CN115959966A - Method for producing divinylbenzene by dehydrogenating diethylbenzene - Google Patents
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Abstract
The invention relates to a method for producing divinylbenzene by dehydrogenating diethylbenzene, which comprises the following steps: the raw material containing the diethylbenzene contacts with a dehydrogenation catalyst in the presence of water vapor to carry out dehydrogenation reaction to obtain a product containing the divinylbenzene; the dehydrogenation catalyst comprises Fe 2 O 3 、K 2 O、CeO 2 、MoO 3 CaO; wherein, ceO 2 (100) Exposed crystal face area in CeO 2 More than 65% of the total exposed crystal plane area. The catalyst of the method has high catalytic activity and divinylbenzene selectivity when used for producing divinylbenzene under the condition of low water ratio.
Description
Technical Field
The invention relates to a method for producing divinylbenzene by dehydrogenating diethylbenzene, in particular to a method for producing divinylbenzene by dehydrogenating diethylbenzene under the condition of low water ratio.
Background
Divinylbenzene is an important cross-linking agent and is widely used in ion exchange resin, ion exchange membranes, ABS resin, polystyrene resin, unsaturated polyester resin, synthetic rubber, special plastics, coatings, adhesives and other fields. There are many methods for preparing divinylbenzene, but the industrial production method of divinylbenzene is mainly obtained by dehydrogenation of diethylbenzene.
The dehydrogenation reaction of diethylbenzene is a strong heat absorption reversible reaction with increased molecular number, and the reaction is favorably carried out at high temperature and low pressure. It is common in industry to introduce large amounts of high temperature water vapor to favor the production of the desired product divinylbenzene. Water vapor plays a number of important roles in the reaction: providing heat required by the reaction; reducing the partial pressure of diethylbenzene and promoting the chemical equilibrium to move towards the direction of a product; eliminating carbon deposit on the surface of the catalyst; oxidizing the catalyst surface, maintaining the catalyst activity, and the like. However, the large amount of superheated steam as the dehydrogenation medium makes the process large in energy consumption, large in product condensation amount and high in production cost. Therefore, the diethylbenzene dehydrogenation process seeks to obtain higher divinylbenzene yield at a lower water ratio (mass ratio of water vapor in the feed to diethylbenzene), and the adoption of low water ratio operation is one of important measures for energy conservation and consumption reduction. Meanwhile, the reaction of dehydrogenation of diethylbenzene to generate divinylbenzene is a two-step reversible series reaction of dehydrogenation of diethylbenzene to generate ethylstyrene (monoene) and continuous dehydrogenation of ethylstyrene to generate divinylbenzene (diene), and the dehydrogenation product easily contains the ethylstyrene with higher concentration. Therefore, reducing the ratio of the mono-diene in the product is also an important means for improving the economy of the production process.
The prior diethylbenzene dehydrogenation catalyst is mainly a Fe-K-Ce catalyst, wherein Fe-K oxide is used as a main active component, ce is used as a main auxiliary agent, and meanwhile, the catalyst also contains structural stabilizers such as oxides of Mg, mo, W and Ca and electronic auxiliary agents. The published world patent WO2008090974 (high-strength catalyst for dehydrogenation of alkyl aromatic hydrocarbon, and preparation method and application thereof) uses cerium hydroxide carbonate of 0.5 to 5 microns as a raw material, and the catalyst prepared by increasing the content of cerium can effectively improve the mechanical strength and performance of the catalyst, and is used in industrial production of dehydrogenation of alkyl aromatic hydrocarbon. CN111056909A discloses a method for continuously reacting diethylbenzene with two different iron-potassium-cerium catalysts in a fixed bed reactor, which realizes high conversion rate and low mono-diene/diene ratio of the diethylbenzene. However, the weight ratio of steam/ethylbenzene was 2.0 to 5.0.
The existing production process for diethylbenzene dehydrogenation still has the problems of high steam unit consumption and high energy consumption. The development of a catalyst and a production process suitable for low water ratio and the improvement of the selectivity of the divinylbenzene, thereby reducing the production cost, becomes an urgent need of divinylbenzene production enterprises.
Disclosure of Invention
The invention aims to solve the technical problems of high water vapor consumption, high ratio of single diene in a product and low divinylbenzene selectivity in the prior technology for producing the divinylbenzene by dehydrogenating the diethylbenzene, and provides a method for producing the divinylbenzene by dehydrogenating the diethylbenzene. The catalyst of the method has high catalytic activity and divinylbenzene selectivity when used for producing divinylbenzene under the condition of low water ratio.
The invention provides a method for producing divinylbenzene by dehydrogenating diethylbenzene, which comprises the following steps: the raw material containing the diethylbenzene contacts with a dehydrogenation catalyst in the presence of water vapor to carry out dehydrogenation reaction to obtain a product containing the divinylbenzene; the dehydrogenation catalyst comprises Fe 2 O 3 、K 2 O、CeO 2 、MoO 3 CaO; wherein, ceO 2 (100) Exposed crystal face area of CeO 2 The total exposed crystal face area is more than 65 percent, preferably 65 to 90 percent.
In the above technical solution, the application of the dehydrogenation catalyst in the reaction of producing divinylbenzene by dehydrogenation of diethylbenzene is suitable for low water ratio, i.e. the weight ratio of water/diethylbenzene is less than 2.0, preferably 1.2-2.0.
