CN107793282B - Process for preparing divinylbenzene - Google Patents
Process for preparing divinylbenzene Download PDFInfo
- Publication number
- CN107793282B CN107793282B CN201610805543.XA CN201610805543A CN107793282B CN 107793282 B CN107793282 B CN 107793282B CN 201610805543 A CN201610805543 A CN 201610805543A CN 107793282 B CN107793282 B CN 107793282B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- parts
- diethylbenzene
- hours
- divinylbenzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/889—Manganese, technetium or rhenium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing divinylbenzene, which mainly solves the problems of lower catalyst activity and high single-diene ratio in products in the prior art. The invention uses diethylbenzene as raw material, in the presence of catalyst, the raw material contacts with catalyst, and reacts to generate divinylbenzene; wherein the catalyst comprises the following components in percentage by weight: (a) 65-80% Fe2O3(ii) a (b)6 to 14% of K2O; (c) 8-14% of CeO2(ii) a (d) 0.5-5% MoO3(ii) a (e) 0.5-5% of CaO; (f) 0.5-2% of Na2O; (g) selected from MnO2、TiO2Or Pr2O3The content of at least one or more than one of the above is 0.1-3.5%, the technical problem is solved well, and the method can be used in industrial production of divinylbenzene prepared by diethylbenzene dehydrogenation.
Description
Technical Field
The invention relates to a method for preparing divinylbenzene by dehydrogenating diethylbenzene.
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 uk patent 1100088, although the catalysts have good activity and selectivity, the catalysts contain Cr oxides, which cause environmental pollution. The Ce is used for replacing Cr, so that the activity and stability of the catalyst can be better improved, and the defects of high Cr toxicity and environmental pollution are overcome. 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 mono-diene/diene ratio of the product is high. For this reason, it is an object of the present inventors to find suitable catalysts for increasing the activity of diethylbenzene dehydrogenation catalysts and for decreasing the mono-to bis-olefin ratio in the product.
Disclosure of Invention
The invention aims to solve the technical problem that the ratio of the single diene in the product is high in the prior art, and provides a novel method for preparing divinylbenzene. The method adopts a new catalyst for the dehydrogenation reaction of diethylbenzene, and has the characteristic of low ratio of single diene in the product.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for preparing divinylbenzene takes diethylbenzene as raw material, under the existence of catalyst, the raw material contacts with catalyst, react and produce divinylbenzene; the catalyst comprises the following components in percentage by weight:
(a) 65-80% Fe2O3；
(b)6 to 14% of K2O；
(c) 8-14% of CeO2；
(d) 0.5-5% MoO3；
(e) 0.5-5% of CaO;
(f)0.5 to 3.0% of Na2O；
(g)MnO2、TiO2Or Pr2O30.1-3.5% of at least one or more of (A).
In the above technical scheme, the reaction: the reaction pressure is preferably normal pressure; the reaction temperature is preferably 580-650 ℃; the mass ratio of water to diethylbenzene is preferably 1.5-5.0; the preferred volume space velocity of the diethylbenzene liquid is 0.3-2.0 h-1。
In the above technical scheme, the Na2The content of O is 0.8-1.8%; the content of the component (g) is 0.5-2%.
In the technical scheme, in the aspect of reducing the ratio of the mono-diene product, the Na in the auxiliary agent of the catalyst has an interaction promoting effect with the (g) component, such as but not limited to a promoting effect between Na and Mn.
In the above technical scheme, the component (g) of the catalyst preferably also comprises MnO2And TiO2Or MnO of2And Pr2O3Or TiO2And Pr2O3The two oxides have a binary synergistic effect in the aspect of reducing the ratio of the product mono-diene; said (g) component preferably also comprises MnO2、TiO2And Pr2O3And at the moment, the three oxides have ternary synergistic effect on reducing the ratio of the mono-diene to the bis-diene of the product and improving the activity of the catalyst.
In the above technical solution, the preparation method of the catalyst preferably includes the following steps: the catalyst is prepared by uniformly mixing the required amount of iron source, potassium source, cerium source, molybdenum source, calcium source, component source (g) and pore-forming agent in percentage by weight, adding water to prepare a sticky dough-like substance suitable for extrusion, extruding, forming and drying the dough-like substance, and roasting the dough-like substance in an atmosphere box furnace to prepare the catalyst.
