styrene
Technical Field
The present invention relates to a high-strength catalyst for preparing styrene.
Background
The ethylbenzene catalytic dehydrogenation process is the leading technical route for industrially producing styrene, the production capacity of the ethylbenzene catalytic dehydrogenation process accounts for about 85 percent of the total production capacity of the styrene, and one of the key points of the process is a catalyst for preparing the styrene by ethylbenzene dehydrogenation. The basic components of the catalyst for preparing styrene by ethylbenzene dehydrogenation in the industry at present comprise a main catalyst, a cocatalyst, a pore-forming agent, a binder and the like. Early catalysts were the Fe-K-Cr system, as disclosed in U.S. Pat. No. 4467046 and European patent 0296285A 1. Although the catalyst has better activity and stability, the catalyst contains Cr oxide, which causes certain pollution to the environment and is gradually eliminated. Then, the catalyst is developed into Fe-K-Ce-Mo series, and Ce and Mo are used for replacing Cr, so that the activity and the stability of the catalyst can be better improved, and the defects of high Cr toxicity and environmental pollution are overcome. The addition of Ce can greatly improve the activity of the catalyst, and particularly has obvious influence on the catalyst with high potassium content, but when the catalyst with high potassium content is placed in the air, the catalyst is easy to adsorb moisture, so that the crushing resistance of the catalyst is low, and the catalyst is easy to pulverize. Further, during the dehydrogenation reaction, potassium gradually migrates into the particles or is easily washed away, which results in a decrease in catalyst stability and affects catalyst service life, and therefore, most of the current research is focused on low-potassium catalysts. To improve the strength of low-potassium catalysts, some attempts have been made by researchers based on literature reports to date. For example, in the published Chinese patent CN1209194, the pressure measurement intensity of the catalyst can be greatly enhanced by adding vanadium, cobalt, manganese and titanium oxide combination in a Fe-K-Ce-Mo-Mg system and optimizing the preparation process, but the catalyst contains vanadium, is toxic and can pollute the environment. The lateral pressure strength of the catalyst disclosed in the Chinese patent CN100443170 is more than or equal to 25N/mm, but the catalyst needs to be added with 1-9% of cement and silica gel as reinforcing agents, the reinforcing agents are generally acidic substances, and the reinforcing agents are added into the catalyst to easily cause side reactions such as cracking and the like, so that the selectivity of the catalyst is influenced.
With the increasing development of large-scale and super-large-scale new styrene devices, the scale of many new devices is more than 35 ten thousand tons/year, and the high-strength catalyst can reduce the bed resistance and prolong the long-period operation capacity of the catalyst, so that the strength of the catalyst is more and more a focus of attention of people.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to use a low potassium catalyst (K) existing in the prior art2O is less than 16 percent), the mechanical strength of the catalyst is not high enough under the condition of not adding ordinary calcium silicate cement, thereby causing the problem of insufficient long-period operation capability of the catalyst, and providing a novel high-strength catalyst for ethylbenzene dehydrogenation. The catalyst has the characteristics of high mechanical strength and good long-period operation capability while maintaining good catalytic performance of the low-potassium catalyst.
The second technical problem to be solved by the present invention is to provide a preparation method suitable for the catalyst to solve the first technical problem.
The third technical problem to be solved by the present invention is a method for preparing styrene by using the catalyst of one of the above technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a high strength catalyst for ethylbenzene dehydrogenation comprising the following composition in weight percent:
(a) 61-84% Fe2O3；
(b)7 to 14% of K2O；
(c) 6-14% of CeO2；
(d) 0.5-5% MoO3；
(e) 0.25-4.8% of CaO;
(f) 0.1-2% of Na2O；
Wherein, CaO: na (Na)2The weight ratio of O is 1-9: 1.
in the above technical scheme, CaO: na (Na)2The weight ratio of O is 2-6: 1, preferably, CaO: na (Na)2The weight ratio of O is 3-5.5: 1; the CaO content is 0.6-2.4%; na (Na)2The content of O is 0.25-1.0%; the catalyst also contains 0.01-1.0% of manganese or zinc oxide.