In the technical scheme, water is preheated to be water vapor before entering the reactor and is fully mixed with the raw material gas.
In the technical scheme, the outlet pressure of the reaction bed is 20-80 kPa, preferably 20-50 kPa; the pressure is absolute pressure; the outlet temperature of the reaction bed is 560-620 ℃;
in the technical scheme, the mass space velocity of the diethylbenzene is 0.2-2.0 h -1 。
In the above technical scheme, the dehydrogenation catalyst comprises the following components in terms of mass fraction based on the total mass of the dehydrogenation catalyst:
(a) 61-86% of Fe 2 O 3 ；
(b) 5% -14% of K 2 O；
(c) 6 to 14 percent of CeO 2 ；
(d) 0.5 to 5 percent of MoO 3 ；
(e) 0.3 to 7 percent of CaO.
In the above technical means, it is preferable that the dehydrogenation catalyst contains 0.01 to 2.0% by mass of Na based on the total mass of the dehydrogenation catalyst 2 O。
In the above technical means, the dehydrogenation catalyst may further comprise 0.01 to 2.0% by mass of TiO based on the total mass of the dehydrogenation catalyst 2 And other metal oxides.
In the above technical solution, preferably, the CeO 2 (100) Exposed crystal face area of CeO 2 More than 70% of the total exposed crystal face area; such as but not limited to 70%,75%,80%,85%,87%,90%, etc.
In the above technical scheme, the preparation method of the dehydrogenation catalyst comprises the following steps:
uniformly mixing a Fe source, a Ce source, a Mo source, a Ca source, an optional first K source and an optional pore-foaming agent, adding an alkaline solution, standing for reaction, forming and roasting to obtain the dehydrogenation catalyst;
wherein K in the dehydrogenation catalyst 2 O is derived from the first K source and/or the alkaline solution.
In the above technical solution, in the preparation method of the dehydrogenation catalyst, the alkaline solution is an aqueous solution of potassium hydroxide and/or sodium hydroxide, preferably an aqueous solution of sodium hydroxide and potassium hydroxide. When the alkaline solution is the aqueous solution of sodium hydroxide and potassium hydroxide, the sodium hydroxide is Na 2 O and K is potassium hydroxide 2 The mass ratio in terms of O is preferably 1:2 to 23. The concentration of hydroxide in the alkaline solution is 1-8 mol/L. In the preparation method of the dehydrogenation catalyst, the alkaline solution is used in an amount enough to ensure that the cerium source is dissolved in the liquid phase for reaction.
In the above technical scheme, in the preparation method of the dehydrogenation catalyst, K in the dehydrogenation catalyst 2 O is derived from the first K source and/or the basic solution, preferably K in the dehydrogenation catalyst 2 The O originates at least in part from an alkaline solution. Preferably, K in the dehydrogenation catalyst 2 At least 50% of the O is derived from the K-containing alkaline solution, the remainder being derived from the first K source. K in dehydrogenation catalysts 2 Instead of using the first K source, the whole of O may also be derived from a K-containing alkaline solution.
In the above technical solution, in the preparation method of the dehydrogenation catalyst, the Fe source is oxide Fe 2 O 3 Adding the mixture in a form. The Fe source is preferably selected from red iron oxide and/or yellow iron oxide, more preferably a combination of red and yellow iron oxide, wherein the red and yellow iron oxide are in Fe 2 O 3 The mass ratio is 1.0-3.5. The first K source is added as a potassium salt; the potassium salt is one or more of potassium carbonate, potassium nitrate and potassium bicarbonate. The Ce source is added in the form of cerium salt; the cerium salt is cerium nitrate. The Mo source is added in the form of molybdenum salt or oxide; the molybdenum salt is ammonium molybdate. The calcium source is added in the form of an oxide or hydroxide. The pore-forming agent is active carbon, graphite, sodium carboxymethyl cellulose andany one or more of polystyrene microspheres. The addition amount of the pore-foaming agent is less than 5 percent of the mass of the dehydrogenation catalyst, and further ranges from 0.01 percent to 5 percent. In the preparation method of the dehydrogenation catalyst, a Fe source, a Ce source, a Mo source, a Ca source, a first K source and a pore-forming agent are added in a solid-phase powder mode.
In the above technical scheme, in the preparation method of the dehydrogenation catalyst, the raw material also contains a Ti source; the Ti source, the Fe source, the Ce source, the Mo source, the Ca source, the optional first K source and the optional pore-foaming agent are mixed and added uniformly. The Ti source is added in the form of titanium salt or oxide; the titanium salt is any one or two of titanium tetrachloride or titanium tetrabromide.
In the above technical solution, in the preparation method of the dehydrogenation catalyst, the mixing may be performed by using a conventional mechanical stirring method.
In the above technical scheme, in the preparation method of the dehydrogenation catalyst, the standing reaction condition is that the standing reaction is carried out for 12-48 h at 120-180 ℃. The vessel for the standing reaction is preferably an autoclave. The pressure of the standing reaction is not particularly limited.
In the above technical scheme, in the preparation method of the dehydrogenation catalyst, the molding may be extrusion molding, and the strip may be a particle with a diameter of 2-5 mm and a length of 3-10 mm. If the material after reaction can not meet the molding requirement, partial water can be removed by adopting a mode of evaporation and the like or a proper amount of water is added, and then molding is carried out.