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 17-33% of the total weight of the catalyst raw material.
In the technical scheme, the roasting is preferably carried out for 1-8 hours at the temperature of 150-400 ℃, and then is carried out for 2-16 hours at the temperature of 650-1000 ℃; the drying temperature is preferably 35-150 ℃; the drying time is preferably 2 to 20 hours.
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; mo used is added in the form of its salt or oxide; the Mg is added in the form of oxide, 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 graphite, sesbania powder, polystyrene microspheres and sodium carboxymethylcellulose, and the addition amount of the pore-forming agent is 2-6% of the total weight of the catalyst. .
In the technical scheme, the roasting atmosphere of the atmosphere box type furnace is air; the flow rate of the air is 10-200 ml/min.
The activity evaluation of the prepared catalyst is carried out in an isothermal fixed bed, and for the activity evaluation of the divinylbenzene catalyst prepared by the diethylbenzene 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 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, selectivity and mono-diene/bis-diene ratio are calculated according to the following formula:
ethylvinylbenzene selectivity%, S (EVB) for short
Divinylbenzene selectivity%, S (DVB) for short
Ethyl vinyl benzene yield% (% diethylbenzene conversion%. times. ethyl vinyl benzene selectivity)%
Divinylbenzene yield%
The invention adds proper amount of sodium oxide and MnO into the Fe-K-Ce-Mo-Ca catalyst system2、TiO2Or Pr2O3Has been surprisingly found to have a low mono-diene ratio in the product, at atmospheric pressure and liquid space velocity of 0.5 hours－1Under the conditions of 620 ℃ and 2.5 of steam/diethylbenzene (weight ratio), the conversion rate of the diethylbenzene is 77.35, the ratio of the mono-diene in the product is 0.84, and a better technical effect is achieved.
The invention is further illustrated by the following examples:
Detailed Description
[ example 1 ]
Will correspond to 53.27 parts Fe2O3Iron oxide red of (1), corresponding to 17.76 parts of Fe2O3Iron oxide yellow of (1), corresponding to 12.24 parts of K2Potassium carbonate of O, corresponding to 10.37 parts of CeO2Cerium oxalate equivalent to 2.01 parts of MoO3Ammonium molybdate of (1.85 parts by weight of CaO, calcium carbonate of (1.06 parts by weight of Na)2Sodium hydroxide of O, 1.44 parts MnO2And 4.9 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.1 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.9 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 dried for 2.5 hours at the temperature of 55 ℃, the particles are dried for 8.0 hours at the temperature of 110 ℃, then the particles are placed in an atmosphere box furnace, the air flow rate of the roasting is adjusted to be 60 milliliters per minute, the particles are roasted for 8 hours at the temperature of 150 ℃, and then the particles are roasted for 14. The catalyst composition is listed in table 1.
