CN103930205A - 具有离子改性粘合剂的催化剂 - Google Patents

具有离子改性粘合剂的催化剂 Download PDF

Info

Publication number
CN103930205A
CN103930205A CN201280024806.3A CN201280024806A CN103930205A CN 103930205 A CN103930205 A CN 103930205A CN 201280024806 A CN201280024806 A CN 201280024806A CN 103930205 A CN103930205 A CN 103930205A
Authority
CN
China
Prior art keywords
catalyst
adhesive
zeolite
ion
ion modification
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201280024806.3A
Other languages
English (en)
Inventor
S·钦塔
J·佩拉蒂
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.)
Fina Technology Inc
Original Assignee
Fina Technology Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fina Technology Inc filed Critical Fina Technology Inc
Publication of CN103930205A publication Critical patent/CN103930205A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
    • 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
    • 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
    • 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
    • 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
    • B01J29/072—Iron group metals or copper
    • 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
    • B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/087—X-type faujasite
    • 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
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • 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
    • B01J29/14—Iron group metals or copper
    • B01J29/143—X-type faujasite
    • 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
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • 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
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/163—X-type faujasite
    • 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
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
    • B01J29/24—Iron group metals or copper
    • 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
    • B01J29/505—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
    • B01J29/52—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing iron group metals, noble metals or copper
    • B01J29/56—Iron group metals or copper
    • 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
    • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
    • B01J29/58—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
    • B01J29/605—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
    • B01J29/61—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789 containing iron group metals, noble metals or copper
    • B01J29/63—Iron group metals or copper
    • 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
    • B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
    • B01J29/64—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7053—A-type
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7057—Zeolite Beta
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7607—A-type
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7676—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7807—A-type
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • B01J29/82—Phosphates
    • B01J29/83—Aluminophosphates [APO compounds]
    • 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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • 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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • 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
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • 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
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the 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
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • 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
    • C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/18—Arsenic, antimony or bismuth
    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/20—Vanadium, niobium or tantalum
    • C07C2523/22—Vanadium
    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/32—Manganese, technetium or rhenium
    • C07C2523/34—Manganese
    • 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
    • C07C2523/72—Copper
    • 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
    • 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
    • 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
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一烷基化催化剂，所述烷基化催化剂具有一沸石催化剂组分和为所述沸石催化剂组分提供支撑的粘合剂组分。所述粘合剂是离子改性粘合剂，所述离子改性粘合剂可包括选自下组的金属离子：Co、Mn、Ti、Zr、V、Nb、K、Cs、Ga、B、P、Rb、Ag、Na、Cu、Mg、Fe、Mo、Ce及其组合。该金属离子减少所述沸石催化剂组分的酸性位点的数目。该金属离子可占基于所述离子改性粘合剂总重量的0.1至50重量%。可选的，所述离子改性粘合剂可以以占基于所述催化剂总重量的1至80重量%的数量存在。

