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WO1997026990A1 - A catalyst for producing alkyl-benzene and method of producing alkyl-benzene using the catalyst - Google Patents

A catalyst for producing alkyl-benzene and method of producing alkyl-benzene using the catalyst Download PDF

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Publication number
WO1997026990A1
WO1997026990A1 PCT/CN1997/000002 CN9700002W WO9726990A1 WO 1997026990 A1 WO1997026990 A1 WO 1997026990A1 CN 9700002 W CN9700002 W CN 9700002W WO 9726990 A1 WO9726990 A1 WO 9726990A1
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Prior art keywords
catalyst
zeolite
weight
benzene
nickel
Prior art date
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Ceased
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PCT/CN1997/000002
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English (en)
French (fr)
Inventor
Yongcheng Fang
Bin Zhou
Debin Dai
Guixiu Jiang
Jin Xiong
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Priority claimed from CN96116225A external-priority patent/CN1053175C/zh
Priority claimed from CN96116227A external-priority patent/CN1055876C/zh
Application filed by Sinopec Shanghai Research Institute of Petrochemical Technology, China Petrochemical Corp filed Critical Sinopec Shanghai Research Institute of Petrochemical Technology
Priority to EP97900192A priority Critical patent/EP0818238A4/en
Publication of WO1997026990A1 publication Critical patent/WO1997026990A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/068—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/12—Noble metals
    • B01J29/126—Y-type faujasite
    • 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
    • C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
    • 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/48—Silver or gold
    • C07C2523/50—Silver
    • 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
    • C07C2523/74—Iron group metals
    • C07C2523/745—Iron
    • 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
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • C07C2529/068—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • C07C2529/12—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • C07C2529/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
    • C07C2529/22—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/44—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
    • C07C2529/74—Noble metals
    • 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 present invention relates to a catalyst for preparing alkylbenzene and a method for preparing alkylbenzene by using the catalyst. More specifically, the present invention relates to a zeolite catalyst bearing metal palladium and a co-catalyst and a method for preparing isopropylbenzene and ethylbenzene using the same method.
  • Ethylbenzene and cumene are important organic chemical raw materials.
  • cumene is the main intermediate compound for the production of phenanthrene, propylene, and (1-methylstyrene), and it is also used as an auxiliary component of aviation gasoline to increase the octane number of gasoline.
  • Propylene and benzene synthesize cumene
  • catalysts include crystalline and amorphous silica, boron fluoride, alumina and phosphoric acid, aluminum trichloride, and solid phosphoric acid catalysts. These traditional catalytic processes have severe corrosion, large equipment investment, Three wastes and many other shortcomings.
  • EP0272830 reports a new technology for making isopropylbenzene using Y-type zeolite molecular sieve.
  • the patented technology overcomes the shortcomings of using traditional catalysts, but it also has poor catalyst stability, short regeneration cycle (for example, it needs to be regenerated after 700 hours of driving), low reaction space velocity (for example, only 0.10 hours as propylene) and equipment. Disadvantages such as low production capacity.
  • An object of the present invention is to provide a catalyst for preparing alkylbenzene with good activity, selectivity and stability, which comprises:
  • Another object of the present invention is to provide a method for preparing alkylbenzene with improved production capacity and long catalyst regeneration period, which is included in the liquid phase at 150-250 X: temperature, 0.7-4.0MPa reaction pressure and 4-20 benzene. : Under the condition of olefin molar ratio, an olefin is reacted with benzene to prepare an alkylbenzene. The reaction is performed in the presence of a catalyst containing the following components:
  • a catalyst for preparing alkylbenzene which comprises: a) a zeolite having a silicon to aluminum ratio of 2-20; and a zeolite supported thereon;
  • Gold is and optionally one or more metals selected from gallium, nickel, cobalt, silver, and iridium.