100 ml of catalyst was charged to the reactionAt normal pressure, the space velocity of the diethylbenzene liquid volume is 1.0 hour－1The activity was evaluated at 620 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ COMPARATIVE EXAMPLE 1 ]
Except that Na is not added2O and MnO2In addition, the catalyst preparation method and the catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 54.64 parts of Fe2O3Iron oxide red of (1), corresponding to 18.21 parts of Fe2O3Iron oxide yellow of (1), corresponding to 12.55 parts of K2Potassium carbonate of O, corresponding to 10.64 parts of CeO2Cerium oxalate equivalent to 2.06 parts of MoO3Stirring ammonium molybdate, calcium carbonate equivalent to 1.90 parts of CaO and 4.9 parts of graphite in a kneader for 1.5 hours, adding deionized water accounting for 25.1 percent of the total weight of the raw materials of the catalyst, stirring for 0.9 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, drying for 2.5 hours at 55 ℃, drying for 8.0 hours at 110 ℃, then placing the particles into an atmosphere box furnace, adjusting the flow rate of roasting air to be 60 milliliters per minute, roasting for 8 hours at 150 ℃, and then roasting for 14 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 620 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ COMPARATIVE EXAMPLE 2 ]
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 53.84 parts of Fe2O3Iron oxide red of (1), corresponding to 17.95 parts of Fe2O3Iron oxide yellow of (1), corresponding to 12.37 parts of K2Potassium carbonate of O, corresponding to 10.48 parts of CeO2Cerium oxalate, equivalent to 2.03 parts of MoO3Ammonium molybdate of (1.87 parts), calcium carbonate equivalent to CaO of (1.87 parts), MnO of (1.46 parts)2Stirring 4.9 parts of graphite in a kneader for 1.5 hours, adding deionized water accounting for 25.1 percent of the total weight of the catalyst raw materials, stirring for 0.9 hour, taking out the extruded strips, and extruding into the diameter3 mm and 5 mm long particles are put into an oven, baked for 2.5 hours at 55 ℃, baked for 8.0 hours at 110 ℃, then put into an atmosphere box type furnace, the air flow rate of the baking is adjusted to 60 ml/min, the particles are baked for 8 hours at 150 ℃, and then the particles are baked for 14 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 620 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 2 ]
Except using TiO2Replacement of MnO2In addition, the catalyst preparation method and the catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 53.27 parts Fe2O3Iron oxide red of (1), corresponding to 17.76 parts of Fe2O3Iron oxide yellow of (1), corresponding to 12.24 parts of K2Potassium carbonate of O, corresponding to 10.37 parts of CeO2Cerium oxalate equivalent to 2.01 parts of MoO3Ammonium molybdate of (1.85 parts by weight of CaO, calcium carbonate of (1.06 parts by weight of Na)2Sodium hydroxide of O, 1.44 parts of TiO2And 4.9 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.1 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.9 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 dried for 2.5 hours at the temperature of 55 ℃, the particles are dried for 8.0 hours at the temperature of 110 ℃, then the particles are placed in an atmosphere box furnace, the air flow rate of the roasting is adjusted to be 60 milliliters per minute, the particles are roasted for 8 hours at the temperature of 150 ℃, and then the particles are roasted for 14. 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 620 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 3 ]
Except using Pr2O3Replacement of MnO2In addition, the catalyst preparation method and the catalyst evaluation conditions were the same as in example 1, specifically:
would correspond to 53.27 parts of Fe2O3Iron oxide red of (1), corresponding to 17.76 parts of Fe2O3Iron oxide yellow of (1), corresponding to 12.24 parts of K2Potassium carbonate of O, corresponding to 10.37 parts of CeO2Cerium oxalate equivalent to 2.01 parts of MoO3Ammonium molybdate of (1.85 parts by weight of CaO, calcium carbonate of (1.06 parts by weight of Na)2Sodium hydroxide of O, 1.44 parts of Pr2O3And 4.9 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25.1 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.9 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 dried for 2.5 hours at the temperature of 55 ℃, the particles are dried for 8.0 hours at the temperature of 110 ℃, then the particles are placed in an atmosphere box furnace, the air flow rate of the roasting is adjusted to be 60 milliliters per minute, the particles are roasted for 8 hours at the temperature of 150 ℃, and then the particles are roasted for 14. 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 620 ℃ 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 evaluated by the same procedures as in example 1, except that 0.72 part of MnO was used2And 0.72 part of TiO2Substitution of 1.44 parts MnO2。
The catalyst composition is shown in Table 1, and the evaluation results are shown in Table 2.
[ example 5 ]
A catalyst was prepared and evaluated by the same procedures as in example 1, except that 0.72 part of MnO was used2And equivalent to 0.72 part of Pr2O3Nitric acid spectrum of (1.44 parts of MnO)2。
The catalyst composition is shown in Table 1, and the evaluation results are shown in Table 2.
[ example 6 ]
A catalyst was prepared and the catalyst was evaluated as in example 1, except that 0.72 part of TiO was used2And equivalent to 0.72 part of Pr2O3Nitric acid spectrum of (1.44 parts of MnO)2。
The catalyst composition is shown in Table 1, and the evaluation results are shown in Table 2.
