WO2020078303A1 - 用于烷基芳烃脱氢的催化剂及其制备方法 - Google Patents

用于烷基芳烃脱氢的催化剂及其制备方法 Download PDF

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WO2020078303A1
WO2020078303A1 PCT/CN2019/110935 CN2019110935W WO2020078303A1 WO 2020078303 A1 WO2020078303 A1 WO 2020078303A1 CN 2019110935 W CN2019110935 W CN 2019110935W WO 2020078303 A1 WO2020078303 A1 WO 2020078303A1
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catalyst
potassium
parts
dehydrogenation
hours
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French (fr)
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缪长喜
危春玲
宋磊
陈铜
倪军平
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority claimed from CN201811201536.4A external-priority patent/CN111054369B/zh
Priority claimed from CN201811201422.XA external-priority patent/CN111054345A/zh
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to ES19873017T priority Critical patent/ES3041768T3/es
Priority to EP19873017.8A priority patent/EP3868468B1/en
Priority to PL19873017.8T priority patent/PL3868468T3/pl
Priority to CA3116597A priority patent/CA3116597C/en
Priority to MYPI2021002073A priority patent/MY208398A/en
Publication of WO2020078303A1 publication Critical patent/WO2020078303A1/zh
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    • 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
    • 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
    • B01J23/70—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
    • B01J23/88—Molybdenum
    • B01J23/881—Molybdenum and iron
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
    • C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the name of the invention is "Catalyst for Dehydrogenation of Alkyl Aromatics", and the Chinese patent application with the application number of CN201811201536.4;
  • the name of the invention is "Catalyst for the production of alkenyl aromatic hydrocarbons", and the Chinese patent application with the application number of CN201811201422.X;
  • the invention relates to a catalyst for dehydrogenation of alkyl aromatic hydrocarbons and a preparation method thereof, in particular to a catalyst including a compound containing iron and potassium and a preparation method thereof, and belongs to the field of dehydrogenation of alkyl aromatic hydrocarbons.
  • the industrial production method of alkenyl aromatic hydrocarbons is mainly obtained by dehydrogenation of alkyl aromatic hydrocarbons.
  • the industrial production method of styrene is mainly ethylbenzene catalytic dehydrogenation. Its production capacity accounts for about 85% of the total production capacity of styrene.
  • One of the key is the catalyst for dehydrogenation of ethylbenzene to styrene.
  • the basic composition of ethylbenzene dehydrogenation to styrene catalyst in industry includes main catalyst, cocatalyst, pore-forming agent and binder. Early catalysts were Fe-K-Cr systems, such as published US Patent No.
  • iron oxide is the main catalyst and potassium is the main co-catalyst.
  • the addition of potassium can increase the catalyst activity by more than an order of magnitude.
  • the catalyst For Fe-K-Ce-Mo catalyst, after roasting at high temperature, the catalyst generally contains ⁇ -Fe 2 O 3 and iron-potassium compound phases.
  • iron-potassium compounds are the main active phase or precursor of the active phase of the alkane dehydrogenation catalyst. Therefore, the formation and structure of iron-potassium compounds have important significance for the activity of the catalyst.
  • a new catalyst for dehydrogenation of alkyl aromatic hydrocarbons is provided.
  • the catalyst includes a compound containing iron and potassium,
  • the compound has a special X-ray diffraction pattern (XRD), and the catalyst has the characteristics of high activity.
  • the second technical problem to be solved by the present invention is to provide a preparation method suitable for a catalyst that solves one of the technical problems.
  • the third technical problem to be solved by the present invention is a method for dehydrogenating alkyl aromatic hydrocarbons by using a catalyst of one of the above technical problems.
  • the present invention provides a catalyst for dehydrogenation of alkyl aromatic hydrocarbons, the catalyst comprising a compound containing iron and potassium, the compound containing iron and potassium is composed of K 2 Fe 10 O 16 phase And K 2 Fe 22 O 34 phase composition.
  • the iron-containing potassium compound has an X-ray diffraction pattern (XRD) as shown in the following table,
  • the X-ray diffraction pattern further includes X-ray diffraction peaks as shown in the following table,
  • the mass ratio of the K 2 Fe 10 O 16 phase to the K 2 Fe 22 O 34 phase in the iron-containing potassium compound is 1.1-3.3, preferably 1.2-2.0.
  • the catalyst includes the following composition: (a) 65-80% Fe 2 O 3 ; (b) 6-14% K 2 O; (c) 9- 13.5% CeO 2 ; (d) 0.5-5% MoO 3 ; (e) 0.2-5% CaO.
  • the present invention provides a method for preparing a catalyst for dehydrogenation of alkyl aromatic hydrocarbons, including the following steps:
  • the catalyst includes the following components in weight percent: (a) 65 to 80% Fe 2 O 3 ; (b) 6 to 14% K 2 O; (c) 9 to 13.5% CeO 2 ; (d) 0.5 ⁇ 5% MoO 3 ; (e) 0.2 ⁇ 5% CaO; no free ⁇ -Fe 2 O 3 phase in the catalyst;
  • the sum of the weights of the first part potassium source and the second part potassium source is the total weight of the required amount of potassium source, and the weight of the first part potassium source is the required amount of total potassium source 60 to 90% of the weight.
  • the iron source in step 1) is added in the form of at least one of iron oxide red and iron oxide yellow; the first part of the potassium source is at least one of potassium salt and potassium hydroxide Add in the form; the cerium source is added in the form of cerium salt; the molybdenum source is added in the form of at least one of molybdenum salt and molybdenum oxide; the calcium source is added in the form of at least one of calcium salt, calcium oxide and calcium hydroxide.
  • the second part of the potassium source in step 2) is added in the form of at least one of potassium hydroxide and potassium carbonate.
  • the amount of water added in step 2) is not particularly limited, and those skilled in the art can reasonably control the dry humidity for the purpose of extrusion, such as but not limited to the amount of water added to the total weight of the catalyst raw materials 18 ⁇ 32%.
  • the water is deionized water.
  • the pore-forming agent is a combustible material known to those skilled in the art, such as sodium carboxymethylcellulose, polymethylstyrene microspheres, methylcellulose, hydroxyethyl
  • the added amount of base cellulose, cyanine powder and graphite is 2.1-5.8% of the total weight of the catalyst.
  • the preparation method further includes the following steps:
  • step 3 The steps of wet kneading, extruding, molding, drying and calcining the finished catalyst obtained in step 2).
  • the drying temperature in the step 3) is 45-130 ° C, and the drying time is 4-24 hours.
  • the firing in the step 3) is firing at 200-400 ° C for 5-12 hours, and then firing at 750-950 ° C for 3-8 hours.
  • the catalyst includes a compound containing iron and potassium, which is composed of a phase of K 2 Fe 10 O 16 and a phase of K 2 Fe 22 O 34 .
  • the iron-containing potassium compound has an X-ray diffraction pattern (XRD) as shown in the following table,
  • the X-ray diffraction pattern further includes X-ray diffraction peaks as shown in the following table,
  • the mass ratio of the K 2 Fe 10 O 16 phase to the K 2 Fe 22 O 34 phase in the iron-containing potassium compound is 1.1-3.3, preferably 1.2-2.0.
  • the catalyst particles prepared by the present invention can be solid cylindrical, hollow cylindrical, trilobal, diamond, plum blossom, honeycomb, and other shapes, and their diameter and particle length are not limited.
  • the recommended diameter of the catalyst is 3 ⁇ 3.5 mm, solid cylindrical particles 5 to 10 mm long.
  • the present invention provides an application of the above catalyst or the catalyst prepared by the above method in the dehydrogenation of alkyl aromatic hydrocarbon to prepare alkenyl aromatic hydrocarbon.