  • the zeolite used in the catalyst of the present invention may be a Y-type zeolite, a P-type zeolite, a mordenite, or a ZSM-5 zeolite, and the silica-to-aluminum ratio (molar ratio of silica to alumina) of the zeolite used is 2 to 20, Preferably 2-8.
  • the catalyst of the present invention contains 0.003% to 3.0% by weight, preferably 1% to 1.5% by weight of metal palladium relative to zeolite, and 0 to 3.0% by weight, Youyi 0.5 ⁇ 2.0% (weight) one or more metals selected from gallium, nickel, cobalt, silver and iridium.
  • the catalyst of the present invention can be prepared as follows:
  • the acids and ammonium salts used to treat the zeolite can be commonly used acids and ammonium salts, such as hydrochloric acid, acid, nitric acid, or phosphoric acid, and ammonium chloride, ammonium sulfate, ammonium phosphate, and the like.
  • the catalyst of the present invention is suitable for preparing alkylbenzene, and is particularly preferably used for preparing cumene and ethylbenzene.
  • a method for preparing alkylbenzene is provided.
  • the method is performed in the liquid phase in the presence of the catalyst of the present invention.
  • the reaction temperature is 150-250 V, preferably 180-210.
  • the reaction pressure is 0.7-4.0. MPa, preferably 2.0-3.5MPa, and the molar ratio of benzene to olefin is 4-20.
  • the method of the present invention is suitable for preparing low-carbon alkylbenzenes, such as alkylbenzenes having alkyl groups with less than 6 carbon atoms, and is particularly suitable for preparing isopropylbenzyl and ethylbenzene.
  • the method of the present invention is often performed in a fixed bed manner.
  • the catalyst of the present invention has good activity, selectivity and stability.
  • the method for preparing alkylbenzene using the catalyst of the present invention has high liquid phase space velocity and large production capacity.
  • Examples 1 to 7 are catalyst preparation examples.
  • Example 2 100 g of NaY-type zeolite raw powder having a silicon-aluminum ratio of 2.0 was exchanged with an acid, and then exchanged with an ammonium salt, so that the Na + ion content in the zeolite was less than 0.1 ° /. .
  • the zeolite was dried and ground uniformly.
  • the zeolite and alumina were kneaded at a ratio of 90:10, and pressure-molded into a shape of "j) 1.6 mm.
  • Example 2 100 g of NaY-type zeolite raw powder having a silicon-aluminum ratio of 2.0 was exchanged with an acid, and then exchanged with an ammonium salt, so that the Na + ion content in the zeolite was less than 0.1 ° /. .
  • the zeolite was dried and ground uniformly.
  • the zeolite and alumina were kneaded at a ratio of 90:10, and pressure-molded into a shape of
  • zeolite raw powder having a silica-alumina ratio of 5.0 100 g was exchanged with an acid, and then exchanged with an ammonium salt, so that the Na + ion content in the zeolite was less than 0.1%.
  • the zeolite treated as above was impregnated with a PdCl 2 solution, a Ni (N0 3 ) 2 solution, and a Co (N0 3 ) 2 solution, so that the metal palladium content in the catalyst was 0.003% by weight and the metal nickel content was 0.5% by weight. 2.
  • the content of metallic cobalt is 0.2% by weight. After drying and roasting, the grinding is uniform.
  • the metal-bearing zeolite and alumina were kneaded in an amount of 90:10, and pressure-molded into a shape of ⁇ 1.6 ⁇ .
  • the metal-bearing zeolite and alumina are kneaded in an amount of 90:10, and pressure-molded into a shape of ⁇ . ⁇ .
  • the catalyst was prepared according to Example 3, but the zeolite used was a P-type zeolite with a silica-alumina ratio of 14.0, and the impregnated metal was 1.2% by weight of palladium and 0.1 of gallium. / «(Weight), nickel 0.3% (weight), Cobalt 0.7% (weight), silver 0.2% (weight).
  • the metal-loaded zeolite and alumina were kneaded in an amount of 90:10, and pressed into a shape of ⁇ M.6mm.
