CN119303601B - Catalysts for the dehydrogenation of ethylbenzene to styrene, their preparation methods and applications - Google Patents
Catalysts for the dehydrogenation of ethylbenzene to styrene, their preparation methods and applicationsInfo
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- 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
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Abstract
The invention discloses a catalyst for preparing styrene by ethylbenzene dehydrogenation and a preparation method and application thereof. The catalyst comprises Fe, K, ce, mo, alkaline earth metal, carbon and at least one selected from Cl element and Br element. The catalyst is used in ethylbenzene dehydrogenation reaction, and can remarkably improve the selectivity of styrene while maintaining the high conversion rate of ethylbenzene.
Description
Technical Field
The invention belongs to the field of ethylbenzene dehydrogenation catalysts, and particularly relates to a catalyst for preparing styrene by ethylbenzene dehydrogenation, and a preparation method and application thereof.
Background
Styrene is an important bulk chemical raw material, and is mainly used as a monomer for synthetic rubber and plastics to produce materials such as expandable polystyrene, polystyrene and ABS (acrylonitrile-butadiene-styrene). Styrene has wide application and rapid demand growth, and drives the styrene industry to develop rapidly.
The main production methods of styrene are ethylbenzene catalytic dehydrogenation and styrene-propylene oxide co-production. The ethylbenzene catalytic dehydrogenation method takes ethylbenzene as a raw material, and the ethylbenzene is catalytically dehydrogenated in the presence of steam to produce styrene, and the styrene production capacity is about 85wt%.
In recent years, with the massive release of styrene productivity, the price of styrene is under pressure, and higher requirements are put on the economy of the styrene production process. For the important petrochemical catalysis process of preparing styrene by ethylbenzene dehydrogenation, the catalyst plays a key role in the production of styrene, and the performance of the catalyst determines the economical efficiency of an ethylbenzene dehydrogenation production device to a great extent.
The existing ethylbenzene dehydrogenation catalyst mostly takes Fe-K-Ce series catalysts as main active components, wherein Fe-K oxide is taken as a main active component of the catalyst, ce oxide is taken as a main auxiliary agent, and other metal oxides are also contained as a structure stabilizer or an electronic auxiliary agent. CN101279269a discloses a catalyst in which bismuth oxide and beryllium oxide are added to an iron-potassium-cerium-tungsten-calcium catalytic system, which improves the activity of ethylbenzene dehydrogenation catalyst. CN106582689a discloses a technical scheme of adding In 2O3 on the basis of a Fe-K-Ce-W-Mg-Ca catalyst system, and simultaneously adding at least one of HfO 2、Nb2O5 or Ta 2O5, which improves the catalyst selectivity. However, the existing production method for preparing styrene by ethylbenzene dehydrogenation still has the problem that the selectivity of styrene is not high enough.
The catalyst reported above has the problems of more reaction byproducts and lower styrene selectivity in the ethylbenzene dehydrogenation reaction to different degrees. It is therefore of great importance to develop a catalyst suitable for ethylbenzene dehydrogenation.
Disclosure of Invention
Aiming at the problems of more byproducts and lower styrene selectivity in the application of ethylbenzene dehydrogenation catalysts in the prior art, the invention provides a catalyst for preparing styrene by ethylbenzene dehydrogenation and a preparation method and application thereof. The catalyst is used in ethylbenzene dehydrogenation reaction, and can remarkably improve the selectivity of styrene while maintaining the high conversion rate of ethylbenzene.
In a first aspect, the invention provides a catalyst for the dehydrogenation of ethylbenzene to styrene. The catalyst comprises Fe, K, ce, mo, alkaline earth metal, carbon and at least one selected from Cl element and Br element.
According to the present invention, preferably, the carbon is carbon deposit.
According to the invention, the carbon in the catalyst is introduced by chemical vapor deposition. Specifically, after a catalyst precursor including Fe, K, ce, mo, an alkaline earth metal element and a catalyst selected from Cl element and Br element is prepared according to a conventional method, chemical vapor deposition is performed on the catalyst precursor, and carbon element is introduced into a catalyst composition.