  • the present invention also provides a method for dehydrogenating alkyl aromatic hydrocarbons, comprising the step of contacting the alkyl aromatic hydrocarbon-containing feed stream with the above catalyst or the catalyst prepared by the above method to obtain an alkenyl aromatic hydrocarbon-containing reaction stream.
  • the application can be applied by those skilled in the art according to the prior art process
  • the alkyl aromatic hydrocarbon includes at least one of ethylbenzene, methylethylbenzene, diethylbenzene or polyalkylbenzene, Preferably it is diethylbenzene or ethylbenzene.
  • ethylbenzene is used as a raw material. In the presence of a catalyst, the raw material contacts the catalyst and reacts to produce styrene.
  • the activity of the prepared catalyst is evaluated in an isothermal fixed bed.
  • the process is briefly described as follows:
  • the reaction raw materials are respectively input into a preheating mixer through a metering pump, and then preheated and mixed into a gaseous state, and then enter the reactor.
  • the reactor is heated by an electric heating wire to make it reach a predetermined temperature.
  • the reactant flowing out of the reactor was condensed with water, and its composition was analyzed with a gas chromatograph.
  • Ethylbenzene conversion rate and styrene selectivity are calculated according to the following formula:
  • the XRD test of the catalyst in the present invention is carried out on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detector It is a solid state detector.
  • I represents the peak area of the corresponding diffraction peak
  • I 0 represents the peak area of the strongest diffraction peak
  • W, M, S, and VS represent the intensity of the diffraction peak
  • W is weak
  • M medium
  • S strong
  • VS very strong, which is well known to those skilled in the art.
  • W is less than 20; M is 20-40; S is 40-70; VS is greater than 70.
  • the catalyst has the characteristics of high activity
  • the catalyst of the present invention is used for ethylbenzene under the conditions of reaction pressure -55kPa, liquid space velocity 1.0 hour -1 , 620 °C, steam / ethylbenzene (weight ratio) 1.2
  • reaction pressure -55kPa
  • liquid space velocity 1.0 hour -1 , 620 °C
  • the conversion rate can reach 81.2% and the selectivity can reach 95.1%, which has achieved good technical effects.
  • FIG. 1 is an XRD spectrum of the catalyst prepared in Example 1 of the present invention.
  • Red iron oxide equivalent to 59.74 parts Fe 2 O 3 , yellow iron oxide equivalent to 14.94 parts Fe 2 O 3 , potassium carbonate equivalent to 8.51 parts K 2 O, cerium oxalate equivalent to 10.62 parts CeO 2 , equivalent to 1.25 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 1.29 parts of CaO, and 5.0 parts of sodium carboxymethyl cellulose were stirred in the kneader for 1.5 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 3.65 parts K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, then added to the catalyst precursor I, wet kneaded for 0.6 hours, the extruded strip was taken out, extruded to a diameter of 3 mm and long The 5 mm particles were placed in an oven, baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 350 ° C for 6 hours, and then calcined at 850 ° C for 5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst XRD test was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection The detector is a solid-state detector.
  • the XRD spectrum of the catalyst is shown in Figure 1.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Fig. 1 is the XRD spectrum of the catalyst prepared in Example 1. It can be seen from Fig. 1 that the characteristics of the ⁇ -Fe 2 O 3 phase do not appear at 2 ⁇ of 24.14 °, 33.15 °, 40.85 °, 49.48 °, and 63.99 °. The diffraction peak indicates that the catalyst does not contain ⁇ -Fe 2 O 3 phase. The diffraction peaks at 2 ⁇ of 28.55 °, 33.08 °, 47.48 °, and 56.34 ° in Fig.
  • the characteristic diffraction peaks indicate that the iron and potassium in the catalyst completely produce iron-containing potassium compounds, and the iron-containing potassium compounds are composed of K 2 Fe 22 O 34 and K 2 Fe 10 O 16 phases.
  • Red iron oxide equivalent to 59.74 parts Fe 2 O 3 , yellow iron oxide equivalent to 14.94 parts Fe 2 O 3 , potassium carbonate equivalent to 7.30 parts K 2 O, cerium oxalate equivalent to 10.62 parts CeO 2 , equivalent to 1.25 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 1.29 parts of CaO, and 5.0 parts of sodium carboxymethyl cellulose were stirred in the kneader for 1.5 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 4.86 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 350 ° C for 6 hours, and then calcined at 850 ° C for 5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 59.74 parts Fe 2 O 3 , yellow iron oxide equivalent to 14.94 parts Fe 2 O 3 , potassium carbonate equivalent to 9.73 parts K 2 O, cerium oxalate equivalent to 10.62 parts CeO 2 , equivalent to 1.25 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 1.29 parts of CaO, and 5.0 parts of sodium carboxymethyl cellulose were stirred in the kneader for 1.5 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 2.43 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded rod was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 350 ° C for 6 hours, and then calcined at 850 ° C for 5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 59.74 parts Fe 2 O 3 , yellow iron oxide equivalent to 14.94 parts Fe 2 O 3 , potassium carbonate equivalent to 10.34 parts K 2 O, cerium oxalate equivalent to 10.62 parts CeO 2 , equivalent to 1.25 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 1.29 parts of CaO, and 5.0 parts of sodium carboxymethyl cellulose were stirred in the kneader for 1.5 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 1.82 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded rod was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 350 ° C for 6 hours, and then calcined at 850 ° C for 5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 59.74 parts Fe 2 O 3 , yellow iron oxide equivalent to 14.94 parts Fe 2 O 3 , cerium oxalate equivalent to 10.62 parts CeO 2 , ammonium molybdate equivalent to 1.25 parts MoO 3 , equivalent to 1.29 parts of calcium carbonate of CaO and 5.0 parts of sodium carboxymethyl cellulose were stirred in a kneader for 1.5 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 12.16 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 350 ° C for 6 hours, and then calcined at 850 ° C for 5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 59.74 parts Fe 2 O 3 , yellow iron oxide equivalent to 14.94 parts Fe 2 O 3 , potassium carbonate equivalent to 2.43 parts K 2 O, cerium oxalate equivalent to 10.62 parts CeO 2 , equivalent to 1.25 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 1.29 parts of CaO, and 5.0 parts of sodium carboxymethyl cellulose were stirred in the kneader for 1.5 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 9.73 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 350 ° C for 6 hours, and then calcined at 850 ° C for 5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 59.74 parts Fe 2 O 3 , yellow iron oxide equivalent to 14.94 parts Fe 2 O 3 , potassium carbonate equivalent to 11.55 parts K 2 O, cerium oxalate equivalent to 10.62 parts CeO 2 , equivalent to 1.25 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 1.29 parts of CaO, and 5.0 parts of sodium carboxymethyl cellulose were stirred in the kneader for 1.5 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 0.61 part of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 350 ° C for 6 hours, and then calcined at 850 ° C for 5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 59.74 parts Fe 2 O 3 , yellow iron oxide equivalent to 14.94 parts Fe 2 O 3 , potassium carbonate equivalent to 6.08 parts K 2 O, cerium oxalate equivalent to 10.62 parts CeO 2 , equivalent to 1.25 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 1.29 parts of CaO, and 5.0 parts of sodium carboxymethyl cellulose were stirred in the kneader for 1.5 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 6.08 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 350 ° C for 6 hours, and then calcined at 850 ° C for 5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Potassium carbonate equivalent to 5.11 parts of K 2 O was dissolved in deionized water which added 22.7% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet kneaded for 0.8 hours, and the extruded rod was taken out and extruded to a diameter of 3 mm
  • the granules with a length of 5 mm are placed in an oven and baked at 40 ° C for 6 hours, at 110 ° C for 12 hours, then calcined at 200 ° C for 12 hours, and then calcined at 900 ° C for 4 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 63.96 parts Fe 2 O 3 , yellow iron oxide equivalent to 15.99 parts Fe 2 O 3 , potassium carbonate equivalent to 3.91 parts K 2 O, cerium oxalate equivalent to 13.01 parts CeO 2 , equivalent to 0.51 parts of ammonium molybdate of MoO 3 , calcium hydroxide equivalent to 0.52 parts of CaO, and 5.1 parts of sodium carboxymethyl cellulose were stirred for 1.5 hours in a kneader to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 2.10 parts K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet kneaded for 0.8 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 60 ° C for 3 hours, 120 ° C for 10 hours, then calcined at 380 ° C for 6 hours, and then calcined at 870 ° C for 4.5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Potassium carbonate equivalent to 4.20 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, then added to the catalyst precursor I, wet-kneaded for 0.7 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 75 ° C for 2 hours, 130 ° C for 4 hours, then calcined at 400 ° C for 5 hours, and then baked at 750 ° C for 8 hours to obtain a finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 58.46 parts Fe 2 O 3 , yellow iron oxide equivalent to 14.61 parts Fe 2 O 3 , potassium carbonate equivalent to 9.01 parts K 2 O, cerium oxalate equivalent to 9.01 parts CeO 2 , equivalent to 3.56 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 2.34 parts of CaO, and 5.4 parts of sodium carboxymethyl cellulose were stirred in a kneader for 1.8 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 3.01 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet kneaded for 0.9 hours, and the extruded strip was taken out to 3 mm in diameter and length
  • the 5 mm particles were placed in an oven, baked at 55 ° C for 4.5 hours, 120 ° C for 8 hours, then calcined at 360 ° C for 9 hours, and then calcined at 830 ° C for 4.5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 60.54 parts Fe 2 O 3 , yellow iron oxide equivalent to 15.14 parts Fe 2 O 3 , potassium carbonate equivalent to 8.90 parts K 2 O, cerium oxalate equivalent to 11.07 parts CeO 2 , equivalent to 0.98 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 1.15 parts of CaO, and 4.9 parts of cyanine powder were stirred in a kneader for 1.1 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 2.22 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, then added to the catalyst precursor I, wet kneaded for 0.5 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 55 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 360 ° C for 6 hours, and then calcined at 880 ° C for 4 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Potassium carbonate equivalent to 1.95 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, then added to the catalyst precursor I, wet kneaded for 0.7 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven and baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 360 ° C for 6 hours, and then calcined at 800 ° C for 5 hours to obtain a finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 56.34 parts Fe 2 O 3 , yellow iron oxide equivalent to 18.78 parts Fe 2 O 3 , potassium carbonate equivalent to 7.67 parts K 2 O, cerium oxalate equivalent to 12.51 parts CeO 2 , equivalent to 2.03 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 1.82 parts of CaO, and 5.8 parts of sodium carboxymethyl cellulose were stirred in a kneader for 1.3 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 0.85 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded rod was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 55 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 370 ° C for 6 hours, and then calcined at 860 ° C for 5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 59.24 parts Fe 2 O 3 , yellow iron oxide equivalent to 19.75 parts Fe 2 O 3 , potassium carbonate equivalent to 7.71 parts K 2 O, cerium oxalate equivalent to 8.05 parts CeO 2 , equivalent to 1.24 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 1.01 part of CaO, and 5.6 parts of sodium carboxymethyl cellulose were stirred in the kneader for 1.3 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 3.00 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 55 ° C for 4.5 hours, 120 ° C for 8 hours, then calcined at 390 ° C for 5 hours, and then calcined at 810 ° C for 5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Potassium carbonate equivalent to 2.28 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 360 ° C for 6 hours, and then calcined at 820 ° C for 5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 56.49 parts Fe 2 O 3 , yellow iron oxide equivalent to 18.83 parts Fe 2 O 3 , potassium carbonate equivalent to 6.91 parts K 2 O, cerium oxalate equivalent to 10.62 parts CeO 2 , equivalent to 2.21 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 1.69 parts of CaO, and 5.1 parts of graphite were stirred in a kneader for 1.5 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 3.25 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 340 ° C for 7 hours, and then calcined at 880 ° C for 4 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 55.23 parts Fe 2 O 3 , yellow iron oxide equivalent to 18.41 parts Fe 2 O 3 , potassium carbonate equivalent to 8.74 parts K 2 O, cerium oxalate equivalent to 12.43 parts CeO 2 , equivalent to 1.05 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 0.21 part of CaO, and 5.4 parts of sodium carboxymethyl cellulose were stirred in a kneader for 1.5 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 3.93 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded rod was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 370 ° C for 6 hours, and then calcined at 825 ° C for 5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Potassium carbonate equivalent to 2.15 parts K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 55 ° C for 3.5 hours, 120 ° C for 10 hours, then calcined at 370 ° C for 9 hours, and then calcined at 810 ° C for 5 hours to obtain a finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 54.82 parts Fe 2 O 3 , yellow iron oxide equivalent to 18.27 parts Fe 2 O 3 , potassium carbonate equivalent to 10.47 parts K 2 O, cerium oxalate equivalent to 11.35 parts CeO 2 , equivalent to 1.51 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 2.02 parts of CaO, and 5.1 parts of sodium carboxymethyl cellulose were stirred in a kneader for 1.5 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 1.56 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 375 ° C for 6 hours, and then calcined at 820 ° C for 5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Potassium carbonate equivalent to 2.95 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet kneaded for 0.6 hours, and the extruded rod was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 50 ° C for 4.5 hours, 120 ° C for 10 hours, then calcined at 385 ° C for 6.5 hours, and then calcined at 815 ° C for 5.5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 59.04 parts Fe 2 O 3 , yellow iron oxide equivalent to 19.68 parts Fe 2 O 3 , potassium carbonate equivalent to 3.61 parts K 2 O, cerium oxalate equivalent to 8.10 parts CeO 2 , equivalent to 3.91 parts of ammonium molybdate of MoO 3 , calcium hydroxide equivalent to 3.26 parts of CaO, and 5.2 parts of sodium carboxymethyl cellulose were stirred in a kneader for 1.6 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 2.40 parts K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, and then added to the catalyst precursor I, wet-kneaded for 0.7 hours, and the extruded rod was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 60 ° C for 3 hours, 120 ° C for 10 hours, then calcined at 380 ° C for 6 hours, and then calcined at 870 ° C for 4.5 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Red iron oxide equivalent to 50.69 parts Fe 2 O 3 , yellow iron oxide equivalent to 16.90 parts Fe 2 O 3 , potassium carbonate equivalent to 12.59 parts K 2 O, cerium carbonate equivalent to 10.37 parts CeO 2 , equivalent to 3.78 parts of ammonium molybdate of MoO 3 , calcium carbonate equivalent to 4.27 parts of CaO, and 5.5 parts of sodium carboxymethyl cellulose were stirred in a kneader for 2 hours to obtain catalyst precursor I.
  • Potassium carbonate equivalent to 1.40 parts of K 2 O was dissolved in deionized water accounting for 23.5% of the total weight of the catalyst raw material, then added to the catalyst precursor I, wet kneaded for 0.7 hours, and the extruded strip was taken out, extruded to a diameter of 3 mm and long
  • the 5 mm particles were placed in an oven, baked at 75 ° C for 2 hours, 130 ° C for 4 hours, then calcined at 400 ° C for 5 hours, and then baked at 750 ° C for 8 hours to obtain the finished catalyst.
  • the catalyst composition is shown in Table 1.
  • XRD measurement of the catalyst was performed on Bruker D8 advance X-ray powder diffractometer, tube voltage 40kV, tube current 250mA, Cu target, scanning range 4 ⁇ 70 °, scanning speed 6 (°) / min, detection
  • the detector is a solid-state detector.
  • the composition of the crystal phase in the sample is shown in Table 2.
  • Example 1-4 The amount of each raw material in Example 1-4 is the same, but the addition amount of the potassium source in the first part is different; as can be seen from the results of Examples 1-4, the addition amount of potassium source in the first part will change the iron-containing potassium in the catalyst The crystal phase composition of the compound.
