WO2013159251A1 - Catalyseur pour la préparation du styrène par déshydrogénation de l'éthylbenzène et son procédé de préparation - Google Patents

Catalyseur pour la préparation du styrène par déshydrogénation de l'éthylbenzène et son procédé de préparation Download PDF

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WO2013159251A1
WO2013159251A1 PCT/CN2012/000625 CN2012000625W WO2013159251A1 WO 2013159251 A1 WO2013159251 A1 WO 2013159251A1 CN 2012000625 W CN2012000625 W CN 2012000625W WO 2013159251 A1 WO2013159251 A1 WO 2013159251A1
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catalyst
parts
oxide
hours
catalyst according
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Chinese (zh)
Inventor
颉伟
姚文君
印会鸣
王继龙
林宏
李晓艳
范国宁
柏介军
王涛
常晓昕
黄德华
仇国贤
边虎
胡晓丽
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • B01J23/85—Chromium, molybdenum or tungsten
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    • B01J23/85—Chromium, molybdenum or tungsten
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    • 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
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    • 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
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    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2523/24—Chromium, molybdenum or tungsten
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    • C07C2523/745—Iron
    • 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
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    • 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 invention relates to a chemical catalyst and a preparation method thereof, in particular to an oxide catalyst for preparing styrene for dehydrogenation of ethylbenzene and a preparation method thereof.
  • the series of catalysts are generally prepared by a dry mixing-kneading-extruding-forming-drying-baking process, wherein three stages are formed by high-temperature calcination, namely, Ce0 2 , a-Fe 2 0 3 and Fe 2 . 0 3 interacts with K 2 0 to form potassium ferrite KFe0 2 and/or KFe réelle 0 17 crystal phase.
  • KFe0 2 and/or KFe Korean 0 17 crystal phase.
  • Stabilizer The more the content of the phase formed in the catalyst, the better the degree of crystallization, the higher the activity of the catalyst, and the better the stability.
  • U.S. Patent No. 6,551,958 B1 reports a catalyst system having a basic composition of Fe-K-Ce-Mg.
  • German patent DE3821431 reports a catalyst with K 2 Fe 22 0 34 as the main active phase obtained by calcination at 900 ° C.
  • the catalyst is prepared by using special iron oxide and any potassium-containing compound by mixing-baking- It was washed with water to prepare a thin layered article having a diameter of 0.5 to 5 ⁇ m.
  • Chinese patent CN1323767A reported a catalyst system with a basic composition of Fe-K-Ce-Mo-Mg.
  • the catalyst has KFe0 2 as the main crystal phase, which improves the activity and regeneration performance of the catalyst and prolongs the service life.
  • Chinese patent CN1207330A reports the method of pre-forming KFeschreib 0 17 by impregnating iron oxide paste with KOH solution for calcination.
  • Chinese patent CN1765753A reports the method of pre-forming potassium ferrate KFeschreib0 17 by dry powder mixing method, and controlling grain size at the same time.
  • Chinese patent CN1765495 A reported the use of potassium perovskite KFegrass0 17 and calcium oxide or magnesium oxide components in cerium oxide and molybdenum oxide, which better solved the introduction of potassium ferrate KFeflower0 17 into the catalyst composition. The problem of catalyst performance changes.
  • the dehydrogenation catalyst disclosed in the above prior art needs to be improved in activity and stability, and it is required to further extend the service life of the catalyst.
  • the invention provides a potassium ferrate potassium K 2 Fe 1 () 0 16 (high heterogeneity crystal phase) and a K 2 Fe 22 0 34 (normal hexagonal crystal phase) combination for the main active phase for ethylbenzene Oxidation of styrene by dehydrogenation
  • the catalyst has good activity, stability and long service life, and is suitable for long-cycle operation.
  • the invention also discloses a preparation method of the catalyst.
  • the present invention discloses a catalyst for dehydrogenation of ethylbenzene to styrene, which comprises the following components in terms of a catalyst mass of 100 parts:
  • the mass content ratio of K 2 Fe 1() 0 16 to K 2 Fe 22 0 34 is from 1.0 to 3.5:1, preferably from 2.0 to 3.0:1.
