TWI469829B - 雙金屬觸媒及彼於製造二甲苯上之用途 - Google Patents
雙金屬觸媒及彼於製造二甲苯上之用途 Download PDFInfo
- Publication number
- TWI469829B TWI469829B TW102103735A TW102103735A TWI469829B TW I469829 B TWI469829 B TW I469829B TW 102103735 A TW102103735 A TW 102103735A TW 102103735 A TW102103735 A TW 102103735A TW I469829 B TWI469829 B TW I469829B
- Authority
- TW
- Taiwan
- Prior art keywords
- bed
- metal
- group
- catalyst
- tin
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
- C07C5/2708—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J16/00—Chemical processes in general for reacting liquids with non- particulate solids, e.g. sheet material; Apparatus specially adapted therefor
- B01J16/005—Chemical processes in general for reacting liquids with non- particulate solids, e.g. sheet material; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
-
- 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
- B01J29/44—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
- B01J29/40—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
- 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)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
- C07C5/222—Catalytic processes not covered by C07C5/23 - C07C5/31 with crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
- C07C5/25—Migration of carbon-to-carbon double bonds
- C07C5/2506—Catalytic processes
- C07C5/2556—Catalytic processes with metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/2754—Catalytic processes with 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/36—Steaming
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/628—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/08—Xylenes
-
- 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
-
- 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
Description
本申請案主張2012年2月29日提出之美國臨時申請案61/604,926之權益,其揭示以全文引用方式併入本文中。
本發明係關於用於製備二甲苯類,且更具體地說用於乙苯脫烷作用-二甲苯異構化作用系統以製造對二甲苯類之雙金屬觸媒。
石化廠和煉油廠中所發現之一般芳族烴流(諸如)可藉由重組和裂解石油腦產生,包括C8芳族烴異構物乙苯和二甲苯異構物對二甲苯、間二甲苯和鄰二甲苯。因為對二甲苯係用作聚酯纖維的主要原料材料,所以如相較於其他異構物,其價值較高。鄰二甲苯(可用於諸如製造塑化劑用酞酸酯)比間二甲苯更有價值。不幸的是,二甲苯類之平衡混合物含有間二甲苯差不多為對-或鄰二甲苯
約兩倍多。
為了優先回收對二甲苯,通常透過對二甲苯
回收階段(諸如吸附方法(例如,ParexTM
或EluxylTM
吸收分離單元)或結晶方法)處理C8芳族烴流,以回收對二甲苯富含流和對二甲苯-耗乏流。對二甲苯-耗乏流然後可觸媒異構化至平衡以再回收於對二甲苯回收回路中。乙苯需要從回路移除且一種進行該移除之方法解釋如下。