Description

具有离子改性粘合剂的催化剂
相关申请的交叉参考
本申请是2008年12月29日提交的申请号为12/345,593的部分继续申请。
领域
本发明一般的涉及粘合剂，所述粘合剂与催化剂如沸石一起用于烷基化和其他反应。更具体的，本发明涉及甲苯与甲醇和/或甲醛使用含粘合剂的催化剂时的烷基化。
背景
沸石是一种晶体铝硅酸盐催化剂，已熟知它可用于多个应用。沸石已用于脱烷基化、烷基转移、异构化、裂解和歧化过程等。它高度有序的结构由通过氧原子连接的四面体AlO4 -4和SiO4 -4组成，形成了孔径通常在至数量级的孔系统。这些孔创建了高内部表面区域，并使得沸石可基于分子的形状和尺寸选择性的吸附某些分子同时排出其他分子。因此，沸石可归类为分子筛。沸石还可称为“形状选择性催化剂”。沸石的小孔可将反应限制在某些过渡态或某些产物，防止产生不符合所述孔轮廓或尺寸的形状。
沸石的孔一般被水分子和阳离子占据。阳离子用于平衡由氧负离子四面体配位的三价铝阳离子产生的负电荷。沸石可把自身的阳离子与其他阳离子交换；例如可把铝离子与钠离子交换。在一些离子交换的形式，如沸石的氢形式，该催化剂是强酸性的。该酸性活性位点可用于烷基化和其他许多反应。例如，沸石可替代对反应器有腐蚀和损坏作用的传统的三氯化铝或其他液体酸性催化剂，用作弗里德尔-克拉夫兹（Friedel-Crafts）烷基化的固体酸性催化剂。
可使用沸石的烷基化反应之一是甲苯与甲醇和/或甲醛形成苯乙烯的烷基化。苯乙烯（也称作乙烯基苯），是具有化学分子式C6H5CHCH2的有机化合物。单体苯乙烯可聚合形成聚苯乙烯。聚苯乙烯是一种塑料，可形成许多有用的产品，包括模制产品和泡沫产品，所有这些都增加了对苯乙烯产量的需求。
在苯乙烯的制备过程中，可使用沸石催化剂。用于苯乙烯制备的沸石可归类为非均相催化剂，因为它处于与反应物不同的相。沸石催化剂是固体且通常用氧化铝或二氧化硅粘合剂负载以提高其在反应器床的机械稳定性。相反，反应物可以是液体、蒸汽或超临界相。通过烷基化的苯乙烯制备已通过甲苯在气相中进行，但也可使用所需温度更低的液相烷基化。液相烷基化在某些情况下更加经济，以及可降低不需要的副产物的产量。
体相沸石催化剂通常包含大量酸性位点。存在烷基化反应时，这些酸性位点和典型烷基化沸石催化剂的整体形状选择性可导致不需要的副产物如二甲苯的产生。
因此，需要减少用于苯乙烯生产中的沸石催化剂的酸性位点数量。还需要使用能提高对苯乙烯选择性的烷基化催化剂。
概述
本发明在其许多实施方式中涉及用于通过甲苯的烷基化制备苯乙烯的一催化剂。本发明的一实施方式包括烷基化催化剂，所述烷基化催化剂具有催化剂组分和为所述沸石催化剂组分提供机械支撑的粘合剂组分。本实施方式中所述粘合剂是离子改性粘合剂，所述离子改性粘合剂包括选自下组的金属离子：Co、Mn、Ti、Zr、V、Nb、K、Cs、Ga、B、P、Rb、Ag、Na、Cu、Mg、Fe、Mo、Ce及其组合。该金属离子减少所述沸石催化剂组分的酸性位点的数目。该金属离子可占基于所述离子改性粘合剂总重量的0.1至50重量%。所述离子改性粘合剂可以以占基于所述催化剂总重量的1至80重量%的数量存在。
在一实施方式中，所述离子改性粘合剂上的金属离子可改变所述催化剂的空间结构。所述粘合剂可包括非晶体的二氧化硅或氧化铝。所述催化剂可以是分子筛催化剂，也可以是沸石。在一实施方式中，Cs可以以硅酸铯的形式存在于所述粘合剂中。
在一实施方式中，一种通过甲苯的烷基化制备苯乙烯的方法包括：将甲苯和C1源提供至一个或多个反应器以及使所述甲苯与所述C1源在所述一个或多个反应器中反应以形成包括乙基苯和苯乙烯的产物流。所述C1源可选自下组：甲醇和甲醛及其组合。在本方法中，所述一个或多个反应器中的至少一反应器包括催化剂组分，所述催化剂组分包括为所述催化剂组分提供机械支撑的粘合剂组分，其中所述粘合剂组分减少所述沸石催化剂上酸性位点的数目。所述粘合剂组分可包括非晶体的二氧化硅或氧化铝。可选的，铯以硅酸铯的形式存在于所述粘合剂中。
在一实施方式中，其自身或与其他任意实施方式组合，所述粘合剂组分是离子改性粘合剂。所述离子改性粘合剂可改变所述催化剂的形状选择性，因此与使用非离子改性粘合剂相比可增加产物选择性。所述离子改性粘合剂可包括占基于所述离子改性粘合剂总重量的0.1至50重量%数量的金属离子。可选的，所述离子改性粘合剂可包括占基于所述离子改性粘合剂总重量的0.1至20重量%数量的金属离子。金属离子可选自下组：Co、Mn、Ti、Zr、V、Nb、K、Cs、Ga、B、P、Rb、Ag、Na、Cu、Mg、Fe、Mo、Ce及其组合。
在一实施方式中，其自身或与其他任意实施方式组合，所述离子改性粘合剂以占基于所述催化剂总重量的1至80重量%的数量存在于所述催化剂中。可选的，所述离子改性粘合剂以占基于所述催化剂总重量的5至60重量%的数量存在于所述催化剂中。可选的，所述催化剂是一分子筛催化剂。在一非限制性实施方式中，所述催化剂是沸石。
还在本发明的另一实施方式中，用于制备沸石烷基化催化剂的方法包括：将金属离子通过初湿法(incipient wetness)添加至粘合剂以形成离子改性粘合剂以及将所述离子改性粘合剂与沸石结合以形成沸石聚集体。进一步加工所述沸石聚集体以形成沸石烷基化催化剂。所述沸石烷基化催化剂可用在用于甲苯与甲醇烷基化的反应床。在本实施方式中，所述离子改性粘合剂减少所述沸石上的酸性位点的数目以及所述离子改性粘合剂上的金属离子改变所述沸石的空间结构。金属离子可选自下组：Co、Mn、Ti、Zr、V、Nb、K、Cs、Ga、B、P、Rb、Ag、Na、Cu、Mg、Fe、Mo、Ce及其组合，以及在一实施方式中，所述离子改性粘合剂可包括硅酸铯并改变所述沸石的形状选择性。
其他可行的实施方式包括两个或更多本发明上述的实施方式。在一个实施方式中，所述方法包括上述所有的实施方式以及可以以任意顺序进行的各种方法。
附图简述
图1显示了通过甲醛和甲苯的反应制备苯乙烯的流程图，其中所述甲醛首先在分离的反应器中通过甲醇的脱氢化或氧化制备且随后与甲苯反应以制备苯乙烯。
图2显示了通过甲醛和甲苯的反应制备苯乙烯的流程图，其中甲醇和甲苯被进料至反应器，其中所述甲醇被转化为甲醛以及所述甲醛与甲苯反应以制备苯乙烯。
详述
本发明涉及提高烷基化过程的选择性，具体为甲苯与甲醇的烷基化（ATM）过程。更具体的，本发明涉及用于催化剂如沸石催化剂的粘合剂的改性，以减少所述催化剂上的酸性位点数量。此外，所述粘合剂可通过添加活性金属物质改性，该方式可改变所述沸石催化剂的形状选择性，从而抑制副产物的形成以及提高苯乙烯选择性。此外，本发明的包括优化在所述催化剂形式中的粘合剂组分，从而提高所述催化剂的活性和选择性。
沸石和其他催化剂的粉末形式因为缺乏机械稳定性，可能不适于在反应器中使用，使得很难进行烷基化和其他所需的反应。为了使催化剂变得适用于所述反应器，可将所述沸石催化剂组分与粘合剂结合以形成聚集体，如沸石聚集体。粘合剂改性的沸石如沸石聚集体，具有比未与粘合剂结合或粉末形式的沸石更强的机械稳定性和强度。可将所述聚集体加工如成形或挤出成适于反应床的形式。所述粘合剂可如所希望的抗拒温度和机械应力，以及理想的不干扰吸附至所述催化剂的反应物。所述粘合剂可形成尺寸比所述催化剂的孔大很多的大孔，提供改进的反应物至所述催化剂的扩散入口。
适于本发明的粘合剂材料包括，但不限于：二氧化硅、氧化铝、二氧化钛、氧化锆、氧化锌、氧化镁、氧化硼、二氧化硅－氧化铝、氧化铝－氧化镁、氧化铬－氧化铝、氧化铝－氧化硼、二氧化硅－氧化锆、硅胶、粘土、高岭土、蒙脱土、改性粘土、类似物质，及其任意组合。最常用的粘合剂是非晶态的二氧化硅和氧化铝，包括γ-、η-和θ-氧化铝。应指出，粘合剂可与多种不同催化剂一起使用，包括需要机械支撑的各种形式的沸石和非沸石催化剂。
根据本发明，改性所述粘合剂从而它提供机械支撑并执行粘合剂的其他典型功能，以及减少所述催化剂上的酸性位点的数目。还根据本发明，通过添加金属改性所述粘合剂从而它改变所述催化剂的形状选择性。本发明的所述粘合剂可由氧化铝或二氧化硅或类似的非晶态材料组成且包括金属离子或类似物质。所述活性金属离子可以是下述非限制性离子的离子：Co、Mn、Ti、Zr、V、Nb、K、Cs、Ga、B、P、Rb、Ag、Na、Cu、Mg、Fe、Mo、Ce、或类似物质如金属氧化物、纳米颗粒、或混合的金属氧化物相。在另一实施方式中，所述活性金属离子可包括选自下组的离子：Ce、Cu、P、Cs、B、Co、Ga、或其组合。也可使用未列出的其他类似的金属离子和物质、以及任何列出的和为列出的金属离子和类似物质的组合。
如本文所使用，术语“金属离子”用于包括能添加至粘合剂并且能使所述粘合剂降低所述被负载的催化剂的酸性或提高其碱性或碱性强度又不给所述粘合剂负载的所述催化剂带来有害影响或在反应条件下致使明显的副产物形成的所有活性金属离子和类似物质如金属氧化物、纳米颗粒、或混合的金属氧化物相。此外，如本文所使用，术语“离子改性粘合剂”指用金属离子改性的、用于催化剂的粘合剂。
所述金属离子可以以占所述粘合剂重量的0.1%至50%，可选的0.1%至20%，可选的0.1%to5%的数量添加至所述粘合剂。所述金属离子可通过本领域技术人员已知的任何方法添加至所述粘合剂。可使用的方法之一是初湿法浸润，其中所述金属离子前体被添加至液相溶液，该液相溶液倾倒至所述粘合剂上。静置一特定时期后，干燥和烧结所述粘合剂，从而去除水且所述金属离子沉积在所述粘合剂表面上。然后，可通过本领域技术人员已知的任何方法将所述离子改性粘合剂与催化剂混合，如通过复合、淤浆混合等。可通过挤出或一些其他方法将所述混合物成形为如小丸、片剂、圆柱、苜蓿叶、哑铃、对称的和非对称的多叶状（polylobates）、小球的形式或适于反应床的其它任意形式。然后，通常干燥和烧结成形的形式。可在100℃至200℃的温度范围内干燥。可在基本上干燥的环境中，在400℃至1000℃温度范围内进行烧结。所述得到的催化剂聚集体可包括占所述催化剂聚集体重量1%至80%，可选的5%至50%，可选的10%至30%的离子改性粘合剂。粘合剂占所述催化剂的重量百分数可根据所述催化剂使用的反应区的温度而改变。一般的，所述粘合剂能抗拒更高的温度，以及对于更高温度的应用可添加更高百分数的粘合剂。例如，在将沸石用于烷基化反应的应用中，约50%沸石和50%粘合剂可用于更高温度烷基化催化剂床，以及约75%沸石和25%粘合剂可用于更低温度烷基化催化剂床。
在一具体实施方式中，可将铯促进剂以硅酸铯如Cs6Si10O23的形式与粘合剂结合。硅酸铯晶体可通过玻璃Cs2O·4SiO2的结晶制备。硅酸铯晶体可用于在所述催化剂中创建受限空间，从而所述催化性的活性位点可选择性的达到所需反应物。在一实施方式中，铯被添加至二氧化硅－氧化铝材料的二氧化硅部分，因此得到连接至二氧化硅－氧化铝材料的硅酸铯部分。所述硅酸铯是大分子，当添加至所述二氧化硅部分时，创建能容纳催化性活性位点的空腔。这些空腔是甲苯和C1源能进入、反应和离开的受限空间。这些空腔可改变所述过程的选择性，导致产物选择性提高。
对于本发明，通过离子改性粘合剂负载和保护的所述催化剂可以是沸石，但也可以是非沸石。沸石一般是多孔结晶铝硅酸盐，且它可天然的或合成的形成。形成合成沸石的方法之一是二氧化硅、氧化铝、钠或其它碱金属氧化物、和有机模板剂的水热煮解。每一反应物的数量以及包括不同的金属氧化物可导致多种不同的合成的沸石组合物。此外，通常通过多种方法改变沸石以调节其特征如孔尺寸、结构、活性、酸度和二氧化硅/氧化铝摩尔比。因此，可得到许多不同形式的沸石。如本文所使用，与粘合剂组分相反，沸石催化剂组分可指沸石或非沸石组合物。沸石催化剂组分可指在添加所述粘合剂组分以形成聚集体如沸石聚集体之前的沸石或非沸石组合物。
适于本发明的沸石材料可包括硅酸盐基沸石和非晶态的化合物如八面沸石、丝光沸石、菱沸石、菱钾沸石、斜发沸石、毛沸石、高硅沸石（sihealite）等。硅酸盐基沸石由交替的SiO2和MOx四面体构成，其中M是选自元素周期表（新IUPAC）第1-16族的元素。这些类型的沸石具有4-、6-、8-、10-、或12-元氧环通道。本发明的沸石的例子之一可包括八面沸石。其它合适的沸石材料包括：沸石A,沸石L,沸石β,沸石X,沸石Y,ZSM-5,MCM-22,和MCM-41。在一更具体的实施方式中，所述沸石是X－类沸石。还可考虑的可选的分子筛是类沸石材料如晶体硅铝磷酸盐(SAPO)和铝磷酸盐(ALPO)。