  • the catalyst was prepared according to Example 3, but the zeolite used was a mordenite with a silica-alumina ratio of 15, and the impregnated metal was 1.5% by weight of palladium, 0.1% by weight of gallium, 0.8% by weight of nickel, and 0.2% of cobalt by weight. ), 0.1% by weight of iridium.
  • the metal-bearing zeolite and alumina were kneaded in an amount of 90:10, and pressure-molded into a shape of ⁇ . ⁇ .
  • the catalyst was prepared according to Example 3, but the zeolite used was a ZSM-5 zeolite with a silica-alumina ratio of 20.
  • the impregnated metal was palladium 2.0% by weight, nickel 0.4% by weight, cobalt 0.2% by weight, and silver 0.1%. (Weight), iridium 0.1% (weight).
  • the metal-bearing zeolite and alumina were kneaded in an amount of 90:10, and pressure-molded into a shape of ⁇ . ⁇ .
  • the metal-supported zeolite and alumina were kneaded in an amount of 90:10, and pressure-molded into a shape of (M.6mm).
  • Examples 8-14 are examples of catalyst evaluation.
  • Example 2 21 grams of the catalyst obtained in Example 1 was placed in a fixed-bed reactor. At a temperature of 182 1C and a pressure of 2.0 MPa, benzene and propylene were reacted through the catalyst bed, in which the wrong feed amount was 702 g / The feeding amount of propylene was 42 g / h. Based on propylene, the weight liquid space velocity was 2.0 hours. After 1,000 hours of investigation, no propylene was detected in the reaction product, and the activity and selectivity of the catalyst did not decrease. Its cumene selectivity is 98.7%.
  • Example 3 21 grams of the catalyst obtained in Example 3 was placed in a fixed bed reactor. At a temperature of 210 and a pressure of 2.6 MPa, benzene and propylene were allowed to react through the catalyst bed, wherein the bulk feed rate was 702 g / hr and the propylene feed rate was 42 g / hr. After 1000 hours of investigation, no propylene was detected in the reaction product, and the activity and selectivity of the catalyst did not decrease. Its cumene selectivity is 97.1%.
  • Example 12 21 grams of the catalyst obtained in Example 4 was placed in a fixed bed reactor. The reaction was carried out under the conditions of Example 10. After 1000 hours of reaction, no propylene was detected in the reaction product, and the activity and selectivity of the catalyst did not decrease. Its cumene selectivity is 96.4%.
  • Example 12 21 grams of the catalyst obtained in Example 4 was placed in a fixed bed reactor. The reaction was carried out under the conditions of Example 10. After 1000 hours of reaction, no propylene was detected in the reaction product, and the activity and selectivity of the catalyst did not decrease. Its cumene selectivity is 96.4%.
  • Example 12 21 grams of the catalyst obtained in Example 4 was placed in a fixed bed reactor. The reaction was carried out under the conditions of Example 10. After 1000 hours of reaction, no propylene was detected in the reaction product, and the activity and selectivity of the catalyst did not decrease. Its cumene selectivity is 96.4%.
  • Example 12 21 grams of the catalyst obtained in Example 4 was placed in a fixed bed reactor. The reaction was carried out under
  • Example 5 84 grams of the catalyst prepared in Example 5 was placed in a fixed bed reactor. The reaction was performed under the conditions of Example 10. After 45 hours of reaction, no propylene was detected in the reaction product, and the activity and selectivity of the catalyst did not decrease. Its cumene selectivity is 95.2%.
  • Example 6 168 grams of the catalyst prepared in Example 6 was placed in a fixed bed reactor. The reaction was carried out under the conditions of Example 10. After 20 hours of reaction, no propylene was detected in the reaction product, and the activity and selectivity of the catalyst did not decrease. Its cumene selectivity is 96.9%.