In the technical scheme, in the preparation method of the dehydrogenation catalyst, the roasting temperature is 600-1000 ℃, and the roasting time is 2-8 h.
In the above technical scheme, in the preparation method of the dehydrogenation catalyst, as a preferred roasting condition, two-step roasting is adopted, for example, but not limited to roasting at 600-800 ℃ for 2-4 h, and then roasting at 900-1000 ℃ for 2-4 h. The firing is carried out in a muffle furnace.
In the above technical solution, in the preparation method of the dehydrogenation catalyst, the formed material may be dried before being calcined. The drying temperature is 50-200 ℃, and the drying time is 1-24 h.
Compared with the prior art, the invention has obvious advantages and outstanding effects, and specifically comprises the following steps:
1. in the process of dehydrogenation reaction of diethylbenzene, after the dehydrogenation catalyst captures H in alkylbenzene molecules, the surface of the alkylbenzene molecules is covered by H, and the surface is reduced, and the H is required to be removed 2 To restore reactivity. Surface dehydrogenation of active phase potassium ferrite in Fe-K-Ce-Mo series dehydrogenation catalyst 2 The rate of (a) is low, limiting the dehydrogenation catalyst reactivity. H on the surface of the active phase of the dehydrogenation catalyst can migrate to CeO under the promotion of water 2 Surface, rapid formation of H 2 The catalyst is separated from the surface of the dehydrogenation catalyst, so that the reaction energy barrier is reduced, the reaction is promoted, and the catalytic activity of the dehydrogenation catalyst is improved. The inventor finds that the reaction performance and the surface structure of the Fe-K-Ce-Mo series diethylbenzene dehydrogenation catalyst are highly correlated, and different CeO 2 Exposing crystal planes can result in a significant difference in catalyst dehydrogenation activity and stability. The inventors have further studied and found that CeO 2 (100) The area occupation ratio of the exposed crystal face is high, particularly more than 65%, the reoxidation of active sites of the catalyst in dehydrogenation reaction is promoted, and the reduction temperature of the catalyst is improved by matching with an auxiliary agent, so that the catalyst has good activity.
2. In the invention, the inventor discovers that CeO on the surface of the prepared catalyst is enabled to be on the one hand by controlling the alkalinity of the system and the wet reaction conditions in the preparation process of the Fe-K-Ce-Mo system diethylbenzene dehydrogenation catalyst 2 (100) The exposed crystal face occupation ratio is high, and on the other hand, the preparation method promotes the interaction between the auxiliary agent component and the active component, and improves the stability of the crystal structure in the catalyst. Compared with the conventional dry preparation method, the method is more favorable for improving the catalytic performance of the diethylbenzene dehydrogenation catalyst. The preparation process of the catalyst is simple, and the obtained catalyst has the advantages of high activity and high divinylbenzene selectivity.
3. The reaction of dehydrogenating diethylbenzene to produce divinylbenzene is a two-step reversible series reaction of dehydrogenating diethylbenzene to produce ethylstyrene (monoene) and continuously dehydrogenating ethylstyrene to produce divinylbenzene (diene), and thermodynamic analysis shows that the equilibrium conversion rates of the two-step dehydrogenation reaction are relatively close under the same conditions. The dehydrogenation product tends to contain a relatively high concentration of ethyl styrene, subject to reaction conditions and dehydrogenation catalyst performance limitations. In order to increase the conversion of diethylbenzene and the selectivity of the target product divinylbenzene, it is common in industry to introduce a large amount of water vapor (water/diethylbenzene weight ratio: 2.5 or more) into the reaction system to shift the reaction equilibrium toward dehydrogenation. Aiming at the reaction characteristics, the invention improves the equilibrium conversion rate by properly controlling the pressure at the outlet of the reaction bed layer and the temperature at the outlet of the reaction bed layer, adopts a high-performance catalyst to ensure that the two-step dehydrogenation reaction achieves high conversion rate, obviously reduces the water vapor consumption, improves the diethylbenzene conversion rate and the selectivity of a target product, namely divinylbenzene, and obtains better technical effects.
By adopting the technical scheme of the invention, the dehydrogenation catalyst is subjected to activity evaluation in a heat-insulating fixed bed, the pressure at the outlet of a reaction bed layer is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The conversion rate can reach more than 75 percent, the total selectivity of the ethylvinylbenzene and the divinylbenzene can reach more than 91 percent, and the selectivity of the divinylbenzene can reach more than 61 percent, when the temperature of the bed layer outlet is 600 ℃ and the water ratio is 1.8 (weight). The method for preparing the divinylbenzene by dehydrogenating the diethylbenzene under the condition of low water ratio has better technical effect.
Drawings
FIG. 1 is a graph of the major exposed crystal planes of the HAADF-STEM test of the dehydrogenation catalyst of example 1;
FIG. 2 is a graph of the major exposed crystal planes of the HAADF-STEM test of the dehydrogenation catalyst of comparative example 1.
Detailed Description
The invention is further illustrated by the following examples, without restricting its scope.
