WO2022078371A1 - 铁-钾-铈基复合氧化物催化剂及其制备和应用 - Google Patents

铁-钾-铈基复合氧化物催化剂及其制备和应用 Download PDF

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WO2022078371A1
WO2022078371A1 PCT/CN2021/123478 CN2021123478W WO2022078371A1 WO 2022078371 A1 WO2022078371 A1 WO 2022078371A1 CN 2021123478 W CN2021123478 W CN 2021123478W WO 2022078371 A1 WO2022078371 A1 WO 2022078371A1
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catalyst
source
weight
group
metal element
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PCT/CN2021/123478
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French (fr)
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宋磊
缪长喜
朱敏
危春玲
徐永繁
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中国石油化工股份有限公司
中国石油化工股份有限公司上海石油化工研究院
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Priority to JP2023522817A priority Critical patent/JP2023545174A/ja
Priority to US18/248,775 priority patent/US20230381751A1/en
Priority to EP21879414.7A priority patent/EP4219004A4/en
Priority to KR1020237016270A priority patent/KR20230087573A/ko
Publication of WO2022078371A1 publication Critical patent/WO2022078371A1/zh

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Definitions

  • the present application relates to the technical field of dehydrogenation catalysts, in particular to an iron-potassium-cerium-based composite oxide catalyst and its preparation and application.
  • the catalytic dehydrogenation of ethylbenzene has always been the dominant technical route for the production of styrene at home and abroad, and its production capacity accounts for about 85% of the total production capacity of styrene.
  • Toluene and benzene are the main by-products.
  • the by-product benzene needs to be separated by the rectification unit and then returned to the ethylbenzene unit for recycling.
  • Toluene is sold as a by-product. Reducing the amount of benzene and toluene generated can improve the utilization rate of raw materials and reduce the material consumption of the device.
  • One of the keys to the catalytic dehydrogenation of ethylbenzene is the catalyst for the production of styrene from the dehydrogenation of ethylbenzene.
  • the Fe-K-Ce series of catalysts successfully developed in the early 1980s enabled the catalyst to greatly improve the activity on the basis of maintaining the original stability, and at the same time avoided the pollution of the environment by Cr oxides. used by the manufacturer.
  • CN104096568A discloses a catalyst for producing styrene composite oxide by dehydrogenation of ethylbenzene.
  • the mass percentages of iron, potassium, magnesium, cerium and molybdenum oxides are composed as follows: 1) iron oxides, 68%-75% , as Fe 2 O 3 ; 2) Potassium oxides, 8%-13%, as K 2 O; 3) Magnesium oxides, 0.5%-6%, as MgO; 4) Cerium oxides , 8%-15%, based on CeO 2 ; 5) Molybdenum oxide, 1%-6%, based on MoO 3 ; 6) Binder, 0.5%-10%;
  • the body includes anhydrous iron oxide (iron oxide red) and hydrated iron oxide (iron oxide yellow).
  • the precursor of the oxide is potassium carbonate;
  • the oxide of magnesium is commercially available magnesium oxide;
  • the precursor of the oxide of cerium is selected from cerium nitrate and nano-cerium oxide, and the content of nano-cerium oxide accounts for the total amount of cerium oxide.
  • the content of nano-cerium trioxide (in mass percentage) is preferably 25%-40% of the total amount of cerium oxide;
  • the precursor of molybdenum oxide is ammonium molybdate (NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O;
  • the binder can be selected from at least one of kaolin, diatomite, cement and the like.
  • the catalyst has a low conversion rate of ethylbenzene, all below 65%, and the selectivity of styrene is low.
  • the amount of by-products is an important indicator for evaluating the performance of the catalyst. Under the same conditions, the catalyst with few by-products and good styrene selectivity is preferred for the styrene dehydrogenation process.
  • the published US patent documents US5190906A and US4804799A also have the problem of low styrene selectivity, and the isothermal dehydrogenation reaction styrene selectivity is generally lower than 95.0%, the total content of benzene and toluene in the product is higher than 4%, and the material consumption is relatively high. high, and increase the difficulty of subsequent separation.
  • the purpose of this application is to provide an iron-potassium-cerium-based composite oxide catalyst and its preparation and application.
  • the catalyst can be used even at a lower reaction temperature (not higher than 620° C.). ) and ultra-low water ratio, it also has high selectivity, catalytic activity and stability, and less by-products of benzene and toluene, with low material consumption and low energy consumption.
  • the present application provides an iron-potassium-cerium-based composite oxide catalyst, in addition to the metal elements Fe, K and Ce, the catalyst further comprises a metal element M, the metal element M At least one selected from IIA group metal elements, non-Cr VIB group metal elements and IVA group metal elements, wherein the total alkali content of the catalyst is in the range of 0.32-0.46mmol/g, and the strong alkali content is 0.061- in the range of 0.082 mmol/g.
  • a method for preparing the iron-potassium-cerium-based composite oxide catalyst of the present application comprising combining Fe source, K source, Ce source, M source, optional IVB group metal element source, optional A source of Group VA metal element and optional ferrite are mixed with a porogen and solvent and shaped, optionally dried and/or calcined, to obtain the catalyst.
  • the application of the iron-potassium-cerium-based composite oxide catalyst of the present application in the dehydrogenation reaction of alkyl aromatic hydrocarbons is provided.
  • the present application provides a method for dehydrogenation of alkyl aromatic hydrocarbons, comprising the step of contacting and reacting alkyl aromatic hydrocarbons with the iron-potassium-cerium-based composite oxide catalyst of the present application under dehydrogenation reaction conditions.
  • the catalyst of the present application When the catalyst of the present application is used in the dehydrogenation of alkyl aromatic hydrocarbons, even at a lower reaction temperature and an ultra-low water ratio, it still exhibits strong catalytic activity, high selectivity and good stability, and has low material consumption and low energy consumption.
  • Fig. 1 is the CO 2 -TPD spectrum of the catalyst obtained in Example 1 of the application before and after the reaction.
  • FIG. 2 is the H 2 -TPR spectrum of the catalysts obtained in Example 1 and Comparative Example 9 of the present application.
  • 3A to 3D show the SEM pictures of the catalysts obtained in Example 1 and Comparative Example 9 of the present application before and after the reaction.
  • any specific numerical value disclosed herein, including the endpoints of a numerical range, is not limited to the precise value of the numerical value, but is to be understood to encompass values approximating the precise value, such as within ⁇ 5% of the precise value. all possible values. And, for the disclosed numerical range, between the endpoint values of the range, between the endpoint values and the specific point values in the range, and between the specific point values, one or more new values can be obtained in any combination. Numerical ranges, these new numerical ranges should also be considered to be specifically disclosed herein.
  • the total alkali content and strong alkali content of the catalyst are obtained by analyzing the carbon dioxide-temperature programmed desorption method (CO 2 -TPD method).
  • any matter or matter not mentioned is directly applicable to those known in the art without any change.
  • any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are regarded as part of the original disclosure or original record of this application, and should not be It is considered to be new content not disclosed or anticipated herein, unless a person skilled in the art considers that the combination is obviously unreasonable.
  • the present application provides an iron-potassium-cerium-based composite oxide catalyst, the catalyst further comprises a metal element M in addition to the metal elements Fe, K and Ce, and the metal element M is selected from at least one of group IIA metal elements, non-Cr VIB group metal elements and IVA group metal elements, wherein the total alkali content of the catalyst is in the range of 0.32-0.46 mmol/g, and the strong alkali content is 0.061 -0.082mmol/g range.
  • the metal element M is a combination of at least two selected from group IIA metal elements, non-Cr VIB group metal elements and IVA group metal elements, preferably at least one group IIA metal element, at least one A combination of a VIB metal element other than Cr and at least one IVA metal element.
  • the group IIA metal element contained in the catalyst is not Mg, more preferably Sr.
  • the VIB group metal elements contained in the catalyst are not Cr and Mo, preferably W.
  • the Group IVA metal element contained in the catalyst is selected from Ge, Sn and Pb, or a combination thereof.
  • the crushing strength of the catalyst After reacting for 1500 hours under the conditions of a pressure of -45kPa, a mass space velocity of ethylbenzene of 0.75h -1 , a temperature of 600°C, and a weight ratio of water to ethylbenzene of 0.9, the crushing strength of the catalyst
  • the retention rate is above 80%.
  • the total alkali content of the catalyst remains The rate is above 82%, and the retention rate of strong alkali is above 80%.
  • the reduction completion temperature of the catalyst is above 730°C.
  • the catalyst contains 66-80 wt % Fe 2 O 3 , for example, the weight content of Fe 2 O 3 may be 66 wt %, 67 wt %, 68 wt % %, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 80%, and any two values any value in between.
  • the catalyst contains 2.3-6 wt % K 2 O, preferably 2.3-5.5 wt % K 2 O, and the content of K 2 O can be, for example, 2.3 wt %, 2.8 wt %, 3.3 wt %, 3.8 wt %, 4.3 wt %, 4.8 wt %, 5.3 wt %, 5.5 wt %, and any value in between.
  • the catalyst contains 6-12 wt % CeO 2 , for example, 6 wt %, 6.5 wt %, 7 wt %, 7.5 wt %, 8 wt % , 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, and any value in between.
  • the catalyst contains 66-80 wt% Fe 2 O 3 , 2.3-6 wt % K 2 O, 6 12% by weight of CeO 2 and 2-16% by weight of oxides of the metal element M.
  • the metal element M is usually present in the form of an oxide in its highest valence state. The inventors of the present application found that under this content range, the catalyst of the present application showed better catalytic activity, higher selectivity and better stability at lower temperature and ultra-low water ratio, And less by-product benzene and toluene.
  • the content of K 2 O in the conventional catalyst is higher than 10 wt %, which is easy to be lost during the catalytic dehydrogenation process, which reduces the catalytic activity, while the content of K 2 O in the catalyst of the present application is 2.3-6 wt %.
  • the content of O is significantly lower than that of conventional catalysts. Even with extremely low content of K 2 O, it still shows better catalytic activity, higher selectivity and better stability, and the by-products of benzene and toluene are more Compared with conventional catalysts, it has higher application advantages.
  • the oxide of the metal element M is at least one of WO 3 , SrO and oxides of Group IVA metal elements. Adopting this preferred embodiment can further improve the catalytic activity, selectivity and stability of the catalyst, and have lower amounts of by-products of benzene and toluene.
  • the oxide of the metal element M is selected from at least two of the oxides of WO 3 , SrO and Group IVA metal elements, when the oxide of the metal element M is selected from WO 3 .
  • the content selection range of each component in the oxide of metal element M is not particularly limited, and the content of each component may be the same or different.
  • the oxides of the metal element M are selected from the group consisting of WO 3 , SrO and the oxides of group IVA metal elements
  • the contents of the two oxides may be the same or different.
  • the respective contents of the two oxides are not particularly limited.
  • the oxide of metal element M is a combination of WO 3 , SrO and oxides of group IVA metal elements.
  • the catalyst contains 0.5-5 wt% of WO 3 , for example, the content of WO 3 can be 0.5 wt %, 1 wt %, 1.5 wt %, 2 wt % , 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, and any value between any two values.
  • the catalyst contains 0.5-5% by weight of SrO, and the content of SrO can be 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight %, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, and any value between any two values.
  • the catalyst contains 0.5-5 wt % oxides of Group IVA metal elements, such as 0.5 wt %, 1 wt %, 1.5 wt %, 2 wt % %, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, and any value between any two values.
  • the catalyst contains 67.5-79 wt% Fe 2 O 3 , 2.3-5.5 wt % K 2 O, 6 12% by weight of CeO 2 , 0.5-5% by weight of WO 3 , 0.5-5% by weight of SrO and 0.5-5% by weight of oxides of group IVA metal elements.
  • the catalyst of the present application shows better catalytic activity, higher selectivity and better stability at lower temperature and ultra-low water ratio, and the by-products of benzene and toluene are higher. few.
  • the oxide of the Group IVA metal element is selected from at least one of GeO 2 , SnO 2 and PbO 2 .
  • Using this preferred embodiment can further improve the catalytic activity and selectivity of the catalyst, and have lower amounts of by-product benzene and toluene.
  • the oxide of group IVA metal element is selected from at least two of GeO 2 , SnO 2 and PbO 2 , there is no particular selection range for the content of each component in the oxide of group IVA metal element.
  • the content of each component can be the same or different.
  • the contents of the two oxides may be the same or different.
  • the contents of the two oxides are different, there is no particular limitation on the respective contents of the two oxides.
  • the content ratio is 1:0.5-1.5, more preferably 1:0.8-1.2.
  • the oxide of the Group IVA metal element is a combination of GeO 2 , SnO 2 and PbO 2 .
  • the oxides of the IVA metal elements are a combination of GeO 2 , SnO 2 and PbO 2
  • the contents of the three oxides may be the same or different.