  • Comparative Examples 1 and 2 have the same amounts of raw materials as in Examples 1-4, except that the potassium source is not added in steps, and the catalyst prepared contains free ⁇ -Fe 2 O 3 phases and does not contain K 2 Fe 10 O 16 phase, the catalyst is used in the dehydrogenation of alkyl aromatics, the conversion of the reactants is low.
  • the amount of each raw material in Comparative Examples 3-5 is the same as that in Examples 1-4, except that the amount of potassium source added in the first part is outside the scope of the present invention; the catalyst prepared therefrom contains K 2 Fe 10 O 16 and K 2 In addition to the Fe 22 O 34 phase, it also contains the free ⁇ -Fe 2 O 3 phase or other phases containing iron and potassium compounds.
  • the catalyst is used in the dehydrogenation of alkyl aromatics, and the conversion of the reactants is low.
  • the catalyst was prepared according to the method of Example 1. The results of the catalyst composition and crystal phase composition were the same as in Example 1.
  • the obtained catalyst was crushed and sieved, and the particle size of 0.5-0.7 mm was separated for use.
  • the measured ethylbenzene conversion rate was 75.1%, and the styrene selectivity was 95.2%.
  • the ethylbenzene conversion rate and styrene selectivity are determined by the following formula:
  • Ethylbenzene conversion rate (mol%) [(A ⁇ M f -B ⁇ M P ) / (A ⁇ M f )] ⁇ 100
  • A ethylbenzene concentration at the reactor inlet (wt%)
  • B ethylbenzene concentration at the reactor outlet (wt%)
  • C Styrene concentration at the inlet of the reactor (% by weight); D: Styrene concentration at the outlet of the reactor (% by weight)
  • M f average molar mass of raw materials
  • M P average molar mass of products
  • M EB molar mass of ethylbenzene
  • M ST molar mass of styrene

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Abstract

一种用于烷基芳烃脱氢的催化剂及其制备方法和应用，催化剂中包括含铁钾的化合物，含铁钾的化合物由K 2Fe 10O 16物相和K 2Fe 22O 34物相组成，含铁化合物具有特殊的X射线衍射图案(XRD)。通过将第一部分钾源和铁源、铈源、钼源、钙源、制孔剂干混，得催化剂前体I；将第二部分钾源用水溶解，加入催化剂前体I得到成品催化剂；催化剂以重量百分比计包括以下组份：65～80％的Fe 2O 3；6～14％的K 2O；9～13.5％的CeO 2；0.5～5％的MoO 3；0.2～5％的CaO；钾采用分步加入的技术方案，较好地解决了以往技术中存在的催化剂活性不够高的问题，可用于烷基芳烃脱氢制备烷烯基芳烃的工业生产中。

Description

用于烷基芳烃脱氢的催化剂及其制备方法
本申请要求享有2018年10月16日提交的以下专利申请的优先权：
1、发明名称为“用于烷基芳烃脱氢的催化剂”，申请号为CN201811201536.4的中国专利申请；
2、发明名称为“用于生产烷烯基芳烃的催化剂”，申请号为CN201811201422.X的中国专利申请；
其全部内容通过引用并入本文中。
技术领域
本发明涉及一种用于烷基芳烃脱氢的催化剂及其制备方法，尤其涉及包括含铁钾的化合物的催化剂及其制备方法，属于烷基芳烃脱氢领域。
背景技术
烷烯基芳烃的工业生产方法主要通过烷基芳烃脱氢而得，例如苯乙烯的工业生产方法主要是乙苯催化脱氢法，其生产能力约占苯乙烯总生产能力的85％，该方法的关键之一是乙苯脱氢制苯乙烯催化剂。目前工业上乙苯脱氢制备苯乙烯催化剂的基本组成包括主催化剂、助催化剂、制孔剂和粘结剂等。早期的催化剂为Fe-K-Cr体系，如已公开的美国专利4467046(脱氢催化剂)和欧洲专利0296285A1(具有改善耐水性能的脱氢催化剂及其制备方法)。虽然该类催化剂的活性和稳定性较好，但由于催化剂含Cr的氧化物，对环境造成一定的污染，已被逐渐淘汰。之后演变为Fe-K-Ce-Mo系列，用Ce、Mo替代了Cr，可较好地改善催化剂的活性和稳定性，同时又克服了Cr毒性大，污染环境的弊端。
烷基芳烃脱氢制备烷烯基芳烃的催化剂中，氧化铁为主催化剂，钾为主要的助催化剂，钾的加入可以使催化剂活性提高一个数量级以上。对于Fe-K-Ce-Mo催化剂，经高温焙烧后，催化剂中一般含α-Fe 2O 3和铁钾化合物物相。而大量研究结果表明，铁钾化合物是烷烃脱氢催化剂的主活性相或活性相前身，因此，铁钾化合物的生成及其结构对催化剂的活性有着重要的意义。
如何简便获得所需的催化剂物相及结构，从而进一步提高催化剂的活性，一直是研究人员感兴趣的课题。
发明内容
本发明所要解决的技术问题之一是以往技术中存在催化剂活性不够高的技术问题，提供一种新的用于烷基芳烃脱氢的催化剂，催化剂中包括含铁钾的化合物，含铁钾的化合物具有特殊的X射线衍射图案(XRD)，该催化剂具有活性高的特点。
本发明要解决的技术问题之二是提供一种与解决技术问题之一的催化剂相适应的制备方法。
本发明所要解决的技术问题之三是采用上述技术问题之一的催化剂用于烷基芳烃脱氢的方法。
为解决上述技术问题之一，本发明提供了一种用于烷基芳烃脱氢的催化剂，所述催化剂包括含铁钾的化合物，所述含铁钾的化合物由K 2Fe 10O 16物相和K 2Fe 22O 34物相组成。
根据本发明的优选实施方式，所述含铁钾的化合物具有如下表所示的X射线衍射图案(XRD)，
Figure PCTCN2019110935-appb-000001
根据本发明的优选实施方式，所述X射线衍射图案还包括如下表所示的X射线衍射峰，
Figure PCTCN2019110935-appb-000002
Figure PCTCN2019110935-appb-000003
根据本发明的优选实施方式，所述含铁钾的化合物中K 2Fe 10O 16物相与K 2Fe 22O 34物相的质量比为1.1～3.3，优选为1.2～2.0。
根据本发明的优选实施方式，所述催化剂中无游离α-Fe 2O 3物相。
根据本发明的优选实施方式，以重量百分比计，所述催化剂包括以下组成：(a)65～80％的Fe 2O 3；(b)6～14％的K 2O；(c)9～13.5％的CeO 2；(d)0.5～5％的MoO 3；(e)0.2～5％的CaO。
为解决上述技术问题之二，本发明提供了一种用于烷基芳烃脱氢的催化剂的制备方法，包括以下步骤：
1)将第一部分钾源和铁源、铈源、钼源、钙源、制孔剂在捏合机中干混，得催化剂前体I；
2)将第二部分钾源用水溶解，加入催化剂前体I得到成品催化剂；
所述催化剂以重量百分比计包括以下组成：(a)65～80％的Fe 2O 3；(b)6～14％的K 2O；(c)9～13.5％的CeO 2；(d)0.5～5％的MoO 3；(e)0.2～5％的CaO；催化剂中无游离α-Fe 2O 3物相；
其中，以含K 2O的量计，第一部分钾源与第二部分钾源的重量总和为所需量的钾源的总重量，且第一部分钾源的重量为所需量的钾源总重量的60～90％。
根据本发明的优选实施方式，所述步骤1)中的铁源以氧化铁红、氧化铁黄中的至少一种的形式加入；第一部分钾源以钾盐、氢氧化钾中的至少一种形式加入；铈源以铈盐的形式加入；钼源以钼盐、钼的氧化物中的至少一种形式加入；钙源以钙盐、氧化钙、氢氧化钙中的至少一种形式加入。