In the invention, the area of an exposed crystal face is tested by adopting a characterization means of a high-angle annular dark field image scanning transmission electron microscope (HAADF-STEM), and a testing instrument is a Titan cube Themis G2 300 transmission electron microscope for double spherical aberration correction of FEI company. CeO (CeO) 2 (100) Crystal face of CeO 2 The proportion of the total exposed crystal face area is obtained by counting and calculating HAADF-STEM morphology pictures and geometric structural characteristics of catalyst samples, namely the observed CeO 2 (100) Crystal face area occupied observed CeO 2 Proportion of total exposed crystal plane area. CeO (CeO) 2 Total exposed crystal face area of CeO 2 (100)、CeO 2 (110)、CeO 2 (111) And CeO 2 (311) Sum of exposed crystal plane areas. Observation of CeO by scanning Transmission Electron microscope 2 (100) Exposed crystal face, with [100 ]]Two mutually perpendicular directions [020 ] are visible in a plane perpendicular to the viewing direction]And [002]The spacing between crystal faces is 260-290 pm, and the exposed crystal face is proved to be CeO 2 (100)。
In the invention, the performance of the dehydrogenation catalyst of the invention is evaluated in the diethylbenzene dehydrogenation reaction in an adiabatic fixed bed, and the process is briefly described as follows:
the reactor is a stainless steel tube with the inner diameter of 1' and is filled with 50-150 ml of dehydrogenation catalyst with the diameter of 3-10 mm. The deionized water and diethylbenzene are respectively fed into a preheating mixer by a metering pump, preheated and mixed into a gaseous state, and then fed into a reactor, and the reactor is heated by an electric heating wire to reach a preset temperature. The composition of the reactants exiting the reactor was analyzed by gas chromatography after condensation of water.
The water ratio (wt) is the ratio of the amount of steam charged to the amount of diethylbenzene charged per unit time, i.e., the ratio of the flow rate of steam to the flow rate of diethylbenzene.
The diethylbenzene conversion, ethylvinylbenzene selectivity, divinylbenzene selectivity and bis-mono-olefin ratio were calculated as follows:
total% selectivity of diolefins =% selectivity of ethylstyrene + selectivity of divinylbenzene,
ethyl vinyl benzene yield% = diethylbenzene conversion% × ethyl vinyl benzene selectivity%,
divinylbenzene yield% = divinylbenzene conversion% × divinylbenzene selectivity%,
[ example 1 ]
Weighed corresponding to 50.1 parts of Fe 2 O 3 Iron oxide red of (1), 21.4 parts of Fe 2 O 3 Iron oxide yellow (equivalent to 10.5 parts of CeO) 2 Corresponding to 2.8 parts of MoO 3 The ammonium molybdate, 3.2 parts of calcium oxide and 3.05 parts of polystyrene microspheres are stirred in a mixer for 2 hours until the mixture is uniformly mixed. Then, 0.8 part of Na is added 2 NaOH of O and corresponding to 11.2 parts of K 2 A mixed aqueous solution of KOH containing O, wherein the concentration of hydroxyl in the mixed aqueous solution is 3.2mol/L. The reaction was allowed to stand in an autoclave at 140 ℃ for 20 hours. And then, adjusting the water content of the mixture, extruding into strips, cutting into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying for 4h at 80 ℃ and drying for 4h at 150 ℃, then putting the granules into a muffle furnace, roasting for 2h at 650 ℃ and roasting for 2h at 900 ℃ to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into a reactor, the pressure at the outlet of a reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance evaluation was carried out under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1. The test results of 1000h reaction are shown in Table 2.
[ example 2 ] A method for producing a polycarbonate
Weighing 36.2 parts of Fe 2 O 3 26.6 parts of Fe 2 O 3 Yellow iron oxide equivalent to11.6 parts of CeO 2 Equivalent to 4.8 parts of MoO 3 Ammonium molybdate, 5.4 parts of calcium oxide and 2.6 parts of polystyrene microspheres, and stirring in a mixer for 2 hours until the materials are uniformly mixed. Then, 1.8 parts of Na was added 2 NaOH of O and corresponding 13.6 parts of K 2 A mixed aqueous solution of KOH containing O, wherein the concentration of hydroxyl in the mixed aqueous solution is 6.5mol/L. The reaction was allowed to stand in an autoclave at 120 ℃ for 48 hours. And then, adjusting the water content of the mixture, extruding into strips, cutting into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying for 4h at 80 ℃ and drying for 4h at 150 ℃, then putting the granules into a muffle furnace, roasting for 2h at 650 ℃ and roasting for 2h at 900 ℃ to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into the reactor, the pressure at the outlet of the reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance evaluation was carried out under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1.
[ example 3 ]
Weighed equivalent to 45.6 parts Fe 2 O 3 23.8 parts of Fe 2 O 3 Corresponding to 13.8 parts of CeO 2 Equivalent to 3.6 parts of MoO 3 Ammonium molybdate and 1.5 parts of calcium oxide, in a mixer for 2 hours until mixed uniformly. Then, 0.9 part of Na was added 2 NaOH of O and corresponding to 10.8 parts of K 2 A mixed aqueous solution of KOH containing O, wherein the concentration of hydroxyl in the mixed aqueous solution is 2.5mol/L. The reaction was allowed to stand in an autoclave at 170 ℃ for 12 hours. And then, adjusting the water content of the mixture, extruding into strips, cutting into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying for 4h at 80 ℃ and drying for 4h at 150 ℃, then putting the granules into a muffle furnace, roasting for 2h at 650 ℃ and roasting for 2h at 900 ℃ to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into a reactor, the pressure at the outlet of a reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance evaluation is carried out under the conditions that the outlet temperature of the reaction bed is 600 ℃ and the water ratio is 1.8 (wt), and the reaction is carried out for 100 hoursThe results are shown in Table 1.