According to the invention, the catalyst comprises the following components in parts by weight:
(a) 60-85 parts of Fe 2O3;
(b) 8-18 parts of K 2 O;
(c) 4-11 parts of CeO 2;
(d) 0.5-5 parts of MoO 3;
(e) 0.2-6 parts of alkaline earth metal oxide;
(f) 0.1-1 part of Cl and/or Br;
(g) 0.01-10 parts of carbon.
According to the invention, in the composition of the catalyst, the metal elements are in the form of oxides, the Cl and/or Br are in the form of elements themselves, and the carbon is in the form of carbon elements themselves.
According to the invention, the weight part of carbon in the catalyst is 0.1-5.
According to the invention, the weight ratio of the component (f) Cl and/or Br to the component (g) carbon in the catalyst is 0.05-30:1, preferably 0.10-0.35. The two have synergistic effect, and can obviously improve the selectivity of the catalyst in the reaction of preparing styrene by ethylbenzene dehydrogenation.
According to the invention, the catalyst contains Cl element and/or Br element, preferably Cl and Br, and further the weight ratio of Cl to Br is 1:2-5:1.
According to the invention, the alkaline earth metal is selected from Ca and/or Mg, preferably Ca.
The second aspect of the invention provides a method for preparing the catalyst. The preparation method comprises the following steps:
mixing a Fe source, a K source, a Ce source, a Mo source, an alkaline earth metal source, an optional pore-forming agent and at least one of a Cl source and a Br source, forming and roasting to obtain a catalyst precursor, and introducing carbon elements into the precursor to obtain the catalyst.
According to the invention, the precursor is subjected to chemical vapor deposition and carbon element is introduced to obtain the catalyst.
According to the invention, the gas in the chemical vapor deposition process is one or more of alkane, alkene and alkyne. Further, the gas includes at least one of ethane, ethylene, and acetylene. The mass airspeed of the gas is 1-100 h -1.
According to the invention, the treatment temperature in the chemical vapor deposition is 700-1000 ℃ and the time is 1-48 h.
According to the invention, no binder is added during the preparation of the catalyst.
According to the invention, the dosage of the pore-forming agent is 0.01% -5% of the total weight of the catalyst raw material.
According to the invention, a suitable amount of water may be added during the kneading. The water adding mode adopts slow adding, the water adding amount is not particularly limited, the water adding amount can be regulated according to the dry and wet degree of the materials, and the water adding amount is generally 15% -35% of the total mass of the mixed materials.
According to the invention, the molding can be performed by extrusion, and the strip can be particles with the diameter of 2-5 mm and the length of 3-10 mm.
According to the invention, the roasting condition is that the roasting temperature is 600-1000 ℃ and the roasting time is 2-24 hours.
According to the invention, the shaped material may be subjected to a drying step prior to calcination. The drying temperature is 30-200 ℃, and the drying time is 1-24 h.
According to the invention, the Fe source is selected from the group of oxides of Fe, preferably red iron oxide and/or yellow iron oxide. The K source is selected from potassium salt, preferably one or more of potassium carbonate, potassium nitrate and potassium bicarbonate. The Ce source is selected from one or more of cerium salt, preferably cerium nitrate, cerium oxalate and cerium carbonate. The Mo source is selected from molybdenum salts and/or molybdenum oxides, preferably one or more of ammonium molybdate and molybdenum oxide. The alkaline earth metal source is selected from one or more of alkaline earth oxides and alkaline earth metal hydroxides. The Cl source is selected from HCl. The Br source is selected from HBr. The pore-forming agent is selected from one or more of activated carbon, graphite, sodium hydroxymethyl cellulose and polystyrene microspheres.
In a third aspect, the invention provides the use of the catalyst described above or a catalyst prepared by the method described above in the dehydrogenation of ethylbenzene to styrene.
According to the invention, the method comprises the step of carrying out dehydrogenation reaction on the ethylbenzene-containing raw material in contact with the catalyst in the presence of water vapor to obtain a styrene-containing product.