改变沸石的另一方法是通过离子交换。例如，可通过β沸石与铵离子的离子交换制备沸石的氢形式。金属离子还可通过离子交换或其它方法包括进入沸石。此外，所述沸石的二氧化硅/氧化铝比例可通过许多方法如蒸汽或酸洗脱来提高二氧化硅/氧化铝比例而改变。提高二氧化硅相对于氧化铝的数量具有提高所述催化剂疏水性的影响。所述二氧化硅/氧化铝比例范围可为小于0.5至500或更大。除了沸石催化剂以外，一些催化剂也可与本发明的粘合剂一起使用，包括落入分子筛和/或固体酸性催化剂总体类目的催化剂。
因此，多种沸石和非沸石可与本发明的离子改性粘合剂联用。前两段列举的各种催化剂并不是穷指清单，但用于显示可使用离子改性粘合剂的催化剂的类型。催化剂的选择取决于所述催化剂使用的反应类型和反应条件。本领域技术人员可选择任意能满足目标反应需求的沸石或非沸石催化剂，前提是离子改性粘合剂可用于负载所述催化剂和减少所述催化剂上的酸性位点数目和/或改变所述催化剂的形状选择性以提高产物选择性。
一旦所述催化剂被所述离子改性粘合剂负载，所述离子改性粘合剂的金属离子可连接至所述催化剂的催化性活性酸性位点，因此降低所述催化剂的酸性或其酸性位点的总数目。当所述金属离子连接至所述催化剂的酸性位点时，所述催化剂的结构尺寸也可改变。所述催化剂改变的结构尺寸可导致所述催化剂具有改变的形状选择性。在一实施方式中，一旦所述催化剂被所述离子改性粘合剂负载，所述离子改性粘合剂的金属离子可连接至所述催化剂的催化性活性酸性位点，因此改变所述催化剂的结构尺寸，导致所述催化剂具有改变的形状选择性。
可通过用化学化合物处理分子筛沸石以抑制外部酸性位点和最小化环位置的芳香烷基化，实现侧链烷基化选择性的提高。提高侧链烷基化选择性的另一方法可以是给所述催化剂结构施加限制以促进侧链烷基化。在一实施方式中，本发明的一实施方式使用的所述催化剂是碱性或中性催化剂。
适于本发明的催化反应系统可包括被改性以用于侧链烷基化选择性的一个或多个所述沸石或非晶态材料。一非限制性例子可以是用下述一个或多个促进的沸石：Co、Mn、Ti、Zr、V、Nb、K、Cs、Ga、B、P、Rb、Ag、Na、Cu、Mg、Fe、Mo、Ce或其组合。在一个实施方式中，所述沸石可由Ce、Cu、P、Cs、B、Co、Ga或其组合中的一种或多种促进。一般的，所述促进剂与沸石内的Na交换。所述促进剂也可以以堵塞的方式连接至所述沸石。在一实施方式中，促进剂的数量通过产生小于0.5摩尔％环烷基化产物如从甲苯和C1源偶联反应中的二甲苯所需的量决定的。
在一实施方式中，所述催化剂包含超过基于该催化剂总重量0.1重量%的至少一种促进剂。在另一个实施方式中，所述催化剂包含最高至5重量%的至少一种促进剂。在另一个实施方式中，所述催化剂包含1至3重量%的至少一种促进剂。
可使用离子改性粘合剂的过程包括，但不限于：氧化、还原、吸附、二聚、寡聚、聚合、醚化、酯化、水合、脱水、冷凝、缩醛化、去烷基化、环化、烷基化、脱氢化、加氢脱烷基化、烷基转移、异构化、裂解、歧化、加氢异构化、加氢裂解、芳香化，及使用分子筛催化剂且希望减少酸性位点总数量的任意过程。在一实施方式中，所述离子改性粘合剂用于烷基化和脱氢化过程。
烷基化反应可有许多不同形式。一般的，当由一个或多个碳原子组成的烷基化剂添加至可烷基化底物时，发生烷基化。可用于烷基化反应的烷基化剂一般是烯烃。烯烃可以是短链的如乙烯、丙烯、丁烯和戊烯，或者它可以是具有更高碳原子数目的长链。它可以是α-烯烃、异构化烯烃、支链烯烃或其混合物。除了烯烃以外，烷基化剂包括炔、烷基卤化物、醇、醚和酯。在一些情况下，所述烷基化剂在引入所述反应床前用稀释剂稀释。特别是对于乙烯，可使用如惰性或非反应性气体如氮气的稀释剂。在一实施方式中，在稀释的进料流中，所述稀释剂的浓度可大于所述烷基化剂的浓度，例如约70%稀释剂和30%烷基化剂。
可烷基化底物通常为不饱和烃或芳烃。如果所述可烷基化底物是芳香化合物，它可以是未取代的、单取代的或多取代的，且其具有直接结合至芳环或一些其他位点的、允许烷基化发生的至少一氢原子。所述芳环可以是苯环或包括多于一个芳环的化合物，如萘、蒽、并四苯、苝、蔻(coronene)和菲。具有芳香特征但环包括一杂原子的化合物也可使用，前提是它们不会引起不需要的副反应。所述芳环的取代基可以是烷基、羟基、烷氧基、芳基、烷芳基、芳氧基、环烷基、卤素和/或不会干扰烷基化反应且包括1至20碳原子的其它基团。可通过烷基化剂烷基化的芳香底物包括：苯、甲苯、二甲苯、联苯、乙苯、异丙苯、正丙苯、丁苯、戊苯、己基苯、庚基苯、辛基苯、壬基苯、十二烷基苯、十五烷基苯、己基甲苯、壬基甲苯、十二烷基甲苯、十五烷基甲苯、α-甲基萘、均三甲苯、均四甲苯、甲基异丙苯、假枯烯、二乙苯、异戊苯、异己苯、五乙苯、五甲苯、四乙苯、四甲苯、三乙苯、三甲苯、丁基甲苯、二乙基甲苯、乙基甲苯、丙基甲苯、二甲基萘、乙基萘、二甲基蒽、乙基蒽、甲基蒽、二甲基菲、菲酚、甲酚、苯甲醚、苯乙醚、苯丙醚、苯丁醚、苯戊醚、苯己醚，它们的任意异构体等等。在一实施方式中，用于烷基化的芳香底物是甲苯。在另一实施方式中，本发明的所述烷基化反应包括甲苯与甲醇和/或甲醛的烷基化。
甲苯烷基化的反应物通常包括甲醇作为烷基化剂以及甲苯作为可烷基化底物。一般的，甲苯与C1源反应以制备苯乙烯和乙苯。所述C1源可包括甲醇或甲醛或两者的混合物。可选的，甲苯可与下面的一个或多个反应：福尔马林、三噁烷、甲福尔赛(methylformcel)、多聚甲醛、甲缩醛及二甲醚。在另一实施方式中，所述C1源选择下组：甲醇、甲醛、福尔马林（H2CO在水和MeOH中的37%-50%溶液）、三噁烷（1，3，5－三噁烷）、甲福尔赛（H2CO在甲醇中的55%溶液）、多聚甲醛和甲缩醛（二甲氧基甲烷），及其组合。
虽然该反应中甲苯和C1源的摩尔比为1:1，但进料流的比例不限于本发明且可根据操作条件和反应体系的效率改变。若将过量的甲苯或C1源加料进反应区，则可后续的分离未反应的部分，并使其循环到所述过程中。在一实施方式中，甲苯与C1源的比例范围是100:1至1:100之间。在另一实施方式中，甲苯与C1源的比例范围为50:1至1:50，20:1至1:20，10:1至1:10，5:1至1:5，2:1至1:2之间。
反应器和分离器的操作条件因体系而异，可随进料组成和产物流组成变化。用于将甲醇转变成甲醛以及甲苯与甲醛反应的反应器将在升高的温度下操作。温度范围的非限制性例子为250℃至750℃,可选的300℃至500℃,可选的375℃至450℃。压力范围的非限制性例子为0.1大气压至70大气压,可选的0.1大气压至35大气压,可选的0.1大气压至10大气压,可选的0.1大气压至5大气压。
图1是上述苯乙烯制备过程的一实施方式的简化的流程图。在一实施方式中，第一反应器（2）是脱氢反应器或者氧化反应器。在一实施方式中，这个反应器被设计用来将第一甲醇进料（1）转化为甲醛。然后，将该反应器的气体产物(3)送至气体分离单元(4)，在这里甲醛与任何未反应的甲醇和不需要的副产物分离。然后，可使任何未反应的甲醇（6）循环回到第一反应器（2）。将副产物（5）与清洁的甲醛（7）分离。
在一实施方式中，第一反应器（2）是生成甲醛和氢气的脱氢反应器，而所述分离单元（4）是能够从产物流（3）除去氢气的膜。
在另一实施方式中，第一反应器（2）是氧化反应器，生成包含甲醛和水的产物流（3）。然后，可将包含甲醛和水的产物流（3）送至第二反应器（9），不需要分离单元（4）。
然后，所述甲醛进料流(7)在第二反应器(9)中与甲苯进料流(8)反应。甲苯与甲醛反应生成苯乙烯。然后，可将第二反应器（9）中的产物（10）送至可选的分离单元（11），可在此将不需要的副产物（15）（如水）与苯乙烯、未反应的甲醛和未反应的甲苯分离。然后，可使任何未反应的甲醛（12）和所述未反应的甲苯（13）循环回到反应器（9）。可从分离单元（11）移出苯乙烯产物流（14），若需要的话，对其进一步进行处理或加工。
反应器和分离器的操作条件因体系而异，可随进料组成和产物流组成变化。用于甲苯和甲醛反应的所述反应器(9)将在升高的温度下操作，如非限制性例子为250℃至750℃且压力为0.1大气压至70大气压，以及可包含碱性或中性催化剂体系。
图2是上述苯乙烯过程的另一实施方式的简化的流程图。将包含甲醇的进料流（21）随甲苯进料流（22）一起进料至反应器（23）。所述甲醇与催化剂在该反应器中反应以生成甲醛。然后，甲苯与甲醛反应生成苯乙烯。然后，可将反应器（23）的产物（24）送至可选的分离单元（25），可在此将任何不需要的副产物（26）与苯乙烯、未反应的甲醇、未反应的甲醛和未反应的甲苯分离。可使任何未反应的甲醇（27）、未反应的甲醛（28）和所述未反应的甲苯（29）循环回到反应器（23）。可从分离单元（25）移出苯乙烯产物流（30），若需要的话，对其进一步进行处理或加工。
反应器和分离器的操作条件因体系而异，可随进料组成和产物流组成变化。用于将甲醇转变成甲醛以及甲苯和甲醛反应的所述反应器(23)将在升高的温度下操作，如非限制性例子为250℃至750℃且压力为0.1大气压至70大气压，以及可包含碱性或中性催化剂体系。
沸石失活通常需要执行一再生过程。再生沸石的一些方法包括加热去除吸附的材料、与钠离子交换以去除不需要的阳离子、或变压以去除吸附的气体。再生过程可涉及在高温下用再生气体和氧气处理所述催化剂。根据一过程，可这样再生β沸石：首先在无氧环境中将所述催化剂加热至300℃以上的温度。然后，将一氧化再生气体提供至所述催化剂床，氧化相对多孔焦炭组分的一部分，以产生透过所述催化剂床的放热移动。可累进的提高温度或所述气体中的氧含量以氧化焦炭的多孔组分。同样，可提供再生气体，其中所述气体具有更高的氧含量或更高的温度以氧化所述焦炭中更少孔的耐火组分。可通过在降低温度下，使一惰性气体透过所述催化剂床完成该再生过程。
如本文所使用，术语“离子改性粘合剂”指用金属离子改性的、用于催化剂的粘合剂。
术语“分子筛”表示具有固定开放的网络结构、通常为晶体的材料，可以使用这些材料通过选择性封堵一种或多种成分从而分离烃或其他混合物，或者可以使用这些材料作为催化转化过程中的催化剂。
对权利要求中的任意要素使用术语“可选的”是用来表示主题要素是需要的，或是不需要的。这两个选择项都规定为在权利要求的范围之内。应理解，广义词语，如“包含”、“包括”、“具有”等的使用应提供对狭义词语如由“……组成”、“主要由……组成”、“基本由……组成”等的支持。
术语“再生的催化剂”表示再次获得足够活性，在指定过程中有效的催化剂。这种效率通过各个工艺参数确定。
术语“再生”表示在催化剂的活性到达不可接受/无效水平之后恢复催化剂活性和/或使催化剂能够重新使用的方法。这种再生的例子可以包括例如在催化剂床上通蒸汽或者烧去碳残余物。
术语“沸石”表示包含硅酸盐晶格、通常结合有例如铝、硼、镓、铁和/或钛的分子筛。在以下讨论和说明书全文中，术语“分子筛”和“沸石”或多或少可以互换使用。本领域普通技术人员能够理解，关于沸石说明的内容也可以应用于称为分子筛的更一般的材料种类。
本发明的各种实施方式可与本发明的其他实施方式相结合，以及本文列出的实施方式并无意限制本发明。即使本文没有给出具体的例子，本发明的各种实施方式的所有组合都是可行的。
虽然显示并描述了说明性实施方式，但是，本领域技术人员在不偏离本发明的精神和内容的情况下可以对其进行各种变动。清楚地指出数值范围或限值时，应理解，这些明确范围或限值包括落在该明确表示的范围或限值内的同样量级的重复范围或限值（如，约1-10包括2、3、4等；大于0.10包括0.11、0.12、0.13等）。
根据上下文，本文所有提到的“发明”，在一些情况下都可以仅指某些具体的实施方式。在其它情况下，它可能指在一个或多个但不必是所有权利要求中列出的主题。虽然前面的内容是就本发明的实施方式、形式和实例而言的，但列举它们的目的是使本领域的普通技术人员在将本专利的信息与可获得的其他信息和技术结合时能够实现和利用本发明，本发明不仅限于这些特定的实施方式、形式和实例。同样地，本文所揭示的实施方式可与本文所揭示的每一个其他实施方式一起使用和结合且在本文的范围之内，因此，本文允许本文揭示的实施方式的任意与所有结合。只要不偏离本发明的基本范围，可以设计本发明的其它和进一步的实施方式、形式和实例，本发明的范围由权利要求书确定。