[ example 7 ]
A catalyst was prepared and evaluated by the same procedures as in example 1, except that 0.48 part of MnO was used20.48 part of TiO2And equivalent to 0.48 part of Pr2O3Nitric acid spectrum of (1.44 parts of MnO)2。
The catalyst composition is shown in Table 1, and the evaluation results are shown in Table 2.
[ example 8 ]
Will correspond to 64.09 parts Fe2O3Iron oxide red of (1), equivalent to 16.02 parts of Fe2O3Iron oxide yellow of (1), corresponding to 6.63 parts of K2Potassium carbonate of O, corresponding to 9.66 parts of CeO2Corresponding to 0.66 part of MoO3Ammonium molybdate (D), calcium hydroxide corresponding to 0.72 part of CaO, and Na corresponding to 0.61 part of2Sodium carbonate of O, 0.72 part of MnO20.13 part of TiO20.76 parts of MgO and 5.6 parts of sesbania powder are stirred in a kneader for 2.2 hours, deionized water accounting for 20.1 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, baked for 2 hours at the temperature of 60 ℃ and 10 hours at the temperature of 100 ℃, then the particles are put into an atmosphere box type furnace, the baking air flow is adjusted to be 100 milliliters per minute, the particles are baked for 4 hours at the temperature of 350 ℃, and then the particles are baked for 5 hours at the temperature of 850 ℃ to obtain the finished catalyst, wherein.
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 620 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 9 ]
Will correspond to 47.57 parts Fe2O323.79 parts of Fe2O3Iron oxide yellow of (1), corresponding to 11.51 parts of K2Potassium hydroxide of O, corresponding to 10.12 parts of CeO2Cerium oxalate, equivalent to 2.14 parts of MoO3Ammonium molybdate (D), calcium hydroxide corresponding to 0.85 part of CaO, and Na corresponding to 0.81 part of2Sodium carbonate of O, 1.23 parts of MnO20.12 portion of TiO2Equivalent to 1.86 parts of Pr2O3Stirring the mixture in a kneader for 1.5 hours, adding deionized water accounting for 18.6 percent of the total weight of the catalyst raw materials, stirring for 0.9 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 2 hours at 70 ℃, baking for 8 hours at 110 ℃, then putting the particles into an atmosphere box furnace, adjusting the baking air flow to 190 milliliters per minute, baking for 4 hours at 350 ℃, and then baking for 3 hours at 900 ℃ to obtain the finished catalyst, wherein 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 620 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 10 ]
Will correspond to 43.79 parts Fe2O3Iron oxide red of (1), corresponding to 21.89 parts of Fe2O3Iron oxide yellow of (1), corresponding to 13.84 parts of K2Potassium carbonate of O, corresponding to 8.27 parts of CeO2Corresponding to 4.61 parts of MoO3Ammonium molybdate (D), calcium carbonate corresponding to 2.14 parts of CaO, and Na corresponding to 2.76 parts of2Sodium carbonate of O, 1.46 parts of MnO21.24 parts of TiO2Stirring the mixture 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 0.9 hour, taking out extruded strips, extruding the extruded strips into particles with the diameter of 3 millimeters and the length of 5 millimeters, putting the particles into an oven, baking the particles for 2 hours at the temperature of 80 ℃, baking the particles for 2 hours at the temperature of 120 ℃, then putting the particles into an atmosphere box furnace, regulating the baking air flow to be 150 milliliters per minute, baking the particles for 4 hours at the temperature of 400 ℃, and then baking the particles for 6 hours at the temperature of 800 ℃ to obtain the finished catalyst, wherein the composition of the catalyst 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 620 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
[ example 11 ]
Will correspond to 52.433 parts of Fe2O3Iron oxide ofRed, equivalent to 17.48 parts Fe2O3Iron oxide yellow of (1), corresponding to 10.15 parts of K2Potassium carbonate of O, equivalent to 13.01 parts of CeO2Corresponding to 1.23 parts of MoO3Ammonium molybdate (D), calcium hydroxide corresponding to 2.51 parts of CaO, and Na corresponding to 1.15 parts of2Sodium carbonate of O, 1.82 parts of MnO2Equivalent to 0.22 part of Pr2O3Stirring the mixture in a kneader for 1.5 hours, adding deionized water accounting for 33.6 percent of the total weight of the catalyst raw materials, stirring for 0.9 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 3 hours at 70 ℃, baking for 8 hours at 100 ℃, then putting the particles into an atmosphere box furnace, adjusting the baking air flow to be 110 milliliters per minute, baking for 3 hours at 300 ℃, and then baking for 6 hours at 830 ℃ to obtain the finished catalyst, wherein 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 620 ℃ and a water ratio (by weight) of 2.5, and the evaluation results are shown in Table 2.