  • Example 7 21 grams of the catalyst prepared in Example 7 was placed in a fixed bed reactor. At temperature 250 At a pressure of 4.0 MPa, benzene and ethylene were allowed to react through the catalyst bed. The benzene feed was 400 g / h and the ethylene feed was 10.5 g / h. Based on ethylene, the weight liquid space velocity was 0.5. After 1,000 hours of investigation, the reaction was not detected. Ethylene was not detected in the reaction product, and the activity and selectivity of the catalyst did not decrease. The ethylbenzene selectivity was 90% (calculated as ethyl group).

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Description

制备烷基苯的催化剂及采用该催化剂
制烷基笨的方法 发明领域
本发明涉及制备烷基苯的催化剂及采用该催化剂制备烷基苯的方 法， 更具体地说， 本发明涉及负栽金属钯及助催化剂的沸石催化剂及采 用它来制备异丙笨及乙苯的方法。
发明背景
乙苯、 异丙苯等是重要的有机化工原料。 例如， 异丙苯是生产苯盼、 丙 ¾和(1 -甲基苯乙烯的主要中间化合物， 同时也是用作航空汽油的辅 助成分， 以增加汽油的辛烷值。 丙烯和苯合成异丙苯的催化剂有多种， 传统的催化剂有结晶和非结晶二氧化硅、 氟化硼、 氧化铝和磷酸、 三氯 化铝以及固体磷酸催化剂等。 这些传统催化工艺均存在腐蚀严重、 设备 投资大、 三废多等缺点. 近年来， 随着分子筛研究的曰益深入， 人们着 眼于开发利用沸石催化剂的制备异丙苯的新技术. EP0272830 报道了 利用 Y型沸石分子筛制取异丙笨的新技术.该专利技术克服了使用传统 催化剂的不足，但其也存在催化剂稳定性差、再生周期短（例如开车 700 小时就需再生） ， 反应空速低（例如以丙烯计空速仅 0.10小时 " ) 及装 置生产能力低等缺点.
发明的公开
本发明的一个目的在于提供一种活性、 选择性及稳定性均好的制备 烷基笨的催化剂， 它包含：
a)硅铝比（二氧化硅 /三氧化二铝的摩尔比） 为 2 - 20的沸石； 和 栽于其上的
b)金属钯及任选加入的一种或一种以上选自镓、 镍、 钴、 银和 /或铱 的金属.
本发明的另一个目的在于提供一种生产能力提高、 催化剂再生周期 长的烷基苯制备方法，包括在液相中，于 150 - 250 X：温度， 0.7-4.0MPa 反应压力及 4 - 20苯： 烯烃摩尔比条件下， 使烯烃与苯反应制备烷基 笨， 反应在包含下列组分的催化剂存在下进行：
a)硅铝比为 2 - 20的沸石； 和栽于其上的 b)金属钯及任选加入的一种或一种以上选自镓、 镍、 钴、 银及铱的 金属。
实施发明的最佳方式
在本发明的一个方面， 提供了一种制备烷基笨的催化剂， 它包含： a)硅铝比为 2 ― 20的沸石； 和栽于其上的
b)金爲 及任选加入的一种或一种以上的选自镓、 镍、 钴、 银及铱 的金属。
用于本发明催化剂的沸石可为 Y 型沸石、 P型沸石、 丝光沸石、 ZSM - 5型沸石， 所用沸石的硅铝比（二氧化硅与三氧化二铝的摩尔 比） 为 2 - 20 , 优选 2 - 8 .
在本发明的一个优选实施方案中， 相对于沸石， 本发明的催化剂含 有 0.003%~3.0% (重量），优选 1 % - 1.5% (重量）的金属钯， 以及 0 ~ 3.0% (重量） ， 优逸 0.5〜2.0 % (重量） 一种或一种以上选自镓、 镍、 钴、 银及铱的金属.