  • the contents of the three oxides are different, there is no particular restriction on the respective contents of the three oxides.
  • the three oxides GeO 2.
  • the content ratio of SnO 2 and PbO 2 is 1:0.5-1.5:0.5-1.5, more preferably 1:0.8-1.2:0.8-1.2.
  • the catalyst also contains ferrite, such as manganese ferrite, zinc ferrite, copper ferrite, nickel ferrite, etc., preferably ZnFe 2 O 4 .
  • ferrite such as manganese ferrite, zinc ferrite, copper ferrite, nickel ferrite, etc.
  • ZnFe 2 O 4 preferably ZnFe 2 O 4 .
  • the inventors of the present application have found through research that when a certain amount of Fe element in the form of ferrite is added, compared with the case where Fe element in the form of oxide is simply added, for example, adding ZnFe 2 O 4 is compared to adding the same amount of ZnO and iron oxides, the resulting catalysts are more active, more selective, more stable and have less by-products of benzene and toluene.
  • the catalyst contains 0.5-8% by weight of ferrite, preferably ZnFe 2 O 4 , such as 0.5% by weight, 1.5% by weight, 2.5% by weight, 3.5 wt%, 4.5 wt%, 5.5 wt%, 6.5 wt%, 7.5 wt%, 8 wt%, and any value in between.
  • ferrite preferably ZnFe 2 O 4
  • ZnFe 2 O 4 such as 0.5% by weight, 1.5% by weight, 2.5% by weight, 3.5 wt%, 4.5 wt%, 5.5 wt%, 6.5 wt%, 7.5 wt%, 8 wt%, and any value in between.
  • the content of ferrite such as ZnFe 2 O 4 in the catalyst is 1- 7% by weight, more preferably 2-6% by weight.
  • the catalyst contains 2-6 wt % of ZnFe 2 O 4 , and the content of ZnFe 2 O 4 can be, for example, 2 wt %, 2.5 wt %, 3 wt % %, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, and any value between any two values.
  • the catalyst may also contain other metal promoters, such as Group IVB metal oxides, such as HfO 2 , and/or Group VA metal oxides, such as Sb 2 O 5 .
  • the catalyst based on the total amount of the catalyst, contains 0.05-0.5% by weight of a group IVB metal oxide, preferably HfO 2 , and/or 0.5-1.5% by weight of a group VA metal oxide, preferably Sb 2 O 5 .
  • the catalyst in order to further improve the catalytic activity, selectivity and stability of the catalyst at low temperature, and further reduce the generation amount of by-product benzene and toluene, preferably, the catalyst does not contain molybdenum.
  • the catalyst in order to further improve the activity of the catalyst under low water ratio and reduce the dehydrogenation reaction temperature, preferably, the catalyst does not contain magnesium.
  • the catalyst does not contain a binder, such as montmorillonite, diatomite, cement, pseudohalloysite, saponite, kaolin, halloysite, hydrotalcite , sepiolite, rectorite, attapulgite, bentonite, or any combination thereof.
  • a binder such as montmorillonite, diatomite, cement, pseudohalloysite, saponite, kaolin, halloysite, hydrotalcite , sepiolite, rectorite, attapulgite, bentonite, or any combination thereof.
  • the catalyst of the present application contains Fe element, K element, Ce element and metal element M, and at least one of ZnFe 2 O 4 , HfO 2 and Sb 2 O 5 , the metal element M is selected from at least one of W element, Sr element and Group IVA metal element. Further preferably, the catalyst comprises ZnFe 2 O 4 and at least one of HfO 2 and Sb 2 O 5 .
  • the content of each element is as described above, and details are not repeated here.
  • the inventor of the application found through research that when the iron-potassium-cerium-based composite oxide catalyst contains the metal components defined above, and the total alkali content of the catalyst is in the range of 0.32-0.46 mmol/g, the strong alkali content is in the range of 0.32-0.46 mmol/g. In the range of 0.061-0.082mmol/g, when the catalyst is used in the dehydrogenation of alkyl aromatic hydrocarbons, even at a lower reaction temperature (for example, not higher than 620°C) and ultra-low water ratio, it still shows relatively high performance. Strong catalytic activity, high selectivity and good stability.
  • the prior art has not recognized the superiority of controlling the total alkali content and strong alkali content of the alkyl aromatic hydrocarbon dehydrogenation catalyst within the above-mentioned specific range, so the total alkali content and strong alkali content of the catalyst and the alkali content in the reaction process are not recognized.
  • the stability of the catalyst is not strictly required, and the total alkali content of the existing catalyst is usually below 0.32 mmol/g.
  • the catalyst provided by the present application can obtain a specific range of total alkali content and strong alkali content by using specific elements, which reduces the introduction of low-efficiency substances.
  • it When used in ethylbenzene dehydrogenation reaction, it can reduce the generation of benzene and toluene, and improve the efficiency of benzene and benzene.
  • the selectivity of ethylene is improved, the utilization rate of raw materials is improved, and the fluctuation of alkali amount before and after the reaction is small.
  • the crushing strength of the catalyst obtained in the present application can reach 3.88Kg /mm, and the activity evaluation is carried out in an isothermal fixed bed.
  • the total content of benzene and toluene in the product is as low as 2.26%, the selectivity of styrene can reach 97.17%, and the conversion rate of ethylbenzene can reach 77.6%;
  • the total toluene content is as low as 1.93%, the styrene selectivity can reach 97.99%, and the ethylbenzene conversion rate can reach 76.7%;
  • the total alkali content retention rate of the catalyst after 1500 hours of reaction can reach 94.96%, and the strong alkali content retention rate can reach 92.41% , the crushing strength retention rate can reach 94.85%, showing good catalyst stability.
  • the total alkali content of the catalyst is 0.32-0.42 mmol/g, preferably 0.324-0.397 mmol/g, particularly preferably 0.384-0.397 mmol/g, such as 0.384 mmol/g, 0.386 mmol/g , 0.388mmol/g, 0.39mmol/g, 0.392mmol/g, 0.394mmol/g, 0.396mmol/g, 0.397mmol/g, and any value between any two values.
  • the amount of strong base of the catalyst is 0.061-0.080mmol/g, preferably 0.061-0.079mmol/g, particularly preferably 0.072-0.079mmol/g, for example, it can be 0.072mmol/g, 0.074mmol/g , 0.076mmol/g, 0.078mmol/g, 0.079mmol/g, and any value between any two values.
  • the total alkali content of the catalyst of the present application is 0.384-0.397 mmol/g, and the strong alkali content is 0.072-0.079 mmol/g. Under the condition of hydrogen reaction, it exhibits better catalytic activity, higher selectivity and better stability, and the content of benzene and toluene in the product is lower.
  • a method for preparing the iron-potassium-cerium-based composite oxide catalyst of the present application comprising combining Fe source, K source, Ce source, M source, optional IVB group metal element source, optional A source of Group VA metal element and optional ferrite are mixed with a porogen and a solvent and shaped, optionally dried and/or calcined, to obtain the catalyst;
  • the M source is selected from at least one selected from the group IIA metal element source, non-Cr VIB group metal element source and IVA group metal element source, preferably at least one of W source, Sr source and IVA group metal element source One, more preferably a combination of at least two of a W source, a Sr source and a source of Group IVA metal elements, particularly preferably a combination of a source of W, a Sr source and at least one source of Group IVA metal elements.
  • the Group IVB metal element, Group VA metal element, ferrite, Group IIA metal element, Group VIB metal element other than Cr, Group IVA metal element, etc. are as defined above, and herein No longer.
  • the method of the present application does not have strict restrictions on the specific manner of the mixing, as long as the Fe source, K source, Ce source, M source, porogen, solvent, optional source of IVB group metal elements, optional The source of the Group VA metal element and the optional ferrite may be uniformly mixed.
  • the method of the present application comprises the following steps:
  • step 2) mixing the mixture obtained in step 1) with ferrite, preferably ZnFe 2 O 4 ;
  • step 2) The mixture obtained in step 2) is mixed with a solvent and shaped, and optionally dried and/or calcined to obtain the catalyst.
  • Adopting this preferred embodiment is more favorable for uniform mixing, can further improve catalytic activity, selectivity and stability, and further reduce the generation amount of by-product benzene and toluene.
  • the mixing time of step 1), step 2) and step 3 is independently 0.1-2h; further preferably, the mixing time of step 1) The time of mixing is 0.1-0.6h, the mixing time of step 2) is 1-2h, and the mixing time of step 3) is 0.2-1h.
  • the embodiment of mixing can be selected in various ways, for example, it can be carried out under stirring conditions.
  • the mixing can also be carried out in a kneader.
  • the selection of the Fe source is not particularly limited, and can be any iron-containing compound that can be converted into Fe 2 O 3 in the subsequent roasting process.
  • the Fe source is red iron oxide and/or yellow iron oxide, more preferably red iron oxide and yellow iron oxide.
  • the dosage ratio of red iron oxide and yellow iron oxide in this application can be selected within a wide range, preferably, in terms of oxides, the weight ratio of red iron oxide and yellow iron oxide is 2-4:1; for example, Can be 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, and any two any value in between.
  • the selection of the Ce source is not particularly limited, and can be any cerium-containing compound that can be converted into CeO 2 in the subsequent calcination process.
  • the Ce source is cerium hydroxide and/or cerium acetate. This preferred embodiment can not only meet the environmental protection requirements (cerium nitrate will release nitrogen-containing gas during the roasting process), but also further improve the strength of the prepared catalyst.
  • the selection of the K source is not particularly limited, and can be any potassium-containing compound that can be converted into K 2 O in the subsequent calcination process.
  • the K source is potassium carbonate and/or potassium bicarbonate; more preferably potassium carbonate.
  • the source of Group VIB metal element there is no particular limitation on the selection of the source of Group VIB metal element, and it can be any compound containing Group VIB metal element that can be converted into Group VIB metal oxide in the subsequent calcination process, and can be any compound containing Group VIB metal element. Salts and/or oxides of Group VIB metal elements.
  • the selection of the W source is not particularly limited, and can be any tungsten-containing compound that can be converted into WO 3 in the subsequent roasting process.
  • the W source is selected from ammonium tungstate, metatungstic acid At least one of ammonium and tungsten trioxide; more preferably ammonium tungstate.
  • the source of Group IIA metal element there is no particular limitation on the selection of the source of Group IIA metal element, and it can be any compound containing Group IIA metal element that can be converted into Group IIA metal oxide in the subsequent calcination process, and can be a compound containing Group IIA metal element. Salts and/or oxides of Group IIA metal elements.
  • the selection of the Sr source is not particularly limited, and can be any strontium-containing compound that can be converted into SrO in the subsequent roasting process.
  • the Sr source is strontium carbonate and/or strontium hydroxide.
  • the source of Group IVA metal elements there is no particular limitation on the selection of the source of Group IVA metal elements, and it can be any compound containing Group IVA metal elements that can be converted into Group IVA metal oxides in the subsequent calcination process, and can be any compound containing Group IVA metal elements. Salts and/or oxides of Group IVA metal elements.
  • the source of Group IVA metal elements is selected from oxides containing Group IVA metal elements.
  • the source of Group IVB metal elements there is no particular limitation on the selection of the source of Group IVB metal elements, and it can be any compound containing Group IVB metal elements that can be converted into Group IVB metal oxides in the subsequent calcination process, and can be any compound containing Group IVB metal elements. Salts and/or oxides of Group IVB metal elements.
  • the selection of the Hf source is not particularly limited, and can be any Hf element-containing salt and/or oxide that can be converted into Hf oxide in the subsequent calcination process, preferably HfO 2 .
  • the source of Group VA metal element there is no particular limitation on the selection of the source of Group VA metal element, and it can be any Group VA metal element-containing compound that can be converted into a Group VA metal oxide in the subsequent calcination process, and can be a Group VA metal element-containing compound. Salts and/or oxides of Group VA metal elements.
  • the selection of the Sb source is not particularly limited, and can be any salt and/or oxide containing Sb element that can be converted into Sb oxide in the subsequent calcination process, preferably Sb 2 O 5 .
  • the addition amount of the porogen is not particularly limited.
  • the addition amount of the porogen is the Fe source. , K source, Ce source, M source, optional ferrite, optional Group IVB metal element source and optional Group VA metal element source of the total added amount of 2.2-6.3% by weight, preferably 3.8-5.6% weight%.
  • the type of the porogen is not particularly limited, and it can be various porogens conventionally used in the art.
  • the porogen is selected from at least one of polystyrene, graphite, cellulose and derivatives thereof.
  • the type of graphite described in this application can be selected from a wide range, and it can be natural graphite or artificial graphite, which is not particularly limited in this application.
  • the cellulose and its derivatives are preferably at least one of methyl cellulose, hydroxymethyl cellulose, ethyl cellulose and sodium hydroxymethyl cellulose.