[ example 4 ]
Weighed to 49.2 parts Fe 2 O 3 Iron oxide red of (1), 34.9 parts of Fe 2 O 3 Iron oxide yellow (equivalent to 8.3 parts of CeO) 2 Corresponding to 1.2 parts of MoO 3 Ammonium molybdate, 0.4 part of calcium oxide and 4.8 parts of polystyrene microspheres, and stirring in a mixer for 2 hours until the mixture is uniformly mixed. Then, 0.8 part of Na was added 2 NaOH of O and corresponding to 5.2 parts of K 2 A mixed aqueous solution of KOH of O, wherein the concentration of hydroxyl in the mixed aqueous solution is 2.0mol/L. The reaction was allowed to stand in an autoclave at 140 ℃ for 20 hours. And then, adjusting the water content of the mixture, extruding into strips, cutting into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying for 4h at 80 ℃ and drying for 4h at 150 ℃, then putting the granules into a muffle furnace, and roasting for 4h at 600 ℃ and 2h at 900 ℃ to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is shown in Table 1.
100 ml of dehydrogenation catalyst is loaded into the reactor, the pressure at the outlet of the reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance was evaluated under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1.
[ example 5 ]
Weighed corresponding to 52.3 parts of Fe 2 O 3 Iron oxide red of 28.0 parts of Fe 2 O 3 Iron oxide yellow (equivalent to 8.1 parts of CeO) 2 Corresponding to 0.6 part of MoO 3 2.6 parts of calcium oxide and 2.5 parts of polystyrene microspheres, and stirring in a mixer for 2 hours until the components are uniformly mixed. Then, 1.0 part of Na was added 2 NaOH of O and corresponding to 7.4 parts of K 2 A mixed aqueous solution of KOH containing O, wherein the concentration of hydroxyl in the mixed aqueous solution is 2.6mol/L. The reaction was allowed to stand in an autoclave at 140 ℃ for 20 hours. And then, adjusting the water content of the mixture, extruding into strips, cutting into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying for 4h at 80 ℃ and drying for 4h at 150 ℃, then putting the granules into a muffle furnace, roasting for 2h at 750 ℃ and roasting for 2h at 900 ℃ to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into a reactor, the pressure at the outlet of a reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance evaluation was carried out under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1.
[ example 6 ]
Weighed in an amount corresponding to 50.6 parts of Fe 2 O 3 Iron oxide red of (1), 20.3 parts of Fe 2 O 3 Yellow iron oxide (equivalent to 6.9 parts of CeO) 2 Equivalent to 3.5 parts of MoO 3 Ammonium molybdate, 6.9 parts of calcium oxide, 0.06 part of titanium dioxide and 2.6 parts of polystyrene microspheres, and stirring for 2 hours in a mixer until the materials are uniformly mixed. Then, 0.6 part of Na is added 2 NaOH of O and corresponding to 11.14 parts of K 2 A mixed aqueous solution of KOH as O, wherein the concentration of hydroxyl in the mixed aqueous solution is 3.1mol/L. The reaction was allowed to stand in an autoclave at 140 ℃ for 20 hours. And then, adjusting the water content of the mixture, extruding the mixture into strips, cutting the strips into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying the granules for 4h at 80 ℃ and drying the granules for 4h at 150 ℃, then putting the granules into a muffle furnace, roasting the granules for 2h at 650 ℃ and roasting the granules for 2h at 980 ℃ to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into a reactor, the pressure at the outlet of a reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance evaluation was carried out under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1.
[ example 7 ]
Weighing 54.4 parts of Fe 2 O 3 Iron oxide red of (1), 16.0 parts of Fe 2 O 3 Yellow iron oxide (equivalent to 11.2 parts of CeO) 2 Cerium nitrate, 3.0 parts of MoO 3 Calcium carbonate equivalent to 3.2 parts of CaO and 3.1 parts of polystyrene microspheres, and stirring in a mixer for 2 hours until the mixture is uniformly mixed. Then, 1.6 parts of Na were added 2 NaOH of O and corresponding to 10.6 parts of K 2 A mixed aqueous solution of KOH containing O, wherein the concentration of hydroxyl in the mixed aqueous solution is 3.0mol/L. The mixture is kept still in an autoclave for reaction for 20 hours at 140 ℃. Then will be atAnd (3) adjusting the water content of the mixture, extruding into strips, cutting into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying at 50 ℃ for 12h, drying at 150 ℃ for 4h, then putting the granules into a muffle furnace, roasting at 650 ℃ for 2h and roasting at 900 ℃ for 2h to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into a reactor, the pressure at the outlet of a reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance was evaluated under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1. The test results for 1000h of reaction are shown in Table 2.