According to the invention, the water is preheated to steam and thoroughly mixed with the feed gas before entering the reactor.
According to the invention, the reaction temperature is 550-640 ℃.
According to the invention, the reaction pressure is 20-100 kPa.
According to the invention, the mass space velocity of ethylbenzene is 0.2-2.0 h -1.
Compared with the prior art, the invention has remarkable advantages and outstanding effects, and is concretely as follows:
1. In the present invention, the selectivity of the Fe-K-Ce based dehydrogenation catalyst is directly related to the composition of the catalyst and the properties of the catalyst surface layer. The inventor finds that the composition of the catalyst comprises Cl element and/or Br element, and when the surface layer of the catalyst contains a certain amount of carbon, the catalyst and the catalyst have synergistic effect, so that the selectivity of the catalyst can be obviously improved. The surface carbon of the catalyst regulates the surface property of the catalyst, covers part of active sites with side reactions, further passivates uncovered active sites with side reactions, greatly reduces the generation of byproducts, and remarkably improves the styrene selectivity of the catalyst.
2. In the preparation method of the catalyst, raw materials containing all components are uniformly mixed, formed and roasted to obtain a catalyst precursor, carbon elements are introduced into the precursor to obtain the catalyst, and preferably, the precursor is subjected to chemical vapor deposition to introduce the carbon elements. The precursor is treated by a chemical vapor deposition method, so that the surface of the catalyst contains a proper amount of carbon. The catalyst comprises Cl element and/or Br element, and the surface layer of the catalyst has synergistic effect when a certain amount of carbon deposit is contained, so that the selectivity of styrene can be obviously improved while the high ethylbenzene conversion rate is maintained.
3. The catalyst provided by the invention is used in the reaction of preparing styrene by ethylbenzene dehydrogenation, has high selectivity under higher catalytic activity, and achieves better technical effect.
By adopting the technical scheme, the catalyst is subjected to activity evaluation in an isothermal fixed bed, and is evaluated under the conditions of 55kPa (absolute pressure), 0.5h -1 of ethylbenzene mass space velocity, 600 ℃ and water ratio reduced from 2.0 weight to 1.2 weight. The ethylbenzene conversion rate can reach 75.2%, and the styrene selectivity can reach 97.8%. The catalyst disclosed by the invention is used for the reaction of preparing styrene by ethylbenzene dehydrogenation, has very high styrene selectivity and good activity, and achieves good technical effects.
Drawings
FIG. 1 is a Raman spectrum of the catalysts prepared in example 1, example 6 and comparative example 1 of the present invention.
Detailed Description
In the present invention, chemical vapor deposition refers to a process of generating solid deposits by reacting the gaseous substances on the catalyst surface.
In the invention, the carbon deposition amount of the catalyst is tested by a Vario EL III element analyzer, and the operation mode is CHN and the decomposition temperature is 1000 ℃.
In the invention, raman (Raman) spectrum is measured by LabRAM Aramis model of Horiba Jobin Yvon company, and laser wavelength is 532nm. In the Raman spectrum of the catalyst, the spectral peaks at 1330+/-15 cm -1 and 1580+/-15 cm -1 are carbon characteristic diffraction peaks of the catalyst.
In the invention, the catalyst of the invention carries out ethylbenzene dehydrogenation reaction performance evaluation in a negative pressure isothermal fixed bed, and the process is briefly described as follows:
The reactor is a stainless steel tube with an inner diameter of 1', and is filled with 50-150 milliliters of catalyst with a diameter of 3-10 millimeters. Deionized water and ethylbenzene are respectively input into a preheating mixer through a metering pump, preheated and mixed into a gaseous state, and then enter into a reactor, and the reactor is heated by an electric heating wire to reach a preset temperature. The reaction product flowing out of the reactor was condensed and analyzed for its composition by gas chromatography.
The ethylbenzene conversion and styrene selectivity were calculated according to the following formula:
styrene yield% = ethylbenzene conversion% = styrene selectivity%.
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited by the examples.