根据本发明的优选实施方式，所述步骤2)中的第二部分钾源以氢氧化钾、碳酸钾中的至少一种形式加入。
根据本发明的优选实施方式，所述步骤2)中水的加入量没有特别限制，本领域技术人员为了挤出需要可以合理掌握干湿度，例如但不限于水的加入量占催化剂原料总重量的18～32％。优选所述水为去离子水。
根据本发明的优选实施方式，所述制孔剂为本领域人员已知的可燃尽材料，例如可选择为羧甲基纤维素钠、聚甲基苯乙烯微球、甲基纤维素、羟乙基纤维素、田菁粉和石墨等，其加入量为催化剂总重量的2.1～5.8％。
根据本发明的优选实施方式，所述制备方法还包括如下步骤：
3)对步骤2)得到的成品催化剂进行湿捏、挤条、成型、干燥和焙烧处理的步骤。
根据本发明的优选实施方式，所述步骤3)中的干燥温度为45～130℃，干燥时间为4～24小时。
根据本发明的优选实施方式，所述步骤3)中的焙烧为在200～400℃下焙烧5～12小时，然后在750～950℃下焙烧3～8小时。
根据本发明的优选实施方式，所述催化剂包括含铁钾的化合物，所述含铁钾的化合物由K 2Fe 10O 16物相和K 2Fe 22O 34物相组成。
根据本发明的优选实施方式，所述含铁钾的化合物具有如下表所示的X射线衍射图案(XRD)，
Figure PCTCN2019110935-appb-000004
根据本发明的优选实施方式，所述X射线衍射图案还包括如下表所示的X射线衍射峰，
Figure PCTCN2019110935-appb-000005
根据本发明的优选实施方式，所述含铁钾的化合物中K 2Fe 10O 16物相与K 2Fe 22O 34物相的 质量比为1.1～3.3，优选为1.2～2.0。
本发明制得的催化剂颗粒可以为实心圆柱形、空心圆柱形、三叶形、菱形、梅花形、蜂窝型等各种形状，其直径和颗粒长度也没有固定的限制，推荐催化剂采用直径为3～3.5毫米、长5～10毫米的实心圆柱形颗粒。
为解决上述技术问题之三，本发明提供了一种上述催化剂或上述方法制备的催化剂在烷基芳烃脱氢制备烷烯基芳烃中的应用。
本发明还提供了一种烷基芳烃脱氢方法，包括使含烷基芳烃的原料物流与上述催化剂或上述方法制备的催化剂接触得到含烷烯基芳烃反应物流的步骤。
根据本发明的优选实施方式，所述应用本领域技术人员可以根据现有技术工艺加以应用，所述烷基芳烃包括乙苯、甲乙苯、二乙苯或多烷基苯中的至少一种，优选为二乙苯或乙苯。例如以乙苯为原料，在催化剂存在下，原料与催化剂接触，反应生成苯乙烯。
制得的催化剂在等温式固定床中进行活性评价，对乙苯脱氢制苯乙烯催化剂活性评价而言，过程简述如下：
将反应原料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。由反应器流出的反应物经水冷凝后用气相色谱仪分析其组成。
乙苯转化率、苯乙烯选择性按以下公式计算：
Figure PCTCN2019110935-appb-000006
Figure PCTCN2019110935-appb-000007
本发明中催化剂的XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器。在本说明书的上下文中，催化剂的XRD数据中，其中I表示相应衍射峰的峰面积，I 0表示最强衍射峰的峰面积，W、M、S、VS代表衍射峰强度，W为弱，M为中等，S为强，VS为非常强，这为本领域技术人员所熟知的。一般而言，W为小于20；M为20-40；S为40-70；VS为大于70。
本发明通过在铁-钾-铈-钼-钙体系中，钾采用分步加入的方式，制得成品催化剂中铁钾化合物以K 2Fe 10O 16与K 2Fe 22O 34物相同时存在的技术方案，催化剂具有活性高的特点，使用本发明的催化剂，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2 条件下，用于乙苯脱氢制备苯乙烯的反应，其转化率可达81.2％、选择性可达95.1％，取得了较好的技术效果。
附图说明
图1为本发明实施例1制备的催化剂的XRD谱图。
具体实施方式
下面通过实施例对本发明作进一步阐述。
【实施例1】
将相当于59.74份Fe 2O 3的氧化铁红、相当于14.94份Fe 2O 3的氧化铁黄、相当于8.51份K 2O的碳酸钾、相当于10.62份CeO 2的草酸铈、相当于1.25份MoO 3的钼酸铵、相当于1.29份CaO的碳酸钙和5.0份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当于3.65份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在350℃下焙烧6小时，然后在850℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，催化剂的XRD谱图如图1所示，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
图1为实施例1制备的催化剂的XRD谱图，由图1可知，在2θ为24.14°、33.15°、40.85°、49.48°、63.99°处均未出现α-Fe 2O 3物相的特征衍射峰，说明催化剂中不含α-Fe 2O 3物相。图1中2θ为28.55°、33.08°、47.48°、56.34°处出现的衍射峰均为CeO 2的特征衍射峰，剩余的衍射峰则归属为K 2Fe 22O 34和K 2Fe 10O 16的特征衍射峰，说明催化剂中铁与钾完全生成了含铁钾的化合物，且含铁钾的化合物由K 2Fe 22O 34和K 2Fe 10O 16的物相组成。
【实施例2】
将相当于59.74份Fe 2O 3的氧化铁红、相当于14.94份Fe 2O 3的氧化铁黄、相当于7.30份K 2O的碳酸钾、相当于10.62份CeO 2的草酸铈、相当于1.25份MoO 3的钼酸铵、相当于1.29 份CaO的碳酸钙和5.0份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当于4.86份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在350℃下焙烧6小时，然后在850℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例3】
将相当于59.74份Fe 2O 3的氧化铁红、相当于14.94份Fe 2O 3的氧化铁黄、相当于9.73份K 2O的碳酸钾、相当于10.62份CeO 2的草酸铈、相当于1.25份MoO 3的钼酸铵、相当于1.29份CaO的碳酸钙和5.0份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当于2.43份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在350℃下焙烧6小时，然后在850℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例4】
将相当于59.74份Fe 2O 3的氧化铁红、相当于14.94份Fe 2O 3的氧化铁黄、相当于10.34份K 2O的碳酸钾、相当于10.62份CeO 2的草酸铈、相当于1.25份MoO 3的钼酸铵、相当于1.29份CaO的碳酸钙和5.0份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当于1.82份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化 剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在350℃下焙烧6小时，然后在850℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【比较例1】
除了将K的加入全部采用干混的方式外，催化剂制备方法和催化剂评价条件同实施例1，具体为：
将相当于59.74份Fe 2O 3的氧化铁红、相当于14.94份Fe 2O 3的氧化铁黄、相当于12.16份K 2O的碳酸钾、相当于10.62份CeO 2的草酸铈、相当于1.25份MoO 3的钼酸铵、相当于1.29份CaO的碳酸钙和5.0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23.5％的去离子水，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在350℃下焙烧6小时，然后在850℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【比较例2】
除了将K的加入全部采用水溶解的方式外，催化剂制备方法和催化剂评价条件同实施例1，具体为：
将相当于59.74份Fe 2O 3的氧化铁红、相当于14.94份Fe 2O 3的氧化铁黄、相当于10.62份CeO 2的草酸铈、相当于1.25份MoO 3的钼酸铵、相当于1.29份CaO的碳酸钙和5.0份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当于12.16份K 2O的碳酸钾用 占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在350℃下焙烧6小时，然后在850℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【比较例3】