  • the porogen is selected from at least one of graphite, polystyrene (which can be microspheres) and sodium carboxymethyl cellulose.
  • the amount of solvent added is not particularly limited, as long as the mixing requirements of the materials can be met.
  • the added amount of the solvent is 15-35% by weight of the total weight of the catalyst raw materials, preferably 22-32% by weight.
  • the solvent can be selected in a wide range as long as the mixed environment can be provided, and preferably, the solvent is water.
  • the shape of the catalyst is not particularly limited, for example, it may be in the form of particles, strips, and the like.
  • Those skilled in the art can shape the material obtained by mixing in step 3) into various available specifications according to the specific requirements in actual production, for example, it can be extruded into particles with a diameter of 3 mm and a length of 6 mm, but the application is not limited to this.
  • the drying conditions in step 3) include: the temperature is 30-145°C, and the time is 1-8h; more preferably, the drying includes: drying at 35-95°C for 0.5-4h, and then The temperature was raised to 95-145°C and dried for 0.5-4h.
  • the conditions for the roasting in step 3) include: a temperature of 320-960° C. and a time of 2-8 hours. More preferably, the roasting comprises: roasting at 320-750° C. for 1-4 hours, and then heating to 750-960° C. for 1-4 hours.
  • an iron-potassium-cerium-based composite oxide catalyst prepared by the method of the present application is provided.
  • the application of the iron-potassium-cerium-based composite oxide catalyst of the present application in the dehydrogenation reaction of alkyl aromatics is provided.
  • the present application provides a method for dehydrogenation of alkyl aromatic hydrocarbons, comprising the step of contacting and reacting alkyl aromatic hydrocarbons with the iron-potassium-cerium-based composite oxide catalyst of the present application under dehydrogenation reaction conditions.
  • the alkyl aromatic hydrocarbon is one or more of C 8 -C 10 alkylbenzenes, more preferably ethylbenzene.
  • the catalyst provided by the application has high catalytic activity, selectivity and stability even under the reaction conditions of low temperature and ultra-low water ratio, and the content of by-product benzene and toluene in the product is low.
  • the dehydrogenation temperature of the alkyl aromatic hydrocarbon is 580-620°C, more preferably 590-610°C, for example, it can be 590°C, 595°C, 600°C, 605°C, 610°C, and Any value between any two values.
  • the mass space velocity of the alkyl aromatic hydrocarbon is 0.5-1h -1 , more preferably 0.6-0.8h -1 , for example, it can be 0.6h -1 , 0.65h -1 . , 0.7h -1 , 0.75h -1 , 0.8h -1 , and any value in between.
  • the weight ratio of the water to the alkyl aromatic hydrocarbon is 0.7-1, more preferably 0.8-1, for example, 0.8, 0.82, 0.84, 0.86, 0.88, 0.9 , 0.92, 0.94, 0.96, 0.98, 1, and any value in between.
  • the pressure for the dehydrogenation of the alkyl aromatic hydrocarbons can be selected within a wide range, preferably, the pressure is -60kPa to normal pressure, more preferably -50kPa to normal pressure, further preferably -50kPa to -20kPa, for example, can be -50kPa, -48kPa, -46kPa, -44kPa, -42kPa, -40kPa, -38kPa, -36kPa, -34kPa, -32kPa, -30kPa, -28kPa, -26kPa, -24kPa, -22kPa, -20kPa, and any value in between.
  • the dehydrogenation conditions may include: the temperature is 580-620°C, the mass space velocity of the alkyl aromatic hydrocarbon is 0.5-1 h -1 , the weight ratio of water to the alkyl aromatic hydrocarbon is 0.7-1, and the pressure is -60kPa to normal pressure; further preferably, the dehydrogenation conditions of the alkyl aromatic hydrocarbons include: the temperature is 590-610 ° C, the mass space velocity is 0.6-0.8h -1 , and the weight ratio of water to the alkyl aromatic hydrocarbons is 0.8- 1. The pressure is -50kPa to normal pressure.
  • the performance of the catalyst is characterized by the conversion rate of ethylbenzene, the selectivity of styrene, and the generation amount of benzene and toluene in the product, respectively.
  • the performance of the catalyst was evaluated in an isothermal fixed bed, and the process was briefly described as follows: deionized water and ethylbenzene were respectively input into the preheating mixer through a metering pump, and then entered into the reactor after preheating and mixing into a gaseous state.
  • the heating wire is heated to make it reach a predetermined temperature, the inner diameter of the reactor is a stainless steel tube of 1 inch, and the catalyst is filled with 100 milliliters. %), styrene concentration (wt %) and benzene and toluene concentrations (wt %);
  • Ethylbenzene conversion % (initial ethylbenzene concentration (weight %) in reaction mass-ethylbenzene concentration (weight %) in reaction product) ⁇ initial ethylbenzene concentration (weight %) in reaction mass;
  • Styrene selectivity % styrene concentration in reaction product (weight %) ⁇ (initial ethylbenzene concentration in reaction material (weight %) - ethylbenzene concentration in reaction product (weight %));
  • the total alkali content and strong alkali content of the catalyst were analyzed by the carbon dioxide-temperature programmed desorption method.
  • 0.1 g of the catalyst was activated at 600° C. in a He gas stream for 2 hours, then cooled to 80° C. and adsorbed.
  • a typical CO 2 -TPD spectrum is shown in Figure 1.
  • the peak in the low temperature region (temperature 80-400 °C) is the desorption peak corresponding to the amount of weak base
  • the peak in the high temperature region (temperature 400-600 °C) is the desorption peak.
  • the peak is the desorption peak corresponding to the amount of strong base.
  • Alkali, total alkali is the sum of weak alkali and strong alkali.
  • the alkali amount retention rate is the ratio of the amount of alkali after the reaction to the amount of alkali before the reaction.
  • the electron microscope photos of the catalysts were taken on a JSM-35 scanning electron microscope produced by Japan Electronics Co., Ltd., the working acceleration voltages were 15, 25kV, the working distance was 20mm, the magnification was 20,000, and the resolution was 3.5nm. .
  • the crushing strength test method of the catalyst is carried out according to HG/T 2782-2011, and is measured by QCY-602 particle strength meter. The average value was used to calculate the crush strength of the samples.
  • Strength retention is the ratio of the crushing strength after the reaction to the crushing strength before the reaction.
  • the change of catalyst reduction temperature was observed by temperature programmed reduction (TPR) method,
  • TPR temperature programmed reduction
  • the method is to place 50 mg of the catalyst sample in a U-shaped tube quartz reactor, raise the temperature to 400 °C under He atmosphere, then drop to room temperature, and switch to H2 / N2 reducing gas ( H2 concentration of 10 vol%) to carry out the program.
  • the temperature was increased for reduction, and the temperature was increased to 850°C at a rate of 10°C/min.
  • the temperature-programmed reduction (TPR) method was used to observe the change of the reduction temperature of the catalyst obtained in Example 1, and the obtained H 2 -TPR spectrum was shown in Figure 2 . It can be seen from Figure 2 that the reduction completion temperature of the obtained catalyst (that is, in the H 2 -TPR spectrum The temperature corresponding to the peak of the curve) is 746°C.
  • the total alkali content and strong alkali content of the catalyst obtained in Example 1 before and after 1500 hours of reaction were analyzed by carbon dioxide-temperature programmed desorption method, and the obtained CO 2 -TPD spectrum is shown in FIG. 1 .
  • the peak in the low temperature region is the desorption peak corresponding to the amount of weak alkali
  • the peak in the high temperature region is the desorption peak corresponding to the amount of strong alkali.
  • liquid nitrogen was used to collect the desorbed CO 2.
  • the amount of strong base and total base before and after the reaction of the catalyst obtained in Example 1 and the retention rate of base amount are listed in Table 4.
  • the crushing strength of the catalyst obtained in Example 1 before the reaction was 3.35Kg/mm
  • the strength after the reaction was 2.88Kg/mm
  • the strength retention rate was 85.97%.
  • the results are shown in Table 4. .
  • the catalyst was prepared according to the method of Example 1, except that ZnFe 2 O 4 and GeO 2 were not added, specifically:
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was prepared, evaluated and analyzed according to the method of Example 1, except that ZnFe 2 O 4 was not added, and ZnFe 2 O 4 was replaced by red iron oxide, yellow iron oxide and ZnO with the same element oxide content, and the remaining components
  • the relative proportional relationship, catalyst preparation method, catalyst evaluation conditions and analysis method are the same as in Example 1, the catalyst composition is listed in Table 1, the alkali analysis and strength test results are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was prepared, evaluated and analyzed according to the method of Example 1, except that SnO 2 was used instead of GeO 2 .
  • the catalysts were prepared, evaluated and analyzed as in Example 1, except that SnO 2 was used instead of GeO 2 , no ZnFe 2 O 4 was added, and ZnFe 2 O 4 was calculated as oxide, using iron oxide with an equivalent elemental oxide content Red, iron oxide yellow and ZnO are replaced, the catalyst composition is listed in Table 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was prepared, evaluated and analyzed according to the method of Example 1, except that PbO 2 was used instead of GeO 2 .
  • the catalysts were prepared, evaluated and analyzed according to the method of Example 1 , except that PbO2 was used instead of GeO2 , no ZnFe2O4 was added, and ZnFe2O4 was calculated as oxide , with the same element oxide content of iron oxide for ZnFe2O4 Red, iron oxide yellow and ZnO are replaced, the catalyst composition is listed in Table 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was prepared, evaluated and analyzed according to the method of Example 1, except that 0.84 parts by weight of GeO 2 and 0.84 parts by weight of SnO 2 were used to replace 1.68 parts by weight of GeO 2 .
  • the composition of the catalyst is listed in Table 1, and the results of alkali analysis and strength test Table 4 and evaluation results are listed in Table 5.
  • the catalyst was prepared, evaluated and analyzed according to the method of Example 1, except that 0.84 parts by weight of GeO 2 and 0.84 parts by weight of PbO 2 were used to replace 1.68 parts by weight of GeO 2 .
  • the composition of the catalyst is listed in Table 1, and the results of alkali analysis and strength test Table 4 and evaluation results are listed in Table 5.
  • the catalyst was prepared, evaluated and analyzed according to the method of Example 1, except that 0.84 parts by weight of SnO 2 and 0.84 parts by weight of PbO 2 were used instead of 1.68 parts by weight of GeO 2 .
  • the strength test results are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was prepared, evaluated and analyzed according to the method of Example 1, except that 0.56 parts by weight of GeO 2 , 0.56 parts by weight of SnO 2 and 0.56 parts by weight of PbO 2 were used instead of 1.68 parts by weight of GeO 2 .
  • the composition of the catalyst is listed in Table 1, The results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was prepared according to the method of Example 1 , except that ZnFe2O4 was combined with red iron oxide , yellow iron oxide, potassium carbonate, cerium acetate, ammonium tungstate, strontium carbonate, GeO2 and HfO2 together with carboxymethyl fiber
  • the plain sodium was stirred together for 2 hours, deionized water accounting for 26.3% of the total weight of the catalyst raw materials was added, and the mixture was stirred and mixed for 0.5 hours.
  • Other addition ratios and subsequent steps were the same as those in Example 1.
  • the H 2 -TPR spectrum of the obtained catalyst is shown in FIG. 2
  • the electron microscope photos of the catalyst before and after the reaction are shown in FIG. 3C and FIG. 3D respectively, and the analysis method is the same as that in Example 1.
  • the reduction completion temperature of the catalyst obtained in Comparative Example 9 is 674 °C
  • the reduction completion temperature of the catalyst obtained in Example 1 is 72 °C higher than that in Comparative Example 9, indicating that the catalyst obtained in Example 1 has better resistance to Restore performance.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst was prepared according to the method of Example 1, except that 8.88 parts by weight of cerium acetate were calculated as CeO 2 , and the magnesium hydroxide equivalent to 1.01 parts of MgO was also added while adding cerium acetate. Other addition ratios and preparation steps and implementation Example 1 is the same.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the particles were put into an oven, baked at 60°C for 2 hours, at 130°C for 3 hours, then placed in a muffle furnace, calcined at 650°C for 3 hours, and calcined at 920°C for 3 hours to obtain a finished catalyst.
  • the catalyst composition is listed in Table 2.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst composition is listed in Table 3.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the catalyst composition is listed in Table 3.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • Deionized water with a weight of 26.3% mix for 0.5 hours, take out the extruded strands, extrude them into granules with a diameter of 3 mm and a length of 6 mm, put them in an oven, bake at 60°C for 2 hours, and bake at 130°C for 3 hours, and then place them in a muffle furnace. calcined at 650° C. for 3 hours, and calcined at 920° C. for 3 hours to obtain a finished catalyst.