Claims (24)

1.一种烷基化催化剂，其包括：
催化剂组分；和
为所述催化剂组分提供机械支撑的粘合剂组分；
其中，所述粘合剂组分包括离子改性粘合剂，所述离子改性粘合剂包括金属离子；
其中，所述金属离子可选自下组：Co、Mn、Ti、Zr、V、Nb、K、Cs、Ga、B、P、Rb、Ag、Na、Cu、Mg、Fe、Mo、Ce及其组合；以及
其中，所述金属离子减少所述沸石催化剂组分的酸性位点的数目。
2.如权利要求1所述的催化剂，其特征在于，所述离子改性粘合剂包括占基于所述离子改性粘合剂总重量的0.1至50重量%数量的金属离子。
3.如权利要求1所述的方法，其特征在于，所述离子改性粘合剂包括占基于所述离子改性粘合剂总重量的0.1至20重量%数量的金属离子。
4.如权利要求1所述的催化剂，其特征在于，所述离子改性粘合剂以占基于所述催化剂总重量的1至80重量%的数量存在。
5.如权利要求1所述的催化剂，其特征在于，所述离子改性粘合剂以占基于所述催化剂总重量的5至60重量%的数量存在。
6.如权利要求1所述的催化剂，其特征在于，在所述离子改性粘合剂上的所述金属离子改变所述催化剂的空间结构。
7.如权利要求1所述的催化剂，其特征在于，所述粘合剂包括非晶态二氧化硅或氧化铝。
8.如权利要求1所述的催化剂，其特征在于，所述催化剂是分子筛催化剂。
9.如权利要求1所述的催化剂，其特征在于，所述催化剂是沸石。
10.如权利要求2所述的催化剂，其特征在于，Cs以硅酸铯的形式存在于所述粘合剂中。
11.一种用于通过甲苯烷基化制备苯乙烯的方法，所述方法包括：
将甲苯和C1源提供至一个或多个反应器；以及
在所述一个或多个反应器中使所述甲苯与C1源反应以形成包括乙苯和苯乙烯的产物流；
其中，所述一个或多个反应器中的至少一反应器包括催化剂，所述催化剂包括为所述催化剂提供机械支撑的粘合剂组分，其中所述粘合剂组分减少所述沸石催化剂上酸性位点的数目。
12.如权利要求11所述的方法，其特征在于，所述粘合剂是离子改性粘合剂。
13.如权利要求12所述的方法，其特征在于，所述离子改性粘合剂改变所述催化剂的形状选择性，与使用非离子改性粘合剂相比可增加产物选择性。
14.如权利要求11所述的方法，其特征在于，所述粘合剂包括非晶态二氧化硅或氧化铝。
15.如权利要求12所述的方法，其特征在于，所述离子改性粘合剂包括占基于所述离子改性粘合剂总重量的0.1至50重量%数量的金属离子。
16.如权利要求15所述的方法，其特征在于，所述金属离子选自下组：Co、Mn、Ti、Zr、V、Nb、K、Cs、Ga、B、P、Rb、Ag、Na、Cu、Mg、Fe、Mo、Ce及其组合。
17.如权利要求12所述的方法，其特征在于，所述离子改性粘合剂以占基于所述催化剂总重量的1至80重量%的数量存在。
20.如权利要求11所述的方法，其特征在于，所述催化剂是分子筛催化剂。
21.如权利要求11所述的方法，其特征在于，所述催化剂是沸石。
22.如权利要求12所述的方法，其特征在于，Cs以硅酸铯的形式存在于所述粘合剂中。
23.如权利要求11所述的方法，其特征在于，所述C1源选自甲醇、甲醛及其组合。
24.一种制备沸石烷基化催化剂的方法，所述方法包括：
将金属离子通过初湿法添加至粘合剂以形成离子改性粘合剂；以及
将所述离子改性粘合剂与沸石结合以形成沸石聚集体；
加工所述沸石聚集体以形成沸石烷基化催化剂；
其中，所述沸石烷基化催化剂可用在用于甲苯与甲醇烷基化的反应床；
其中，所述离子改性粘合剂减少沸石上酸性位点的数目；以及
其中，所述离子改性粘合剂上的金属离子改变所述沸石的空间结构。
25.如权利要求24所述的方法，其特征在于，所述金属离子选自下组：Ce、Cu、P、Cs、B、Co、Ga及其组合。
26.如权利要求24所述的方法，其特征在于，所述离子改性粘合剂包括硅酸铯，其中所述离子改性粘合剂改变所述沸石的形状选择性。
CN201280024806.3A 2011-05-22 2012-05-14 具有离子改性粘合剂的催化剂 Pending CN103930205A (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US13/113,063 US8912109B2 (en) 2008-12-29 2011-05-22 Catalyst with an ion-modified binder
US13/113,063 2011-05-22
PCT/US2012/037699 WO2012161990A2 (en) 2011-05-22 2012-05-14 Catalyst with an ion-modified binder