  • the catalyst of the present invention potassium ferrate is added in the form of ⁇ 0 16 and K 2 Fe 22 0 34 , and the particle size of K 2 Fe 10 O 16 and K 2 Fe 22 0 34 is 0. ⁇ , It is preferably 0.5 to 5 m.
  • the catalyst of the present invention is added in the form of an oxide or a salt, and the content of Ce 2 0 3 is 1 to 12 parts, preferably 5 to 12 parts; tungsten and/or molybdenum is added in the form of an oxide or a salt, W0 3 And/or the content of Mo0 3 is 1 to 10 parts, preferably 1 to 7 parts; calcium and/or magnesium is added in the form of an oxide or a salt, and the content of CaO and/or MgO is 1 to 10 parts, preferably 1 to 5 parts.
  • the catalyst according to the present invention may also contain 2 0 5, Mn0 2, Sn0 2, Co 2 0 3, La one or more 2 0 3, Ti0 2, Zr0 2, Hf0 2 auxiliaries V, added 001 ⁇ 0. 5 ⁇ The amount of the amount of the 0.001 ⁇ 0. 5 parts.
  • the catalyst may also contain other commonly used functional auxiliaries, such as 1 ⁇ 10. Parts of reinforcing cement and / or 1 to 10 parts of the porogen sodium carboxymethyl cellulose.
  • the main active phase potassium ferrate in the catalyst of the present invention is mainly added in the form of a combination of ? 6
  • the catalyst of the present invention based on the basic composition of Ce-Mo (or W)-Ca (or Mg), introduces potassium ferrate, potassium ferrate to ⁇ 6 1() 0 16 and K 2 Fe 22 0 34 in the form of complex was added, so that a suitable proportion of Fe-K catalyst, the dehydrogenation reaction is prevented during the catalyst component ⁇ : 20 migration and loss, so that the catalyst exhibits excellent activity and selectivity, but also greatly reduced
  • the rate of deactivation of the catalyst increases its stability and service life.
  • the invention also discloses a preparation method of the catalyst: the components of the catalyst are first dry mixed for 1-5 hours, kneaded by adding deionized water for 1-5 hours, and after forming, dried, activated and calcined for 10-24 hours.
  • the finished catalyst is carried out by a general method, and the invention is not particularly limited, for example, drying at 60-150 ° C, and activation at 200-1000 ° C; likewise, the shape of the catalyst is not particularly limited in the present invention, and the recommended catalyst is preferably Extrusion pelletizing, such as a cylindrical catalyst of 0 (2.8-3.3) mmx (5-7) mm.
  • the potassium ferrate K 2 Fe 1 () 0 16 is pre-formed before the preparation of the catalyst, and the pre-forming method is as follows: Fe 2 0 3 and K 2 C0 3 are in accordance with K 2 Fe 1Q 0 16 after uniformly mixing a stoichiometric ratio, 100 ° C for 2 hours and then calcined at 900-1200 ° C 2-6 hours, and finally by jet milling, ball milling or the like can be obtained in the potassium ferrate diameter less ⁇ ⁇ 6
  • Potassium ferrate K 2 Fe 22 0 34 is also known, and K 2 Fe 22 0 34 and KF ei l 0 17 are one substance, for example, in CN1765495A, a potassium ferrate K 2 Fe 22 0 is introduced in the composition.
  • preparation of styrene ethylbenzene dehydrogenation catalyst 34, wherein the potassium ferrate K 2 Fe 22 0 34 pre-generated before the preparation of the catalyst: the Fe 2 0 3 and K 2 C0 3 in a ratio of the calculated amount of uniformly mixed, added deionized Water was prepared into a paste, dried at 120 ° C for 4 hours, and then calcined at 900 ° C for 4 hours.
  • a method for preparing potassium ferrate K 2 Fe 22 0 34 is also disclosed in CN1765753A: firstly, an iron oxide, a hydroxide or a salt thereof and a powder of potassium oxide, hydroxide or a salt thereof are uniformly mixed. It is extruded, shaped, dried and fired at a temperature of 800-1100 °C.
