CN112237922A - Ultra-low water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof - Google Patents

Ultra-low water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof Download PDF

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CN112237922A
CN112237922A CN201910652302.XA CN201910652302A CN112237922A CN 112237922 A CN112237922 A CN 112237922A CN 201910652302 A CN201910652302 A CN 201910652302A CN 112237922 A CN112237922 A CN 112237922A
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water ratio
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宋磊
朱敏
缪长喜
徐永繁
张征湃
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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Abstract

The invention relates to an ethylbenzene dehydrogenation catalyst with an ultra-low water ratio and a preparation method thereof, and mainly solves the problems of poor stability and low activity of a low-potassium catalyst under the condition of the ultra-low water ratio in the prior art. The invention adopts an ultra-low water ratio ethylbenzene dehydrogenation catalyst, which comprises the following components in percentage by weight: 66-79% Fe2O3(ii) a 4 to 9% of K2O; 6-11% of CeO2(ii) a 0.5-5% of WO3(ii) a 0.5-5% of BaO; 0.1-5% of TiO2(ii) a 0.5-5% of heavy rare earth oxide; said heavy rare earth oxide is selected from Er2O3、Tm2O3Or Yb2O3At least one of (a); the specific surface area of the obtained catalyst is 2.2-2.8 m2The crushing strength is more than or equal to 30N/mm, the problem is better solved, andthe method is used for the industrial production of preparing styrene by ethylbenzene dehydrogenation under the condition of ultra-low water ratio.

Description

Ultra-low water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof
Technical Field
The invention relates to a catalyst for preparing styrene by ethylbenzene dehydrogenation with an ultralow water ratio 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 recent development trend in the technology for producing styrene by ethylbenzene dehydrogenation is to reduce raw material consumption and improve energy efficiency. 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. The development of a low water ratio catalyst suitable for isothermal fixed beds having a water ratio of less than 1.0 (wt) to reduce the operating water ratio of industrial plants has become an urgent need for styrene plants, particularly large-scale styrene plants.
In the industrial production of styrene by ethylbenzene dehydrogenation, an iron catalyst which takes iron oxide as a main active component and potassium oxide as a main cocatalyst is generally adopted, the potassium content is usually more than 15%, but 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.
In this regard, many attempts have been made in light of the literature reports so far. Chinese patent 200510111471.0 reports that after at least two light rare earth compounds except cerium are added in a Fe-K-Ce-W system, the stability of a low-potassium catalyst under the condition of low water ratio of 1.8 (weight) is obviously improved, and the catalyst has high activity. Chinese patent 200510093637.0 discloses a catalyst for preparing styrene by ethylbenzene dehydrogenation and a preparation method thereof, wherein the catalyst is prepared by adding copper oxide and lanthanum oxide into a Fe-K-Ce-Mo-Mg system, and the ethylbenzene conversion rate of the prepared catalyst is more than or equal to 70% and the styrene selectivity is more than or equal to 94.5% under the condition that the water ratio is 1.3 (by weight). However, the water ratio is still high and needs to be further reduced.
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 with higher activity suitable for operation under ultra-low water ratio conditions 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 and high activity under the condition of ultralow water ratio.
The second technical problem to be solved by the present invention is to provide a preparation method of an ultra-low water ratio ethylbenzene dehydrogenation catalyst corresponding to the first technical problem.
The invention aims to solve the third technical problem and provide a method for preparing styrene by dehydrogenation of ethylbenzene with ultralow water ratio, which corresponds to 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 catalyst comprises the following components: a first group of primary metal oxides, a second group of metal oxides, and a third group of metal oxides; the first group of main metal oxides are iron, potassium and cerium; the second group of metal oxides are tungsten and barium; the third group of metal oxide is at least one of titanium and erbium, thulium and ytterbium, the catalyst comprises 0.1-5 wt% of titanium in the third group of metal oxide, and the crushing strength of the catalyst is more than or equal to 30N/mm.
In the above technical scheme, the catalyst comprises, by weight: 66-79% Fe in the first group of main metal oxides2O3(ii) a 4 to 9% of K2O; 6-11% of CeO2(ii) a WO 0.5-5% of a second group of metal oxides3(ii) a 0.5 to 5% of BaO and 0.5 to 5% of Er2O3、Tm2O3And Yb2O3At least one of (1).
In the technical scheme, the specific surface area of the catalyst is 2.2-2.8 m2The catalyst has a crush strength of 30 to 40N/mm.
In the above technical scheme, the heavy rare earth oxide is selected from Er2O3、Tm2O3Or Yb2O3Preferably, the content of (a) is 0.9 to 4%.
In the above technical solution, the heavy rare earth oxide preferably includes Er at the same time2O3And Tm2O3Or Er2O3And Yb2O3Or Tm2O3And Yb2O3The two heavy rare earth oxides have a binary synergistic effect on the activity and stability of the catalyst at an ultra-low water ratio; more preferably both Er2O3、Tm2O3And Yb2O3At this time, the three heavy rare earth oxides have a ternary synergistic effect on the activity and stability of the catalyst at an ultra-low water ratio.
In the above technical scheme, TiO2The content is preferably 0.5 to 4.5%, more preferably 0.8 to 3.5%.
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 iron oxide red and iron oxide yellow, and the proportion is preferably 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 Ti 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 hydroxide.
In the above technical scheme, the drying temperature is not particularly limited, for example, 80-180 ℃, and the drying time can be 2-8 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 80-120 ℃ for 1.5-4 hours, and then drying at 140-180 ℃ for 0.5-4 hours.
In the technical scheme, the roasting adopts a three-step method, namely the roasting temperature is 200-500 ℃ for 1-4 hours, the roasting temperature is 550-750 ℃ for 1-4 hours, and the roasting temperature is 800-950 ℃ for 1-4 hours
In order to solve the third technical problem, ethylbenzene is used as a raw material, the reaction temperature is 610-650 ℃, the dosage of a catalyst is 50-150 ml, and the liquid airspeed is 1.0-1.8 hours－1And the 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 the 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, hydroxide or carbonate; the Ti is added in the form of oxide; the remaining elements are added in the form of oxides. In the preparation process of the invention, besides the main components of the catalyst, a pore-forming agent is added, wherein the pore-forming agent can be selected from graphite, polystyrene microspheres or sodium carboxymethylcellulose, and the addition amount of the pore-forming agent is 2-6% of the total weight of the catalyst.
The specific surface area of the catalyst is measured by a PORESIZER 9320 mercury porosimeter manufactured by Micromeritics of America, and is more than or equal to 0.01m2(ii) in terms of/g. The crushing strength test method is carried out according to HG/T2782-2011, the QCY-602 particle strength meter is used for measuring, 40 samples to be measured are taken by the quartering method, and the arithmetic mean value of the measurement results is usedThe crush strength of the sample was calculated.
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 BDA0002135664160000041
Figure BDA0002135664160000042
the invention adds proper amount of titanium oxide and heavy rare earth oxide Er in the Fe-K-Ce-W-Ba catalyst system2O3、Tm2O3Or Yb2O3The catalyst has proper specific surface area and high crushing strength, and can raise the electron transferring capacity of the active phase, raise the alkalinity of the system, stabilize and disperse the active phase of the catalyst, speed the water gas reaction between water vapor and carbon deposit on the surface of the catalyst and raise the self-regenerating capacity of the catalyst. The activity of the catalyst prepared by the invention is evaluated in an isothermal fixed bed, and the normal pressure and liquid space velocity are increased from 1.0 to 1.2 hours－1The temperature is increased from the usual 620 ℃ to 640 ℃, the water ratio is reduced from the usual 2.0 (weight) by 62.5 percent to 0.75 (weight), the ethylbenzene conversion rate is up to 79.5 percent, the ethylbenzene conversion rate is only reduced by 0.7 percent after the stable operation is carried out for 1000 hours, and the low-potassium catalyst is obviously improved under the condition of the ultralow water ratioActivity and stability, and obtains better technical effect.
The invention is further illustrated by the following examples:
Detailed Description
[ example 1]
Will correspond to 56.7 parts Fe2O3Iron oxide red of (1), corresponding to 19.2 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.55 parts of K2Potassium carbonate of O, corresponding to 7.75 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.38 parts of BaO, and 3.16 parts of TiO21.68 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 for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 2 hours at 450 ℃, 3 hours at 650 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1. The specific surface area of the catalyst is measured by a PORESIZER 9320 mercury porosimeter manufactured by Micromeritics of America, and is more than or equal to 0.01m2(ii) in terms of/g. The crushing strength test method is carried out according to HG/T2782-2011, the QCY-602 particle strength meter is used for measuring, 40 samples to be measured are taken by the quartering method, and the crushing strength of the samples is calculated according to the arithmetic mean of the measurement results. Example 1 has a specific surface area of 2.6m2(iv)/g, crush strength 32N/mm.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity for 1.2 hours－1The activity was evaluated at 640 ℃ and a water ratio (by weight) of 0.75, and the test results are shown in Table 2.
Comparative example 1
Except without using TiO2And Er2O3Except for the above, the relative proportions of the remaining components, the catalyst preparation method, the catalyst evaluation conditions, and the analysis method were the same as in example 1, specifically:
will correspond to 59.58 parts Fe2O3Iron oxide red of (1), corresponding to 20.18 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.93 parts of K2Potassium carbonate of O, corresponding to 8.14 parts of CeO2Cerium oxalate of (1), corresponding to 2.71 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.45 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, dried for 2 hours at 90 ℃ and dried for 3 hours at 160 ℃, then the particles are put into a muffle furnace and roasted for 2 hours at 450 ℃, roasted for 3 hours at 650 ℃ and roasted for 3 hours at 920 ℃ to obtain the finished catalyst, and the catalyst composition is listed in Table 1. The test results are shown in Table 2.
Comparative example 2
Except without using TiO2Except for the above, the relative proportions of the remaining components, the catalyst preparation method, the catalyst evaluation conditions, and the analysis method were the same as in example 1, specifically:
will correspond to 58.55 parts Fe2O3Iron oxide red of (1), corresponding to 19.83 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.8 parts of K2Potassium carbonate of O, corresponding to 8.0 parts of CeO2Cerium oxalate of (1), corresponding to 2.66 parts of WO3Ammonium tungstate (D), barium carbonate equivalent to 1.43 parts of BaO, and 1.73 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 for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 2 hours at 450 ℃, 3 hours at 650 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1. The test results are shown in Table 2.
[ example 2]
Except using Tm2O3Substitute Er2O3Except for the above, the catalyst preparation method, the catalyst evaluation conditions, and the analysis method were the same as in example 1, and specifically:
will correspond to 56.7 parts Fe2O3Iron oxide red of (1), corresponding to 19.2 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.55 parts of K2Potassium carbonate of O, corresponding to 7.75 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.38 parts of BaO, and 3.16 parts of TiO21.68 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 for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 2 hours at 450 ℃, 3 hours at 650 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1. The test results are shown in Table 2.
Comparative example 3
Except without using TiO2Except for the above, the relative proportions of the remaining components, the catalyst preparation method, the catalyst evaluation conditions, and the analysis method were the same as in example 2, specifically:
will correspond to 58.55 parts Fe2O3Iron oxide red of (1), corresponding to 19.83 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.8 parts of K2Potassium carbonate of O, corresponding to 8.0 parts of CeO2Cerium oxalate of (1), corresponding to 2.66 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.43 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 for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 5 hours at 650 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1. The test results are shown in Table 2.
[ example 3]
Except for Yb2O3Substitute Er2O3Except for the above, the catalyst preparation method, the catalyst evaluation conditions, and the analysis method were the same as in example 1, and specifically:
will correspond to 56.7 parts Fe2O3Iron oxide red of (1) corresponding to19.2 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.55 parts of K2Potassium carbonate of O, corresponding to 7.75 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.38 parts of BaO, and 3.16 parts of TiO21.68 parts of Yb2O3And 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 for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 2 hours at 450 ℃, 3 hours at 650 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1. The test results are shown in Table 2.
Comparative example 4
Will correspond to 58.55 parts Fe2O3Iron oxide red of (1), corresponding to 19.83 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.8 parts of K2Potassium carbonate of O, corresponding to 7.66 parts of CeO2Cerium oxalate of (1), corresponding to 2.66 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.43 parts of BaO, 0.35 part of TiO21.73 parts of Yb2O3And 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 for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 2 hours at 450 ℃, 3 hours at 650 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ example 4]
A catalyst was prepared, evaluated and analyzed as in example 1, except that 0.84 parts Er was used2O3And 0.84 part Tm2O3Substitute 1.68 parts Er2O3。
Will correspond to 56.7 parts Fe2O3Iron oxide red of (1), corresponding to 19.2 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.55 parts of K2Potassium carbonate of O, corresponding to 7.75 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.38 parts of BaO, and 3.16 parts of TiO20.84 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 for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 2 hours at 450 ℃, 3 hours at 650 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1. The test results are shown in Table 2.
[ example 5]
A catalyst was prepared, evaluated and analyzed as in example 1, except that 0.84 parts Er was used2O3And 0.84 part Yb2O3Substitute 1.68 parts Er2O3。
Will correspond to 56.7 parts Fe2O3Iron oxide red of (1), corresponding to 19.2 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.55 parts of K2Potassium carbonate of O, corresponding to 7.75 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.38 parts of BaO, and 3.16 parts of TiO20.84 portion of Er2O30.84 part of Yb2O3And 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 for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 2 hours at 450 ℃, 3 hours at 650 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1. The test results are shown in Table 2.
[ example 6]
A catalyst was prepared, evaluated and analyzed as in example 1, except that 0.84 part Tm was used2O3And 0.84 part Yb2O3Substitute 1.68 parts Er2O3。
Will correspond to 56.7 parts Fe2O3Iron oxide red of (1), corresponding to 19.2 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.55 parts of K2Potassium carbonate of O, corresponding to 7.75 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.38 parts of BaO, and 3.16 parts of TiO20.84 part Tm2O30.84 part of Yb2O3And 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 for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 2 hours at 450 ℃, 3 hours at 650 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1. The test results are shown in Table 2.
[ example 7]
A catalyst was prepared, evaluated and analyzed as in example 1, except that 0.56 parts Er was used2O30.56 part Tm2O3And 0.56 part of Yb2O3Substitute 1.68 parts Er2O3。
Will correspond to 56.7 parts Fe2O3Iron oxide red of (1), corresponding to 19.2 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.55 parts of K2Potassium carbonate of O, corresponding to 7.75 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.38 parts of BaO, and 3.16 parts of TiO20.56 part of Er2O30.56 part Tm2O30.56 part of Yb2O3And 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 dried at 90 ℃ for 2 hours and 160 ℃ for 3 hours, then the particles are put into a muffle furnace and calcined at 450 ℃ for 2 hours, 650 ℃ for 3 hours and 920 ℃ for 3 hours to obtain the finished catalyst, and the catalyst is prepared by the steps ofThe compositions are listed in Table 1. The test results are shown in Table 2.
[ example 8]
Will correspond to 53.88 parts Fe2O3Iron oxide red of (1), corresponding to 17.05 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 TiO20.85 parts of Er2O30.49 part of HfO2And 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 for 2 hours at the temperature of 90 ℃, 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 2 hours at the temperature of 450 ℃, 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 shown in Table.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ example 9]
Will correspond to 53.99 parts Fe2O3Iron oxide red of (1), corresponding to 12.45 parts of Fe2O3Iron oxide yellow of (1), corresponding to 8.55 parts of K2Potassium carbonate of O, corresponding to 10.55 parts of CeO2Corresponding to 1.21 parts of WO3Ammonium tungstate, barium carbonate equivalent to 4.95 parts of BaO, and 3.9 parts of TiO24.4 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 for 2 hours at the temperature of 90 ℃, 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 2 hours at the temperature of 450 ℃, 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 shown in Table.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
Comparative example 5
Will correspond to 55.73 parts of Fe2O3Iron oxide red of (1), corresponding to 15.94 parts of Fe2O3Iron oxide yellow of (1), corresponding to 4.55 parts of K2Potassium carbonate of O, corresponding to 8.55 parts of CeO2Corresponding to 1.71 parts of WO3Ammonium tungstate, barium carbonate corresponding to 4.95 parts of BaO, and 3.16 parts of TiO23.9 parts of Er2O31.51 parts 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 for 2 hours at the temperature of 90 ℃, 3 hours at the temperature of 160 ℃, then the particles are put into a muffle furnace and baked for 2 hours at the temperature of 450 ℃, 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 shown in Table.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
Comparative example 6
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 2.53 parts of BaO, 0.72 part of TiO23.88 portions 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, extruding into particles with the diameter of 3 millimeters and the length of 6 millimeters, putting into an oven, baking at 90 ℃ for 2 hours and at 160 ℃ for 3 hours, then putting into a muffle furnace, baking at 450 ℃ for 2 hours, baking at 650 ℃ for 3 hours and baking at 920 ℃ for 3 hours to obtain the finished catalyst, wherein the composition of the catalyst is listed in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ example 10]
Will correspond to 61.27 parts Fe2O3Iron oxide red of (1), corresponding to 17.36 parts of Fe2O3Iron oxide yellow of (1), corresponding to 6.75 parts of K2Potassium carbonate of O, corresponding to 6.35 parts of CeO2Corresponding to 0.75 part of WO3Ammonium tungstate, barium carbonate corresponding to 0.55 parts of BaO, 4.95 parts of TiO22.02 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 for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 2 hours at 450 ℃, 3 hours at 650 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
Comparative example 7
Except for using CeO2The preparation method of the catalyst, the evaluation conditions of the catalyst and the analysis method are the same as those in example 1 except that cerium oxalate is replaced, and specifically, the method comprises the following steps:
will correspond to 56.7 parts Fe2O3Iron oxide red of (1), corresponding to 19.2 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.55 parts of K2Potassium carbonate of O, 7.75 parts of CeO2Equivalent to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.38 parts of BaO, and 3.16 parts of TiO21.68 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 for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 2 hours at 450 ℃, 3 hours at 650 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1.
[ example 11]
Will correspond to 56.7 parts Fe2O3Iron oxide red of (1), corresponding to 19.2 parts of Fe2O3Iron oxide yellow of (1), corresponding to 7.55 parts of K2Potassium carbonate of O, corresponding to 6.81 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate (D)Barium carbonate equivalent to 1.38 parts of BaO, 4.1 parts of TiO21.68 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 for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 2 hours at 450 ℃, 3 hours at 650 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
[ example 12]
Will correspond to 56.7 parts Fe2O3Iron oxide red of (1), corresponding to 19.2 parts of Fe2O3Iron oxide yellow of (1), corresponding to 6.85 parts of K2Potassium carbonate of O, corresponding to 6.81 parts of CeO2Corresponding to 2.58 parts of WO3Ammonium tungstate, barium carbonate corresponding to 1.38 parts of BaO, 4.8 parts of TiO21.68 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 for 2 hours at 90 ℃ and 3 hours at 160 ℃, and then the particles are put into a muffle furnace and baked for 2 hours at 450 ℃, 3 hours at 650 ℃ and 3 hours at 920 ℃ to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1.
The catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
Comparative example 8
Will correspond to 56.7 parts Fe2O3Iron oxide red of (1), corresponding to 19.2 parts of Fe2O3Iron oxide yellow of (1), corresponding to 4.55 parts of K2Potassium carbonate of O, corresponding to 6.75 parts of CeO2Corresponding to 0.85 part of WO3Ammonium tungstate, barium carbonate corresponding to 0.65 parts of BaO, and 5.8 parts of TiO25.5 parts of Er2O3And 5.69 parts of sodium carboxymethylcellulose were stirred in a kneader for 1.5 hoursAdding deionized water accounting for 25 percent of the total weight of the catalyst raw materials, stirring for 0.5 hour, taking out extruded strips, 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 90 ℃ and 3 hours at 160 ℃, then placing the particles into a muffle furnace, roasting for 2 hours at 450 ℃, 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 catalyst was prepared, evaluated and analyzed as in example 1, and the test results are shown in Table 2.
TABLE 1 weight percent composition of (to be) catalyst
Figure BDA0002135664160000111
Figure BDA0002135664160000121
TABLE 2 comparison of catalyst Performance
Figure BDA0002135664160000122
Figure BDA0002135664160000131
The above examples illustrate the addition of titanium oxide and an amount of an oxide selected from the heavy rare earth oxides Er to an Fe-K-Ce-W-Ba catalytic system2O3、Tm2O3Or Yb2O3The obtained catalyst has reasonable specific surface and high crushing strength, provides a condition for maintaining high activity under an ultra-low water ratio, improves the activity and stability of the low-potassium catalyst under the ultra-low water ratio, has obvious energy-saving effect, contributes 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 ultra-low water ratio.

Claims (12)

1. The catalyst for the dehydrogenation of the ethylbenzene with the ultra-low water ratio comprises the following components: a first group of primary metal oxides, a second group of metal oxides, and a third group of metal oxides; the first group of main metal oxides are iron, potassium and cerium; the second group of metal oxides are tungsten and barium; the third group of metal oxide is at least one of titanium and erbium, thulium and ytterbium, the content of element titanium in the third group of metal oxide is 0.1-5% by weight of the catalyst, and the crushing strength of the catalyst is more than or equal to 30N/mm.
2. The ultra-low water ratio ethylbenzene dehydrogenation catalyst of claim 1, comprising, in weight percent: 66-79% Fe in the first group of main metal oxides2O3(ii) a 4 to 9% of K2O; 6-11% of CeO2(ii) a WO 0.5-5% of a second group of metal oxides3(ii) a 0.5 to 5% of BaO and 0.5 to 5% of Er2O3、Tm2O3And Yb2O3At least one of (1).
3. The catalyst for ethylbenzene dehydrogenation with ultra-low water ratio according to claim 1, wherein the specific surface area of the catalyst is 2.2-2.8 m2The catalyst has a crush strength of 30 to 40N/mm.
4. The ultra-low water ratio ethylbenzene dehydrogenation catalyst of claim 1, wherein the TiO is2The content is 0.5 to 4.5%, preferably 0.8 to 3.5%.
5. The ultra-low water ratio ethylbenzene dehydrogenation catalyst of claim 1, wherein the content of the heavy rare earth oxides erbium, thulium and ytterbium is 0.9-4%.
6. The ultra low water ratio ethylbenzene dehydrogenation catalyst of claim 1, wherein the catalyst does not contain molybdenum oxide.
7. The ultra-low water ratio ethylbenzene dehydrogenation catalyst of claim 1 wherein no binder is added during the catalyst preparation process, the binder comprising kaolin, diatomaceous earth and cement.
8. A preparation method of an ethylbenzene dehydrogenation catalyst comprises the following steps: fe source, K source, Ce source, W source, Ba source, Ti source and heavy rare earth oxide Er according to the proportion2O3、Tm2O3And Yb2O3And uniformly contacting the pore-forming agent with water to obtain the catalyst.
9. The method of claim 8, further comprising the steps of extruding, drying, and firing; the drying temperature is 80-180 ℃, and the drying time is 2-8 hours.
10. The preparation method of claim 8, wherein the roasting is performed by a three-step method, that is, the roasting temperature is 200-500 ℃ for 1-4 hours, the roasting temperature is 550-750 ℃ for 1-4 hours, and the roasting temperature is 800-950 ℃ for 1-4 hours.
11. The method according to claim 8, wherein the Ce source is added in the form of cerium oxalate or cerium hydroxide.
12. A method for preparing styrene by ethylbenzene dehydrogenation takes ethylbenzene as a raw material, the reaction temperature is 610-650 ℃, and the liquid airspeed is 1.0-1.8 hours－1And the water ratio (weight) is 0.7-1.0, the pressure is-40 KPa-normal pressure, and the raw material is in contact reaction with the ethylbenzene dehydrogenation catalyst with the ultra-low water ratio to obtain the styrene.
CN201910652302.XA 2019-07-19 2019-07-19 Ultra-low water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof Pending CN112237922A (en)

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