Publications (1)

Publication Number Publication Date
CN103930205A true CN103930205A (zh) 2014-07-16

Family

ID=47217967

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201280024806.3A Pending CN103930205A (zh) 2011-05-22 2012-05-14 具有离子改性粘合剂的催化剂

Country Status (5)

Country Link
US (3) US8912109B2 (zh)
EP (1) EP2714627A4 (zh)
CN (1) CN103930205A (zh)
BR (1) BR112013028921A2 (zh)
WO (1) WO2012161990A2 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105348032A (zh) * 2015-12-11 2016-02-24 中国海洋石油总公司 一种甲苯甲醇侧链烷基化生产苯乙烯的工艺方法
CN106187755A (zh) * 2016-07-05 2016-12-07 崇明本 一种合成二异硬脂醇苹果酸酯的方法

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2484911B (en) * 2010-10-22 2013-04-03 Johnson Matthey Plc NOx absorber catalyst comprising caesium silicate and at least one platinum group metal
AU2013207783B2 (en) 2012-01-13 2017-07-13 Lummus Technology Llc Process for providing C2 hydrocarbons via oxidative coupling of methane and for separating hydrocarbon compounds
US9670113B2 (en) 2012-07-09 2017-06-06 Siluria Technologies, Inc. Natural gas processing and systems
AU2013355038B2 (en) 2012-12-07 2017-11-02 Lummus Technology Llc Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products
EP3074119B1 (en) 2013-11-27 2019-01-09 Siluria Technologies, Inc. Reactors and systems for oxidative coupling of methane
WO2015105911A1 (en) 2014-01-08 2015-07-16 Siluria Technologies, Inc. Ethylene-to-liquids systems and methods
US10377682B2 (en) 2014-01-09 2019-08-13 Siluria Technologies, Inc. Reactors and systems for oxidative coupling of methane
EP3097068A4 (en) 2014-01-09 2017-08-16 Siluria Technologies, Inc. Oxidative coupling of methane implementations for olefin production
US10793490B2 (en) 2015-03-17 2020-10-06 Lummus Technology Llc Oxidative coupling of methane methods and systems
US9334204B1 (en) 2015-03-17 2016-05-10 Siluria Technologies, Inc. Efficient oxidative coupling of methane processes and systems
US20160289143A1 (en) 2015-04-01 2016-10-06 Siluria Technologies, Inc. Advanced oxidative coupling of methane
US9328297B1 (en) 2015-06-16 2016-05-03 Siluria Technologies, Inc. Ethylene-to-liquids systems and methods
WO2017065947A1 (en) 2015-10-16 2017-04-20 Siluria Technologies, Inc. Separation methods and systems for oxidative coupling of methane
CA3019396A1 (en) 2016-04-13 2017-10-19 Siluria Technologies, Inc. Oxidative coupling of methane for olefin production
EP3554672A4 (en) 2016-12-19 2020-08-12 Siluria Technologies, Inc. PROCEDURES AND SYSTEMS FOR CHEMICAL DEPOSITION
HUE064375T2 (hu) 2017-05-23 2024-03-28 Lummus Technology Inc Metán oxidatív csatolási folyamatainak integrálása
US10836689B2 (en) 2017-07-07 2020-11-17 Lummus Technology Llc Systems and methods for the oxidative coupling of methane
CN111215126B (zh) * 2018-11-26 2021-11-02 中国科学院大连化学物理研究所 一种催化剂的制备方法及其应用
US11413605B2 (en) 2019-08-28 2022-08-16 King Fahd University Of Petroleum And Minerals Molybdenum based catalyst supported on titania-modified zeolite
CN112110457B (zh) * 2020-09-23 2022-02-11 中国海洋石油集团有限公司 一种定向堆砌生长的zsm-5纳米薄片团聚体的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4483937A (en) * 1983-04-22 1984-11-20 Exxon Research & Engineering Co. Modified zeolite catalyst composition for alkylating toluene with methanol to form styrene
FR2623423A1 (fr) * 1987-11-23 1989-05-26 Centre Nat Rech Scient Nouveaux catalyseurs a base de zeolithes modifiees par des elements alcalins sous forme metallique, leur preparation et leur application a l'alkylation des derives alkyl-aromatiques
WO2000017105A1 (en) * 1998-09-22 2000-03-30 Exxon Chemical Patents Inc. Preparation of high silica zeolites bound by zeolite and use thereof
US6864399B2 (en) * 2000-10-18 2005-03-08 Fina Technology, Inc. Silica-supported alkylation catalyst
CN101550051A (zh) * 2009-04-23 2009-10-07 天脊煤化工集团股份有限公司 一种提高甲醇芳构化制取芳烃选择性的工艺及其催化剂的制备方法
US20100167913A1 (en) * 2008-12-29 2010-07-01 Fina Technology, Inc. Catalyst with an Ion-Modified Binder