除了干混K占总K的量不同外，催化剂制备方法和催化剂评价条件同实施例1，具体为：
将相当于59.74份Fe 2O 3的氧化铁红、相当于14.94份Fe 2O 3的氧化铁黄、相当于2.43份K 2O的碳酸钾、相当于10.62份CeO 2的草酸铈、相当于1.25份MoO 3的钼酸铵、相当于1.29份CaO的碳酸钙和5.0份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当于9.73份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在350℃下焙烧6小时，然后在850℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【比较例4】
除了干混K占总K的量不同外，催化剂制备方法和催化剂评价条件同实施例1，具体为：
将相当于59.74份Fe 2O 3的氧化铁红、相当于14.94份Fe 2O 3的氧化铁黄、相当于11.55份K 2O的碳酸钾、相当于10.62份CeO 2的草酸铈、相当于1.25份MoO 3的钼酸铵、相当于1.29份CaO的碳酸钙和5.0份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当于0.61份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化 剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在350℃下焙烧6小时，然后在850℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【比较例5】
除了干混K占总K的量不同外，催化剂制备方法和催化剂评价条件同实施例1，具体为：
将相当于59.74份Fe 2O 3的氧化铁红、相当于14.94份Fe 2O 3的氧化铁黄、相当于6.08份K 2O的碳酸钾、相当于10.62份CeO 2的草酸铈、相当于1.25份MoO 3的钼酸铵、相当于1.29份CaO的碳酸钙和5.0份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当于6.08份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在350℃下焙烧6小时，然后在850℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例5】
将相当于57.61份Fe 2O 3的氧化铁红、相当于14.40份Fe 2O 3的氧化铁黄、相当于7.67份K 2O的碳酸钾、相当于11.34份CeO 2的草酸铈、相当于1.75份MoO 3的钼酸铵、相当于2.12份CaO的氢氧化钙和5.5份羧甲基纤维素钠在捏合机中搅拌1.3小时，得催化剂前体I。将相当于5.11份K 2O的碳酸钾用加入占催化剂原料总重22.7％的去离子水溶解，然后再加入到催化剂前体I中，湿捏0.8小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱， 40℃烘6小时，110℃烘12小时，然后在200℃下焙烧12小时，然后在900℃下焙烧4小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例6】
将相当于63.96份Fe 2O 3的氧化铁红、相当于15.99份Fe 2O 3的氧化铁黄、相当于3.91份K 2O的碳酸钾、相当于13.01份CeO 2的草酸铈、相当于0.51份MoO 3的钼酸铵、相当于0.52份CaO的氢氧化钙和5.1份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当于2.10份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.8小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，60℃烘3小时，120℃烘10小时，然后在380℃下焙烧6小时，然后在870℃下焙烧4.5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例7】
将相当于52.01份Fe 2O 3的氧化铁红、相当于13.00份Fe 2O 3的氧化铁黄、相当于9.79份K 2O的碳酸钾、相当于11.04份CeO 2的碳酸铈、相当于4.98份MoO 3的钼酸铵、相当于2.98份CaO的碳酸钙和相当于2.0份CaO的氢氧化钙和5.5份羧甲基纤维素钠在捏合机中搅拌2小时，得催化剂前体I。将相当于4.20份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.7小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，75℃烘2小时，130℃烘4小时，然后在400℃下焙烧5小时，然后在750℃下焙烧8小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例8】
将相当于58.46份Fe 2O 3的氧化铁红、相当于14.61份Fe 2O 3的氧化铁黄、相当于9.01份K 2O的碳酸钾、相当于9.01份CeO 2的草酸铈、相当于3.56份MoO 3的钼酸铵、相当于2.34份CaO的碳酸钙和5.4份羧甲基纤维素钠在捏合机中搅拌1.8小时，得催化剂前体I。将相当于3.01份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.9小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，55℃烘4.5小时，120℃烘8小时，然后在360℃下焙烧9小时，然后在830℃下焙烧4.5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例9】
将相当于60.54份Fe 2O 3的氧化铁红、相当于15.14份Fe 2O 3的氧化铁黄、相当于8.90份K 2O的碳酸钾、相当于11.07份CeO 2的草酸铈、相当于0.98份MoO 3的钼酸铵、相当于1.15份CaO的碳酸钙和4.9份田菁粉在捏合机中搅拌1.1小时，得催化剂前体I。将相当于2.22份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.5小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，55℃烘4.5小时，120℃烘10小时，然后在360℃下焙烧6小时，然后在880℃下焙烧4小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器 为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例10】
将相当于53.38份Fe 2O 3的氧化铁红、相当于13.34份Fe 2O 3的氧化铁黄、相当于11.03份K 2O的碳酸钾、相当于12.86份CeO 2的碳酸铈、相当于3.28份MoO 3的钼酸铵、相当于4.11份CaO的碳酸钙、0.05份TiO 2、3.1份羧甲基纤维素钠和2.2份田菁粉在捏合机中搅拌1.2小时，得催化剂前体I。将相当于1.95份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.7小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在360℃下焙烧6小时，然后在800℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例11】
将相当于56.34份Fe 2O 3的氧化铁红、相当于18.78份Fe 2O 3的氧化铁黄、相当于7.67份K 2O的碳酸钾、相当于12.51份CeO 2的草酸铈、相当于2.03份MoO 3的钼酸铵、相当于1.82份CaO的碳酸钙和5.8份羧甲基纤维素钠在捏合机中搅拌1.3小时，得催化剂前体I。将相当于0.85份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，55℃烘4.5小时，120℃烘10小时，然后在370℃下焙烧6小时，然后在860℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0 小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例12】
将相当于59.24份Fe 2O 3的氧化铁红、相当于19.75份Fe 2O 3的氧化铁黄、相当于7.71份K 2O的碳酸钾、相当于8.05份CeO 2的草酸铈、相当于1.24份MoO 3的钼酸铵、相当于1.01份CaO的碳酸钙和5.6份羧甲基纤维素钠在捏合机中搅拌1.3小时，得催化剂前体I。将相当于3.00份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，55℃烘4.5小时，120℃烘8小时，然后在390℃下焙烧5小时，然后在810℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例13】