  • the catalyst composition is listed in Table 3.
  • the catalyst was evaluated and analyzed according to the method of Example 1, the results of alkali analysis and strength test are listed in Table 4, and the evaluation results are listed in Table 5.
  • the test results of the above examples and comparative examples show that, compared with the catalysts of the comparative examples and the prior art, the catalyst of the present application is coordinated by using specific elements, and the total alkali content is controlled within the range of 0.32-0.46 mmol/g and strong alkali In the range of 0.061-0.082mmol/g, it has the outstanding advantages of high ethylbenzene conversion rate, less by-product benzene and toluene, high styrene selectivity, stable catalytic performance, stable strength and stable alkali content before and after the reaction, which is beneficial to benzene
  • the ethylene plant reduces costs and increases efficiency, and is a dehydrogenation catalyst that meets market demand. It can be well used in the industrial production of styrene by dehydrogenation of ethylbenzene at lower reaction temperature and ultra-low water ratio.

Abstract

公开了一种铁-钾-铈基复合氧化物催化剂及其制备和应用，除金属元素Fe、K和Ce之外，所述催化剂还包含金属元素M，所述金属元素M选自IIA族金属元素、非Cr的VIB族金属元素和IVA族金属元素中的至少一种，其中所述催化剂的总碱量在0.32-0.46mmol/g范围内，且强碱量在0.061-0.082mmol/g范围内。该催化剂用于烷基芳烃脱氢反应时，即便在较低的脱氢反应温度和超低水比下，也具有较高的选择性、催化活性和稳定性，副产物少，具有低物耗和低能耗的特点。

Description

铁-钾-铈基复合氧化物催化剂及其制备和应用
相关申请的交叉引用
本申请要求2020年10月14日提交的、申请号为202011099425.4、名称为“低甲苯副产的乙苯脱氢制苯乙烯用催化剂及其制备方法和应用以及乙苯脱氢方法”的专利申请的优先权，其内容经此引用全文并入本文。
技术领域
本申请涉及脱氢催化剂的技术领域，具体涉及一种铁-钾-铈基复合氧化物催化剂及其制备和应用。
背景技术
乙苯催化脱氢法一直是国内外生产苯乙烯的主导技术路线，其生产能力约占苯乙烯总生产能力的85％，乙苯脱氢的主反应为C 6H 5-C 2H 5→C 6H 5CH＝CH 2+H 2+124KJ/mol，是强吸热反应。甲苯和苯是主要副产物，副产苯需要通过精馏单元分离后返回乙苯单元循环利用，甲苯作为副产销售，降低苯和甲苯生成量可以提高原料利用率，降低装置物耗。
乙苯催化脱氢法的关键之一是乙苯脱氢制苯乙烯催化剂，该催化剂的基本组成为主催化剂、助催化剂和致孔剂、增强剂等。20世纪80年代初开发成功的Fe-K-Ce系列催化剂使得催化剂在维持原有稳定性的基础上，活性有较大幅度的提高，同时避免了Cr的氧化物污染环境，被世界各国苯乙烯生产厂家所采用。
CN104096568A公开了一种乙苯脱氢制苯乙烯复合氧化物催化剂，该催化剂中，铁、钾、镁、铈、钼氧化物的质量百分比组成如下：1)铁的氧化物，68％-75％，以Fe 2O 3计；2)钾的氧化物，8％-13％，以K 2O计；3)镁的氧化物，0.5％-6％，以MgO计；4)铈的氧化物，8％-15％，以CeO 2计；5)钼的氧化物，1％-6％，以MoO 3计；6)粘结剂，0.5％-10％；其中，铁的氧化物的前躯体包括无水氧化铁(氧化铁红)和含水氧化铁(氧化铁黄)，氧化铁红和氧化铁黄用量的质量比为：氧化铁红∶氧化铁黄＝4.5-5.5∶1；钾的氧化物的前躯体是碳酸钾；镁的氧化物是 市售氧化镁；铈的氧化物的前躯体选自硝酸铈和纳米三氧化二铈，纳米三氧化二铈含量占铈的氧化物总量的10％-50％；所述纳米三氧化二铈含量(以质量百分比计)优选为占铈的氧化物总量的25％-40％；钼的氧化物的前躯体是钼酸铵(NH 4) 6Mo 7O 24·4H 2O；所述粘结剂可选自高岭土、硅藻土、水泥等中的至少一种。但是，该催化剂对乙苯的转化率较低，均在65％以下，苯乙烯的选择性较低。
副产物多少是考核催化剂性能的一个重要指标，在其它相同的情况下，苯乙烯脱氢工艺优先选用副产少、苯乙烯选择性好的催化剂。已公开的美国专利文献US5190906A、US4804799A也存在苯乙烯选择性不高的问题，且等温床脱氢反应苯乙烯选择性普遍低于95.0％，产物中苯和甲苯含量合计高于4％，物耗较高，且增加了后续分离的难度。
虽然已公开的美国专利申请US6177602A报道了含有贵金属的氧化铁系催化剂，使用该催化剂可以获得较高的选择性、副产苯和甲苯较少，但该专利申请使用了贵金属，催化剂成本高，难于实现工业应用。
世界上乙苯脱氢生成苯乙烯的工业装置规模绝大部分在10万吨/年以上，最大规模达到80万吨/年，反应温度高，一般都在620℃以上，水比高，工业装置一般都在1.3(wt)以上，副产多，物耗和能耗高，一直是困扰苯乙烯生产厂家的难题。因此，研制一种选择性高、副产少的脱氢催化剂，大幅度降低物耗和能耗，是目前乙苯脱氢生成苯乙烯需要解决的技术难题。
发明内容
本申请的目的是提供一种铁-钾-铈基复合氧化物催化剂及其制备和应用，当用于烷基芳烃脱氢反应时，该催化剂即便在较低的反应温度(不高于620℃)和超低水比下，也具有较高的选择性、催化活性和稳定性，且副产苯和甲苯少，具有低物耗和低能耗的特点。
为了实现上述目的，一个方面，本申请提供了一种铁-钾-铈基复合氧化物催化剂，除金属元素Fe、K和Ce之外，所述催化剂还包含金属元素M，所述金属元素M选自IIA族金属元素、非Cr的VIB族金属元素和IVA族金属元素中的至少一种，其中所述催化剂的总碱量在0.32-0.46mmol/g范围内，且强碱量在0.061-0.082mmol/g范围内。
另一方面，提供了一种制备本申请的铁-钾-铈基复合氧化物催化剂的方法，包括将Fe源、K源、Ce源、M源、任选的IVB族金属元素源、任选的VA族金属元素源和任选的铁酸盐与致孔剂和溶剂混合并成型，任选地干燥和/或焙烧，得到所述催化剂。
再一方面，提供了本申请的铁-钾-铈基复合氧化物催化剂在烷基芳烃脱氢反应中的应用。
又一方面，本申请提供了一种烷基芳烃脱氢方法，包括在脱氢反应条件下，使烷基芳烃与本申请的铁-钾-铈基复合氧化物催化剂接触反应的步骤。
本申请的催化剂用于烷基芳烃脱氢反应时，即便在较低的反应温度和超低水比下，仍然表现出较强的催化活性、较高的选择性和良好的稳定性，具有低物耗和低能耗的特点。
本申请的其他特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本申请的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本申请，但并不构成对本申请的限制。在附图中：
图1为本申请实施例1中所得催化剂在反应前后的CO 2-TPD图谱。
图2为本申请实施例1和对比例9中所得催化剂的H 2-TPR图谱。
图3A至图3D显示了本申请实施例1和对比例9中所得催化剂在反应前后的SEM照片。
具体实施方式
以下结合附图对本申请的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本申请，并不用于限制本申请。
在本文中所披露的任何具体数值(包括数值范围的端点)都不限于该数值的精确值，而应当理解为还涵盖了接近该精确值的值，例如在该精确值±5％范围内的所有可能的数值。并且，对于所披露的数值范围而言，在该范围的端点值之间、端点值与范围内的具体点值之间， 以及各具体点值之间可以任意组合而得到一个或多个新的数值范围，这些新的数值范围也应被视为在本文中具体公开。
除非另有说明，本文所用的术语具有与本领域技术人员通常所理解的相同的含义，如果术语在本文中有定义，且其定义与本领域的通常理解不同，则以本文的定义为准。
在本申请中，如无明确表示，所给压力均为表压。
在本申请中，催化剂的总碱量和强碱量采用二氧化碳-程序升温脱附方法(CO 2-TPD方法)分析得到。
本申请中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此形成的技术方案或技术思想均视为本申请原始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合明显不合理。
在本文中提及的所有专利和非专利文献，包括但不限于教科书和期刊文章等，均通过引用方式全文并入本文。
如上所述，在第一方面，本申请提供了一种铁-钾-铈基复合氧化物催化剂，除金属元素Fe、K和Ce之外，所述催化剂还包含金属元素M，所述金属元素M选自IIA族金属元素、非Cr的VIB族金属元素和IVA族金属元素中的至少一种，其中所述催化剂的总碱量在0.32-0.46mmol/g范围内，且强碱量在0.061-0.082mmol/g范围内。
在优选的实施方式中，所述金属元素M为选自IIA族金属元素、非Cr的VIB族金属元素和IVA族金属元素中至少两种的组合，优选为至少一种IIA族金属元素、至少一种非Cr的VIB族金属元素与至少一种IVA金属元素的组合。
在优选的实施方式中，所述催化剂中所含的IIA族金属元素不为Mg，更优选为Sr。
在优选的实施方式中，所述催化剂中所含的VIB族金属元素不为Cr和Mo，优选为W。
在优选的实施方式中，所述催化剂中所含的IVA族金属元素选自Ge、Sn和Pb，或者它们的组合。
在优选的实施方式中，在压力-45kPa、乙苯质量空速0.75h -1、温度 600℃、水与乙苯的重量比为0.9的条件下反应1500h后，所述催化剂的抗压碎强度保持率在80％以上。
在优选的实施方式中，在压力-45kPa、乙苯质量空速0.75h -1、温度600℃、水与乙苯的重量比为0.9的条件下反应1500h后，所述催化剂的总碱量保持率在82％以上，强碱量保持率在80％以上。
在优选的实施方式中，根据H 2-TPR测试，所述催化剂的还原完成温度在730℃以上。
在优选的实施方式中，以该催化剂的总量为基准，该催化剂含有66-80重量％的Fe 2O 3，例如Fe 2O 3的重量含量可以为66重量％、67重量％、68重量％、69重量％、70重量％、71重量％、72重量％、73重量％、74重量％、75重量％、76重量％、77重量％、78重量％、80重量％，以及任意两数值之间的任意值。
在优选的实施方式中，以该催化剂的总量为基准，该催化剂含有2.3-6重量％的K 2O，优选含有2.3-5.5重量％的K 2O，K 2O的含量例如可以为2.3重量％、2.8重量％、3.3重量％、3.8重量％、4.3重量％、4.8重量％、5.3重量％、5.5重量％，以及任意两数值之间的任意值。
在优选的实施方式中，以该催化剂的总量为基准，该催化剂含有6-12重量％的CeO 2，例如可以为6重量％、6.5重量％、7重量％、7.5重量％、8重量％、8.5重量％、9重量％、9.5重量％、10重量％、10.5重量％、11重量％、11.5重量％、12重量％，以及任意两数值之间的任意值。