[ example 8 ]
Weighed equivalent to 37.5 parts Fe 2 O 3 Iron oxide red of (1), 35.1 parts of Fe 2 O 3 Corresponding to 11.9 parts of CeO 2 Corresponding to 2.1 parts of MoO 3 Ammonium molybdate (b), calcium nitrate corresponding to 3.3 parts of CaO and 3.5 parts of activated carbon, are stirred in a mixer for 2 hours until they are uniformly mixed. Then, 1.5 parts of Na were added 2 NaOH of O and corresponding to 8.6 parts of K 2 A mixed aqueous solution of KOH of O, wherein the concentration of hydroxyl in the mixed aqueous solution is 2.8mol/L. The reaction was allowed to stand in an autoclave at 140 ℃ for 20 hours. And then, adjusting the water content of the mixture, extruding the mixture into strips, cutting the strips into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying the granules for 4h at 100 ℃ and drying the granules for 4h at 150 ℃, then putting the granules into a muffle furnace, roasting the granules for 2h at 650 ℃ and roasting the granules for 2h at 900 ℃ to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into a reactor, the pressure at the outlet of a reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance evaluation was carried out under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1.
[ example 9 ] A method for producing a polycarbonate
Weighed corresponding to 40.0 parts of Fe 2 O 3 Iron oxide red of (2), 32.5 parts of Fe 2 O 3 Iron oxide yellow (equivalent to 10.6 parts of CeO) 2 Corresponding to 2.1 parts of MoO 3 Of (2)Ammonium sulfate, calcium chloride equivalent to 2.9 parts CaO and 3.2 parts graphite were stirred in a mixer for 2h to mix well. Then, 0.5 part of Na was added 2 NaOH of O and corresponding to 11.4 parts of K 2 A mixed aqueous solution of KOH containing O, wherein the concentration of hydroxyl in the mixed aqueous solution is 3.5mol/L. The reaction was allowed to stand in an autoclave at 140 ℃ for 20 hours. And then, adjusting the water content of the mixture, extruding into strips, cutting into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying at 120 ℃ for 4h and drying at 150 ℃ for 4h, then putting the granules into a muffle furnace, roasting at 650 ℃ for 2h and roasting at 900 ℃ for 2h to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into the reactor, the pressure at the outlet of the reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance evaluation was carried out under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1.
[ example 10 ] A method for producing a polycarbonate
Weighed corresponding to 50.5 parts of Fe 2 O 3 Iron oxide red of (1), 19.7 parts of Fe 2 O 3 Iron oxide yellow (equivalent to 12.0 parts of CeO) 2 Cerium nitrate, 2.6 parts of MoO 3 3.5 parts of calcium oxide and 3.2 parts of hydroxymethyl cellulose, and stirring in a mixer for 2 hours until the mixture is uniform. Then, 1.1 parts of Na is added 2 NaOH of O and corresponding to 10.6 parts of K 2 A mixed aqueous solution of KOH containing O, wherein the concentration of hydroxyl in the mixed aqueous solution is 3.4mol/L. The reaction was allowed to stand in an autoclave at 140 ℃ for 20 hours. And then, adjusting the water content of the mixture, extruding the mixture into strips, cutting the strips into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying the granules for 4h at 80 ℃ and drying the granules for 4h at 180 ℃, then putting the granules into a muffle furnace, roasting the granules for 2h at 650 ℃ and roasting the granules for 2h at 900 ℃ to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into the reactor, the pressure at the outlet of the reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance evaluation was carried out under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1.
[ example 11 ] A method for producing a polycarbonate
Weighed in an amount equivalent to 50.9 parts of Fe 2 O 3 23.4 parts of Fe 2 O 3 Yellow iron oxide (equivalent to 11.2 parts of CeO) 2 Corresponding to 1.8 parts of MoO 3 Ammonium molybdate (b), calcium carbonate corresponding to 2.7 parts of CaO, and 3.2 parts of graphite were stirred in a mixer for 2 hours until they were uniformly mixed. Then, 0.5 part of Na was added 2 NaOH of O and corresponding to 9.5 parts of K 2 A mixed aqueous solution of KOH containing O, wherein the concentration of hydroxide in the mixed aqueous solution is 2.9mol/L. The reaction was allowed to stand in an autoclave at 140 ℃ for 20 hours. And then, adjusting the water content of the mixture, extruding into strips, cutting into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying for 4h at 80 ℃, drying for 2h at 200 ℃, then putting the granules into a muffle furnace, roasting for 2h at 650 ℃, and roasting for 2h at 900 ℃ to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into the reactor, the pressure at the outlet of the reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance evaluation was carried out under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1.
[ example 12 ]
Weighed corresponding to 50.1 parts of Fe 2 O 3 Iron oxide red of (1), 21.4 parts of Fe 2 O 3 Iron oxide yellow (equivalent to 10.5 parts of CeO) 2 Corresponding to 9.6 parts of K 2 Potassium nitrate of O, equivalent to 2.8 parts of MoO 3 The ammonium molybdate, 3.2 parts of calcium oxide and 3.05 parts of polystyrene microspheres are stirred in a mixer for 2 hours until the components are uniformly mixed. Then, 0.8 part of Na was added 2 NaOH of O and corresponding to 1.6 parts of K 2 A mixed aqueous solution of KOH of O, wherein the concentration of hydroxyl in the mixed aqueous solution is 3.2mol/L. The reaction was allowed to stand in an autoclave at 140 ℃ for 20 hours. And then, adjusting the water content of the mixture, extruding into strips, cutting into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying for 4h at 80 ℃ and drying for 4h at 150 ℃, then putting the granules into a muffle furnace, roasting for 2h at 650 ℃ and roasting for 2h at 900 ℃ to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into a reactor, the pressure at the outlet of a reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance was evaluated under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1. The test results of 1000h reaction are shown in Table 2.