Example 1
Iron oxide red corresponding to 72.0 parts of Fe 2O3, HCl corresponding to 0.4 parts of Cl and HBr corresponding to 0.2 parts of Br are weighed and stirred in a mixer, and then potassium carbonate corresponding to 11.0 parts of K 2 O, cerium nitrate corresponding to 9.6 parts of CeO 2, ammonium molybdate corresponding to 3.2 parts of MoO 3, calcium hydroxide corresponding to 3.6 parts of CaO and 2 parts of sodium hydroxymethyl cellulose are weighed and added into the mixer and stirred for 2 hours until uniform mixing is achieved. Deionized water accounting for 24 percent of the total weight of the dehydrogenation catalyst raw material is added and mixed for 2 hours. The mixture was then extruded and pelletized to give pellets having a diameter of 3mm and a length of 6mm, which were placed in an oven, dried at 60℃for 5 hours, and then placed in a muffle furnace, and calcined at 800℃for 4 hours to give dehydrogenation catalysts having the composition shown in Table 1. The catalyst was then treated with acetylene at a mass space velocity of 50h -1 at 850 ℃ for 10h.
Catalyst evaluation 100 ml of dehydrogenation catalyst was charged into the reactor and performance evaluation was carried out under conditions of 55kPa (absolute pressure), 0.5h -1 of mass space velocity of ethylbenzene, reaction temperature of 600C and water ratio of 1.2 (wt), and the test results of the reaction are shown in table 1.
Example 2
Iron oxide red corresponding to 63.0 parts of Fe 2O3, HCl corresponding to 0.2 parts of Cl and HBr corresponding to 0.1 part of Br are weighed and stirred in a mixer, and then potassium carbonate corresponding to 18.0 parts of K 2 O, cerium nitrate corresponding to 8.0 parts of CeO 2, ammonium molybdate corresponding to 4.8 parts of MoO 3, calcium hydroxide corresponding to 5.9 parts of CaO and 2 parts of sodium hydroxymethyl cellulose are weighed and added into the mixer and stirred for 2 hours until uniform mixing is achieved. Deionized water accounting for 28 percent of the total weight of the dehydrogenation catalyst raw material is added and mixed for 2 hours. The mixture was then extruded and pelletized to give pellets 3mm in diameter and 6mm long, which were placed in an oven, dried at 40 ℃ for 10 hours, and then placed in a muffle furnace, and calcined at 750 ℃ for 8 hours to give dehydrogenation catalysts, the dehydrogenation catalyst compositions being shown in table 1. The catalyst was then treated with acetylene at a mass space velocity of 50h -1 at 850 ℃ for 10h.
Catalyst evaluation 100 ml of dehydrogenation catalyst was charged into the reactor and performance evaluation was carried out under conditions of 55kPa (absolute pressure), 0.5h -1 of mass space velocity of ethylbenzene, reaction temperature of 600C and water ratio of 1.2 (wt), and the test results of the reaction are shown in table 1.
Example 3
Iron oxide red corresponding to 73.0 parts of Fe 2O3, HCl corresponding to 0.3 parts of Cl and HBr corresponding to 0.4 parts of Br are weighed and stirred in a mixer, and then potassium carbonate corresponding to 12.0 parts of K 2 O, cerium nitrate corresponding to 11.0 parts of CeO 2, ammonium molybdate corresponding to 1.4 parts of MoO 3, calcium hydroxide corresponding to 1.9 parts of CaO and 2 parts of sodium hydroxymethyl cellulose are weighed and added into the mixer and stirred for 2 hours until uniform mixing is achieved. Deionized water accounting for 20 percent of the total weight of the dehydrogenation catalyst raw material is added and mixed for 2 hours. The mixture was then extruded and pelletized to give pellets having a diameter of 3mm and a length of 6mm, which were placed in an oven, dried at 100℃for 4 hours, and then placed in a muffle furnace, and calcined at 950℃for 3 hours to give dehydrogenation catalysts having the composition shown in Table 1. The catalyst was then treated with acetylene at a mass space velocity of 50h -1 at 850 ℃ for 10h.