在进一步优选的实施方式中，以所述催化剂的总量为基准，以氧化物计，所述催化剂中含有66-80重量％的Fe 2O 3，2.3-6重量％的K 2O，6-12重量％的CeO 2和2-16重量％的金属元素M的氧化物。根据本申请，在所述催化剂中，金属元素M通常以其最高价态的氧化物形式存在。本申请的发明人发现，在此含量范围情况下，本申请的催化剂在较低的温度和超低水比下，表现出更好的催化活性、更高的选择性以及更佳的稳定性，而且副产苯和甲苯更少。不仅如此，常规催化剂中K 2O含量高于10重量％，易在催化脱氢过程中流失使得催化活性降低，而本申请的催化剂中的K 2O的含量为2.3-6重量％，K 2O的含量显著低于常规的催化剂，在极低的K 2O的含量情况下，依然表现出更好的催化活性、更高的选择性和更佳的稳定性，而且副产苯和甲苯更少，相 较于常规的催化剂，具有更高的应用优势。
在特别优选的实施方式中，所述金属元素M的氧化物为WO 3、SrO和IVA族金属元素的氧化物中的至少一种。采用该种优选实施方式能够进一步提高所述催化剂的催化活性、选择性和稳定性，并且具有更低量的副产苯和甲苯。
在本申请中，优选地，所述金属元素M的氧化物选自WO 3、SrO和IVA族金属元素的氧化物中的至少两种，当所述金属元素M的氧化物选自WO 3、SrO和IVA族金属元素的氧化物中的至少两种时，对于金属元素M的氧化物中各组分的含量选择范围没有特别的限定，各组分的含量可以相同或不同。
可以理解的是，当金属元素M的氧化物选自WO 3、SrO和IVA族金属元素的氧化物中的两种时，两种氧化物的含量可以相同，也可以不同。当两种氧化物的含量不同时，对两种氧化物各自的含量没有特别的限制。进一步优选地，金属元素M的氧化物为WO 3、SrO和IVA族金属元素的氧化物的组合。
在优选的实施方式中，以该催化剂的总量为基准，该催化剂含有0.5-5重量％的WO 3，例如WO 3的含量可以为0.5重量％、1重量％、1.5重量％、2重量％、2.5重量％、3重量％、3.5重量％、4重量％、4.5重量％、5重量％，以及任意两数值之间的任意值。
在优选的实施方式中，以该催化剂的总量为基准，该催化剂含有0.5-5重量％的SrO，SrO的含量可以为0.5重量％、1重量％、1.5重量％、2重量％、2.5重量％、3重量％、3.5重量％、4重量％、4.5重量％、5重量％，以及任意两数值之间的任意值。
在优选的实施方式中，以该催化剂的总量为基准，该催化剂含有0.5-5重量％的IVA族金属元素的氧化物，例如可以为0.5重量％、1重量％、1.5重量％、2重量％、2.5重量％、3重量％、3.5重量％、4重量％、4.5重量％、5重量％，以及任意两数值之间的任意值。
在进一步优选的实施方式中，以所述催化剂的总量为基准，以氧化物计，所述催化剂中含有67.5-79重量％的Fe 2O 3，2.3-5.5重量％的K 2O，6-12重量％的CeO 2，0.5-5重量％的WO 3，0.5-5重量％的SrO和0.5-5重量％的IVA族金属元素的氧化物。在此含量范围情况下，本申请的催化剂在较低的温度和超低水比下，表现出更好的催化活性、 更高的选择性以及更佳的稳定性，而且副产苯和甲苯更少。
在优选的实施方式中，IVA族金属元素的氧化物选自GeO 2、SnO 2和PbO 2中的至少一种。采用该优选实施方式能够进一步提高所述催化剂的催化活性和选择性，并且具有更低量的副产苯和甲苯。
在本申请中，当所述IVA族金属元素的氧化物选自GeO 2、SnO 2和PbO 2中的至少两种时，对于IVA族金属元素的氧化物中各组分的含量选择范围没有特别的限定，各组分的含量可以相同或不同。
可以理解的是，当IVA族金属元素的氧化物选自GeO 2、SnO 2和PbO 2中的两种时，两种氧化物的含量可以相同，也可以不同。当两种氧化物的含量不同时，对两种氧化物各自的含量没有特别的限制，优选地，以氧化物计，以IVA族金属元素的总量为基准，所选择的两种氧化物的含量比为1∶0.5-1.5，更优选为1∶0.8-1.2。
在进一步优选的实施方式中，所述IVA族金属元素的氧化物为GeO 2、SnO 2和PbO 2的组合。
可以理解的是，当IVA族金属元素的氧化物为GeO 2、SnO 2和PbO 2的组合时，三种氧化物的含量可以相同，也可以不同。当三种氧化物的含量不同时，对三种氧化物各自的含量没有特别的限制，优选地，以氧化物计，以IVA族金属元素的氧化物的总量为基准，三种氧化物GeO 2、SnO 2和PbO 2的含量比为1∶0.5-1.5∶0.5-1.5，更优选为1∶0.8-1.2∶0.8-1.2。
在优选的实施方式中，该催化剂中还含有铁酸盐，例如铁酸锰、铁酸锌、铁酸铜、铁酸镍等，优选ZnFe 2O 4。本申请的发明人通过研究发现，当添加一定量的铁酸盐形式的Fe元素时，相较于单纯添加氧化物形式的Fe元素的情况，例如添加ZnFe 2O 4相比添加等量的ZnO和铁氧化物，所得的催化剂的活性更高、选择性更好，更稳定且副产苯和甲苯更少。
在优选的实施方式中，以该催化剂的总量为基准，该催化剂含有0.5-8重量％的铁酸盐，优选ZnFe 2O 4，例如可以为0.5重量％、1.5重量％、2.5重量％、3.5重量％、4.5重量％、5.5重量％、6.5重量％、7.5重量％、8重量％，以及任意两数值之间的任意值。
在进一步优选的实施方式中，为了进一步提高催化剂的催化活性、选择性和稳定性，并进一步降低副产苯和甲苯的生成量，所述催化剂 中铁酸盐如ZnFe 2O 4的含量为1-7重量％，进一步优选为2-6重量％。
在特别优选的实施方式中，以该催化剂的总量为基准，该催化剂含有2-6重量％的ZnFe 2O 4，ZnFe 2O 4的含量例如可以为2重量％、2.5重量％、3重量％、3.5重量％、4重量％、4.5重量％、5重量％、5.5重量％、6重量％，以及任意两数值之间的任意值。
在优选的实施方式中，该催化剂中还可以含有其他的金属助剂，例如IVB族金属氧化物，如HfO 2，和/或VA族金属氧化物，如Sb 2O 5。优选地，以该催化剂的总量为基准，所述催化剂含有0.05-0.5重量％的IVB族金属氧化物，优选HfO 2，和/或0.5-1.5重量％VA族金属氧化物，优选Sb 2O 5。
根据本申请，为了进一步提高所述催化剂在低温下的催化活性、选择性和稳定性，并进一步降低副产苯和甲苯的生成量，优选地，所述催化剂不含钼。
根据本申请，为了进一步提高催化剂在低水比下的活性，降低脱氢反应温度，优选地，所述催化剂不含镁。
在优选的实施方式中，所述催化剂中不含有粘结剂，所述粘结剂例如为蒙脱土、硅藻土、水泥、准埃洛石、皂石、高岭土、埃洛石、水滑石、海泡石、累托土、凹凸棒石、膨润土或它们的任意组合。本申请的发明人在研究过程中发现，在本申请所述的催化剂中，加入粘结剂不利于其催化活性和稳定性的提高，采用上述优选方式，更有利于提高催化剂的催化活性和稳定性。
在特别优选的实施方式中，本申请的催化剂中含有Fe元素、K元素、Ce元素和金属元素M，以及ZnFe 2O 4、HfO 2和Sb 2O 5中的至少一种，所述金属元素M选自W元素、Sr元素和IVA族金属元素中的至少一种。进一步优选地，所述催化剂包含ZnFe 2O 4，并且包含HfO 2和Sb 2O 5中的至少一种。所述各元素的含量如上文所述，在此不再赘述。
申请的发明人通过研究发现，当铁-钾-铈基复合氧化物催化剂中包含上文所定义的金属组分，且催化剂的总碱量在0.32-0.46mmol/g范围内，强碱量在0.061-0.082mmol/g范围内的情况下，该催化剂用于烷基芳烃脱氢反应时，即便在较低的反应温度(例如不高于620℃)和超低水比下，仍然表现出较强的催化活性、较高的选择性和良好的稳定性。现有技术中并未认识到将烷基芳烃脱氢催化剂的总碱量和强碱量控制 在上述特定范围内的优越性，因而对催化剂的总碱量和强碱量以及反应过程中碱量的稳定性并没有严格的要求，现有催化剂的总碱量通常在0.32mmol/g以下。
本申请提供的催化剂通过采用特定元素配合，得到特定范围的总碱量和强碱量，减少了低效物质的引入，用于乙苯脱氢反应时，可以降低苯和甲苯的生成、提高苯乙烯选择性，提高原料利用率，同时反应前后碱量波动小。例如，本申请所得催化剂的抗压碎强度可达3.88Kg/mm，在等温式固定床进行活性评价，在-45kPa、乙苯液体质量空速0.75h -1、反应温度600℃、水比(即水与乙苯重量比)0.9条件下，产物中苯和甲苯含量合计低至2.26％，苯乙烯选择性可达97.17％、乙苯转化率可达77.6％；反应1500小时后产物中苯和甲苯含量合计低至1.93％，苯乙烯选择性可达97.99％、乙苯转化率可达76.7％；反应1500小时催化剂的总碱量保持率可达94.96％，强碱量保持率可达92.41％，抗压碎强度保持率可达94.85％，显示出良好的催化剂稳定性。
在优选的实施方式中，该催化剂的总碱量为0.32-0.42mmol/g，优选0.324-0.397mmol/g，特别优选0.384-0.397mmol/g，例如可以为0.384mmol/g，0.386mmol/g，0.388mmol/g，0.39mmol/g，0.392mmol/g，0.394mmol/g，0.396mmol/g，0.397mmol/g，以及任意两数值之间的任意值。
在优选的实施方式中，该催化剂的强碱量为0.061-0.080mmol/g，优选0.061-0.079mmol/g，特别优选0.072-0.079mmol/g，例如可以为0.072mmol/g，0.074mmol/g，0.076mmol/g，0.078mmol/g，0.079mmol/g，以及任意两数值之间的任意值。
在特别优选的实施方式中，本申请催化剂的总碱量为0.384-0.397mmol/g，且强碱量为0.072-0.079mmol/g，在此情况下，本申请的催化剂在较劣的催化脱氢反应条件下，表现出更好的催化活性、更高的选择性以及更佳的稳定性，而且产物中的苯和甲苯的含量更低。
在第二方面，提供了制备本申请的铁-钾-铈基复合氧化物催化剂的方法，包括将Fe源、K源、Ce源、M源、任选的IVB族金属元素源、任选的VA族金属元素源和任选的铁酸盐与致孔剂和溶剂混合并成型，任选地干燥和/或焙烧，得到所述催化剂；
其中所述M源选自选自IIA族金属元素源、非Cr的VIB族金属 元素源和IVA族金属元素源中的至少一种，优选W源、Sr源和IVA族金属元素源中的至少一种，更优选W源、Sr源和IVA族金属元素源中至少两种的组合，特别优选W源、Sr源与至少一种IVA族金属元素源的组合。
在本申请的第二方面中，所述IVB族金属元素、VA族金属元素、铁酸盐、IIA族金属元素、非Cr的VIB族金属元素和IVA族金属元素等如上文中所定义，在此不再赘述。
本申请方法对所述混合的具体方式没有严格的限制，只要能够使所述Fe源、K源、Ce源、M源、致孔剂、溶剂、任选的IVB族金属元素源、任选的VA族金属元素源和任选的铁酸盐均匀混合即可。
为了进一步提高所得催化剂在低温条件下的催化活性和选择性并降低产物中甲苯的含量，在优选的实施方式中，本申请的方法包括如下步骤：
1)将Fe源、K源、Ce源、M源、任选的IVB族金属元素源和任选的VA族金属元素源与致孔剂混合；
2)将步骤1)所得的混合物料与铁酸盐混合，所述铁酸盐优选ZnFe 2O 4；以及
3)将步骤2)所得的混合物与溶剂混合并成型，以及任选地干燥和/或焙烧，得到所述催化剂。
采用这种优选实施方式，更有利于混合均匀，可以进一步提高催化活性、选择性和稳定性，并进一步降低副产苯和甲苯的生成量。
在上述优选实施方式中，对于步骤1)、步骤2)和步骤3)的混合的时间没有特别的要求，可以在较宽范围内调整，只要能够使得在上述的加料顺序下将物料混合均匀即可。为了在保证物料混合均匀的情况下节约能耗，优选地，所述步骤1)、步骤2)和步骤3)的混合的时间各自独立地为0.1-2h；进一步优选地，步骤1)的混合的时间为0.1-0.6h，步骤2)的混合的时间为1-2h，步骤3)的混合的时间为0.2-1h。
在本申请的方法中，混合的实施方式可以有多种选择，例如可以在搅拌条件下进行。所述混合也可以在捏合机中进行。
根据本申请，对所述Fe源的选择没有特别的限制，可以为任何在后续焙烧过程中能够转化为Fe 2O 3的含铁化合物。优选地，所述Fe源为氧化铁红和/或氧化铁黄，更优选为氧化铁红和氧化铁黄。采用该种 优选实施方式，更有利于提高催化剂的催化活性和选择性，并降低副产苯和甲苯的生成量。
本申请中氧化铁红和氧化铁黄的用量比可以在较宽范围内选择，优选地，以氧化物计，所述氧化铁红和氧化铁黄的重量比为2-4∶1；例如，可以为2∶1、2.2∶1、2.4∶1、2.6∶1、2.8∶1、3∶1、3.2∶1、3.4∶1、3.6∶1、3.8∶1、4∶1，以及任意两值之间的任意值。
根据本申请，对所述Ce源的选择没有特别的限制，可以为任何在后续焙烧过程中能够转化为CeO 2的含铈化合物。优选地，所述Ce源为氢氧化铈和/或醋酸铈。采用该种优选实施方式既可以满足环保要求(硝酸铈在焙烧过程中会释放含氮气体)，又可以进一步提高制得的催化剂的强度。
根据本申请，对所述K源的选择没有特别的限制，可以为任何在后续焙烧过程中能够转化为K 2O的含钾化合物。优选地，K源为碳酸钾和/或碳酸氢钾；更优选为碳酸钾。