To solve the second technical problem, the invention adopts the following technical scheme: a method of making a high strength catalyst for ethylbenzene dehydrogenation comprising the steps of: the catalyst is prepared by uniformly mixing the components with required amount and the pore-forming agent according to the weight percentage, adding water to prepare a dough-like substance suitable for extrusion, extruding, 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 17-24% of the total weight of the catalyst raw material.
In the technical scheme, the iron is selected from iron oxide red.
In the technical scheme, ordinary calcium silicate cement is not added in the preparation process.
In the technical scheme, the drying temperature is 50-120 ℃, the roasting is carried out for 6-11 hours at 280-400 ℃, and then the roasting is carried out for 3.5-7 hours at 750-950 ℃.
In the above technical scheme, Fe2O3Adding the iron oxide red; 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; mo used is added in the form of its salt or oxide; the Ca is added in the form of oxide, salt or hydroxide; the Na is added in the form of salt or hydroxide; 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 can be selected from sesbania powder, polystyrene microspheres, sodium carboxymethylcellulose and the like, and the addition amount of the pore-forming agent is 2.6-4.9% of the total weight of the catalyst.
The catalyst particles prepared by the method can be in various shapes such as solid cylinders, hollow cylinders, trilobes, diamonds, quincunx shapes, honeycombs and the like, the diameter and the particle length are not limited fixedly, and solid cylindrical particles with the diameter of 3 mm and the length of 5-10 mm are recommended to be used as the catalyst.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the catalyst for solving one of the above-mentioned technical problems is used in a process for preparing styrene.
In the above technical scheme, the above technical scheme can be applied by those skilled in the art according to the prior art process, for example, but not limited to, ethylbenzene is used as a raw material, and the raw material is contacted with a catalyst in the presence of the catalyst to react to produce styrene.
The activity evaluation of the prepared catalyst is carried out in an isothermal fixed bed, and for the activity evaluation of the catalyst for preparing styrene by ethylbenzene dehydrogenation, 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 a1 "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 ethylbenzene conversion and the styrene selectivity are calculated according to the following formulas:
Figure BDA0001830126580000031
Figure BDA0001830126580000032
the mechanical strength of the catalyst of the invention was determined according to the technical requirements specified in Standard HG/T2782-1996, using a DL-II intelligent particle Strength Meter. The test pieces were 5 mm in length and tested in 40 pieces, and the arithmetic mean of the measurement results was taken as the final mechanical strength value in newtons (N).
The invention controls the addition of CaO in an iron-potassium-cerium-molybdenum-calcium system: na (Na)2The proportion of O, under the condition of not adding ordinary calcium silicate cement, the low-potassium catalyst has higher mechanical strength while keeping better catalytic performance, and the catalyst of the invention is used under normal pressure and at the liquid space velocity of 1.0 hour－1The catalyst is used for the reaction of preparing styrene by ethylbenzene dehydrogenation under the conditions of 620 ℃ and 2.0 weight ratio of water vapor/ethylbenzene, the conversion rate can reach 77.0 percent, the selectivity can reach 94.6 percent, the strength of the catalyst reaches 160N, the catalyst can stably run for 1100 hours, and a better technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Will correspond to 74.05 parts Fe2O3Iron oxide red of (1), corresponding to 12.60 parts of K2Potassium carbonate of O, corresponding to 10.58 parts of CeO2Cerium oxalate equivalent to 1.06 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 1.30 parts of CaO, and Na corresponding to 0.37 part of2Stirring sodium carbonate of O, 0.04 part of ZnO and 4.8 parts of sodium carboxymethylcellulose in a kneader for 1.5 hours, adding deionized water accounting for 21.5 percent of the total weight of the catalyst raw materials, stirring for 0.6 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, drying for 4.5 hours at 45 ℃, drying for 10 hours at 100 ℃, then roasting for 9 hours at 370 ℃, and then roasting for 5 hours at 820 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ COMPARATIVE EXAMPLE 1 ]