Catalyst evaluation 100 ml of dehydrogenation catalyst was charged into the reactor and performance evaluation was carried out under conditions of 55kPa (absolute pressure), 0.5h -1 of mass space velocity of ethylbenzene, reaction temperature of 600C and water ratio of 1.2 (wt), and the test results of the reaction are shown in table 1.
Example 4
Iron oxide red corresponding to 84.6 parts of Fe 2O3, HCl corresponding to 0.1 part of Cl and HBr corresponding to 0.1 part of Br are weighed and stirred in a mixer, and then potassium carbonate corresponding to 8.0 parts of K 2 O, cerium nitrate corresponding to 6.5 parts of CeO 2, ammonium molybdate corresponding to 0.5 part of MoO 3, calcium hydroxide corresponding to 0.2 part of CaO and 2 parts of sodium hydroxymethyl cellulose are weighed and added into the mixer to be stirred for 2 hours until uniform mixing. Deionized water accounting for 24 percent of the total weight of the dehydrogenation catalyst raw material is added and mixed for 2 hours. The mixture was then extruded and pelletized to give pellets having a diameter of 3mm and a length of 6mm, which were placed in an oven, dried at 60℃for 5 hours, and then placed in a muffle furnace, and calcined at 850℃for 4 hours to give dehydrogenation catalysts having the composition shown in Table 1. The catalyst was then treated with acetylene at a mass space velocity of 50h -1 at 850 ℃ for 10h.
Catalyst evaluation 100 ml of dehydrogenation catalyst was charged into the reactor and performance evaluation was carried out under conditions of 55kPa (absolute pressure), 0.5h -1 of mass space velocity of ethylbenzene, reaction temperature of 600C and water ratio of 1.2 (wt), and the test results of the reaction are shown in table 1.
Example 5
Iron oxide red corresponding to 72.0 parts of Fe 2O3, HCl corresponding to 0.4 parts of Cl and HBr corresponding to 0.2 parts of Br are weighed and stirred in a mixer, and then potassium carbonate corresponding to 11.0 parts of K 2 O, cerium nitrate corresponding to 9.6 parts of CeO 2, ammonium molybdate corresponding to 3.2 parts of MoO 3, magnesium hydroxide corresponding to 3.6 parts of MgO and 2 parts of sodium hydroxymethyl cellulose are weighed and added into the mixer and stirred for 2 hours until uniform mixing. Deionized water accounting for 24 percent of the total weight of the dehydrogenation catalyst raw material is added and mixed for 2 hours. The mixture was then extruded and pelletized to give pellets having a diameter of 3mm and a length of 6mm, which were placed in an oven, dried at 60℃for 5 hours, and then placed in a muffle furnace, and calcined at 800℃for 4 hours to give dehydrogenation catalysts having the composition shown in Table 1. The catalyst was then treated with acetylene at a mass space velocity of 50h -1 at 850 ℃ for 10h.
Catalyst evaluation 100 ml of dehydrogenation catalyst was charged into the reactor and performance evaluation was carried out under conditions of 55kPa (absolute pressure), 0.5h -1 of mass space velocity of ethylbenzene, reaction temperature of 600C and water ratio of 1.2 (wt), and the test results of the reaction are shown in table 1.
Example 6
Iron oxide red corresponding to 72.0 parts of Fe 2O3, HCl corresponding to 0.4 parts of Cl and HBr corresponding to 0.2 parts of Br are weighed and stirred in a mixer, and then potassium carbonate corresponding to 11.0 parts of K 2 O, cerium nitrate corresponding to 9.6 parts of CeO 2, ammonium molybdate corresponding to 3.2 parts of MoO 3, calcium hydroxide corresponding to 3.6 parts of CaO and 2 parts of sodium hydroxymethyl cellulose are weighed and added into the mixer and stirred for 2 hours until uniform mixing is achieved. Deionized water accounting for 24 percent of the total weight of the dehydrogenation catalyst raw material is added and mixed for 2 hours. The mixture was then extruded and pelletized to give pellets having a diameter of 3mm and a length of 6mm, which were placed in an oven, dried at 60℃for 5 hours, and then placed in a muffle furnace, and calcined at 800℃for 4 hours to give dehydrogenation catalysts having the composition shown in Table 1. The catalyst was then treated with ethane at a mass space velocity of 2h -1 at 720 ℃ for 1h.