  • Fig. 1 is an XRD chart of a dehydrogenation catalyst of Example 5 of the present invention.
  • the abscissa is the diffraction angle 2 ⁇ , and the ordinate is the diffraction intensity;
  • Figure 2 is a SEM photograph of the dehydrogenation catalyst of Example 5 of the present invention, wherein the grain size of the micron-sized potassium ferrate*3 ⁇ 4 ⁇ 1() 0 16 and K 2 Fe 22 0 34 is 0.5 by SEM-20 scanning electron microscopy. ⁇ 5.0 microns.
  • the raw material manufacturers used in the preparation process of the dehydrogenation catalyst of the present invention are: ethylbenzene, a synthetic rubber plant product of Lanzhou Petrochemical Company; iron oxide, a product of Shijiazhuang Tenglong iron oxide pigment factory; potassium oxide, Shenyang Jinnuo Chemical Co., Ltd. Products; yttrium oxide, Weihai Dexinxin New Material Co., Ltd.; Molybdenum Oxide, Tianjin Tongxin Chemical Factory; Tungsten Oxide, Kunshan Xingbang Tungsten & Molybdenum Technology Co., Ltd.
  • the above raw materials are all industrial grade products. Magnesium oxide, chemically pure, Shanghai Dunhuang chemical plant products; Calcium oxide, analytical grade, Shanghai Fengxian Fengcheng Reagent Factory products. Other raw materials are commercially available.
  • K 2 Fe 22 0 34 93.3 g of iron oxide red and 7.2 g of potassium carbonate were dry-mixed in a kneader for 1 hour, and after mixing uniformly, deionized water was added to prepare a paste, which was dried at 120 ° C for 4 hours. Then, it was placed in a muffle furnace and calcined at 900 ° C for 4 hours to obtain potassium ferrate K 2 Fe 22 0 34 .
  • K 2 Fe 10 O 16 302.1 g of iron oxide red and 51.2 g of potassium carbonate were dry-mixed in a kneader for 1 hour, uniformly mixed, dried at 100 ° C for 2 hours, and then calcined at 1120 ° C for 3 hours.
  • Potassium ferrate K 2 Fe 1() 0 16 can be obtained.
  • 331.0 g of K 2 Fe 1 ( )O l6 , 95.4 g of K 2 Fe 22 0 34 , 20.1 g of ammonium tungstate, 16.4 g of calcium oxide, and 25.0 g of carboxymethyl cellulose were dry-mixed in a kneader for 2 hours.
  • the preparation method of potassium ferrate and catalyst in Example 2 is the same as that in Example 1, except that K 2 Fe 10 O 16 275.9 g, K 2 Fe 22 0 34 136.6 g, ammonium molybdate 19.6 g, calcium oxide 12.5 g, 10 g of magnesium oxide, 0.1 g of vanadium pentoxide, 0.05 g of zirconium dioxide, 0.05 g of cerium oxide, 128.7 g of cerium nitrate (added after water dissolution), 0.1 g of cobalt nitrate (added after water dissolution:), 0.05 g of cerium nitrate ( After water-soluble, it is added, dried at 120 ° C for 3 hours, and then calcined at 340 ° C for 1 hour in a muffle furnace, calcined at 600 ° C for 4 hours, calcined at 850 2 for 2 hours, and then naturally cooled to obtain a finished product.
  • the catalyst was evaluated for activity, and the test results are shown in
  • the preparation method of potassium ferrate and catalyst in Example 3 is the same as that in Example 1, except that K 2 Fe 1 () 0 16 339.2 g, K 2 Fe 22 0 34 112.3 g, ammonium molybdate 8.8 g, calcium oxide 9.5. ⁇ , 0.05 g of manganese dioxide, 0.05 g of tin dioxide, 0.1 g of titanium dioxide, 11.0 g of carboxymethyl cellulose, 18.0 g of cement, 83.7 g of lanthanum nitrate (added after water dissolution), and the prepared catalyst was prepared.
  • the activity evaluation, the test results are shown in Table 2.
  • Example 4 The preparation method of potassium ferrate and catalyst in Example 4 is the same as that in Example 1, except that K 2 Fe 1 () 0 16 232.6 g, K 2 Fe 22 0 34 191.3 g, calcium carbonate 8.9 g, ammonium molybdate 25.6 Gram, dry-mixing in a kneader for 3 hours, dissolving 132.9 g of lanthanum nitrate in deionized water and adding it to a kneader to evaluate the activity of the prepared catalyst.
  • the test results are shown in Table 2.
  • Example 5 The catalyst preparation method of Example 5 was the same as that of Example 1, except that 3 ⁇ m of K 2 Fe 10 O 16 300.6 g, 3 ⁇ m of K 2 Fe 22 0 34 121.4 g, ammonium tungstate 18.1 g, and magnesium carbonate 11.0 g. 10.9 g of calcium oxide, 10.0 g of carboxymethylcellulose, 10.0 g of cement, and 122.6 g of lanthanum nitrate (added after water dissolution), and the activity of the prepared catalyst was evaluated. The test results are shown in Table 2.
  • Example 6 Example 6
  • Example 6 The preparation method of potassium ferrate and catalyst in Example 6 is the same as that in Example 1, except that K 2 Fe l() 0 16 315.3 g, K 2 Fe 22 O 34 110.6 g, ammonium molybdate 9.2 g, ammonium tungstate 8.7 g, calcium oxide 7.5 g, magnesium oxide 5.0 g, lanthanum nitrate 123.1 g (water soluble after addition).
  • the material was dry-mixed in a kneader for 2.5 hours, dissolved in water and kneaded for 1.5 hours, and the cylindrical catalyst after extrusion and stripping was dried at 100 ° C for 4 hours, and then calcined at 580 ° C in a muffle furnace. After 4 hours of calcination at 820 ° C for 4 hours, the temperature was naturally lowered, that is, the finished catalyst was prepared for activity evaluation, and the test results are shown in Table 2.
  • Potassium ferrate and catalyst were prepared according to the method of Example 3, except that potassium ferrate was only added.
  • the K 2 Fe 22 0 34 451.5 g was evaluated in the same manner as in Example 3, and the evaluation results are shown in Table 2.
  • 900 g of acicular a-Fe 2 0 3 having an aspect ratio of about 0.4 ⁇ m and an aspect ratio of about 5 was added to the suspension by adding 200 g of potassium carbonate and 200 g of aqueous cesium carbonate (molecular formula). It is represented by Ce 2 (C0 3 ) 3 *xH 2 0 , wherein the cerium content is 40% by weight of the total weight, 40 gram of calcium carbonate, 40 gram of tungsten oxide and 60 gram of basic magnesium carbonate (the molecular formula is 4MgC0 3 , Mg(OH) 2 4H 2 0 means equivalent to 50 g of MgCO 3 ) to 2000 mL of water.
  • the suspension was spray-dried, and the obtained powder was mixed with 120 mL of water for 30 minutes, and then converted into a paste, which was formed into a cylindrical solid of 3 mm ⁇ lcm by extrusion, and dried at 100 ° C for 3 hours, and placed in a muffle furnace.
  • the catalyst is obtained by calcination at 300 ° C for 2 h and then calcination at 760 ° C.
  • the catalyst was evaluated in the same manner as in Example 3, and the evaluation results are shown in Table 2.
  • the ethylbenzene dehydrogenation catalyst for styrene in the present invention is suitable for the dehydrogenation of cumene and p-methylisopropylbenzene to isopropenylbenzene and p-methylisopropenylbenzene.
  • the catalyst prepared by the above method was subjected to evaluation of the activity of the catalyst in an isothermal fixed bed reactor, and the evaluation process is briefly described as follows:
  • the ethylbenzene and the deionized water are respectively input into the preheating mixer through the metering pump, mixed and vaporized, and then enter the reactor, and the reactor is heated by the heating wire to make the reactor reach the predetermined temperature.
  • the reaction tube is a stainless steel tube and can be filled with 100 mL of catalyst.
  • the dehydrogenated product enters the cooler through a chiller, and is subjected to gas-liquid separation through a gas-liquid separator.
  • the liquid product is separated from the oil and water by a water-oil separator, and the oil phase composition is analyzed by gas chromatography.