[ example 13 ]
Weighed corresponding to 50.1 parts of Fe 2 O 3 Iron oxide red of 21.4 parts of Fe 2 O 3 Iron oxide yellow (equivalent to 10.5 parts of CeO) 2 Cerium nitrate of (1), corresponding to 11.2 parts of K 2 Potassium carbonate of O, corresponding to 2.8 parts of MoO 3 The ammonium molybdate, 3.2 parts of calcium oxide and 3.05 parts of polystyrene microspheres are stirred in a mixer for 2 hours until the mixture is uniformly mixed. Then, 0.8 part of Na was added 2 And (3) an aqueous NaOH solution of O, wherein the concentration of hydroxide radicals in the aqueous NaOH solution is 3.2mol/L. The reaction was allowed to stand in an autoclave at 140 ℃ for 20 hours. And then, adjusting the water content of the mixture, extruding the mixture into strips, cutting the strips into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying the granules for 4h at 80 ℃ and drying the granules for 4h at 150 ℃, then putting the granules into a muffle furnace, roasting the granules for 2h at 650 ℃ and roasting the granules for 2h at 900 ℃ to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into a reactor, the pressure at the outlet of a reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance evaluation was carried out under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1.
[ example 14 ] A method for producing a polycarbonate
Weighed corresponding to 50.1 parts of Fe 2 O 3 Iron oxide red of 21.4 parts of Fe 2 O 3 Iron oxide yellow (equivalent to 10.5 parts of CeO) 2 Corresponding to 2.8 parts of MoO 3 3.2 parts of calcium oxide, equivalent to 0.8 part of Na 2 Sodium nitrate of O, and 3.05 parts of polystyrene microspheres, and stirred in a mixer for 2 hours until mixed uniformly. Then adding 11.2 parts of K 2 O KOH in an aqueous solution, the concentration of hydroxide in the aqueous solution being 3.2mol/L. The reaction was allowed to stand in an autoclave at 140 ℃ for 20 hours. Followed byAnd (3) adjusting the water content of the mixture, extruding into strips, cutting into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying at 80 ℃ for 4h and at 150 ℃ for 4h, then putting the granules into a muffle furnace, roasting at 650 ℃ for 2h and roasting at 900 ℃ for 2h to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into the reactor, the pressure at the outlet of the reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance evaluation was carried out under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1. The test results of 1000h reaction are shown in Table 2.
[ example 15 ]
Weighed in an amount corresponding to 50.1 parts of Fe 2 O 3 Iron oxide red of 21.4 parts of Fe 2 O 3 Corresponding to 10.5 parts of CeO 2 Equivalent to 2.8 parts of MoO 3 The ammonium molybdate, 3.2 parts of calcium oxide and 3.05 parts of polystyrene microspheres are stirred in a mixer for 2 hours until the components are uniformly mixed. Then, 11.2 parts of K were added 2 A mixed aqueous solution of KOH of O, wherein the concentration of hydroxyl in the mixed aqueous solution is 3.2mol/L. The mixture is kept still in an autoclave for reaction for 20 hours at 140 ℃. And then, adjusting the water content of the mixture, extruding into strips, cutting into granules to obtain granules with the diameter of 3 mm and the length of 6 mm, putting the granules into an oven, drying for 4h at 80 ℃ and drying for 4h at 150 ℃, then putting the granules into a muffle furnace, roasting for 2h at 650 ℃ and roasting for 2h at 900 ℃ to obtain the finished dehydrogenation catalyst, wherein the composition of the dehydrogenation catalyst is listed in Table 1.
100 ml of dehydrogenation catalyst is loaded into a reactor, the pressure at the outlet of a reaction bed is 30kPa (absolute pressure), and the mass space velocity of diethylbenzene is 1.0h -1 The performance evaluation was carried out under the conditions that the outlet temperature of the reaction bed was 600 ℃ and the water ratio was 1.8 (wt), and the test results of the reaction for 100 hours are shown in Table 1.
Comparative example 1
Weighed in an amount corresponding to 50.1 parts of Fe 2 O 3 Iron oxide red of (1), 21.4 parts of Fe 2 O 3 Iron oxide yellow (equivalent to 10.5 parts of CeO) 2 Cerium nitrate of (D), corresponding to 11.2 parts of K 2 Potassium carbonate of O, corresponding to 2.8 parts of MoO 3 Ammonium molybdate, 4.0 parts of calcium oxide and 3.05 parts of polystyrene microspheres, the same amount of water as in example 1 was added to the mixer and stirred for 2 hours until uniform. The mixture was allowed to stand in an autoclave at 140 ℃ for 20 hours. And extruding and cutting the mixture into strips, obtaining particles with the diameter of 3 mm and the length of 6 mm, putting the particles into an oven, drying the particles for 4h at the temperature of 80 ℃ and drying the particles for 4h at the temperature of 150 ℃, then putting the particles into a muffle furnace, roasting the particles for 2h at the temperature of 650 ℃ and roasting the particles for 2h at the temperature of 900 ℃ to obtain the finished dehydrogenation catalyst. The dehydrogenation catalyst was evaluated in the same manner as in example 1. The test results and the dehydrogenation catalyst composition are shown in tables 1 and 2.