根据本申请，对VIB族金属元素源的选择没有特别的限制，可以为任何在后续焙烧过程中能够转化为VIB族金属氧化物的含VIB族金属元素的化合物，可以为含VIB族金属元素的盐和/或VIB族金属元素的氧化物。
根据本申请，对所述W源的选择没有特别的限制，可以为任何在后续焙烧过程中能够转化为WO 3的含钨化合物，优选地，所述W源选自钨酸铵、偏钨酸铵和三氧化钨中的至少一种；更优选为钨酸铵。
根据本申请，对IIA族金属元素源的选择没有特别的限制，可以为任何在后续焙烧过程中能够转化为IIA族金属氧化物的含IIA族金属元素的化合物，可以为含IIA族金属元素的盐和/或IIA族金属元素的氧化物。
根据本申请，对所述Sr源的选择没有特别的限制，可以为任何在后续焙烧过程中能够转化为SrO的含锶化合物，优选地，所述Sr源为碳酸锶和/或氢氧化锶。
根据本申请，对IVA族金属元素源的选择没有特别的限制，可以为任何在后续焙烧过程中能够转化为IVA族金属氧化物的含IVA族金属元素的化合物，可以为含IVA族金属元素的盐和/或IVA族金属元素氧化物。优选地，IVA族金属元素源选自含IVA族金属元素的氧化物。
根据本申请，对IVB族金属元素源的选择没有特别的限制，可以为任何在后续焙烧过程中能够转化为IVB族金属氧化物的含IVB族金属元素的化合物，可以为含IVB族金属元素的盐和/或IVB族金属元素的氧化物。
根据本申请，对Hf源的选择没有特别的限制，可以为任何在后续焙烧过程中能够转化为Hf氧化物的含Hf元素的盐和/或氧化物，优选为HfO 2。
根据本申请，对VA族金属元素源的选择没有特别的限制，可以为任何在后续焙烧过程中能够转化为VA族金属氧化物的含VA族金属元素的化合物，可以为含VA族金属元素的盐和/或VA族金属元素的氧化物。
根据本申请，对Sb源的选择没有特别的限制，可以为任何在后续焙烧过程中能够转化为Sb氧化物的含Sb元素的盐和/或氧化物，优选为Sb 2O 5。
根据本申请，所述致孔剂的加入量没有特别的限制，为了在保证催化剂具有一定强度的基础上具有较大的比表面积，优选地，所述致孔剂的加入量为所述Fe源、K源、Ce源、M源、任选的铁酸盐、任选的IVB族金属元素源和任选的VA族金属元素源的总加入量的2.2-6.3重量％，优选为3.8-5.6重量％。
根据本申请，对所述致孔剂的种类没有特别的限制，其可以为本领域常规使用的各种致孔剂。优选地，所述致孔剂选自聚苯乙烯、石墨和纤维素及其衍生物中的至少一种。本申请中所述石墨的种类可以在较宽范围内选择，其可以为天然石墨，也可以为人造石墨，本申请对此没有特别的限定。
所述纤维素及其衍生物优选为甲基纤维素、羟甲基纤维素、乙基纤维素和羟甲基纤维素钠中的至少一种。
根据本申请的一种优选实施方式，所述致孔剂选自石墨、聚苯乙烯(可以是微球)和羧甲基纤维素钠中的至少一种。
根据本申请，对溶剂的加入量没有特别的限制，只要能够满足物料的混合要求即可。优选地，所述溶剂的加入量为催化剂原料总重的15-35重量％，优选为22-32重量％。
根据本申请，所述溶剂可以在较宽范围内选择，只要能够提供所 述混合的环境即可，优选地，所述溶剂为水。
根据本申请，对于所述催化剂的形状没有特别的限制，例如可以为颗粒状、条状等。本领域技术人员可以根据实际生产中的具体需求，将步骤3)中混合得到的物料成型为各种可用规格，例如可以挤出为直径3毫米、长6毫米的颗粒，但本申请并不限于此。
在优选的实施方式中，步骤3)所述干燥的条件包括：温度为30-145℃，时间为1-8h；更优选地，所述干燥包括：在35-95℃干燥0.5-4h，然后升温至95-145℃干燥0.5-4h。
在优选的实施方式中，步骤3)所述焙烧的条件包括：温度为320-960℃，时间为2-8h。更优选地，所述焙烧包括：在320-750℃焙烧1-4h，然后升温至750-960℃焙烧1-4h。
在第三方面，提供了通过本申请的方法制备得到的铁-钾-铈基复合氧化物催化剂。
在第四方面，提供了本申请的铁-钾-铈基复合氧化物催化剂在烷基芳烃脱氢反应中的应用。
在第五方面，本申请提供了一种烷基芳烃脱氢方法，包括在脱氢反应条件下，使烷基芳烃与本申请的铁-钾-铈基复合氧化物催化剂接触反应的步骤。
在优选的实施方式中，所述烷基芳烃为C 8-C 10的烷基苯中的一种或多种，更优选为乙苯。
本申请提供的催化剂在烷基芳烃脱氢反应中，即使在低温和超低水比反应条件下也具有较高的催化活性、选择性和稳定性，并且产物中副产苯和甲苯含量低。
在优选的实施方式中，所述烷基芳烃脱氢的温度为580-620℃，进一步优选为590-610℃，例如，可以为590℃、595℃、600℃、605℃、610℃，以及任意两数值之间的任意值。
根据本申请，为了进一步降低物耗，优选地，所述烷基芳烃的质量空速为0.5-1h -1，更优选为0.6-0.8h -1，例如可以为0.6h -1、0.65h -1、0.7h -1、0.75h -1、0.8h -1，以及任意两数值之间的任意值。
根据本申请，为了进一步降低能耗，优选地，所述水与烷基芳烃的重量比为0.7-1，更优选为0.8-1，例如，可以为0.8、0.82、0.84、0.86、0.88、0.9、0.92、0.94、0.96、0.98、1，以及任意两数值之间的任意值。
根据本申请，所述烷基芳烃脱氢的压力可以在较宽的范围内进行选择，优选地，所述压力为-60kPa至常压，更优选为-50kPa至常压，进一步优选为-50kPa至-20kPa，例如，可以为-50kPa、-48kPa、-46kPa、-44kPa、-42kPa、-40kPa、-38kPa、-36kPa、-34kPa、-32kPa、-30kPa、-28kPa、-26kPa、-24kPa、-22kPa、-20kPa，以及任意两数值之间的任意值。
在特别优选的实施方式中，所述脱氢条件可以包括：温度为580-620℃，烷基芳烃质量空速为0.5-1h -1，水与烷基芳烃的重量比为0.7-1，压力为-60kPa至常压；进一步优选地，所述烷基芳烃脱氢条件包括：温度为590-610℃，质量空速为0.6-0.8h -1，水与烷基芳烃的重量比为0.8-1，压力为-50kPa至常压。
实施例
以下将通过实施例对本申请进行详细描述，但本申请并不限于此。
以下实施例和对比例中，所述催化剂的性能分别由乙苯转化率、苯乙烯选择性、以及产物中苯和甲苯的生成量进行表征。具体地，在等温式固定床中对催化剂进行性能评价，过程简述如下：将去离子水和乙苯分别经计量泵输入预热混合器，预热混合成气态后进入反应器，反应器采用电热丝加热，使之达到预定温度，反应器内径为1英寸的不锈钢管，内装填100毫升的催化剂，由反应器流出的反应产物经水冷凝后用气相色谱仪分析其中的乙苯浓度(重量％)、苯乙烯浓度(重量％)以及苯和甲苯浓度(重量％)；
乙苯转化率％＝(反应物料中初始乙苯浓度(重量％)-反应产物中乙苯浓度(重量％))÷反应物料中初始乙苯浓度(重量％)；
苯乙烯选择性％＝反应产物中苯乙烯浓度(重量％)÷(反应物料中初始乙苯浓度(重量％)-反应产物中乙苯浓度(重量％))；
以下实施例和对比例中，催化剂的总碱量和强碱量采用二氧化碳-程序升温脱附方法分析，分析时将0.1g催化剂于He气流中600℃活化2小时，然后降温至80℃，吸附CO 2至平衡，用He气吹扫以除去物理吸附的CO 2，然后以10℃/min从80℃程序升温至600℃，记录CO 2-TPD图谱，同时用液氮收集脱附的CO 2，收集得到的CO 2用气相色谱定量分析。典型的CO 2-TPD图谱如图1所示，图1中，在低温区(温度80-400 ℃)的峰为弱碱量对应的脱附峰，在高温区(温度400-600℃)的峰为强碱量对应的脱附峰，记录CO 2-TPD图谱的同时用液氮收集脱附的CO 2，用气相色谱定量分析收集得到的CO 2量，计算出对应的弱碱量和强碱量，总碱量为弱碱量和强碱量之和。碱量保持率为反应后碱量与反应前碱量之比。
以下实施例和对比例中，催化剂的电镜照片在日本电子株式会社生产的JSM-35型扫描电镜仪上拍摄，工作加速电压分别为15，25kV，工作距离20mm，放大倍率20,000，分辨率3.5nm。
以下实施例和对比例中，催化剂的抗压碎强度测试方法按HG/T 2782-2011进行，使用QCY-602颗粒强度仪测定，用四分法取40颗待测样品，以测定结果的算术平均值计算样品的抗压碎强度。强度保持率为反应后抗压碎强度与反应前抗压碎强度之比。
以下实施例和对比例中，通过程序升温还原(TPR)方法观察催化剂还原温度的变化，
Figure PCTCN2021123478-appb-000001
方法是将50mg催化剂样品放置于U形管石英反应器中，在He气氛下升温到400℃，随后降至室温，切换为H 2/N 2还原气体(H 2浓度为10体积％)进行程序升温还原，以10℃/min速率升温到850℃。
实施例1
将55.2重量份以Fe 2O 3计的氧化铁红、20.1重量份以Fe 2O 3计的氧化铁黄、4.66重量份以K 2O计的碳酸钾、9.89重量份以CeO 2计的醋酸铈、2.61重量份以WO 3计的钨酸铵、2.38重量份以SrO计的碳酸锶、1.68重量份GeO 2、0.32重量份HfO 2和5.69重量份羧甲基纤维素钠(商购自上海长光企业发展有限公司，特级食品用产品，下同)在捏合机中搅拌0.5小时，再加入3.16重量份ZnFe 2O 4继续搅拌1.5小时，然后加入占催化剂原料总重26.3％的去离子水，搅拌混合0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，55℃烘2小时，然后升温至135℃烘3小时，然后置于马福炉中，于455℃焙烧3小时，然后升温至930℃焙烧3小时得到成品催化剂，催化剂组成列于表1。
采用程序升温还原(TPR)方法观察实施例1所得催化剂还原温度的变化，所得H 2-TPR图谱见图2，从图2中可以看出所得催化剂的还原完成温度(即H 2-TPR图谱中曲线的峰值所对应的温度)为746℃。
将100毫升本实施例得到的成品催化剂装入反应器，在-45kPa、质量空速0.75h -1、600℃、水与乙苯的重量比为0.9条件下，进行性能评价，反应100小时和1500小时的测试结果列于表5。
采用二氧化碳-程序升温脱附方法分析反应前和反应1500小时后实施例1所得催化剂的总碱量和强碱量，所得CO 2-TPD图谱如图1所示。图1中，在低温区的峰为弱碱量对应的脱附峰，在高温区的峰为强碱量对应的脱附峰，记录CO 2-TPD图谱的同时用液氮收集脱附的CO 2，用气相色谱定量分析收集得到的CO 2量，计算出对应的弱碱量和强碱量，总碱量为弱碱量和强碱量之和。实施例1所得催化剂反应前后的强碱量和总碱量以及碱量保持率列于表4。
按HG/T 2782-2011方法进行测试，实施例1所得催化剂在反应前的抗压碎强度为3.35Kg/mm，反应后强度为2.88Kg/mm，强度保持率为85.97％，结果见表4。
在扫描电镜仪上拍摄催化剂的电镜照片，实施例1所得催化剂在反应前后的扫描电镜(SEM)照片分别见图3A和图3B。
对比例1
按照实施例1的方法制备催化剂，不同的是，不添加ZnFe 2O 4和GeO 2，具体为：
将58.01重量份以Fe 2O 3计的氧化铁红、21.12重量份以Fe 2O 3计的氧化铁黄、4.9重量份以K 2O计的碳酸钾、10.39重量份以CeO 2计的醋酸铈、2.74重量份以WO 3计的钨酸铵、2.5重量份以SrO计的碳酸锶、0.34重量份HfO 2及5.69重量份羧甲基纤维素钠在捏合机中搅拌2.0小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，55℃烘2小时，135℃烘3小时，然后置于马福炉中，于455℃焙烧3小时，930℃焙烧3小时得到成品催化剂，催化剂组成列于表1。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
对比例2
按照实施例1的方法制备、评价和分析催化剂，不同的是，不添 加ZnFe 2O 4，ZnFe 2O 4用等量元素氧化物含量的氧化铁红、氧化铁黄和ZnO代替，其余组分的相对比例关系、催化剂制备方法和催化剂评价条件以及分析方法同实施例1，催化剂组成列于表1，碱量分析和强度测试结果列于表4，评价结果列于表5。
实施例2
按照实施例1的方法制备、评价和分析催化剂，不同的是，用SnO 2替代GeO 2，催化剂组成列于表1，碱量分析和强度测试结果列于表4，评价结果列于表5。
对比例3
按照实施例1的方法制备、评价和分析催化剂，不同的是，用SnO 2替代GeO 2，不添加ZnFe 2O 4，以氧化物计，ZnFe 2O 4用等量元素氧化物含量的氧化铁红、氧化铁黄和ZnO代替，催化剂组成列于表1，碱量分析和强度测试结果列于表4，评价结果列于表5。
实施例3
按照实施例1的方法制备、评价和分析催化剂，不同的是，用PbO 2替代GeO 2，催化剂组成列于表1，碱量分析和强度测试结果列于表4，评价结果列于表5。
对比例4
按照实施例1的方法制备、评价和分析催化剂，不同的是，用PbO 2替代GeO 2，不添加ZnFe 2O 4，以氧化物计，ZnFe 2O 4用等量元素氧化物含量的氧化铁红、氧化铁黄和ZnO代替，催化剂组成列于表1，碱量分析和强度测试结果列于表4，评价结果列于表5。
实施例4
按实施例1的方法制备、评价和分析催化剂，不同的是，用0.84重量份GeO 2和0.84重量份SnO 2替代1.68重量份GeO 2，催化剂组成列于表1，碱量分析和强度测试结果列于表4，评价结果列于表5。
实施例5
按实施例1的方法制备、评价和分析催化剂，不同的是，用0.84重量份GeO 2和0.84重量份PbO 2替代1.68重量份GeO 2，催化剂组成列于表1，碱量分析和强度测试结果列于表4，评价结果列于表5。
实施例6
按实施例1的方法制备、评价和分析催化剂，不同的是，用0.84重量份以SnO 2和0.84重量份以PbO 2替代1.68重量份以GeO 2，催化剂组成列于表1，碱量分析和强度测试结果列于表4，评价结果列于表5。
实施例7
按实施例1的方法制备、评价和分析催化剂，所不同的是，用0.56重量份GeO 2、0.56重量份SnO 2和0.56重量份PbO 2替代1.68重量份GeO 2，催化剂组成列于表1，碱量分析和强度测试结果列于表4，评价结果列于表5。
实施例8
将54.01重量份以Fe 2O 3计的氧化铁红、16.9重量份以Fe 2O 3计的氧化铁黄、2.37重量份以K 2O计的碳酸钾、11.84重量份以CeO 2计的醋酸铈、4.16重量份以WO 3计的钨酸铵、3.35重量份以SrO计的碳酸锶、0.85重量份GeO 2、0.06重量份HfO 2、0.96重量份Sb 2O 5及5.69重量份羧甲基纤维素钠在捏合机中搅拌1小时，加入5.5重量份以ZnFe 2O 4，再搅拌2小时，加入占催化剂原料总重15％的去离子水，搅拌混合1小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，30℃烘4小时，95℃烘4小时，然后置于马福炉中，于320℃焙烧4小时，750℃焙烧4小时得到成品催化剂，催化剂组成列于表1。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
实施例9
将52.62重量份以Fe 2O 3计的氧化铁红、13.45重量份以Fe 2O 3计的 氧化铁黄、4.66重量份以K 2O计的碳酸钾、10.55重量份以CeO 2计的氢氧化铈、1.72重量份以WO 3计的钨酸铵、4.83重量份以SrO计的碳酸锶、4.4重量份GeO 2、0.12重量份HfO 2及5.69重量份羧甲基纤维素钠在捏合机中搅拌0.4小时，加入7.65重量份ZnFe 2O 4，再搅拌1小时，加入占催化剂原料总重35％的去离子水，拌和1小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，95℃烘0.5小时，145℃烘0.5小时，然后置于马福炉中，于750℃焙烧1小时，960℃焙烧1小时得到成品催化剂，催化剂组成列于表1。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
实施例10
将55.36重量份以Fe 2O 3计的氧化铁红、17.42重量份以Fe 2O 3计的氧化铁黄、3.71重量份以K 2O计的碳酸钾、9.01重量份以CeO 2计的醋酸铈、4.82重量份以WO 3计的钨酸铵、1.83重量份以SrO计的碳酸锶、4.58重量份GeO 2、0.45重量份HfO 2及5.69重量份羧甲基纤维素钠在捏合机中搅拌0.5小时，加入2.82重量份ZnFe 2O 4，再搅拌1.5小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，55℃烘2小时，135℃烘3小时，然后置于马福炉中，于455℃焙烧3小时，930℃焙烧3小时得到成品催化剂，催化剂组成列于表2。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
实施例11
将60.69重量份以Fe 2O 3计的氧化铁红、17.36重量份以Fe 2O 3计的氧化铁黄、5.05重量份以K 2O计的碳酸钾、6.15重量份以CeO 2计的醋酸铈、1.78重量份以WO 3计的钨酸铵、0.55重量份以SrO计的碳酸锶、2.02重量份GeO 2、0.25重量份HfO 2及5.69重量份羧甲基纤维素钠在捏合机中搅拌0.5小时，加入6.15重量份ZnFe 2O 4，再搅拌1.5小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，55℃烘2小时，135℃ 烘3小时，然后置于马福炉中，于455℃焙烧3小时，930℃焙烧3小时得到成品催化剂，催化剂组成列于表2。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
对比例5
将54.4重量份以Fe 2O 3计的氧化铁红、21.1重量份以Fe 2O 3计的氧化铁黄、4.77重量份以K 2O计的碳酸钾、4.55重量份K 2SiO 3、7.75重量份以CeO 2计的醋酸铈、2.58重量份以WO 3计的钨酸铵、1.38重量份以SrO计的碳酸锶、1.48重量份GeO 2、0.02重量份HfO 2及5.69重量份羧甲基纤维素钠在捏合机中搅拌0.5小时，加入3.74重量份ZnFe 2O 4，再搅拌1.5小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，55℃烘2小时，135℃烘3小时，然后置于马福炉中，于455℃焙烧3小时，930℃焙烧3小时得到成品催化剂，催化剂组成列于表2。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
对比例6
将42.9重量份以Fe 2O 3计的氧化铁红、25.8重量份以Fe 2O 3计的氧化铁黄、5.8重量份以K 2O计的碳酸钾、9.1重量份以CeO 2计的醋酸铈、2.5重量份以WO 3计的钨酸铵、4.1重量份以SrO计的碳酸锶、4.77重量份GeO 2、0.13重量份HfO 2及5.69重量份羧甲基纤维素钠在捏合机中搅拌0.5小时，加入4.9重量份ZnFe 2O 4，再搅拌1.5小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，55℃烘2小时，135℃烘3小时，然后置于马福炉中，于455℃焙烧3小时，930℃焙烧3小时得到成品催化剂，催化剂组成列于表2。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
对比例7
将54.8重量份以Fe 2O 3计的氧化铁红、16.04重量份以Fe 2O 3计的氧化铁黄、5.85重量份以K 2O计的碳酸钾、7.11重量份CeO 2、4.42重量份以WO 3计的钨酸铵、3.35重量份以SrO计的碳酸锶、3.85重量份GeO 2、0.99重量份MoO 3、0.09重量份HfO 2及5.69重量份羧甲基纤维素钠在捏合机中搅拌0.5小时，加入3.5重量份ZnFe 2O 4，再搅拌1.5小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，55℃烘2小时，135℃烘3小时，然后置于马福炉中，于455℃焙烧3小时，930℃焙烧3小时得到成品催化剂，催化剂组成列于表2。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
对比例8
将50.5重量份以Fe 2O 3计的氧化铁红、17.01重量份以Fe 2O 3计的氧化铁黄、4.66重量份以K 2O计的碳酸钾、6.15重量份以CeO 2计的醋酸铈、3.29重量份以WO 3计的钨酸铵、2.73重量份以SrO计的碳酸锶、4.53重量份GeO 2、0.75重量份HfO 2、2.1重量份水泥及5.69重量份羧甲基纤维素钠在捏合机中搅拌0.5小时，加入8.28重量份ZnFe 2O 4，再搅拌1.5小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，55℃烘2小时，135℃烘3小时，然后置于马福炉中，于455℃焙烧3小时，930℃焙烧3小时得到成品催化剂，催化剂组成列于表2。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
实施例12
将48.01重量份以Fe 2O 3计的氧化铁红、20.4重量份以Fe 2O 3计的氧化铁黄、5.35重量份以K 2O计的碳酸钾、11.15重量份以CeO 2计的醋酸铈、0.91重量份以WO 3计的钨酸铵、4.85重量份以SrO计的碳酸锶、4.4重量份SnO 2、0.28重量份HfO 2及5.69重量份羧甲基纤维素钠在捏合机中搅拌0.5小时，加入4.65重量份ZnFe 2O 4，再搅拌1.5小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条， 挤成直径3毫米、长6毫米的颗粒，放入烘箱，55℃烘2小时，135℃烘3小时，然后置于马福炉中，于455℃焙烧3小时，930℃焙烧3小时得到成品催化剂，催化剂组成列于表2。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
实施例13
将52.7重量份以Fe 2O 3计的氧化铁红、25.2重量份以Fe 2O 3计的氧化铁黄、5.05重量份以K 2O计的碳酸钾、8.99重量份以CeO 2计的醋酸铈、2.58重量份以WO 3计的钨酸铵、1.38重量份以SrO计的碳酸锶、2.89重量份PbO 2、0.26重量份HfO 2及5.69重量份羧甲基纤维素钠在捏合机中搅拌0.5小时，加入0.95重量份ZnFe 2O 4，再搅拌1.5小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，55℃烘2小时，135℃烘3小时，然后置于马福炉中，于455℃焙烧3小时，930℃焙烧3小时得到成品催化剂，催化剂组成列于表2。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
实施例14
将54.25重量份以Fe 2O 3计的氧化铁红、18.42重量份以Fe 2O 3计的氧化铁黄、5.19重量份以K 2O计的碳酸钾、9.15重量份以CeO 2计的醋酸铈、3.22重量份以WO 3计的钨酸铵、2.69重量份以SrO计的碳酸锶、3.95重量份GeO 2、0.48重量份HfO 2及5.69重量份羧甲基纤维素钠在捏合机中搅拌0.5小时，加入2.65重量份NiFe 2O 4，再搅拌1.5小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，55℃烘2小时，135℃烘3小时，然后置于马福炉中，于455℃焙烧3小时，930℃焙烧3小时得到成品催化剂，催化剂组成列于表2。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
对比例9
按照实施例1的方法制备催化剂，不同的是，ZnFe 2O 4与氧化铁红、氧化铁黄、碳酸钾、醋酸铈、钨酸铵、碳酸锶、GeO 2和HfO 2一起与羧甲基纤维素钠共同搅拌2小时，加入占催化剂原料总重26.3％的去离子水，搅拌混合0.5小时，其他的添加比例以及后续的步骤与实施例1相同。所得催化剂的H 2-TPR图谱见图2，反应前后催化剂的电镜照片分别见图3C和图3D，分析方法同实施例1。
从图2中可以看出，对比例9所得催化剂的还原完成温度为674℃，实施例1所得催化剂的还原完成温度比对比例9高72℃，说明实施例1所得的催化剂具有更好的耐还原性能。
从图3A和图3B中可以看出经历1500小时反应后，实施例1所得催化剂的表面粒子依然轮廓清晰、分布均匀；而从图3C和图3D中可以看出，对比例9所得催化剂在反应后表面出现了颗粒熔结和明显长大的现象，说明实施例1所得的催化剂具有更好的稳定性能。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
对比例10
按照实施例1的方法制备催化剂，不同的是8.88重量份以CeO 2计的醋酸铈，加入醋酸铈的同时还加入了相当于1.01份MgO的氢氧化镁，其他的添加比例以及制备步骤与实施例1相同。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
对比例11
将54.4重量份以Fe 2O 3计的氧化铁红、21.1重量份以Fe 2O 3计的氧化铁黄、2.61重量份以K 2O计的碳酸钾、4.55重量份K 2ZnO 2、10.26重量份以CeO 2计的醋酸铈、2.58重量份以WO 3计的钨酸铵、1.38重量份以SrO计的碳酸锶、3.74重量份ZnFe 2O 4、1.48重量份GeO 2、0.02重量份HfO 2及5.69重量份羧甲基纤维素钠在捏合机中搅拌1.5小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，60℃烘2小时，130℃ 烘3小时，然后置于马福炉中，于650℃焙烧3小时，920℃焙烧3小时得到成品催化剂，催化剂组成列于表2。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
对比例12
将49.7重量份以Fe 2O 3计的氧化铁红、19.5重量份以Fe 2O 3计的氧化铁黄、5.81重量份以K 2O计的碳酸钾、5.73重量份K 2SiO 3、11.23重量份以CeO 2计的硝酸铈、0.74重量份以WO 3计的钨酸铵、4.27重量份以MgO计的氢氧化镁、0.85重量份SrO、1.98重量份Eu 2O 3、0.19重量份GeO 2和5.69重量份石墨在捏合机中搅拌1.5小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，60℃烘2小时，130℃烘3小时，然后置于马福炉中，于650℃焙烧3小时，920℃焙烧3小时得到成品催化剂，催化剂组成列于表3。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
对比例13
将50.2重量份以Fe 2O 3计的氧化铁红、19.0重量份以Fe 2O 3计的氧化铁黄、5.81重量份以K 2O计的碳酸钾、5.73重量份K 2ZnO 2、11.23重量份以CeO 2计的硝酸铈、0.74重量份以WO 3计的钨酸铵、4.27重量份以MgO计的氢氧化镁、0.85重量份SrO、1.98重量份Eu 2O 3、0.19重量份GeO 2和5.69重量份石墨在捏合机中搅拌1.5小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，60℃烘2小时，130℃烘3小时，然后置于马福炉中，于650℃焙烧3小时，920℃焙烧3小时得到成品催化剂，催化剂组成列于表3。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
对比例14
将56.48重量份以Fe 2O 3计的氧化铁红、19.17重量份以Fe 2O 3计的氧化铁黄、8.6重量份以K 2O计的碳酸钾、7.21重量份CeO 2、2.58重量份以WO 3计的钨酸铵、1.12重量份以MgO计的氢氧化镁、4.84重量份ZnFe 2O 4和5.69重量份羧甲基纤维素钠在捏合机中搅拌1.5小时，加入占催化剂原料总重26.3％的去离子水，拌和0.5小时，取出挤条，挤成直径3毫米、长6毫米的颗粒，放入烘箱，60℃烘2小时，130℃烘3小时，然后置于马福炉中，于650℃焙烧3小时，920℃焙烧3小时得到成品催化剂，催化剂组成列于表3。
按实施例1的方法评价和分析催化剂，碱量分析和强度测试结果列于表4，评价结果列于表5。
表1 各实施例和对比例所得催化剂的组成
Figure PCTCN2021123478-appb-000002
表2 各实施例和对比例所得催化剂的组成
Figure PCTCN2021123478-appb-000003
表3 各实施例和对比例所得催化剂的组成
Figure PCTCN2021123478-appb-000004
表4 各实施例和对比例所得催化剂在反应前后的性质变化
Figure PCTCN2021123478-appb-000005
Figure PCTCN2021123478-appb-000006
表5 各实施例和对比例所得催化剂的催化性能测试结果
Figure PCTCN2021123478-appb-000007
Figure PCTCN2021123478-appb-000008
以上实施例和对比例的测试结果说明，与对比例和现有技术的催化剂相比，本申请的催化剂通过采用特定元素配合，并控制总碱量在0.32-0.46mmol/g范围内以及强碱量在0.061-0.082mmol/g范围内，具有乙苯转化率高、副产苯和甲苯少、苯乙烯选择性高、催化性能稳定、强度稳定和反应前后碱量稳定的突出优点，有利于苯乙烯装置降本增效，是一种适应市场需求的脱氢催化剂，能够很好地用于较低反应温度和超低水比下乙苯脱氢制备苯乙烯的工业生产中。
以上详细描述了本申请的优选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本 申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所公开的内容。

Claims (14)

  1. 一种铁-钾-铈基复合氧化物催化剂，除金属元素Fe、K和Ce之外，所述催化剂还包含金属元素M，所述金属元素M选自IIA族金属元素、非Cr的VIB族金属元素和IVA族金属元素中的至少一种，其中所述催化剂的总碱量在0.32-0.46mmol/g范围内，优选0.32-0.42mmol/g范围内，更优选在0.324-0.397mmol/g范围内，特别优选在0.384-0.397mmol/g范围内，且强碱量在0.061-0.082mmol/g范围内，优选在0.061-0.080mmol/g范围内，更优选在0.061-0.079mmol/g范围内，特别优选在0.072-0.079mmol/g范围内。
  2. 根据权利要求1所述的催化剂，其中所述金属元素M为选自IIA族金属元素、非Cr的VIB族金属元素和IVA族金属元素中至少两种的组合，优选为至少一种IIA族金属元素、至少一种非Cr的VIB族金属元素与至少一种IVA金属元素的组合。
  3. 根据权利要求1或2所述的催化剂，其中所述催化剂具有以下特征中的至少一个：
    所述催化剂中所含的IIA族金属元素不为Mg，优选为Sr；
    所述催化剂中所含的VIB族金属元素不为Cr和Mo，优选为W；
    所述催化剂中所含的IVA族金属元素选自Ge、Sn和Pb，或者它们的组合，以及
    所述催化剂中不含粘结剂，所述粘结剂例如为蒙脱土、硅藻土、水泥、准埃洛石、皂石、高岭土、埃洛石、水滑石、海泡石、累托土、凹凸棒石、膨润土或它们的各种组合。
  4. 根据权利要求1-3中任意一项所述的催化剂，其中所述催化剂具有以下特征中的至少一个：
    在压力-45kPa、乙苯质量空速0.75h -1、温度600℃、水与乙苯的重量比为0.9的条件下反应1500h后，所述催化剂的抗压碎强度保持率在80％以上；
    在压力-45kPa、乙苯质量空速0.75h -1、温度600℃、水与乙苯的重量比为0.9的条件下反应1500h后，所述催化剂的总碱量保持率在82％以上，强碱量保持率在80％以上；
    根据H 2-TPR测试，所述催化剂的还原完成温度在730℃以上。
  5. 根据权利要求1-4中任一项所述的催化剂，其中，以所述催化剂的总量为基准，所述催化剂的K 2O含量在2.3-6重量％范围内，优选在2.3-5.5重量％范围内。
  6. 根据权利要求5所述的催化剂，其中，以所述催化剂的总量为基准，所述催化剂的Fe 2O 3含量在66-80重量％、优选67.5-79重量％的范围内；K 2O含量在2.3-6重量％、优选2.3-5.5重量％的范围内；CeO 2含量在6-12重量％的范围内；以及金属元素M氧化物的含量在2-16重量％的范围内；
    优选地，以所述催化剂的总量为基准，所述催化剂中WO 3含量在0.5-5重量％的范围内，SrO含量在0.5-5重量％的范围内，和IVA族金属氧化物含量在0.5-5重量％的范围内。
  7. 根据权利要求1-6中任意一项所述的催化剂，其中，以所述催化剂的总量为基准，所述催化剂还包含0.5-8重量％、优选1-7重量％、更优选2-6重量％的铁酸盐，所述铁酸盐优选为ZnFe 2O 4；
    优选地，以所述催化剂的总量为基准，所述催化剂还包含0.05-0.5重量％的IVB族金属氧化物，优选HfO 2，和/或0.5-1.5重量％的VA族金属氧化物，优选Sb 2O 5。
  8. 制备权利要求1-7中任意一项所述的铁-钾-铈基复合氧化物催化剂的方法，包括将Fe源、K源、Ce源、M源、任选的IVB族金属元素源、任选的VA族金属元素源和任选的铁酸盐与致孔剂和溶剂混合并成型，任选地干燥和/或焙烧，得到所述催化剂，
    其中所述M源选自IIA族金属元素源、非Cr的VIB族金属元素源和IVA族金属元素源中的至少一种，优选W源、Sr源和IVA族金属元素源中的至少一种，更优选W源、Sr源和IVA族金属元素源中至少两种的组合，特别优选W源、Sr源与至少一种IVA族金属元素源的组合。
  9. 根据权利要求8所述的方法，包括如下步骤：
    1)将所述Fe源、K源、Ce源、M源、任选的IVB族金属元素源和任选的VA族金属元素源与所述致孔剂混合；
    2)将步骤1)所得的混合物料与所述铁酸盐混合；以及
    3)将步骤2)所得的混合物与所述溶剂混合并成型，任选地干燥和/或焙烧，得到所述催化剂。
  10. 根据权利要求8或9所述的方法，其中所述方法具有以下特征中的至少一个：
    所述Fe源选自氧化铁红、氧化铁黄或它们的组合，优选为氧化铁红和氧化铁黄的组合，进一步优选地，以Fe 2O 3计，所述氧化铁红和氧化铁黄的重量比为2-4∶1；
    所述Ce源选自醋酸铈、氢氧化铈或它们的组合；
    所述K源选自碳酸钾、碳酸氢钾或它们的组合；
    所述IIA族金属元素源选自IIA族金属元素的盐、IIA族金属元素的氧化物或它们的组合，优选不含Mg；
    所述非Cr的VIB族金属元素源选自VIB族金属元素的盐、VIB族金属元素的氧化物或它们的组合，优选不含Mo；
    所述W源选自钨酸铵、偏钨酸铵、三氧化钨或它们的组合；
    所述Sr源选自碳酸锶、氢氧化锶或它们的组合；
    所述IVA族金属元素源选自IVA族金属元素的盐、IVA族金属元素的氧化物或它们的组合，所述IVA金属元素优选选自Ge、Sn和Pb，或它们的组合；
    所述IVB族金属元素源选自IVB族金属元素的盐、IVB族金属元素的氧化物或它们的组合，优选选自含Hf元素的盐、HfO 2或它们的组合；
    所述VA族金属元素源选自VA族金属元素的盐、VA族金属元素的氧化物或它们的组合，优选选自含Sb元素的盐、Sb 2O 5或它们的组合；以及
    所述铁酸盐为ZnFe 2O 4。
  11. 根据权利要求8-10中任一项所述的方法，其中所述方法具有以下特征中的至少一个：
    所述致孔剂的加入量为所述Fe源、K源、Ce源、M源、任选的铁酸盐、任选的IVB族金属元素源和任选的VA族金属元素源的总加入量的2.2-6.3重量％，优选为3.8-5.6重量％；
    所述致孔剂选自聚苯乙烯、石墨、纤维素及其衍生物，或它们的组合；
    所述溶剂的加入量为催化剂原料总加入量的15-35重量％，优选为22-32重量％；以及
    所述溶剂为水。
  12. 根据权利要求8-11中任意一项所述的方法，其中所述方法具有以下特征中的至少一个；
    步骤1)、步骤2)和步骤3)中的混合的时间各自独立地为0.1-2h，优选地，步骤1)的混合时间为0.1-0.6h，步骤2)的混合时间为1-2h，步骤3)的混合时间为0.2-1h；
    步骤3)所述干燥的条件包括：温度为30-145℃，时间为1-8h，优选地，所述干燥包括：在35-95℃干燥0.5-4h，然后升温至95-145℃干燥0.5-4h；以及
    步骤3)所述焙烧的条件包括：温度为320-960℃，时间为2-8h，优选地，所述焙烧包括：在320-750℃焙烧1-4h，然后升温至750-960℃焙烧1-4h。
  13. 权利要求1-7中任意一项所述的铁-钾-铈基复合氧化物催化剂在烷基芳烃脱氢反应中的应用，优选地，所述烷基芳烃为C 8-C 10的烷基苯中的一种或多种，更优选为乙苯。
  14. 一种烷基芳烃脱氢方法，包括在脱氢反应条件下，使烷基芳烃与权利要求1-7中任意一项所述的铁-钾-铈基复合氧化物催化剂接触反应的步骤；
    优选地，所述脱氢反应条件包括：温度为580-620℃，优选590-610℃，烷基芳烃质量空速为0.5-1h -1，优选0.6-0.8h -1，水与烷基芳烃的重量比为0.7-1，优选0.8-1，压力为-60kPa至常压，优选-50kPa至常压；
    优选地，所述烷基芳烃为C 8-C 10的烷基苯中的一种或多种，更优选为乙苯。
PCT/CN2021/123478 2020-10-14 2021-10-13 铁-钾-铈基复合氧化物催化剂及其制备和应用 WO2022078371A1 (zh)

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