  • the amount of ethylbenzene in the raw material + the amount of styrene in the raw material Styrene selectivity amount of layer styrene - the original amount of ethylene ⁇ ⁇ wake up
  • phase composition of the catalyst in the present invention is determined by XRD, and the measurement is carried out on a D8 ADVANCE type X-ray powder diffractometer of Bruker, Germany. Test conditions: tube voltage 40 kV, current 40 mA, Cu Kal wavelength, scanning range 4-70° , scanning speed 6 min, temperature 25 ° C.
  • Micron-sized potassium ferrate The grain sizes of ⁇ 6 1() 0 16 and K 2 Fe 22 0 34 were determined by scanning electron microscopy (SEM) of PHILIPS XL-20.
  • the rapid aging test is a quick means to judge the stability performance of the catalyst. It means that the catalyst is rapidly deactivated in a short period of time under extreme reaction conditions, and the slower the deactivation rate, indicating that the catalyst stability is better.
  • the aging conditions in the present invention are: reaction temperature 640 ° C, water ratio (weight) 1.50, liquid space velocity 6.0
  • the catalyst aging test data is shown in Table 3.

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Abstract

La présente invention concerne un catalyseur destiné à la préparation du styrène par déshydrogénation de l'éthylbenzène et son procédé de préparation. En prenant la masse du catalyseur comme 100 parties en masse, le catalyseur comprend les constituants suivants : a) de 45 à 75 parties de K2Fe10O16 ; b) de 20 à 50 parties de K2Fe22O34 ; c) de 1 à 12 parties d'oxyde de cérium, calculées en se basant sur Ce2O3 ; d) de 1 à 10 parties d'oxyde de molybdène et/ou d'oxyde de tungstène, calculées en se basant sur MoO3 et/ou WO3 ; et e) de 1 à 10 parties d'oxyde de calcium et/ou d'oxyde de magnésium, calculées en se basant sur CaO et/ou MgO ; le rapport en masse entre K2Fe10O16 et K2Fe22O34 étant situé dans la plage allant de 1,0 à 3,5:1. Le catalyseur présente de meilleures propriétés de résistance au dépôt de carbone et de résistance à la réduction, a de bonnes activité et stabilité, et une longue durée de vie.
PCT/CN2012/000625 2012-04-24 2012-05-09 Catalyseur pour la préparation du styrène par déshydrogénation de l'éthylbenzène et son procédé de préparation Ceased WO2013159251A1 (fr)

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RU2726125C1 (ru) * 2020-01-10 2020-07-09 Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор" Катализатор для дегидрирования алкилароматических углеводородов
CN115957775A (zh) * 2021-10-11 2023-04-14 中国石油化工股份有限公司 一种用于乙苯脱氢制苯乙烯的催化剂及其制备方法和应用
CN119259067A (zh) * 2023-07-05 2025-01-07 中国石油化工股份有限公司 一种乙苯脱氢催化剂及其制备方法和应用

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CN108203365B (zh) * 2016-12-16 2021-01-29 中国石油天然气股份有限公司 用于乙苯脱氢制苯乙烯的方法
CN111056910B (zh) * 2018-10-16 2023-04-07 中国石油化工股份有限公司 用于烷基芳烃脱氢制烷烯基芳烃的方法
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CA3116597C (fr) * 2018-10-16 2024-06-11 China Petroleum & Chemical Corporation Catalyseur pour la deshydrogenation d'un hydrocarbure aromatique d'alkyle et son procede de preparation
CN111054369B (zh) * 2018-10-16 2021-05-11 中国石油化工股份有限公司 用于烷基芳烃脱氢的催化剂
CN112239389B (zh) * 2019-07-19 2023-04-07 中国石油化工股份有限公司 烷烯基芳烃的制造方法
CN112973715B (zh) * 2019-12-13 2023-06-30 中国石油天然气股份有限公司 乙苯脱氢制苯乙烯催化剂的制备方法
CN115475624B (zh) * 2021-06-16 2024-01-30 中国石油化工股份有限公司 一种烷基芳烃脱氢催化剂及其制备方法和应用

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