TABLE 1 dehydrogenation catalyst composition, properties and evaluation results of examples and comparative examples
Note: * Reaction data of 100h of reaction at a water ratio of 1.8;
* Crystal plane ratio: ceO in dehydrogenation catalyst 2 (100) Exposed crystal face area in CeO 2 Proportion of total exposed crystal plane area.
Table 2 results of evaluating stability of dehydrogenation catalysts of examples and comparative examples
As can be seen from FIGS. 1 and 2, the dehydrogenation catalyst of example 1 contains CeO 2 Has CeO as main exposed crystal face 2 (100) Crystal plane(s). Comparative example 1 CeO in dehydrogenation catalyst 2 Has CeO as main exposed crystal face 2 (111) Crystal face, ceO 2 (111) Crystal face of CeO 2 Of total exposed crystal planeThe content was 52%. The results in tables 1 and 2 show that the catalyst has high activity and high divinylbenzene selectivity and good stability, and the conversion rate of diethylbenzene and the divinylbenzene selectivity are not obviously reduced after the dehydrogenation reaction is operated for 1000 hours.
The specific embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A process for the dehydrogenation of diethylbenzene to produce divinylbenzene, said process comprising: the raw material containing the diethylbenzene contacts with a dehydrogenation catalyst in the presence of water vapor to carry out dehydrogenation reaction to obtain a product containing the divinylbenzene; the dehydrogenation catalyst comprises Fe 2 O 3 、K 2 O、CeO 2 、MoO 3 CaO; wherein, ceO 2 (100) Exposed crystal face area in CeO 2 The total exposed crystal face area is more than 65 percent, preferably 65 to 90 percent.
2. The method of claim 1, wherein the dehydrogenation reaction is adapted for dehydrogenation reactions at low water ratios; further, the low water ratio is 2.0 or less, preferably 1.2 to 2.0;
and/or the outlet pressure of the reaction bed layer is 20-80 kPa, preferably 20-50 kPa; the pressure is absolute pressure; the outlet temperature of the reaction bed is 560-620 ℃;
and/or the mass space velocity of the diethylbenzene is 0.2 to 2.0h -1 。
3. The method of claim 1, wherein the dehydrogenation catalyst comprises the following components in mass fraction based on the total mass of the dehydrogenation catalyst:
(a) 61-86% of Fe 2 O 3 ；
(b) 5 to 14 percent of K 2 O；
(c) 6 to 14 percent of CeO 2 ；
(d) 0.5 to 5 percent of MoO 3 ；
(e) 0.3 to 7 percent of CaO.
4. The method according to claim 1, wherein the dehydrogenation catalyst contains Na in an amount of 0.01 to 2.0% by mass based on the total mass of the dehydrogenation catalyst 2 O；
And/or the dehydrogenation catalyst further contains 0.01 to 2.0% by mass of TiO in terms of mass fraction based on the total mass of the dehydrogenation catalyst 2 。
5. The process of any one of claims 1, 3 and 4, wherein the process for preparing the dehydrogenation catalyst comprises the steps of:
uniformly mixing a Fe source, a Ce source, a Mo source, a Ca source, an optional first K source and an optional pore-foaming agent, adding an alkaline solution, standing for reaction, forming and roasting to obtain the dehydrogenation catalyst;
wherein K in the dehydrogenation catalyst 2 O is derived from the first K source and/or the alkaline solution.
6. The method of claim 5, wherein the dehydrogenation catalyst is prepared by a process wherein the alkaline solution is an aqueous solution of potassium hydroxide and/or sodium hydroxide, preferably an aqueous solution of sodium hydroxide and potassium hydroxide; the concentration of hydroxide radicals in the alkaline solution is 1-8 mol/L;
and/or the alkaline solution is an aqueous solution of sodium hydroxide and potassium hydroxide, wherein the sodium hydroxide is Na 2 Calculated by O and K is potassium hydroxide 2 The mass ratio in terms of O is preferably 1:2 to 23.
7. The method of claim 5 or 6, wherein K in the catalyst is 2 O is derived at least in part from an alkaline solution; preferably, K in the catalyst 2 At least 50% of the O is derived from the K-containing alkaline solution, with the remainder derived from the first K source.
8. The method according to claim 5, wherein the dehydrogenation catalyst is prepared under the condition of standing reaction at 120-180 ℃ for 12-48 h.
9. The method of claim 5, wherein the dehydrogenation catalyst is prepared by calcining at a temperature of 600 to 1000 ℃ for a time of 2 to 8 hours.
10. The process according to any one of claims 5 to 9, wherein the dehydrogenation catalyst is prepared by adding the Ce source in the form of a cerium salt, preferably cerium nitrate;
and/or the source of Fe is the oxide Fe 2 O 3 Adding in a form;
and/or the first K source is added in the form of a potassium salt;
and/or the Mo source is added in the form of a molybdenum salt or oxide, preferably ammonium molybdate;
and/or the calcium source is added in the form of an oxide or hydroxide.
11. The method according to any one of claims 5 to 9, wherein the dehydrogenation catalyst is prepared by a method in which a Ti source is further contained in a raw material; the Ti source is added in the form of titanium salt or oxide; the titanium salt is any one or two of titanium tetrachloride or titanium tetrabromide.
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