Catalyst evaluation 100 ml of dehydrogenation catalyst was charged into the reactor and performance evaluation was carried out under conditions of 55kPa (absolute pressure), 0.5h -1 of mass space velocity of ethylbenzene, reaction temperature of 600C and water ratio of 1.2 (wt), and the test results of the reaction are shown in table 1.
Example 7
Iron oxide red corresponding to 72.0 parts of Fe 2O3, HCl corresponding to 0.4 parts of Cl and HBr corresponding to 0.2 parts of Br are weighed and stirred in a mixer, and then potassium carbonate corresponding to 11.0 parts of K 2 O, cerium nitrate corresponding to 9.6 parts of CeO 2, ammonium molybdate corresponding to 3.2 parts of MoO 3, calcium hydroxide corresponding to 3.6 parts of CaO and 2 parts of sodium hydroxymethyl cellulose are weighed and added into the mixer and stirred for 2 hours until uniform mixing is achieved. Deionized water accounting for 24 percent of the total weight of the dehydrogenation catalyst raw material is added and mixed for 2 hours. The mixture was then extruded and pelletized to give pellets having a diameter of 3mm and a length of 6mm, which were placed in an oven, dried at 60℃for 5 hours, and then placed in a muffle furnace, and calcined at 800℃for 4 hours to give dehydrogenation catalysts having the composition shown in Table 1. The catalyst was then treated with acetylene at a mass space velocity of 100h -1 at 980 ℃ for 40h.
Catalyst evaluation 100 ml of dehydrogenation catalyst was charged into the reactor and performance evaluation was carried out under conditions of 55kPa (absolute pressure), 0.5h -1 of mass space velocity of ethylbenzene, reaction temperature of 600C and water ratio of 1.2 (wt), and the test results of the reaction are shown in table 1.
Example 8
Iron oxide red corresponding to 72.0 parts of Fe 2O3 and HBr corresponding to 0.6 parts of Br are weighed and stirred in a mixer, and then potassium carbonate corresponding to 11.0 parts of K 2 O, cerium nitrate corresponding to 9.6 parts of CeO 2, ammonium molybdate corresponding to 3.2 parts of MoO 3, calcium hydroxide corresponding to 3.6 parts of CaO and 2 parts of sodium hydroxymethyl cellulose are weighed and added into the mixer to be stirred for 2 hours until the mixture is uniform. Deionized water accounting for 24 percent of the total weight of the dehydrogenation catalyst raw material is added and mixed for 2 hours. The mixture was then extruded and pelletized to give pellets having a diameter of 3 mm and a length of 6 mm, which were placed in an oven, dried at 60℃for 5 hours, and then placed in a muffle furnace, and calcined at 800℃for 4 hours to give dehydrogenation catalysts having the composition shown in Table 1. The catalyst was then treated with ethylene at a mass space velocity of 60h -1 at 950 ℃ for 20h.
Catalyst evaluation 100 ml of dehydrogenation catalyst was charged into the reactor and performance evaluation was carried out under conditions of 55kPa (absolute pressure), 0.5h -1 of mass space velocity of ethylbenzene, reaction temperature of 600C and water ratio of 1.2 (wt), and the test results of the reaction are shown in table 1.
Comparative example 1
Iron oxide red corresponding to 72.0 parts of Fe 2O3, potassium carbonate corresponding to 11.0 parts of K 2 O, cerium nitrate corresponding to 9.6 parts of CeO 2, ammonium molybdate corresponding to 3.2 parts of MoO 3, calcium hydroxide corresponding to 3.6 parts of CaO and 2 parts of sodium hydroxymethyl cellulose are weighed, added into a mixer and stirred for 2 hours until the mixture is uniform. Deionized water accounting for 24 percent of the total weight of the dehydrogenation catalyst raw material is added and mixed for 2 hours. The mixture was then extruded and pelletized to give pellets having a diameter of 3mm and a length of 6mm, which were placed in an oven, dried at 60℃for 5 hours, and then placed in a muffle furnace, and calcined at 800℃for 4 hours to give dehydrogenation catalysts having the composition shown in Table 1.