Except that Na is not added2In addition, the catalyst preparation method and the catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 74.05 parts Fe2O3Iron oxide red of (1), corresponding to 12.60 parts of K2Potassium carbonate of O, corresponding to 10.58 parts of CeO2Cerium oxalate equivalent to 1.06 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 1.30 parts of CaO, and Na corresponding to 0.37 part of2Stirring sodium carbonate of O, 0.04 part of ZnO and 4.8 parts of sodium carboxymethylcellulose in a kneader for 1.5 hours, adding deionized water accounting for 21.5 percent of the total weight of the catalyst raw materials, stirring for 0.6 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, drying for 4.5 hours at 45 ℃, drying for 10 hours at 100 ℃, then roasting for 9 hours at 370 ℃, and then roasting for 5 hours at 820 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ COMPARATIVE EXAMPLE 2 ]
The preparation method and evaluation conditions of the catalyst were the same as those in example 1 except that no CaO was added, specifically:
will correspond to 74.05 parts Fe2O3Iron oxide red of (1), corresponding to 12.60 parts of K2Potassium carbonate of O, corresponding to 10.58 parts of CeO2Cerium oxalate equivalent to 1.06 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 1.30 parts of CaO, and Na corresponding to 0.37 part of2Stirring sodium carbonate of O, 0.04 part of ZnO and 4.8 parts of sodium carboxymethylcellulose in a kneader for 1.5 hours, adding deionized water accounting for 21.5 percent of the total weight of the catalyst raw materials, stirring for 0.6 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, drying for 4.5 hours at 45 ℃, drying for 10 hours at 100 ℃, then roasting for 9 hours at 370 ℃, and then roasting for 5 hours at 820 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ COMPARATIVE EXAMPLE 3 ]
Except CaO and Na2The addition amount of O was different, and the catalyst preparation method and catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 74.05 parts Fe2O3Iron oxide red of (1), corresponding to 12.60 parts of K2Potassium carbonate of O, corresponding to 10.58 parts of CeO2Cerium oxalate equivalent to 1.06 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 1.30 parts of CaO, and Na corresponding to 0.37 part of2Sodium carbonate of O, 0.04 part of ZnO and 4.8 parts of hydroxylStirring sodium methyl cellulose in a kneader for 1.5 hours, adding deionized water accounting for 21.5 percent of the total weight of the catalyst raw materials, stirring for 0.6 hour, taking out and extruding into particles with the diameter of 3 mm and the length of 5 mm, putting the particles into an oven, baking for 4.5 hours at 45 ℃, baking for 10 hours at 100 ℃, then baking for 9 hours at 370 ℃, and then baking for 5 hours at 820 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ COMPARATIVE EXAMPLE 4 ]
Except CaO and Na2The addition amount of O was different, and the catalyst preparation method and catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 74.05 parts Fe2O3Iron oxide red of (1), corresponding to 12.60 parts of K2Potassium carbonate of O, corresponding to 10.58 parts of CeO2Cerium oxalate equivalent to 1.06 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 1.30 parts of CaO, and Na corresponding to 0.37 part of2Stirring sodium carbonate of O, 0.04 part of ZnO and 4.8 parts of sodium carboxymethylcellulose in a kneader for 1.5 hours, adding deionized water accounting for 21.5 percent of the total weight of the catalyst raw materials, stirring for 0.6 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, drying for 4.5 hours at 45 ℃, drying for 10 hours at 100 ℃, then roasting for 9 hours at 370 ℃, and then roasting for 5 hours at 820 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ COMPARATIVE EXAMPLE 5 ]