本发明的催化剂可按如下方法制备：
a)将硅铝比为 2 - 20的沸石用酸、 铵交换， 使金属钠离子与钾离子 在沸石骨架中的总含量在 0.1%以下， 然后烘干； 和
b)在沸石上浸渍金属钯及任选的镓、 镍、 钴、 银和 /或铱等金属。 用于处理沸石的酸及铵盐可为常用的酸及铵盐， 例如盐酸、 疏酸、 硝酸或磷酸等， 及氯化铵、 硫酸铵、 磷酸铵等。
本发明的催化剂适用于制备烷基笨， 特别优选用于制备异丙苯、 乙 苯。
在本发明的另一个方面， 提供一种制备烷基笨的方法， 该方法在本 发明的催化剂存在下于液相进行， 反应温度为 150 _ 250 V , 优选 180 - 210 反应压力为 0.7-4.0MPa , 优选 2.0-3.5MPa , 笨与烯烃的摩 尔比为 4 - 20 .
本发明的方法适用于制备低碳烷基笨， 例如带 6个碳以下烷基的烷 基苯， 特别适用于制备异丙笨、 乙苯。
本发明的方法常以固定床方式进行.
本发明的催化剂活性、 选择性和稳定性均好， 采用该催化剂的本发 明制备烷基苯的方法液相空速高、 生产能力大。
下面通过实施例详细说明本发明。 实施例 1 - 7
实施例 1 - 7为催化剂制备实施例。
实施例 1
取 100克硅铝比为 2.0的 NaY型沸石原粉用酸进行酸交换， 然后用 铵盐进行铵交换， 使沸石中的 Na +离子含量小于 0.1 %。 将经处理的沸 石用 PdCI2溶液浸渍， 使催化剂的金属钯含量为 0.09% (重量）， 烘干、 焙烧， 研磨均匀。 以 90:10的比例将负栽金属的沸石与氧化铝捏和， 压 力成型为 φ1·6ιηπι的形状.
比较例 1
取 100g硅铝比为 2.0的 NaY型沸石原粉用酸交换， 然后用铵盐交 换， 使沸石中的 Na+离子含量小于 0.1°/。。 将上述沸石烘干， 研磨均匀. 将沸石与氧化铝以 90 : 10的比例捏和， 压力成型为《j)1.6mm的形状。 实施例 2
取 100克硅铝比为 5.0的 NaY型沸石原粉用酸交换， 然后用铵盐交 换，使沸石中的 Na +离子含量小于 0.1 %。将经上述处理的沸石用 PdCl2 溶液、 Ni(N03)2溶液、 Co(N03)2溶液浸渍， 使催化剂中金属钯含量为 0.003% (重量）、 金属镍含量为 0.5% (重量）、 金属钴含量为 0.2% (重 量） ， 烘干、 焙烧后， 研磨均匀.
将负栽金属的沸石和氧化铝以 90 ： 10 的量捏和， 压力成型为 φ1.6ηιπι的形状.
实施例 3
取 100克硅铝比为 3.0的 NaY型沸石原粉用酸交换， 再用铵盐交 换， 使沸石中的 Na +离子含量小于 0.1%, 将经上述处理的沸石浸渍 PdCl2溶液、 Ga(N03)2溶液、 Ni(N03)2溶液、 AgN03溶液、 Ir(N03)2 溶液， 使催化剂中金属钯含量为 0.8% (重量）、 金属镓含量为 0.1% (重 量） 、 金属镍含量为 0.3% (重量） ， 金属银含量为 0.1 % (重量） 、 金 属铱含量为 0.2 % . 烘干、 焙烧后， 研磨均匀。
将负栽金属的沸石和氧化铝以 90 ： 10 的量捏和， 压力成型为 ψΐ.όιηιη的形状.
实施例 4
按实施例 3制备催化剂， 但所用沸石为硅铝比为 14.0的 Ρ型沸石， 浸渍的金属为钯 1.2 % (重量） 、 镓 0.1。/« (重量） 、 镍 0.3% (重量） 、 钴 0.7% (重量）、银 0.2% (重量）.将负栽金属的沸石与氧化铝以 90 : 10的量捏和， 压力成型为 <M.6mm的形状.
实施例 5
按实施例 3制备催化剂， 但所用沸石为硅铝比为 15的丝光沸石， 浸渍的金属为钯 1.5 % (重量）、 镓 0.1% (重量） 、 镍 0.8 % (重量） 、 钴 0.2% (重量） 、 铱 0.1% (重量） .
将负栽金属的沸石与氧化铝以 90 ： 10 的量捏和， 压力成型为 φΐ.όιηπι的形状。
实施例 6
按实施例 3制备催化剂， 但所用沸石为硅铝比为 20的 ZSM - 5沸 石. 浸渍的金属为钯 2.0 % (重量） 、 镍 0.4 % (重量） 、 钴 0.2 % (重 量） 、 银 0.1 % (重量） 、 铱 0.1 % (重量） 。
将负栽金属的沸石与氧化铝以 90 ： 10 的量捏和， 压力成型为 φΐ.όιηηι的形状.
实施例 7
取 100克硅铝比为 5.0的 NaY型沸石原粉， 用酸交换， 再用铵盐交 换， 使沸石中的 Na +离子含量小于 0.1。/。. 将经上述处理的沸石浸渍 PdCl2溶液、 Ni(N03)2溶液、 Co(N03)2溶液，使催化剂中金属钯含量为 0.95% (重量）、 金属镍含量为 0.5% (重量）、 金属钴含量为 0.75% (重 量） ， 烘干后， 焙烧， 研磨均匀.
将负载金属的沸石和氧化铝以 90 ： 10 的量捏和， 压力成型为 (M.6mm的形状。
实施例 8 - 14
实施例 8 - 14为催化剂评价实施例.
实施例 8
取实施例 1的催化剂 21g置于固定床反应器中，在 195 ：、 2.6MPa 条件下， 使苯和丙烯通过催化剂床层进行反应， 其中苯进料量为 468克 /小时， 丙烯进料量为 42克 /小时， 以丙烯计算， 重量液体空速为 2.0小 时 。 该反应经 1000小时考察， 反应产物中未检测到丙烯， 催化剂的活 性、 选择性未下降， 异丙笨的选择性为 98.0% (以丙基计算） 。
比较例 2
取比较例 1制得的催化剂 21g置于固定床反应器中.在温度 195 压力 2.6MPa条件下， 使笨和丙烯通过催化剂床层进行反应， 其中苯的 进料量为 468克 /小时， 丙烯进料量为 42克 /小时， 以丙烯计算， 重量液 体空速为 2.0小时—，. 该反应经过 100小时考察， 经分析， 异丙苯选择 性为 97.8%. 至反应经过 140小时考察 ， 反应产物中开始检测到了丙 烯， 说明此时催化剂已基本失活。
实施例 9
取实施例 1制得的催化剂 21 克置于固定床反应器中. 在温度 182 1C , 压力 2.0MPa条件下， 使苯和丙烯通过催化剂床层进行反应， 其中 笨的进料量为 702克 /小时、 丙烯进料量为 42克 /小时， 以丙烯计算， 重 量液体空速为 2.0小时 该反应经过 1000小时考察， 反应产物中没有 检测到丙烯， 催化剂的活性、 选择性没有下降。 其异丙苯选择性为 98.7 % 。
实施例 10
取实施例 3制得的催化剂 21 克置于固定床反应器中。 在温度 210 压力 2.6MPa条件下， 使苯和丙烯通过催化剂床层进行反应， 其中 笨的进料量为 702克 /小时， 丙烯进料量为 42克 /小时。 该反应经过 1000 小时考察 ， 反应产物中没有检测到丙烯， 催化剂的活性、 选择性没有 下降。 其异丙苯选择性为 97.1%。
实施例 11
取实施例 4制得的催化剂 21克置于固定床反应器中。 按实施例 10 的条件进行反应。 反应经过 1000 小时后考察， 反应产物中没有检测到 丙烯， 催化剂的活性、 选择性没有下降。 其异丙苯选择性为 96.4 % 。 实施例 12
取实施例 5制得的催化剂 84克置于固定床反应器中。 按实施例 10 的条件进行反应. 反应经过 45 小时后考察， 反应产物中没有检测到丙 烯， 催化剂的活性、 选择性没有下降。 其异丙苯选择性为 95.2 % .
实施例 13
取实施例 6制得的催化剂 168克置于固定床反应器中。按实施例 10 的条件进行反应。 反应经过 20 小时后考察， 反应产物中没有检测到丙 烯， 催化剂的活性、 选择性没有下降。 其异丙苯选择性为 96.9 % 。
实施例 14
取实施例 7制得的催化剂 21 克置于固定床反应器中。 在温度 250 、 压力 4.0MPa条件下， 使苯和乙烯通过催化剂床层进行反应， 其中 苯的进料量为 400克 /小时、 乙烯进料量为 10.5克 /小时， 以乙烯计算， 重量液体空速为 0.5小时 该反应经过 1000小时考察， 反应产物中没 有检测到乙烯， 催化剂的活性、 选择性没有下降， 其乙苯选择性为 90 % (按乙基计算） 。

Claims

权 利 要 求
1.一种用于制备烷基苯的烷基化催化剂， 包括
(a)硅铝比（二氧化硅与三氧化二铝的摩尔比） 为 2 - 20的沸石； 和栽于沸石上的
(b)金属钯及任选加入的一种或一种以上选自镓、 镍、 钴、 银和铱的 金属.
2.根据权利要求 1的催化剂， 其中含有 0.003。/« - 3.0% (重量） 的 金属钯及 0 - 3.0 % (重量） 的一种或一种以上选自镓、 镍、 钴、 银和 铱的金属。
3.根据权利要求 1的催化剂， 其中所述沸石为硅铝比为 2 - 8的沸 石。
4.根据权利要求 1的催化剂，其中所述沸石为 Y型沸石、 P型沸石、 丝光沸石和 /或 ZSM - 5沸石。
5.根据权利要求 3的催化剂， 其中所述沸石为 Y型沸石。
6.根据权利要求 1的催化剂， 其中含有 1 ~ 1.5 % (重量） 的金属 钯.
7.根据权利要求 1的催化剂， 其中含有 0.5~2。/« (重量）一种或一种 以上选自镓、 镍、 钴、 银和铱的金属.
8.—种制备烷基苯的方法， 包括在液相中， 于 150 - 250 温度， 0 7-4.0MPa反应压力及 4 - 20苯： 烯烃摩尔比条件下， 使烯烃与苯反 应制备烷基笨， 反应在含有下列组分的催化剂存在下进行：
a)硅铝比为 2 - 20的沸石； 和栽于其上的
b)金属钯及任选加入的一种或一种以上选自镓、 镍、 钴、 银及铱的 金属。
9.根据权利要求 8的方法， 其中所述烷基苯为异丙苯， 所述烯烃为 丙婦.
10.根据权利要求 8的方法， 其中所述烷基笨为乙苯， 所述烯烃为乙 烯,
11.根据权利要求 8的方法， 其中反应温度为 180 - 210 。
12.根据权利要求 8的方法， 其中反应压力为 2.0 - 3.5MPa 。
PCT/CN1997/000002 1996-01-25 1997-01-08 A catalyst for producing alkyl-benzene and method of producing alkyl-benzene using the catalyst Ceased WO1997026990A1 (en)

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CN96116225A CN1053175C (zh) 1996-01-25 1996-01-25 制备烷基苯的工艺
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EP0449485A1 (en) * 1990-03-28 1991-10-02 Mobil Oil Corporation Thermally stable noble metal containing zeolite catalyst
US5149679A (en) * 1990-05-01 1992-09-22 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Gallium-containing zeolite catalysts

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US5149679A (en) * 1990-05-01 1992-09-22 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Gallium-containing zeolite catalysts

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