将相当于54.34份Fe 2O 3的氧化铁红、相当于18.12份Fe 2O 3的氧化铁黄、相当于7.23份K 2O的碳酸钾、相当于13.46份CeO 2的草酸铈、相当于2.01份MoO 3的钼酸铵、相当于2.56份CaO的碳酸钙和5.3份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当于2.28份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在360℃下焙烧6小时，然后在820℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例14】
将相当于56.49份Fe 2O 3的氧化铁红、相当于18.83份Fe 2O 3的氧化铁黄、相当于6.91份K 2O的碳酸钾、相当于10.62份CeO 2的草酸铈、相当于2.21份MoO 3的钼酸铵、相当于1.69份CaO的碳酸钙和5.1份石墨在捏合机中搅拌1.5小时，得催化剂前体I。将相当于3.25份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在340℃下焙烧7小时，然后在880℃下焙烧4小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例15】
将相当于55.23份Fe 2O 3的氧化铁红、相当于18.41份Fe 2O 3的氧化铁黄、相当于8.74份K 2O的碳酸钾、相当于12.43份CeO 2的草酸铈、相当于1.05份MoO 3的钼酸铵、相当于0.21份CaO的碳酸钙和5.4份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当于3.93份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在370℃下焙烧6小时，然后在825℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例16】
将相当于54.61份Fe 2O 3的氧化铁红、相当于18.20份Fe 2O 3的氧化铁黄、相当于9.80份 K 2O的碳酸钾、相当于12.71份CeO 2的草酸铈、相当于1.16份MoO 3的钼酸铵、相当于1.35份CaO的碳酸钙、0.02份TiO 2和5.6份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当于2.15份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，55℃烘3.5小时，120℃烘10小时，然后在370℃下焙烧9小时，然后在810℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例17】
将相当于54.82份Fe 2O 3的氧化铁红、相当于18.27份Fe 2O 3的氧化铁黄、相当于10.47份K 2O的碳酸钾、相当于11.35份CeO 2的草酸铈、相当于1.51份MoO 3的钼酸铵、相当于2.02份CaO的碳酸钙和5.1份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当于1.56份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在375℃下焙烧6小时，然后在820℃下焙烧5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例18】
将相当于54.71份Fe 2O 3的氧化铁红、相当于18.23份Fe 2O 3的氧化铁黄、相当于8.38份K 2O的碳酸钾、相当于11.38份CeO 2的草酸铈、相当于1.52份MoO 3的钼酸铵、相当于2.83份CaO的碳酸钙和5.9份羧甲基纤维素钠在捏合机中搅拌1.5小时，得催化剂前体I。将相当 于2.95份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.6小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，50℃烘4.5小时，120℃烘10小时，然后在385℃下焙烧6.5小时，然后在815℃下焙烧5.5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例19】
将相当于59.04份Fe 2O 3的氧化铁红、相当于19.68份Fe 2O 3的氧化铁黄、相当于3.61份K 2O的碳酸钾、相当于8.10份CeO 2的草酸铈、相当于3.91份MoO 3的钼酸铵、相当于3.26份CaO的氢氧化钙和5.2份羧甲基纤维素钠在捏合机中搅拌1.6小时，得催化剂前体I。将相当于2.40份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.7小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，60℃烘3小时，120℃烘10小时，然后在380℃下焙烧6小时，然后在870℃下焙烧4.5小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
【实施例20】
将相当于50.69份Fe 2O 3的氧化铁红、相当于16.90份Fe 2O 3的氧化铁黄、相当于12.59份K 2O的碳酸钾、相当于10.37份CeO 2的碳酸铈、相当于3.78份MoO 3的钼酸铵、相当于4.27份CaO的碳酸钙和5.5份羧甲基纤维素钠在捏合机中搅拌2小时，得催化剂前体I。将相当于1.40份K 2O的碳酸钾用占催化剂原料总重23.5％的去离子水溶解，然后加入到催化剂前体I中，湿捏0.7小时，取出挤条，挤成直径3毫米、长5毫米的颗粒，放入烘箱，75 ℃烘2小时，130℃烘4小时，然后在400℃下焙烧5小时，然后在750℃下焙烧8小时得成品催化剂。催化剂组成列于表1。
对催化剂进行XRD测定，XRD测试在Bruker公司D8 advance型X射线粉末衍射仪上进行，管电压40kV，管电流250mA，Cu靶，扫描范围4～70°，扫描速度6(°)/min，探测器为固体探测器，样品中的晶相组成结果列于表2。
将100毫升催化剂装入内径为1″的不锈钢管反应器，在反应压力-55kPa、液体空速1.0小时 －1、620℃、水蒸气/乙苯(重量比)1.2条件下，测试结果列于表2。
表1
组成含量(份) Fe 2O 3 K 2O CeO 2 MoO 3 CaO TiO 2 第一部分K占总K量(％)
实施例1 74.68 12.16 10.62 1.25 1.29 0 70
实施例2 74.68 12.16 10.62 1.25 1.29 0 60
实施例3 74.68 12.16 10.62 1.25 1.29 0 80
实施例4 74.68 12.16 10.62 1.25 1.29 0 85
比较例1 74.68 12.16 10.62 1.25 1.29 0 100
比较例2 74.68 12.16 10.62 1.25 1.29 0 0
比较例3 74.68 12.16 10.62 1.25 1.29 0 20
比较例4 74.68 12.16 10.62 1.25 1.29 0 95
比较例5 74.68 12.16 10.62 1.25 1.29 0 50
实施例5 72.01 12.78 11.34 1.75 2.12 0 60
实施例6 79.95 6.01 13.01 0.51 0.52 0 65
实施例7 65.01 13.99 11.04 4.98 4.98 0 70
实施例8 73.07 12.02 9.01 3.56 2.34 0 75
实施例9 75.68 11.12 11.07 0.98 1.15 0 80
实施例10 66.72 12.98 12.86 3.28 4.11 0.05 85
实施例11 75.12 8.52 12.51 2.03 1.82 0 90
实施例12 78.99 10.71 8.05 1.24 1.01 0 72
实施例13 72.46 9.51 13.46 2.01 2.56 0 76
实施例14 75.32 10.16 10.62 2.21 1.69 0 68
实施例15 73.64 12.67 12.43 1.05 0.21 0 69
实施例16 72.81 11.95 12.71 1.16 1.35 0.02 82
实施例17 73.09 12.03 11.35 1.51 2.02 0 87
实施例18 72.94 11.33 11.38 1.52 2.83 0 74
实施例19 78.72 6.01 8.10 3.91 3.26 0 60
实施例20 67.59 13.99 10.37 3.78 4.27 0 90
表2
催化剂 晶相组成 K 2Fe 10O 16/K 2Fe 22O 34 转化率％ 选择性％
实施例1 K 2Fe 10O 16，K 2Fe 22O 34 1.6 80.4 94.9
实施例2 K 2Fe 10O 16，K 2Fe 22O 34 2.5 79.1 95.1
实施例3 K 2Fe 10O 16，K 2Fe 22O 34 1.5 80.3 94.8
实施例4 K 2Fe 10O 16，K 2Fe 22O 34 1.9 80.0 94.8
比较例1 α-Fe 2O 3，K 2Fe 22O 34 - 76.4 95.1
比较例2 α-Fe 2O 3，K 2Fe 22O 34 - 75.8 95.4
比较例3 α-Fe 2O 3，K 2Fe 10O 16，K 2Fe 22O 34 - 77.2 94.4