TABLE 1 weight percent composition of (to be) catalyst
TABLE 1 weight percent composition of (continuous) catalysts
[ COMPARATIVE EXAMPLE 3 ]
A catalyst was prepared as in example 1, except that the catalyst was calcined using a static muffle furnace. The activity evaluation was carried out under the evaluation conditions of example 1, and the test results are shown in Table 2.
TABLE 2 comparison of catalyst Performance
[ example 12 ]
The catalyst prepared in example 7 was charged into a reactor at 620 ℃ and a liquid space velocity of 0.5 hour under normal pressure using diethylbenzene as a starting material and 100 ml of the catalyst－1And steam/diethylbenzene (weight ratio) was 2.5, the starting material was contacted with the catalyst to produce divinylbenzene, and the reaction results are shown in Table 3.
[ example 13 ]
The reaction temperature was adjusted to 590 ℃ and the reaction results are shown in Table 3, which is otherwise the same as in example 12.
[ example 14 ]
The reaction temperature was adjusted to 640 ℃ as in example 12, and the reaction results are shown in Table 3.
[ example 15 ]
The liquid space velocity was changed to 1.0 hour－1The reaction results are shown in Table 3, as in example 12.
[ example 16 ]
The liquid space velocity was changed to 1.8 hours－1The reaction results are shown in Table 3, as in example 12.
[ example 17 ]
The water ratio (by weight) was changed to 2.0, and the rest of the example 12 was conducted, and the reaction results are shown in Table 3.
[ example 18 ]
The water ratio (by weight) was changed to 3.5, and the rest of the example 12 was conducted, and the reaction results are shown in Table 3.
TABLE 3 reaction results of the catalysts
Claims (8)
1. A method for preparing divinylbenzene takes diethylbenzene as raw material, under the existence of catalyst, the raw material contacts with catalyst, react and produce divinylbenzene; wherein the catalyst comprises the following components in percentage by weight:
(a) 65-80% Fe2O3；
(b)6 to 14% of K2O；
(c) 8-14% of CeO2；
(d) 0.5-5% MoO3；
(e) 0.5-5% of CaO;
(f)0.5 to 3.0% of Na2O；
(g)MnO2、TiO2Or Pr2O30.1-3.5% of at least one or more of (A).
2. The method according to claim 1, wherein the reaction pressure is normal pressure.
3. The method for preparing divinylbenzene according to claim 1, wherein the reaction temperature of said reaction is 580 to 650 ℃.
4. The method according to claim 1, wherein the mass ratio of water/diethylbenzene is 1.5 to 5.0.
5. The method for preparing divinylbenzene according to claim 1, wherein the liquid volume space velocity of said diethylbenzene is 0.3 to 2.0h-1。