Except for Fe2O3With red and yellow iron oxideIn addition to the addition of the form, the catalyst preparation method and catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 49.37 parts Fe2O324.68 parts of Fe2O3Iron oxide yellow of (1), corresponding to 12.60 parts of K2Potassium carbonate of O, corresponding to 10.58 parts of CeO2Cerium oxalate equivalent to 1.06 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 1.30 parts of CaO, and Na corresponding to 0.37 part of2Stirring sodium carbonate of O, 0.04 part of ZnO and 4.8 parts of sodium carboxymethylcellulose in a kneader for 1.5 hours, adding deionized water accounting for 21.5 percent of the total weight of the catalyst raw materials, stirring for 0.6 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, drying for 4.5 hours at 45 ℃, drying for 10 hours at 100 ℃, then roasting for 9 hours at 370 ℃, and then roasting for 5 hours at 820 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 2 ]
Will correspond to 83.91 parts of Fe2O3Iron oxide red of (1), corresponding to 7.01 parts of K2Potassium carbonate of O, corresponding to 7.27 parts of CeO2Corresponding to 0.51 part of MoO3Ammonium molybdate (D), calcium hydroxide corresponding to 0.25 part of CaO, and Na corresponding to 0.11 part of2Sodium carbonate of O, 0.94 part of MnO2And 4.5 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.3 hours, deionized water accounting for 22.7 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.8 hour, extruded into particles with the diameter of 3 millimeters and the length of 5 millimeters, the particles are taken out and extruded into particles, the particles are put into an oven, the particles are baked for 6 hours at the temperature of 60 ℃, the particles are baked for 12 hours at the temperature of 120 ℃, then the particles are baked for 12 hours at the temperature of 280 ℃, and then the particles are baked for 3.5 hours at the temperature of 950 ℃. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 3 ]
Will correspond to 81.54 parts Fe2O3Iron oxide red of (1), corresponding to 8.15 parts of K2Potassium carbonate of O, corresponding to 8.07 parts of CeO2Cerium oxalate, corresponding to 0.95 part of MoO3Ammonium molybdate (D), calcium hydroxide corresponding to 1.01 parts of CaO, and Na corresponding to 0.23 part of2Sodium hydroxide of O, 0.05 part of ZnO and 3.8 parts of sodium hydroxymethyl cellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 17.0 percent of the total weight of the catalyst raw materials 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, baked for 3 hours at the temperature of 60 ℃, baked for 10 hours at the temperature of 120 ℃, then baked for 6 hours at the temperature of 380 ℃, and then baked for 4.5 hours at the temperature of 870 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 4 ]
Will correspond to 75.47 parts of Fe2O3Iron oxide red of (1), corresponding to 11.32 parts of K2Potassium carbonate of O, corresponding to 9.36 parts of CeO2Corresponding to 1.37 parts of MoO3Ammonium molybdate of (1), calcium carbonate corresponding to 0.87 parts of CaO, and Na corresponding to 0.87 parts of2Sodium carbonate of O, 0.03 part of MnO20.71 portion of ZnO and 4.6 portions of sodium hydroxymethyl cellulose are stirred in a kneader for 2 hours, deionized water accounting for 24 percent of the total weight of the catalyst raw materials 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 75 ℃ and 4 hours at the temperature of 130 ℃, then the particles are baked for 5 hours at the temperature of 400 ℃ and then baked for 8 hours at the temperature of 750 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 5 ]
Will correspond to 75.32 parts Fe2O3Iron oxide red of (1), corresponding to 10.16 parts of K2Potassium carbonate of O, corresponding to 10.32 parts of CeO2Cerium oxalate equivalent to 2.21 parts of MoO3Ammonium molybdate of (1.35 parts by weight of CaO-equivalent calcium carbonate, and Na-equivalent to 0.15 part by weight of2Sodium carbonate of O, 0.49 part of MnO2And 4.8 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.8 hours, deionized water accounting for 22.7 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.9 hour, 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 4.5 hours at the temperature of 55 ℃ and 8 hours at the temperature of 120 ℃, then baked for 9 hours at the temperature of 360 ℃ and then baked for 4.5 hours at the temperature of 830 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 6 ]
Will correspond to 74.26 parts Fe2O3Iron oxide red of 9.35 parts of K2Potassium carbonate of O, corresponding to 12.86 parts of CeO2Corresponding to 1.23 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 1.83 parts of CaO, and Na corresponding to 0.31 part of2Sodium carbonate of O, 0.16 part of MnO2Stirring 4.9 parts of sesbania powder in a kneader for 1.1 h, adding deionized water accounting for 19.5 percent of the total weight of the catalyst raw materials, stirring for 0.5 h, taking out extruded strips, extruding into particles with the diameter of 3 mm and the length of 5 mm, putting the particles into an oven, baking for 4.5 h at 55 ℃, baking for 10 h at 120 ℃, baking for 6 h at 360 ℃, and then bakingThen roasting for 4 hours at 880 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 7 ]
Will correspond to 73.08 parts of Fe2O3Iron oxide red of (1), corresponding to 13.52 parts of K2Potassium carbonate of O, corresponding to 6.01 parts of CeO2Corresponding to 3.42 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 2.51 parts of CaO, and Na corresponding to 1.45 parts of2Sodium carbonate of O, 0.01 part of MnO2Stirring 3.1 parts of sodium hydroxymethyl cellulose and 1.7 parts of sesbania powder in a kneader for 1.2 hours, adding deionized water accounting for 21.4 percent of the total weight of the catalyst raw materials, stirring for 0.7 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, baking for 4.5 hours at 55 ℃, baking for 10 hours at 120 ℃, then baking for 6 hours at 360 ℃, and then baking for 5 hours at 800 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 8 ]
Will correspond to 72.83 parts of Fe2O3Iron oxide red of (1), corresponding to 11.42 parts of K2Potassium carbonate of O, corresponding to 11.29 parts of CeO2Corresponding to 0.91 part of MoO3Ammonium molybdate of (1), calcium carbonate corresponding to 2.93 parts of CaO, and Na corresponding to 0.57 part of2Stirring sodium carbonate of O, 0.05 part of ZnO and 3.8 parts of sodium carboxymethylcellulose in a kneader for 1.3 hours, adding deionized water accounting for 20.8 percent of the total weight of the catalyst raw materials, stirring for 0.9 hour, taking out the mixture, extruding the mixture into strips with the diameter of 3 millimeters and the length of 3 millimeters5 mm of particles are put into an oven, baked for 4.5 hours at 55 ℃, baked for 10 hours at 120 ℃, then baked for 6 hours at 370 ℃, and then baked for 5 hours at 860 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 9 ]
Will correspond to 72.47 parts of Fe2O3Iron oxide red of (1), corresponding to 12.18 parts of K2Potassium carbonate of O, corresponding to 11.11 parts of CeO2Corresponding to 1.21 parts of MoO3Ammonium molybdate of (1), calcium carbonate corresponding to 2.36 parts of CaO, and Na corresponding to 0.56 part of2Sodium hydroxide of O, 0.11 part of ZnO and 4.6 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.3 hours, deionized water accounting for 23.5 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 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, baked for 4.5 hours at the temperature of 55 ℃, baked for 8 hours at the temperature of 120 ℃, baked for 5 hours at the temperature of 390 ℃, and then baked for 5 hours at the temperature of 810 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 10 ]
Will correspond to 72.13 parts of Fe2O3Iron oxide red of (1), corresponding to 12.69 parts of K2Potassium carbonate of O, corresponding to 12.41 parts of CeO2Cerium oxalate equivalent to 1.09 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 0.97 part of CaO, and Na corresponding to 0.32 part of2Sodium carbonate of O, 0.39 part of MnO2And 4.3 parts of sodium carboxymethylcellulose were stirred in a kneader for 1.5 hours, added in the form of a catalystDeionized water with the weight of 23.5 percent of the total weight of the raw materials is mixed for 0.6 hour, the mixture is taken out and extruded into particles with the diameter of 3 mm and the length of 5 mm, the particles are put into an oven and baked for 3.5 hours at 70 ℃ and 10 hours at 120 ℃, then the particles are baked for 6 hours at 360 ℃ and then baked for 5 hours at 820 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 11 ]
Will correspond to 72.05 parts Fe2O3Iron oxide red of (1), corresponding to 11.95 parts of K2Potassium carbonate of O, corresponding to 12.83 parts of CeO2Corresponding to 1.47 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 1.16 parts of CaO, and Na corresponding to 0.41 part of2Sodium carbonate of O, 0.13 part of MnO2And 4.1 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 23.5 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.6 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 4.5 hours at the temperature of 50 ℃, 10 hours at the temperature of 120 ℃, then the particles are baked for 7 hours at the temperature of 340 ℃ and then baked for 4 hours at the temperature of 880 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 12 ]
Will correspond to 71.81 parts of Fe2O3Iron oxide red of (1), corresponding to 12.06 parts of K2Potassium carbonate of O, corresponding to 10.27 parts of CeO2Corresponding to 1.50 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 3.25 parts of CaO, and Na corresponding to 0.85 part of2Sodium carbonate of O, 0.26 partZnO and 5.4 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 20.2 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.6 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 4.5 hours at the temperature of 50 ℃ and 10 hours at the temperature of 120 ℃, then baked for 6 hours at the temperature of 370 ℃, and then baked for 5 hours at the temperature of 825 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 13 ]
Will correspond to 70.36 parts Fe2O3Iron oxide red of 9.83 parts of K2Potassium carbonate of O, equivalent to 13.58 parts of CeO2Corresponding to 2.61 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 2.00 parts of CaO, calcium hydroxide corresponding to 0.57 part of CaO, and Na corresponding to 0.96 part of2Sodium carbonate of O, 0.09 part of MnO2And 3.6 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 19.8 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.6 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 3.5 hours at the temperature of 55 ℃ and 10 hours at the temperature of 120 ℃, then baked for 9 hours at the temperature of 370 ℃, and then baked for 5 hours at the temperature of 810 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 14 ]
Will correspond to 69.13 parts of Fe2O3Iron oxide red of (1), corresponding to 11.32 parts of K2Potassium carbonate of O, corresponding to 11.08 parts of CeO2Cerium oxalate,Equivalent to 3.35 parts MoO3Ammonium molybdate (D), calcium carbonate corresponding to 1.21 parts of CaO, calcium hydroxide corresponding to 2.74 parts of CaO, and Na corresponding to 0.61 part of2Stirring sodium carbonate of O, 0.56 part of ZnO and 5.1 parts of sodium carboxymethylcellulose in a kneader for 1.5 hours, adding deionized water accounting for 21.1 percent of the total weight of the catalyst raw materials, stirring for 0.6 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, drying for 4.5 hours at 55 ℃, drying for 10 hours at 120 ℃, then roasting for 6 hours at 375 ℃, and then roasting for 5 hours at 820 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 15 ]
Will correspond to 66.82 parts of Fe2O3Iron oxide red of (1), corresponding to 12.86 parts of K2Potassium carbonate of O, corresponding to 11.99 parts of CeO2Cerium oxalate equivalent to 2.68 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 4.98 parts of CaO, and Na corresponding to 0.62 part of Na2Sodium carbonate of O, 0.05 part of MnO2And 3.9 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 20.5 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.6 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 4.5 hours at the temperature of 50 ℃ and 10 hours at the temperature of 120 ℃, then the particles are baked for 6.5 hours at the temperature of 385 ℃, and then the particles are baked for 5.5 hours at the temperature of 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The activity evaluation was carried out at 620 ℃ under the conditions of steam/ethylbenzene (weight ratio) 2.0, and the test results are shown in Table 2.
[ example 16 ]
Will amount to 61.01 partsFe2O3Iron oxide red of (1), corresponding to 13.99 parts of K2Potassium carbonate of O, equivalent to 13.99 parts of CeO2Cerium oxalate, corresponding to 4.98 parts of MoO3Ammonium molybdate of (1), calcium carbonate corresponding to 3.98 parts of CaO, and Na corresponding to 1.99 parts of2Stirring sodium carbonate of O, 0.06 part of ZnO and 4.3 parts of sodium hydroxymethyl cellulose in a kneader for 1.5 hours, adding deionized water accounting for 22.5 percent of the total weight of the catalyst raw materials, stirring for 0.6 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, drying for 4.5 hours at 55 ℃, drying for 10 hours at 120 ℃, then roasting for 6.5 hours at 385 ℃, and then roasting for 5.5 hours at 815 ℃ to obtain the finished catalyst. The catalyst composition is listed in table 1.
The mechanical strength of the catalyst was measured and the test results are shown in Table 2.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour－1The evaluation of the activity was carried out at 620 ℃ and a steam/ethylbenzene (weight ratio) of 2.0, and the test results are shown in Table 2
TABLE 1
Figure BDA0001830126580000121
Figure BDA0001830126580000131
TABLE 2
Figure BDA0001830126580000141

Claims (10)

1. A high strength catalyst for the production of styrene comprising the following composition in weight percent:
(a) 61-84% Fe2O3(ii) a (b)7 to 14% of K2O; (c) 6-14% of CeO2(ii) a (d) 0.5-5% MoO3(ii) a (e) 0.25-4.8% of CaO; (f) 0.1-2% of Na2O; wherein, CaO: na (Na)2The weight ratio of O is 1-9: 1.
2. the high strength catalyst for the production of styrene of claim 1, wherein the CaO: na (Na)2The weight ratio of O is 2-6: 1.
3. the high strength catalyst for preparing styrene according to claim 1, wherein the CaO content is 0.6 to 2.4%; the Na is2The content of O is 0.25-1.0%.
4. The high strength catalyst for the production of styrene of claim 1, wherein the CaO: na (Na)2The weight ratio of O is 3-5.5: 1.
5. the high strength catalyst for preparing styrene according to claim 1, wherein the catalyst further comprises 0.01 to 1.0% by weight of an oxide of manganese or zinc.
6. A process for preparing a high strength catalyst for ethylbenzene dehydrogenation according to any of claims 1 to 5, comprising the steps of: the catalyst is prepared by uniformly mixing the components with required amount and the pore-forming agent according to the weight percentage, adding water to prepare a dough-like substance suitable for extrusion, extruding, drying and roasting.
7. The method according to claim 5, wherein the iron is selected from red iron oxides.
8. The method of claim 5, wherein calcium silicate cement is not added during the preparation.
9. The method according to claim 5, wherein the drying temperature is 50 to 120 ℃, the calcination is carried out at 280 to 400 ℃ for 6 to 11 hours, and then at 750 to 950 ℃ for 3.5 to 7 hours.
10. Use according to any one of claims 1 to 5 for the dehydrogenation of ethylbenzene to styrene.
CN201811201567.XA 2018-10-16 2018-10-16 High strength catalyst for preparing styrene Pending CN111054370A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6166280A (en) * 1996-03-08 2000-12-26 Montecatini Technologies S.R.L. Catalyst for the dehydrogenation of ethylbenzene to styrene
CN106582675A (en) * 2015-10-16 2017-04-26 中国石油化工股份有限公司 Catalyst for preparation of styrene
CN106955682A (en) * 2017-04-24 2017-07-18 苏州拓瑞特新材料有限公司 Ethylbenzene dehydrogenation catalyst with low water ratio
CN106994353A (en) * 2017-04-24 2017-08-01 苏州拓瑞特新材料有限公司 One kind is free of binding agent high intensity ethylbenzene dehydrogenation catalyst with low water ratio
CN107793282A (en) * 2016-09-06 2018-03-13 中国石油化工股份有限公司 The method for preparing divinylbenzene
CN107790149A (en) * 2016-09-06 2018-03-13 中国石油化工股份有限公司 Diethylbenzene dehydrogenation and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6166280A (en) * 1996-03-08 2000-12-26 Montecatini Technologies S.R.L. Catalyst for the dehydrogenation of ethylbenzene to styrene
CN106582675A (en) * 2015-10-16 2017-04-26 中国石油化工股份有限公司 Catalyst for preparation of styrene
CN107793282A (en) * 2016-09-06 2018-03-13 中国石油化工股份有限公司 The method for preparing divinylbenzene
CN107790149A (en) * 2016-09-06 2018-03-13 中国石油化工股份有限公司 Diethylbenzene dehydrogenation and preparation method thereof
CN106955682A (en) * 2017-04-24 2017-07-18 苏州拓瑞特新材料有限公司 Ethylbenzene dehydrogenation catalyst with low water ratio
CN106994353A (en) * 2017-04-24 2017-08-01 苏州拓瑞特新材料有限公司 One kind is free of binding agent high intensity ethylbenzene dehydrogenation catalyst with low water ratio

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