比较例4 α-Fe 2O 3，K 2Fe 10O 16，K 2Fe 22O 34 - 77.8 95.3
比较例5 K 2Fe 4O 7，K 2Fe 10O 16，K 2Fe 22O 34 - 77.5 94.4
实施例5 K 2Fe 10O 16，K 2Fe 22O 34 2.1 80.3 94.8
实施例6 K 2Fe 10O 16，K 2Fe 22O 34 2.9 78.8 94.9
实施例7 K 2Fe 10O 16，K 2Fe 22O 34 1.1 78.4 95.1
实施例8 K 2Fe 10O 16，K 2Fe 22O 34 1.8 79.6 95.0
实施例9 K 2Fe 10O 16，K 2Fe 22O 34 2.0 78.7 94.5
实施例10 K 2Fe 10O 16，K 2Fe 22O 34 1.8 79.3 94.8
实施例11 K 2Fe 10O 16，K 2Fe 22O 34 1.9 79.0 95.4
实施例12 K 2Fe 10O 16，K 2Fe 22O 34 1.2 78.6 95.1
实施例13 K 2Fe 10O 16，K 2Fe 22O 34 1.7 80.4 94.8
实施例14 K 2Fe 10O 16，K 2Fe 22O 34 1.4 79.8 95.0
实施例15 K 2Fe 10O 16，K 2Fe 22O 34 2.1 79.2 94.5
实施例16 K 2Fe 10O 16，K 2Fe 22O 34 1.6 81.2 95.1
实施例17 K 2Fe 10O 16，K 2Fe 22O 34 1.5 80.8 95.1
实施例18 K 2Fe 10O 16，K 2Fe 22O 34 1.3 80.4 94.8
实施例19 K 2Fe 10O 16，K 2Fe 22O 34 4.2 78.2 94.9
实施例20 K 2Fe 10O 16，K 2Fe 22O 34 0.8 78.0 94.8
实施例1-4中各原料的用量相同，只是第一部分钾源的加入量不同；由实施例1-4的结果可以看出，第一部分钾源的加入量不同，会改变催化剂中含铁钾的化合物的晶相组成。比较例1、2与实施例1-4中各原料的用量相同，只是钾源没有分步加入，其制得的催化剂中含有游离的α-Fe 2O 3物相，且不含有K 2Fe 10O 16物相，催化剂用于烷基芳烃脱氢反应中，反应物的转化率较低。比较例3-5与实施例1-4中各原料的用量相同，只是第一部分钾源的加入量不在本发明的范围内；其制得的催化剂中除了含有K 2Fe 10O 16和K 2Fe 22O 34物相外，还含有游离的α-Fe 2O 3物相或其他含铁钾的化合物的物相，催化剂用于烷基芳烃脱氢反应中，反应物 的转化率较低。由实施例1-4和比较例1-5的比较可知，采用本发明的制备方法，可以制备得到含有特殊物相的含铁钾的化合物的催化剂，该催化剂用于烷基芳烃脱氢反应中，反应物的转化率较高。
【实施例21】
按照实施例1的方法制备催化剂，催化剂的组成和晶相组成结果与实施例1相同。
将所得催化剂进行粉碎并筛分，将粒度为0.5-0.7mm的级别分离出来备用。将13.3毫升粒度为0.5-0.7mm的催化剂装入等温管式反应器中，在反应温度为620℃和1atm初始压力下对反应器连续供应14.6g/h乙苯和18.3g/h去离子水，对应于水蒸气/乙苯比例为1.25kg/kg或7.36mol/mol条件下进行催化剂的性能测定，测得的乙苯转化率为75.1％，苯乙烯选择性为95.2％。
乙苯转化率和苯乙烯选择性借助下列公式确定：
乙苯转化率(mol％)＝[(A×M f－B×M P)/(A×M f)]×100
苯乙烯选择性(mol％)＝[(D×M P－C×M f)/(A×M f－B×M P)]×(M EB/M ST)×100
其中：
A：反应器入口处乙苯浓度(重量％)；B：反应器出口处乙苯浓度(重量％)
C：反应器入口处苯乙烯浓度(重量％)；D：反应器出口处苯乙烯浓度(重量％)
M f：原料的平均摩尔质量；M P：产物的平均摩尔质量
M EB：乙苯的摩尔质量；M ST：苯乙烯的摩尔质量

Claims (20)

  1. 一种用于烷基芳烃脱氢的催化剂，所述催化剂包括含铁钾的化合物，所述含铁钾的化合物由K 2Fe 10O 16物相和K 2Fe 22O 34物相组成。
  2. 根据权利要求1所述的用于烷基芳烃脱氢的催化剂，其特征在于，所述含铁钾的化合物具有如下表所示的X射线衍射图案(XRD)，
    Figure PCTCN2019110935-appb-100001
  3. 根据权利要求2所述的用于烷基芳烃脱氢的催化剂，其特征在于，所述X射线衍射图案还包括如下表所示的X射线衍射峰，
    Figure PCTCN2019110935-appb-100002
  4. 根据权利要求1-3中任意一项所述的用于烷基芳烃脱氢的催化剂，其特征在于，所述含铁钾的化合物中K 2Fe 10O 16物相与K 2Fe 22O 34物相的质量比为1.1～3.3，优选为1.2～2.0。
  5. 根据权利要求1-4中任意一项所述的用于烷基芳烃脱氢的催化剂，其特征在于，所述催化剂中无游离α-Fe 2O 3物相。
  6. 根据权利要求1-5中任意一项所述的用于烷基芳烃脱氢的催化剂，其特征在于，以重量百分比计，所述催化剂包括以下组成：(a)65～80％的Fe 2O 3；(b)6～14％的K 2O；(c)9～13.5％的CeO 2；(d)0.5～5％的MoO 3；(e)0.2～5％的CaO。
  7. 一种用于烷基芳烃脱氢的催化剂的制备方法，包括以下步骤：
    1)将第一部分钾源和铁源、铈源、钼源、钙源、制孔剂干混，得催化剂前体I；
    2)将第二部分钾源用水溶解，加入催化剂前体I得到成品催化剂；
    所述催化剂以重量百分比计包括以下组成：(a)65～80％的Fe 2O 3；(b)6～14％的K 2O；(c)9～13.5％的CeO 2；(d)0.5～5％的MoO 3；(e)0.2～5％的CaO；催化剂中无游离α-Fe 2O 3物相；
    其中，以含K 2O的量计，第一部分钾源与第二部分钾源的重量总和为所需量的钾源的总重量，且第一部分钾源的重量为所需量的钾源总重量的60～90％。
  8. 根据权利要求7所述的用于烷基芳烃脱氢的催化剂的制备方法，其特征在于，所述步骤1)中的铁源以氧化铁红、氧化铁黄中的至少一种的形式加入；第一部分钾源以钾盐、氢氧化钾中的至少一种形式加入；铈源以铈盐的形式加入；钼源以钼盐、钼的氧化物中的至少一种形式加入；钙源以钙盐、氧化钙、氢氧化钙中的至少一种形式加入。
  9. 根据权利要求7或8所述的用于烷基芳烃脱氢的催化剂的制备方法，其特征在于，所述步骤2)中的第二部分钾源以氢氧化钾、碳酸钾中的至少一种形式加入。
  10. 根据权利要求7-9中任意一项所述的用于烷基芳烃脱氢的催化剂的制备方法，其特征在于，所述制备方法还包括如下步骤：
    3)对步骤2)得到的成品催化剂进行湿捏、挤条、成型、干燥和焙烧处理的步骤。
  11. 根据权利要求7-10中任意一项所述的用于烷基芳烃脱氢的催化剂的制备方法，其特征在于，所述步骤3)中的干燥温度为45～130℃，干燥时间为4～24小时。
  12. 根据权利要求7-11中任意一项所述的用于烷基芳烃脱氢的催化剂的制备方法，其特征在于，所述步骤3)中的焙烧为在200～400℃下焙烧5～12小时，然后在750～950℃下焙烧3～8小时。
  13. 根据权利要求7-12中任意一项所述的用于烷基芳烃脱氢的催化剂的制备方法，其特征在于，所述催化剂包括含铁钾的化合物，所述含铁钾的化合物由K 2Fe 10O 16物相和K 2Fe 22O 34物相组成。
  14. 根据权利要求7-13中任意一项所述的用于烷基芳烃脱氢的催化剂的制备方法，其特征在于，所述含铁钾的化合物具有如下表所示的X射线衍射图案(XRD)，
    Figure PCTCN2019110935-appb-100003
  15. 根据权利要求14所述的用于烷基芳烃脱氢的催化剂的制备方法，其特征在于，所述X射线衍射图案还包括如下表所示的X射线衍射峰，
    Figure PCTCN2019110935-appb-100004
  16. 根据权利要求13-15中任意一项所述的用于烷基芳烃脱氢的催化剂的制备方法，其特征在于，所述含铁钾的化合物中K 2Fe 10O 16物相与K 2Fe 22O 34物相的质量比为1.1～3.3，优选为1.2～2.0。
  17. 权利要求1～6中任意一项所述的催化剂或者按照权利要求7～16中任意一项所述的制备方法制备的催化剂在烷基芳烃脱氢制备烷烯基芳烃中的应用。
  18. 一种烷基芳烃脱氢方法，包括使含烷基芳烃的原料物流与权利要求1～6中任意一所述的催化剂或者按照权利要求7～16中任意一所述的制备方法制备的催化剂接触得到含烷烯基芳烃反应物流的步骤。
  19. 根据权利要求18所述的烷基芳烃脱氢方法，其特征在于，所述烷基芳烃包括乙苯、甲乙苯、二乙苯或多烷基苯中的至少一种。
  20. 根据权利要求18或19所述的烷基芳烃脱氢方法，其特征在于，所述烷基芳烃为二乙苯或乙苯。
PCT/CN2019/110935 2018-10-16 2019-10-14 用于烷基芳烃脱氢的催化剂及其制备方法 Ceased WO2020078303A1 (zh)

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CN115959967A (zh) * 2021-10-11 2023-04-14 中国石油化工股份有限公司 一种乙苯脱氢制苯乙烯的方法
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