6. The method according to claim 1, wherein Na represents2The content of O is 0.8-1.8%.
7. The method according to claim 1, wherein the component (g) is contained in an amount of 0.5 to 2%.
8. The method for preparing divinylbenzene according to any one of claims 1 to 7, wherein said catalyst is prepared by a method comprising the steps of: the catalyst is prepared by uniformly mixing the required amount of iron source, potassium source, cerium source, molybdenum source, calcium source, component source (g) and pore-forming agent in percentage by weight, adding water to prepare a sticky dough-like substance suitable for extrusion, extruding, forming and drying the dough-like substance, and roasting the dough-like substance in an atmosphere box furnace to prepare the catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610805543.XA CN107793282B (en) | 2016-09-06 | 2016-09-06 | Process for preparing divinylbenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610805543.XA CN107793282B (en) | 2016-09-06 | 2016-09-06 | Process for preparing divinylbenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107793282A CN107793282A (en) | 2018-03-13 |
| CN107793282B true CN107793282B (en) | 2020-01-03 |
Family
ID=61530730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610805543.XA Active CN107793282B (en) | 2016-09-06 | 2016-09-06 | Process for preparing divinylbenzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107793282B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111054370A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | High strength catalyst for preparing styrene |
| CN111056909B (en) * | 2018-10-16 | 2023-03-03 | 中国石油化工股份有限公司 | Method for producing divinylbenzene by dehydrogenating diethylbenzene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728371A (en) * | 2011-04-15 | 2012-10-17 | 廖仕杰 | High cerium content alkylaromatic dehydrogenation catalyst and preparation method thereof |
| CN105080559A (en) * | 2015-08-25 | 2015-11-25 | 营口市风光化工有限公司 | Oxide catalyst for alkyl aromatic dehydrogenation |
| CN105749934A (en) * | 2014-12-15 | 2016-07-13 | 中国石油天然气股份有限公司 | Catalyst used for low steam-to-oil ratio ethylbenzene dehydrogenation to prepare styrene, and preparation method thereof |
-
2016
- 2016-09-06 CN CN201610805543.XA patent/CN107793282B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728371A (en) * | 2011-04-15 | 2012-10-17 | 廖仕杰 | High cerium content alkylaromatic dehydrogenation catalyst and preparation method thereof |
| CN105749934A (en) * | 2014-12-15 | 2016-07-13 | 中国石油天然气股份有限公司 | Catalyst used for low steam-to-oil ratio ethylbenzene dehydrogenation to prepare styrene, and preparation method thereof |
| CN105080559A (en) * | 2015-08-25 | 2015-11-25 | 营口市风光化工有限公司 | Oxide catalyst for alkyl aromatic dehydrogenation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107793282A (en) | 2018-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107790150B (en) | Catalyst for producing alkyl alkenyl arene | |
| CN107793282B (en) | Process for preparing divinylbenzene | |
| CN107790149B (en) | Diethylbenzene dehydrogenation catalyst and preparation method thereof | |
| CN107790148B (en) | Catalyst for preparing divinylbenzene by dehydrogenating diethylbenzene and preparation method and application thereof | |
| CN109569639B (en) | Dehydrogenation catalyst for preparing styrene and preparation method thereof | |
| CN1095399C (en) | Alkyl aromatic hydrocarbon dehydrogenation catalyst and preparation thereof | |
| CN111056909B (en) | Method for producing divinylbenzene by dehydrogenating diethylbenzene | |
| CN107790147B (en) | Catalyst for dehydrogenation of diethylbenzene and preparation method thereof | |
| CN107790146B (en) | Catalyst for preparing divinylbenzene, preparation method and application thereof | |
| CN112657503B (en) | Iron-based catalyst and preparation method and application thereof | |
| CN111054375A (en) | Diethylbenzene dehydrogenation catalyst, preparation method and application | |
| CN111054362A (en) | Catalyst for producing divinylbenzene and preparation method thereof | |
| CN111056910A (en) | Method for preparing alkyl alkenyl arene by dehydrogenating alkyl arene | |
| CN110681391A (en) | Low-water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof | |
| CN105478132B (en) | Catalyst for phenylethylene dehydrogenation of low-carbon type and its preparation method and application | |
| CN103483130B (en) | Method for synthesizing 1,3-butadiene by adopting Bi/Mo/La/Fe four-component composite oxide catalyst | |
| CN110681394A (en) | Dehydrogenation catalyst for preparing styrene, preparation method and application thereof | |
| CN110681390B (en) | Low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method and application thereof | |
| CN107790145B (en) | Catalyst for preparing alkenyl arene and preparation method and application thereof | |
| CN112237919A (en) | Dehydrogenation catalyst for preparing styrene | |
| CN109569637B (en) | Low-water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof | |
| CN101148389A (en) | Method for preparing styrene by ethylbenzene dehydrogenation | |
| TW202026063A (en) | Catalyst for dehydrogenation of alkyl aromatic hydrocarbon and preparation method therefor | |
| CN106582675B (en) | Prepare the catalyst of styrene | |
| CN110681392A (en) | Low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |