CN112237921A - Low-water-ratio high-space-velocity ethylbenzene dehydrogenation catalyst and preparation method thereof - Google Patents

Low-water-ratio high-space-velocity ethylbenzene dehydrogenation catalyst and preparation method thereof Download PDF

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CN112237921A
CN112237921A CN201910638284.XA CN201910638284A CN112237921A CN 112237921 A CN112237921 A CN 112237921A CN 201910638284 A CN201910638284 A CN 201910638284A CN 112237921 A CN112237921 A CN 112237921A
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ethylbenzene dehydrogenation
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宋磊
朱敏
缪长喜
危春玲
徐永繁
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
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Abstract

The invention relates to a low-water-content high-space-velocity ethylbenzene dehydrogenation catalyst and a preparation method thereof, and mainly solves the problems of poor stability and low activity of a low-potassium catalyst under the conditions of low water content and high space velocity in the prior art. The invention adopts a low-water-content high-space-velocity ethylbenzene dehydrogenation catalyst, which comprises the following components in percentage by weight: 65-79% Fe2O3(ii) a 4 to 8% of K2O; 6-11% of CeO2(ii) a 1-5% of WO3(ii) a 0.5-5% of BaO; 0.5-8% of V2O5(ii) a 0.5-5% of heavy rare earth oxide, and the most probable pore size distribution of the obtained catalyst is 0.2731-0.3156 mu m, so that the problem is well solved, and the method can be used in industrial production for preparing styrene by ethylbenzene dehydrogenation under the conditions of low water content and high space velocity.

Description

Low-water-ratio high-space-velocity ethylbenzene dehydrogenation catalyst and preparation method thereof
Technical Field
The invention relates to a catalyst for preparing styrene by low-water-content high-space-velocity ethylbenzene dehydrogenation and a preparation method thereof.
Background
The main reaction of ethylbenzene dehydrogenation is C6H5-C2H5→C6H5CH＝CH2+H2+124 KJ/mol. Thermodynamically, it is advantageous to lower the ethylbenzene partial pressure in the equilibrium, so that it is customary in industry to add steam to promote the reaction in the direction of the product. The latest development trend of the technology for producing styrene by ethylbenzene dehydrogenation is to save energy and reduce consumption. The latent heat of vaporization of water is very large, and a large amount of superheated steam is consumed in the production process of the styrene to be used as a dehydrogenation medium, so that the process has high energy consumption and high production cost. Meanwhile, the method has the advantages that styrene products are obtained as much as possible by exploiting the potential of the styrene device, the production cost is reduced, the benefit is maximized, the ethylbenzene feeding amount of a plurality of styrene devices is over 110% of the design value, and high requirements are provided for the high airspeed resistance of the catalyst. The development of a low water ratio high space velocity catalyst which is suitable for isothermal fixed beds and has a water ratio of less than 1.2 (weight) can obtain styrene products as much as possible, reduce unit consumption and energy consumption, realize maximum benefit and become the urgent need of a plurality of styrene devices, especially large styrene devices, at sea and in the open.
The iron catalyst with iron oxide as main active component and potassium oxide as main cocatalyst is widely used in the industrial dehydrogenation of ethylbenzene to produce styrene. Generally, the content of potassium is more than 15%, but the potassium is not stable enough, so that the potassium is easy to lose and migrate under the flushing of high-temperature steam, the self-regeneration capability and stability of the catalyst are influenced, and the realization of low potassium content within 10% is the mainstream of ethylbenzene dehydrogenation catalyst development. It is generally accepted that potash is the most effective anti-coking auxiliary agent, low potassium catalysts operate at low water ratio, the catalyst surface is particularly prone to coking, the stability is poor, and therefore, the capability of the low potassium catalyst to resist low water ratio must be enhanced.
The dehydrogenation of ethylbenzene to styrene is a reaction controlled by internal diffusion, and requires a catalyst with larger pore channels to facilitate the smooth diffusion of reactants and products. If the pore channel is small, on one hand, the inward diffusion of reactants is not facilitated, the reaction rate is influenced, and the ethylbenzene conversion rate is reduced, on the other hand, the outward diffusion of products is not facilitated, the retention time of styrene on the surface of the catalyst is increased, the deep cracking of the styrene is initiated, and the selectivity of the catalyst is reduced. Researches find that after the ethylbenzene dehydrogenation catalyst is used, micropores with the pore diameter of less than 50nm are completely blocked by carbon deposit, and the macropores have less carbon deposit, and the carbon deposit is one of important reasons for the inactivation of the ethylbenzene dehydrogenation catalyst.
In this regard, many attempts have been made in light of the literature reports so far. For example, Chinese patent ZL200510093637.0 reports that Cu-La combination is added into an Fe-K-Ce-Mo-Mg system as a cocatalyst, and the prepared catalyst is suitable for running at a low water ratio, but the suitable water ratio is still higher than 1.3 (weight), and the liquid space velocity is 0.6 h－1Lower. For example, U.S. Pat. Nos. 4134858 and 4152300 all adopt the method of adding other elements to reduce the ratio of water used on the basis of the main components of iron, potassium and chromium. But selectivity is typically low, not exceeding 94%.
With the large scale of styrene devices, energy saving becomes more and more important. Therefore, the use condition of the dehydrogenation catalyst is slightly improved, and the production enterprises can obtain huge economic benefits without changing any equipment or increasing investment. The development of a low potassium catalyst suitable for operation at low water ratio and high space velocity, with higher activity and better stability, has been the direction of research efforts.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a novel catalyst for preparing styrene by ethylbenzene dehydrogenation, which is used for ethylbenzene dehydrogenation and has the characteristics of good stability, high activity and strong capability of processing more raw materials at low water ratio and high space velocity.
The second technical problem to be solved by the invention is to provide a preparation method of the ethylbenzene dehydrogenation catalyst with low water content and high space velocity corresponding to the first technical problem.
The invention aims to solve the third technical problem and provide a method for preparing styrene by ethylbenzene dehydrogenation, which corresponds to the solution of one of the technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the low-water-ratio high-space-velocity ethylbenzene dehydrogenation catalyst comprises the following components in percentage by weight:
(a) 65-79% Fe2O3(ii) a (b)4 to 8% of K2O; (c) 6-11% of CeO2；
(d) 1-5% of WO3(ii) a (e) 0.5-5% of BaO; (f) 0.5-8% of V2O5；
(g) 0.5-5% of heavy rare earth oxide;
the pore size distribution of the catalyst is 0.2731-0.3156 μm.
In the above technical solution, the heavy rare earth oxide preferably includes Er at the same time2O3And Tm2O3Or Er2O3And Lu2O3Or Tm2O3And Lu2O3The two heavy rare earth oxides have a binary synergistic effect on catalyst activity and stability at low water ratio and high space velocity; more preferably both Er2O3、Tm2O3And Lu2O3There is a ternary synergistic effect on catalyst activity and stability at low water velocities and high space velocities.
In the above technical scheme, V2O5The content is 0.8-5.2%, preferably 1-4%.
In the above technical scheme, the heavy rare earth oxide is selected from Er2O3、Tm2O3Or Lu2O30.8 to 4% by weight of at least one of (A) and (B).
In the above technical solution, the catalyst preferably does not contain molybdenum oxide.
In the technical scheme, the catalyst preferably does not contain a binder, and the binder comprises kaolin, diatomite and cement.
In the above technical scheme, by weight percentage, Fe2O3Preferably from red iron oxide and yellow iron oxide, in a certain proportionPreferably, the iron oxide red: iron oxide yellow is 2.5-4.5: 1.
To solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the catalyst in the technical scheme of one of the technical problems comprises the following steps: uniformly contacting a Fe source, a K source, a Ce source, a W source, a Ba source, a V source, a heavy rare earth oxide and a pore-forming agent which are weighed according to a ratio with water, and obtaining the catalyst through the steps of extruding, drying and roasting. Preferably, the addition amount of the water is 15-35% of the total weight of the catalyst raw materials.
In the above technical scheme, Ce is preferably added in the form of cerium oxalate or cerium carbonate.
In the above technical scheme, the drying temperature is not particularly limited, for example, 50 to 100 ℃, and the drying time can be 0.5 to 8 hours.
In the above technical scheme, as a preferred option, the drying is gradually increased in temperature, for example but not limited to, drying at 50-80 ℃ for 2-4 hours, and then drying at 90-100 ℃ for 0.5-4 hours.
In the technical scheme, the roasting temperature can be 600-1000 ℃, and the roasting time can be 2-8 hours.
In the above technical scheme, as a better roasting condition, the roasting temperature is gradually increased, for example, but not limited to, roasting at 600-800 ℃ for 2-4 hours, and then roasting at 900-1000 ℃ for 2-4 hours.
In order to solve the third technical problem, ethylbenzene is used as a raw material, the reaction temperature is 615-650 ℃, the dosage of a catalyst is 50-150 ml, and the liquid airspeed is 1.3-2.0 hours－1The water ratio (weight) is 0.7-1.0, the pressure is-40 KPa-normal pressure, and the raw material and the ethylbenzene dehydrogenation catalyst are subjected to contact reaction to obtain styrene.
The catalyst component of the present invention uses the following raw materials:
fe used2O3Adding in the form of iron oxide red and iron oxide yellow; the K is added in the form of potassium carbonate; w used is added in the form of its salt or oxide; the Ba is added in the form of oxide or carbonate; the V is added in oxide form; the remaining elements are added in the form of oxides. In the preparation process of the inventionIn the method, a pore-forming agent is added besides the main components of the catalyst, wherein the pore-forming agent can be selected from graphite, polystyrene microspheres or sodium carboxymethyl cellulose, and the addition amount of the pore-forming agent is 2-6% of the total weight of the catalyst.
The pore size and distribution of the catalyst are measured by a PORESIZER 9320 mercury porosimeter manufactured by Micromeritics of America, and the pore diameter measurement range is 10 nm-360 μm.
The amount of carbon accumulated was measured by a Vario EL III element analyzer from Elementar, Germany.
The catalyst prepared by the method is subjected to activity evaluation in an isothermal fixed bed, and for the activity evaluation of the catalyst for preparing styrene by ethylbenzene dehydrogenation, the process is briefly described as follows:
the deionized water and the ethylbenzene 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 an electric heating wire to reach a preset temperature. The reactor was a 1 "internal diameter stainless steel tube filled with 100 ml of a catalyst having a particle size of 3 mm. The composition of the reactants exiting the reactor was analyzed by gas chromatography after condensation of water.
The ethylbenzene conversion and the styrene selectivity are calculated according to the following formulas:
Figure RE-GDA0002249119940000041
Figure RE-GDA0002249119940000042
the invention adds vanadium pentoxide and heavy rare earth oxide Er in the Fe-K-Ce-W-Ba catalyst system2O3、 Tm2O3Or Lu2O3At least one of (1) and (2) the catalyst has a most probable pore size distribution of 0.2731-0.3156 [ mu ] m, thereby improving the electron transfer channel between active sites and leading Fe2+And Fe3+The interconversion between the two is stabilized, the activity of the oxygen transfer dehydrogenation and direct dehydrogenation reaction of the catalyst is improved, the pore distribution is optimized, and the treatment of more raw materials is enhanced(ii) a capability; on the other hand, the alkalinity of the system is improved, the active phase of the catalyst is stabilized and dispersed, the water gas reaction rate of the water vapor and the carbon deposit on the surface of the catalyst is accelerated, and the self-regeneration capability of the catalyst is enhanced. The activity of the catalyst prepared by the invention is evaluated in an isothermal fixed bed at normal pressure and liquid space velocity for 1.0 hour－1Increased to 1.5 hours－1The temperature is 635 ℃, the water ratio is reduced by 62.5 percent to 0.75 percent from the common 2.0 percent (weight), the conversion rate is up to 77.4 percent, the conversion rate is only reduced by 0.6 percent after the stable operation for 900 hours, the carbon deposition amount of the catalyst removed after the reaction is 1.28 percent after the analysis of an element analyzer, the activity and the stability of the low-potassium catalyst under the conditions of low water content and high space velocity are obviously improved, and better technical effect is obtained.
Drawings
FIG. 1 is a graph of the pore distribution of the catalyst of the present invention.
The invention is further illustrated by the following examples:
Detailed Description
[ example 1]
Will correspond to 57.95 parts of Fe2O3Iron oxide red of (1), corresponding to 18.8 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.5 parts of K2Potassium carbonate of O, corresponding to 7.21 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.12 parts of BaO, and 3.16 parts of V2O51.68 parts of Er2O3And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The pore size and distribution of the catalyst were measured using a PORESIZER 9320 mercury porosimeter, manufactured by Micromeritics, USA, with a pore size measurement range of 10nm to 360 μm, the mode pore size of example 1 was 0.2856 μm, and the pore distribution of the catalyst is shown in FIG. 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity for 1.5 hours－1The activity was evaluated at 635 ℃ and a water ratio (by weight) of 0.75, and the results are shown in Table 2. The catalyst removed after the reaction was analyzed by an elemental analyzer, and the amount of carbon deposition was analyzed as shown in Table 2.
Comparative example 1
Except without V2O5And Er2O3Except for the above, the relative proportions of the remaining components, the catalyst preparation method, the catalyst evaluation conditions, the pore distribution measurement of the catalyst and the analysis of the amount of carbon deposit were the same as in example 1, specifically:
will correspond to 60.9 parts Fe2O3Iron oxide red of (1), corresponding to 19.75 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.88 parts of K2Potassium carbonate of O, corresponding to 7.58 parts of CeO2Cerium oxalate of (1), corresponding to 2.71 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.18 parts of BaO and 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, extruded strips are taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven, baked for 2 hours at the temperature of 75 ℃ and 3 hours at the temperature of 95 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 650 ℃ and 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results and the analysis of the amount of carbon deposited are shown in Table 2.
Comparative example 2
Except without V2O5Except for the above, the relative proportions of the remaining components, the catalyst preparation method, the catalyst evaluation conditions, the pore distribution measurement of the catalyst and the analysis of the amount of carbon deposit were the same as in example 1, specifically:
will correspond to 59.84 parts Fe2O3Iron oxide red of (1), corresponding to 19.41 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.74 parts of K2Potassium carbonate of O, corresponding to 7.45 parts of CeO2Cerium oxalate of (1), corresponding to 2.66 parts of WO3Ammonium tungstate (D), barium carbonate equivalent to 1.16 parts of BaO, and 1.73 parts of Er2O3And 5.69 parts of sodium carboxymethylcelluloseStirring in a kneader for 1.5 hours, adding deionized water accounting for 25 percent of the total weight of the catalyst raw materials, stirring for 0.5 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 6 millimeters, putting the particles into an oven, baking for 2 hours at 75 ℃, baking for 3 hours at 95 ℃, then putting the particles into a muffle furnace, roasting for 3 hours at 650 ℃, and roasting for 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is listed in Table 1. The test results and the analysis of the amount of carbon deposited are shown in Table 2.
[ example 2]
Except using Tm2O3Substitute Er2O3Otherwise, the catalyst preparation method, catalyst evaluation conditions, pore distribution measurement of the catalyst, and soot amount analysis were the same as in example 1, specifically:
will correspond to 57.95 parts of Fe2O3Iron oxide red of (1), corresponding to 18.8 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.5 parts of K2Potassium carbonate of O, corresponding to 7.21 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.12 parts of BaO, and 3.16 parts of V2O51.68 parts Tm2O3And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results and the analysis of the amount of carbon deposited are shown in Table 2.
Comparative example 3
Except without V2O5Except for the above, the relative proportions of the remaining components, the catalyst preparation method, the catalyst evaluation conditions, the pore distribution measurement of the catalyst and the analysis of the amount of carbon deposit were the same as in example 2, specifically:
will correspond to 59.84 parts Fe2O3Iron oxide red of (1), corresponding to 19.41 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.74 parts of K2Potassium carbonate of O, corresponding to 7.45 parts of CeO2Cerium oxalate of (1), corresponding to 266 parts of WO3Ammonium tungstate, barium carbonate equivalent to 1.16 parts of BaO, 1.73 parts of Tm2O3And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results and the analysis of the amount of carbon deposited are shown in Table 2.
[ example 3]
Except for using Lu2O3Substitute Er2O3Otherwise, the catalyst preparation method, catalyst evaluation conditions, pore distribution measurement of the catalyst, and soot amount analysis were the same as in example 1, specifically:
will correspond to 57.95 parts of Fe2O3Iron oxide red of (1), corresponding to 18.8 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.5 parts of K2Potassium carbonate of O, corresponding to 7.21 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.12 parts of BaO, and 3.16 parts of V2O51.68 parts of Lu2O3And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results and the analysis of the amount of carbon deposited are shown in Table 2.
Comparative example 4
Except without V2O5Except for the above, the relative proportions of the remaining components, the catalyst preparation method, the catalyst evaluation conditions, the pore distribution measurement of the catalyst and the analysis of the amount of carbon deposit were the same as in example 3, specifically:
will correspond to 59.84 parts Fe2O3Iron oxide red of (1), corresponding to 19.41 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.74 parts of K2Potassium carbonate of O, corresponding to 7.45 parts of CeO2Cerium oxalate of (1), corresponding to 2.66 parts of WO3Ammonium tungstate (D), barium carbonate equivalent to 1.16 parts of BaO, 1.73 parts of Lu2O3And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results and the analysis of the amount of carbon deposited are shown in Table 2.
[ example 4]
A catalyst and test catalyst were prepared as in example 1, except that 0.84 parts Er was used2O3And 0.84 part Tm2O3Substitute 1.68 parts Er2O3The method specifically comprises the following steps:
will correspond to 57.95 parts of Fe2O3Iron oxide red of (1), corresponding to 18.8 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.5 parts of K2Potassium carbonate of O, corresponding to 7.21 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.12 parts of BaO, and 3.16 parts of V2O50.84 portion of Er2O30.84 part Tm2O3And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results and the analysis of the amount of carbon deposited are shown in Table 2.
[ example 5]
A catalyst and test catalyst were prepared as in example 1, except that 0.84 parts Er was used2O3And 0.84 part of Lu2O3Substitute 1.68 parts Er2O3The method specifically comprises the following steps:
will correspond to 57.95 parts of Fe2O3Iron oxide red of (1), corresponding to 18.8 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.5 parts of K2Potassium carbonate of O, corresponding to 7.21 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.12 parts of BaO, and 3.16 parts of V2O50.84 portion of Er2O30.84 portion of Lu2O3And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results and the analysis of the amount of carbon deposited are shown in Table 2.
[ example 6]
A catalyst was prepared and tested as in example 1, except that 0.84 part Tm was used2O3And 0.84 part of Lu2O3Substitute 1.68 parts Er2O3The method specifically comprises the following steps:
will correspond to 57.95 parts of Fe2O3Iron oxide red of (1), corresponding to 18.8 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.5 parts of K2Potassium carbonate of O, corresponding to 7.21 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.12 parts of BaO, and 3.16 parts of V2O50.84 part Tm2O30.84 portion of Lu2O3And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results and the analysis of the amount of carbon deposited are shown in Table 2.
[ example 7]
A catalyst and test catalyst were prepared as in example 1, except that 0.56 parts Er was used2O30.56 part Tm2O3And 0.56 part of Lu2O3Substitute 1.68 parts Er2O3The method specifically comprises the following steps:
will correspond to 57.95 parts of Fe2O3Iron oxide red of (1), corresponding to 18.8 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.5 parts of K2Potassium carbonate of O, corresponding to 7.21 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.12 parts of BaO, and 3.16 parts of V2O50.56 part of Er2O30.56 part Tm2O30.56 part of Lu2O3And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results and the analysis of the amount of carbon deposited are shown in Table 2.
[ example 8]
Will correspond to 53.75 parts of Fe2O3Iron oxide red of (1), corresponding to 17.18 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.85 parts of K2Potassium carbonate of O, corresponding to 8.9 parts of CeO2Corresponding to 4.13 parts of WO3Ammonium tungstate, barium carbonate equivalent to 3.35 parts of BaO, 3.5 parts of V2O50.85 parts of Er2O30.49 part of TiO2And 4.62 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at 650 ℃ for 3 hours and 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is shown in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity for 1.5 hours－1The activity evaluation was carried out at 635 ℃ and a water ratio (by weight) of 0.75, and the pore distribution measurement and the coke formation analysis of the catalyst were the same as in example 1, and the test results and the coke formation analysis are shown in Table 2.
[ example 9]
Will correspond to 52.73 parts of Fe2O3Iron oxide red of (1), corresponding to 13.45 parts of Fe2O3Iron oxide yellow of (1), corresponding to 4.55 parts of K2Potassium carbonate of O, corresponding to 10.55 parts of CeO2Corresponding to 1.21 parts of WO3Ammonium tungstate (D), barium carbonate equivalent to 4.95 parts of BaO, and 7.65 parts of V2O54.4 parts of Er2O30.51 part of MoO3And 4.62 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at 650 ℃ for 3 hours and 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is shown in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity for 1.5 hours－1The activity evaluation was carried out at 635 ℃ and a water ratio (by weight) of 0.75, and the pore distribution measurement and the coke formation analysis of the catalyst were the same as in example 1, and the test results and the coke formation analysis are shown in Table 2.
[ example 10]
Will correspond to 55.36 parts of Fe2O3Iron oxide red of (1), corresponding to 17.42 parts of Fe2O3Iron oxide yellow of (1), corresponding to 5.71 parts of K2Potassium carbonate of O, corresponding to 7.46 parts of CeO2Corresponding to 4.82 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.83 parts of BaO, 0.72 part of V2O54.58 parts of Er2O3Stirring 2.1 parts of cement and 4.95 parts of sodium carboxymethylcellulose in a kneader for 1.5 hours, adding deionized water accounting for 25 percent of the total weight of the catalyst raw materials, stirring for 0.5 hour, taking out extruded strips, and extruding into strips with the diameter of 3 millimeters and the length of 6 millimetersThe particles are put into an oven, baked at 75 ℃ for 2 hours, baked at 95 ℃ for 3 hours, then put into a muffle furnace, baked at 650 ℃ for 3 hours and baked at 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity for 1.5 hours－1The activity evaluation was carried out at 635 ℃ and a water ratio (by weight) of 0.75, and the pore distribution measurement and the coke formation analysis of the catalyst were the same as in example 1, and the test results and the coke formation analysis are shown in Table 2.
[ example 11]
Will correspond to 60.6 parts Fe2O3Iron oxide red of (1), corresponding to 17.45 parts of Fe2O3Iron oxide yellow of (1), corresponding to 6.05 parts of K2Potassium carbonate of O, corresponding to 6.15 parts of CeO2Cerium oxalate of (1), corresponding to 2.03 parts of WO3Ammonium tungstate, barium carbonate corresponding to 0.55 parts of BaO, and 5.15 parts of V2O52.02 parts of Er2O3And 4.95 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and at the temperature of 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity for 1.5 hours－1The activity evaluation was carried out at 635 ℃ and a water ratio (by weight) of 0.75, and the pore distribution measurement and the coke formation analysis of the catalyst were the same as in example 1, and the test results and the coke formation analysis are shown in Table 2.
Comparative example 5
Except for using CeO2The catalyst preparation method, catalyst evaluation conditions, catalyst pore distribution measurement and carbon deposit amount analysis were the same as in example 1 except for cerium oxalate, specifically:
will correspond to 57.95 parts of Fe2O3Iron oxide red of (1), corresponding to 18.8 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.5 parts of K2Potassium carbonate of O, 7.21 parts of CeO2Equivalent to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.12 parts of BaO, and 3.16 parts of V2O51.68 parts of Er2O3And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results and the analysis of the amount of carbon deposited are shown in Table 2.
Comparative example 6
The total amount of iron oxide, the catalyst preparation method, the catalyst evaluation conditions, the pore distribution measurement of the catalyst, and the coke formation analysis were the same as in example 1 except that the ratio of red iron oxide to yellow iron oxide was different, specifically:
will correspond to 50.25 parts Fe2O326.5 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.5 parts of K2Potassium carbonate of O, 7.21 parts of CeO2Equivalent to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.12 parts of BaO, and 3.16 parts of V2O51.68 parts of Er2O3And 5.69 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1. The test results and the analysis of the amount of carbon deposited are shown in Table 2.
Comparative example 7
Will correspond to 54.75 parts Fe2O3Iron oxide red of (1), corresponding to 17.18 parts of Fe2O3Iron oxide yellow of (1), corresponding to 8.85 parts of K2Potassium carbonate of O, corresponding to 11.2 parts of CeO2Corresponding to 1.55 parts of WO3Corresponding to ammonium tungstate3.12 parts of barium carbonate of BaO, 2.5 parts of V2O50.85 parts of Er2O3And 4.62 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the raw materials of the catalyst is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at 75 ℃ for 2 hours and 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at 650 ℃ for 3 hours and 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is shown in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity for 1.5 hours－1The activity evaluation was carried out at 635 ℃ and a water ratio (by weight) of 0.75, and the pore distribution measurement and the coke formation analysis of the catalyst were the same as in example 1, and the test results and the coke formation analysis are shown in Table 2.
[ example 12]
Will correspond to 55.36 parts of Fe2O3Iron oxide red of (1), corresponding to 17.42 parts of Fe2O3Iron oxide yellow of (1), corresponding to 5.78 parts of K2Potassium carbonate of O, corresponding to 9.88 parts of CeO2Corresponding to 3.85 parts of WO3Ammonium tungstate, barium carbonate corresponding to 2.12 parts of BaO, 0.92 part of V2O54.67 parts Tm2O3And 4.95 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and at the temperature of 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity for 1.5 hours－1The activity evaluation was carried out at 635 ℃ and a water ratio (by weight) of 0.75, and the pore distribution measurement and the coke formation analysis of the catalyst were the same as in example 1, and the test results and the coke formation analysis are shown in Table 2.
[ example 13]
Will correspond to 52.36 parts Fe2O3Iron oxide red of (1), corresponding to 16.42 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.92 parts of K2Potassium carbonate of O, corresponding to 9.46 parts of CeO2Corresponding to 4.82 parts of WO3Ammonium tungstate, barium carbonate equivalent to 3.83 parts of BaO, 1.85 parts of V2O53.34 parts of Lu2O3And 4.95 parts of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water accounting for 25 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, the extruded strip is taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked at the temperature of 75 ℃ for 2 hours and at the temperature of 95 ℃ for 3 hours, then the particles are put into a muffle furnace and baked at the temperature of 650 ℃ for 3 hours and at the temperature of 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity for 1.5 hours－1The activity evaluation was carried out at 635 ℃ and a water ratio (by weight) of 0.75, and the pore distribution measurement and the coke formation analysis of the catalyst were the same as in example 1, and the test results and the coke formation analysis are shown in Table 2.
Table 1 (wait for)
Figure RE-GDA0002249119940000121
TABLE 1 (continuation)
Figure RE-GDA0002249119940000122
Figure RE-GDA0002249119940000131
TABLE 2
Figure RE-GDA0002249119940000132
The above examples illustrate the addition of a suitable amount of vanadium pentoxide and a heavy rare earth oxide Er to an Fe-K-Ce-W-Ba catalytic system2O3、Tm2O3Or Lu2O3The obtained catalyst has reasonable pore distribution, improves the activity and stability of the low-potassium catalyst under the conditions of low water ratio and high airspeed, has less carbon deposit, can meet the requirement of treating more raw materials when the styrene market is good, has obvious energy-saving effect, is beneficial to cost reduction and efficiency improvement of a styrene device, and can be used in industrial production for preparing styrene by ethylbenzene dehydrogenation under the conditions of low water ratio and high airspeed.

Claims (11)

1. The low-water-ratio high-space-velocity ethylbenzene dehydrogenation catalyst comprises the following components in percentage by weight:
(a) 65-79% Fe2O3(ii) a (b)4 to 8% of K2O; (c) 6-11% of CeO2；
(d) 1-5% of WO3(ii) a (e) 0.5-5% of BaO; (f) 0.5-8% of V2O5；
(g) 0.5-5% of heavy rare earth oxide; heavy rare earth oxide selected from Er2O3、Tm2O3Or Lu2O3At least one of (1).
2. The low-water-content high-space-velocity ethylbenzene dehydrogenation catalyst as claimed in claim 1, wherein the distribution of the mode pore size of the catalyst is 0.2731-0.3156 μm.
3. The low water content high space velocity ethylbenzene dehydrogenation catalyst of claim 1 wherein the catalyst does not contain molybdenum oxide.
4. The low water content high space velocity ethylbenzene dehydrogenation catalyst of claim 1, wherein V is2O5The content is 0.8-5.2%, preferably 1-4%.
5. The low water content and high space velocity ethylbenzene dehydrogenation catalyst as claimed in claim 1, wherein the heavy rare earth oxide content is 0.8-4%.
6. The low water content high space velocity ethylbenzene dehydrogenation catalyst of claim 1 wherein the catalyst is free of binders including kaolin, diatomaceous earth and cement.
7. A preparation method of an ethylbenzene dehydrogenation catalyst comprises the following steps: fe source, K source and Ce source according to the proportion,
And contacting the W source, the Ba source, the V source, the heavy rare earth oxide and the pore-making agent with water to obtain the catalyst.
8. The preparation method according to claim 7, further comprising the steps of extruding, drying and roasting, wherein the drying temperature is 50-100 ℃.
9. The method according to claim 8, wherein the calcination temperature is 600 to 1000 ℃.
10. The low water content high space velocity ethylbenzene dehydrogenation catalyst of claim 7 wherein the Ce source is added as cerium oxalate or cerium carbonate.
11. A method for preparing styrene by ethylbenzene dehydrogenation takes ethylbenzene as a raw material, the reaction temperature is 615-650 ℃, the dosage of a catalyst is 50-150 ml, and the liquid airspeed is 1.3-2.0 hours－1The water ratio (weight) is 0.7-1.0, the pressure is-40 KPa-normal pressure, and the raw material and the ethylbenzene dehydrogenation catalyst are subjected to contact reaction to obtain styrene.
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CN102371160A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Low-temperature ethyl benzene dehydrogenation catalyst
CN103769152A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 High activity and low water ratio ethylbenzene dehydrogenation catalyst, preparation method and application of catalyst
CN106582684A (en) * 2015-10-16 2017-04-26 中国石油化工股份有限公司 Alkyl aromatic hydrocarbon dehydrogenation catalyst
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WO1996018458A1 (en) * 1994-12-14 1996-06-20 Shell Internationale Research Maatschappij B.V. Dehydrogenation catalyst and process
CN1883796A (en) * 2005-06-22 2006-12-27 中国石油化工股份有限公司 Catalysts for ethyl benzene dehydrogenation preparation of styrene
CN102371160A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Low-temperature ethyl benzene dehydrogenation catalyst
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