Catalyst evaluation 100 ml of dehydrogenation catalyst was charged into the reactor and performance evaluation was carried out under conditions of 55kPa (absolute pressure), 0.5h -1 of mass space velocity of ethylbenzene, reaction temperature of 600C and water ratio of 1.2 (wt), and the test results of the reaction are shown in table 1.
Comparative example 2
Iron oxide red corresponding to 72.0 parts of Fe 2O3, HCl corresponding to 0.4 parts of Cl and HBr corresponding to 0.2 parts of Br are weighed and stirred in a mixer, and then potassium carbonate corresponding to 11.0 parts of K 2 O, cerium nitrate corresponding to 9.6 parts of CeO 2, ammonium molybdate corresponding to 3.2 parts of MoO 3, calcium hydroxide corresponding to 3.6 parts of CaO and 2 parts of sodium hydroxymethyl cellulose are weighed and added into the mixer and stirred for 2 hours until uniform mixing is achieved. Deionized water accounting for 24 percent of the total weight of the dehydrogenation catalyst raw material is added and mixed for 2 hours. The mixture was then extruded and pelletized to give pellets having a diameter of 3mm and a length of 6mm, which were placed in an oven, dried at 60℃for 5 hours, and then placed in a muffle furnace, and calcined at 800℃for 4 hours to give dehydrogenation catalysts having the composition shown in Table 1.
Catalyst evaluation 100 ml of dehydrogenation catalyst was charged into the reactor and performance evaluation was carried out under conditions of 55kPa (absolute pressure), 0.5h -1 of mass space velocity of ethylbenzene, reaction temperature of 600C and water ratio of 1.2 (wt), and the test results of the reaction are shown in table 1.
Comparative example 3
Iron oxide red corresponding to 72.0 parts of Fe 2O3, potassium carbonate corresponding to 11.0 parts of K 2 O, cerium nitrate corresponding to 9.6 parts of CeO 2, ammonium molybdate corresponding to 3.2 parts of MoO 3, calcium hydroxide corresponding to 3.6 parts of CaO and 2 parts of sodium hydroxymethyl cellulose are weighed, added into a mixer and stirred for 2 hours until the mixture is uniform. Deionized water accounting for 24 percent of the total weight of the dehydrogenation catalyst raw material is added and mixed for 2 hours. The mixture was then extruded and pelletized to give pellets having a diameter of 3 mm and a length of 6mm, which were placed in an oven, dried at 60℃for 5 hours, and then placed in a muffle furnace, and calcined at 800℃for 4 hours to give dehydrogenation catalysts having the composition shown in Table 1. The catalyst was then treated with acetylene at a mass space velocity of 50h -1 at 850 ℃ for 10h.
Catalyst evaluation 100 ml of dehydrogenation catalyst was charged into the reactor and performance evaluation was carried out under conditions of 55kPa (absolute pressure), 0.5h -1 of mass space velocity of ethylbenzene, reaction temperature of 600C and water ratio of 1.2 (wt), and the test results of the reaction are shown in table 1.
Table 1 catalyst composition, properties and evaluation results of examples and comparative examples
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (13)
1. A catalyst for preparing styrene by ethylbenzene dehydrogenation comprises Fe, K, ce, mo, alkaline earth metal, carbon and at least one selected from Cl element and Br element;
the catalyst comprises the following components in parts by weight:
(a) 60-85 parts of Fe 2O3;
(b) 8-18 parts of K 2 O;
(c) 4-11 parts of CeO 2;
(d) 0.5-5 parts of MoO 3;
(e) 0.2-6 parts of alkaline earth metal oxide;
(f) 0.1-1 part of Cl and/or Br;
(g) 0.01-10 parts of carbon;
The preparation method of the catalyst comprises the steps of mixing a Fe source, a K source, a Ce source, a Mo source, an alkaline earth metal source, an optional pore-forming agent and at least one selected from a Cl source and a Br source, forming and roasting to obtain a catalyst precursor, performing chemical vapor deposition on the precursor, introducing carbon elements to obtain the catalyst, wherein gas in the chemical vapor deposition process is one or more selected from alkane, alkene and alkyne, the Cl source is selected from HCl, and the Br source is selected from HBr.