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844935A (en) * 1973-01-02 1974-10-29 Phillips Petroleum Co Process for producing lead free motor fuel
US4419271A (en) * 1979-10-15 1983-12-06 Union Oil Company Of California Hydrocarbon conversion catalyst
US4616997A (en) * 1984-03-01 1986-10-14 Seco/Warwick Corporation Ingot pusher furnace
US4962075A (en) * 1988-12-05 1990-10-09 Mobil Oil Corp. Zeolitic copper catalyst
JPH05123578A (ja) * 1991-11-06 1993-05-21 Nippon Oil Co Ltd 炭化水素転化触媒の製造方法
SE503039C2 (sv) * 1994-07-19 1996-03-11 Forskarpatent I Linkoeping Ab Elektroluminescerande anordning samt sätt att framställa denna
BR9714196A (pt) * 1996-12-31 2000-03-28 Chevron Usa Inc Zeólito,e,processos para preparação de um material cristalino, para a conversão de hidricarbonetos, para a conversão de álcoois inferiores e outros hidrocarbonetos oxigenados,e para a redução de óxidos de nitrogênio contidos numa corrente gasosa na presença de oxigênio.
FR2780313B1 (fr) * 1998-06-25 2000-08-11 Inst Francais Du Petrole Procede de sulfuration de catalyseurs par reduction suivie d'une sulfuration
US6699811B1 (en) * 1999-05-05 2004-03-02 Exxon Mobil Chemical Patents Inc. Tailored zeolite bound zeolite catalyst and its use for hydrocarbon conversion
US7084087B2 (en) * 1999-09-07 2006-08-01 Abb Lummus Global Inc. Zeolite composite, method for making and catalytic application thereof
US6555492B2 (en) * 1999-12-29 2003-04-29 Corning Incorporated Zeolite/alumina catalyst support compositions and method of making the same
US6699459B2 (en) 2001-03-01 2004-03-02 The Board Of Regents Of The University Of Texas System Methods of treating lung inflammation
US7393990B2 (en) * 2001-06-26 2008-07-01 Exxonmobil Chemical Patents Inc. Production of light olefins from oxygenate using framework gallium-containing medium pore molecular sieve
FR2843050B1 (fr) * 2002-08-01 2005-04-15 Inst Francais Du Petrole Catalyseur a base de metaux du groupe vi et du groupe viii presents au moins en partie sous la forme d'heteropolyanions dans le precurseur oxyde
WO2004043583A2 (en) * 2002-11-11 2004-05-27 Conocophillips Company Improved supports for high surface area catalysts
US7019185B2 (en) * 2002-12-06 2006-03-28 Exxonmobil Chemical Patents Inc. Aromatic alkylation process
US20050227853A1 (en) * 2004-04-02 2005-10-13 Ranjit Kumar Catalyst compositions comprising metal phosphate bound zeolite and methods of using same to catalytically crack hydrocarbons
CN100425676C (zh) * 2005-04-29 2008-10-15 中国石油化工股份有限公司 一种加氢裂化催化剂组合物
US7309679B2 (en) * 2005-08-08 2007-12-18 Uop Llc Attrition resistant MTO catalyst
KR100979580B1 (ko) * 2008-02-05 2010-09-01 에스케이에너지 주식회사 경질올레핀 생산용 탄화수소 접촉 분해 촉매 및 그제조방법
US8206353B2 (en) 2008-04-11 2012-06-26 Medtronic Minimed, Inc. Reservoir barrier layer systems and methods
EP2331486A2 (en) * 2008-08-27 2011-06-15 Virent Energy Systems Inc. Synthesis of liquid fuels from biomass
US8785706B2 (en) * 2011-05-22 2014-07-22 Fina Technology, Inc. Addition of a base to enhance product yield in alkylation reactions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4483937A (en) * 1983-04-22 1984-11-20 Exxon Research & Engineering Co. Modified zeolite catalyst composition for alkylating toluene with methanol to form styrene
FR2623423A1 (fr) * 1987-11-23 1989-05-26 Centre Nat Rech Scient Nouveaux catalyseurs a base de zeolithes modifiees par des elements alcalins sous forme metallique, leur preparation et leur application a l'alkylation des derives alkyl-aromatiques
WO2000017105A1 (en) * 1998-09-22 2000-03-30 Exxon Chemical Patents Inc. Preparation of high silica zeolites bound by zeolite and use thereof
US6864399B2 (en) * 2000-10-18 2005-03-08 Fina Technology, Inc. Silica-supported alkylation catalyst
US20100167913A1 (en) * 2008-12-29 2010-07-01 Fina Technology, Inc. Catalyst with an Ion-Modified Binder
CN101550051A (zh) * 2009-04-23 2009-10-07 天脊煤化工集团股份有限公司 一种提高甲醇芳构化制取芳烃选择性的工艺及其催化剂的制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105348032A (zh) * 2015-12-11 2016-02-24 中国海洋石油总公司 一种甲苯甲醇侧链烷基化生产苯乙烯的工艺方法
CN106187755A (zh) * 2016-07-05 2016-12-07 崇明本 一种合成二异硬脂醇苹果酸酯的方法
CN106187755B (zh) * 2016-07-05 2018-09-14 崇明本 一种合成二异硬脂醇苹果酸酯的方法

Also Published As

Publication number Publication date
WO2012161990A2 (en) 2012-11-29
EP2714627A4 (en) 2015-07-15
BR112013028921A2 (pt) 2017-02-07
US8912109B2 (en) 2014-12-16
US20110270007A1 (en) 2011-11-03
US20150051063A1 (en) 2015-02-19
US10022710B2 (en) 2018-07-17
US10369552B2 (en) 2019-08-06
EP2714627A2 (en) 2014-04-09
WO2012161990A3 (en) 2014-05-08
US20180297017A1 (en) 2018-10-18

Similar Documents

Publication Publication Date Title
CN103930205A (zh) 具有离子改性粘合剂的催化剂
US7419931B2 (en) Catalyst comprising a 10MR zeolite and a 12MR zeolite, and its use in transalkylation of alkylaromatic hydrocarbons
US8969642B2 (en) Method for providing a co-feed in the coupling of toluene with a carbon source
CN103917504A (zh) 用于侧链烷基化反应的包含金属氧化物的催化剂
US20020137977A1 (en) Aromatic conversion processes and zeolite catalyst useful therein
TWI466721B (zh) 帶有離子改性的黏合劑之觸媒
KR20080024225A (ko) Ｕｚｍ-8 제올라이트를 사용한 알킬화 방법
CN101679882A (zh) 改进的烷基芳族化合物的制备方法
JP2017002051A (ja) オレフィンによる芳香族炭化水素のアルキル化法
CA2510451A1 (en) Catalytic composition and process for the transalkylation of aromatic hydrocarbons
US8785706B2 (en) Addition of a base to enhance product yield in alkylation reactions
JP2019510764A (ja) 芳香族化合物流体のトランスアルキル化のための方法
Garcés et al. Shape selective chemistries with modified mordenite zeolites
Pai et al. Butylation of toluene: Influence of zeolite structure and acidity on 4-tert-butyltoluene selectivity
EP3033172A1 (en) Catalytic composition and process using it for the alkylation of aromatic hydrocarbons with alcohols, or mixtures of alcohols and olefins
Upadhyayula Gas phase toluene isopropylation over high silica mordenite
JP2008055413A (ja) 錫の追加によって相乗効果を発揮するレニウム及びゲルマニウム含有触媒、及び該触媒を用いたアルキル芳香族トランスアルキル化プロセス
TW201307252A (zh) 在甲苯與碳源之偶合中氧化劑的應用
JP2020515389A (ja) 触媒組成物及び芳香族アルキル化プロセスにおけるそれらの使用
US20120296142A1 (en) Addition of basic nitrogen to alkylation reactions
JPS6253489B2 (zh)
EP2714626A1 (en) Metal oxide containing catalyst for side chain alkylation reactions
JP2008055412A (ja) パラジウム及びゲルマニウム含有触媒、及び該触媒を利用したアルキル芳香族トランスアルキル化プロセス
US20120296134A1 (en) Germanium modified catalyst for coupling reactions
Guillon et al. d) Patent Application Publication tio, Pub. No: US 2005/0234279A1

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
AD01 Patent right deemed abandoned

Effective date of abandoning: 20170301

AD01 Patent right deemed abandoned