2. The catalyst according to claim 1, wherein the catalyst comprises 0.1-5 parts by weight of carbon.
3. The catalyst of claim 1 wherein the carbon is carbon deposit.
4. The catalyst of claim 1, wherein the catalyst comprises Cl and Br.
5. The catalyst of claim 4, wherein the weight ratio of Cl to Br is 1:2 to 5:1.
6. The catalyst according to claim 1, wherein the weight ratio of the component (f) Cl and/or Br to the component (g) carbon is 0.05-30:1.
7. A preparation method of the catalyst according to any one of claims 1-6 comprises the steps of mixing a Fe source, a K source, a Ce source, a Mo source, an alkaline earth metal source, an optional pore-forming agent and at least one selected from a Cl source and a Br source, roasting after forming to obtain a catalyst precursor, performing chemical vapor deposition on the precursor to introduce carbon elements to obtain the catalyst, wherein gas in the chemical vapor deposition process is one or more of alkane, alkene and alkyne, and the Cl source is selected from HCl and the Br source is selected from HBr.
8. The method of claim 7, wherein the gas comprises at least one of ethane, ethylene, and acetylene during the chemical vapor deposition.
9. The method according to claim 7, wherein the treatment temperature in the chemical vapor deposition is 700-1000 ℃, and/or the treatment time is 1-48 h, and/or the mass space velocity of the gas is 1-100 h -1.
10. The process according to claim 7, wherein,
The Fe source is selected from oxides of Fe;
and/or, the K source is selected from potassium salts;
and/or, the Ce source is selected from cerium salts;
and/or the Mo source is selected from molybdenum salts and/or oxides of molybdenum;
And/or the alkaline earth metal source is selected from one or more of alkaline earth oxides and alkaline earth metal hydroxides;
And/or the pore-forming agent is selected from one or more of activated carbon, graphite, sodium hydroxymethyl cellulose and polystyrene microspheres.
11. The method according to claim 10, wherein,
The Fe source is selected from iron oxide red and/or iron oxide yellow;
and/or the K source is selected from one or more of potassium carbonate, potassium nitrate and potassium bicarbonate;
And/or the Ce source is selected from one or more of cerium nitrate, cerium oxalate and cerium carbonate;
And/or the Mo source is selected from one or more of ammonium molybdate and molybdenum oxide.
12. Use of the catalyst according to any one of claims 1 to 6 or the catalyst prepared by the preparation method according to any one of claims 7 to 11 in a reaction for preparing styrene by ethylbenzene dehydrogenation.
13. The use according to claim 12, characterized in that the temperature of the reaction is 550-640 ℃, and/or the pressure of the reaction is 20-100 kpa absolute, and/or the mass space velocity of ethylbenzene is 0.2-2.0 h -1.
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| CN106423240A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Styrene catalyst and preparation method thereof |
| CN106890647A (en) * | 2015-12-17 | 2017-06-27 | 中国石油天然气股份有限公司 | Catalyst for preparing isobutene from isobutane dehydrogenation and preparation method thereof |
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| CN104888817A (en) * | 2015-05-27 | 2015-09-09 | 廖仕杰 | Low-water-ratio ethylbenzene dehydrogenation catalyst |
| CN115957772B (en) * | 2021-10-11 | 2025-11-11 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst and preparation method and application thereof |
| CN115957773B (en) * | 2021-10-11 | 2024-05-03 | 中国石油化工股份有限公司 | A kind of ethylbenzene dehydrogenation catalyst and its preparation method and application |
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| CN106890647A (en) * | 2015-12-17 | 2017-06-27 | 中国石油天然气股份有限公司 | Catalyst for preparing isobutene from isobutane dehydrogenation and preparation method thereof |
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