通常用以促進對二甲苯-耗乏流之異構化的觸
媒包含受載有週期表第7-10族之金屬成分(例如,鉑或錸)的沸石。除了促進二甲苯異構物之間的異構化,透過脫烷反應和接著共產物乙烯在該等觸媒存在下之氫化,乙苯可轉化成苯。一不想要副反應為金屬催化之環飽和及另一為C9+芳族烴類之產生。增加對二甲苯回收回路的效率,且特別是對於較佳觸媒的持續需求之研究非常積極。
有關異構化方法之最近的先前技術包括美國
專利號6,028,238;7,247,762;7,270,792;7,271,118;7,626,065;美國專利公開號2011-0190556;及美國申請案序號13/081351。
雙金屬觸媒本身為已知的且使用於許多不同
的煉油和石化方法,諸如使用於二甲苯類之製造方法中之轉烷化及其他二甲苯製造方法。
WO2009034093(US2010/0217057)教示一種
ZSM-5之新穎結構,其具有在每個晶粒的邊緣比中心高之平均二氧化矽對氧化鋁比,在乙苯脫烷作用中提供減少之
二甲苯損失,特別是當與作為黏合劑的二氧化矽和一或多種選自鉑、錫、鉛、銀、銅和鎳之氫化金屬組合時。
WO2007037866(US2007/0060470)教示一種用
於異構化和脫烷活性與低環烷製造的鉑、錫、酸性分子篩和磷酸鋁黏合劑之某些組合的觸媒。
US 7,525,008教示一種含有鉑和隨意地錫之
MTW-型沸石觸媒之C8芳族流的異構化作用。該MTW型沸石具有介於約20:1和45:1之間的二氧化矽對氧化鋁莫耳比。
US 2011/0190556教示一種二甲苯製造方法,
其包含C9+芳族烴原料與C6及/或C7芳族烴原料之轉烷化作用。該等原料在氫存在下與包含第一雙金屬觸媒及其下游,與第二雙金屬觸媒之觸媒系統接觸。該第一雙金屬觸媒包含具有範圍在3至12之限制指數的分子篩,諸如ZSM-5,和該等金屬係選自週期表之第6至12族。該第二雙金屬觸媒包含具有限制指數小於3之分子篩,諸如ZSM-12,和該等金屬係選自週期表之第6至12族。
US 2010/0048381教示一種用於二甲苯異構化
之觸媒,其包括浸漬或混合有金屬鹽的具有二氧化矽對氧化鋁之指定莫耳比的沸石之載體,該載體受載有另外受載有錫、鉍或鉛之第VIII族金屬,或第VII族金屬。
US 2007/0060470教示一種用於二甲苯類之異
構化和乙苯之脫烷的觸媒,其包含鉑和錫。教示具有至少20:1的二氧化矽對氧化鋁比之含金屬分子篩。
其他感興趣的參考文獻包括美國專利號
7,271,118(WO 2006/022991);7,199,070(EP 1495805);5,689,027;5,283,385;4,485,185;及EP 2022564。
然而,上述系統無任何一者有關透過其中脫
烷和異構化之功能可分開管理以改良性能之多床系統來處理對二甲苯-耗乏進料流。再者,以後仍然尋求增加之金屬選擇性(所要乙烯飽和相對於不想要的環飽和)、減少之金屬遷移和降低之對硫毒害敏感性。
本發明人已經意外地發現一種雙金屬系統,
其係用於具有低含量的至少一種第8-10族金屬及至少一種另外金屬的對二甲苯-耗乏C8芳族烴進料流之脫烷作用和異構化作用,在具體實例中,當相較於當前技藝觸媒狀態,其提供於低溫度之高乙烯飽和度和低二甲苯損失。
本發明係有關一種適用於製造二甲苯類之雙金屬觸媒系統、一種用於製造該觸媒系統之方法、和使用該觸媒系統製造二甲苯類之方法,在具體實例中,提供根據較高乙烯飽和度、較低二甲苯損失之至少一者的改良選擇性、減少環損失、減少對因為原料流雜質的毒害之敏感性、及在較不嚴格條件下操作的能力。
在具體實例中,根據本發明之觸媒系統包含第一床,其包含分散在ZSM-5上的至少一種選自第7-10族之第一金屬及至少一種選自銀、銅、釕、銦和錫之第二
金屬,及第二床,其包含分散在受載ZSM-5上的至少一種選自第7-10族之第一金屬及至少一種選自銀、銅、釕、銦和錫之第二金屬,和一種方法,其包含使對二甲苯-耗乏進料蒸汽與該觸媒系統在氫存在下接觸。第一床中之ZSM-5被矽選擇性活化(silicon-selectivated)及第二床中之ZSM-5不被矽選擇性活化。
在具體實例中,該等金屬係藉由初濕(IW)技術加至第一床和藉由研磨加至第二床。
在具體實例中,該載體係選自氧化鋁、二氧化矽、鋁矽酸鹽、黏土、及其組合。
在具體實例中,該方法包含使觸媒系統之第一床與包含包括乙苯和二甲苯異構物之C8芳烴的對二甲苯-耗乏之進料接觸,以將部分之乙苯轉化至苯和乙烷,以製造乙苯耗乏中間流,和然後使中間流與觸媒系統之第二床接觸,而異構化二甲苯類及提供一種包含當與該進料比較時對二甲苯量增加和乙苯量減少的最終產物。
在具體實例中,該觸媒系統包含第一床,其包含如下製造之觸媒:藉由以初濕(IW)技術將至少一種選自第7-10族之第一金屬及至少一種與該第一金屬不同且選自銀、銅、釕、銦和錫之第二金屬加至選擇性活化之ZSM-5觸媒,及第二床,其包含如下製造之觸媒:藉由組合包含至少一種選自第7-10族之第一金屬及至少一種與該第一金屬不同且選自銀、銅、釕、銦和錫之第二金屬和水的金屬溶液及ZSM-5分子篩並與載體諸如氧化鋁、二
氧化矽及其組合一起研磨以分佈材料。將所得組成物擠壓且然後乾燥、煅燒和蒸汽處理。第二床中之ZSM-5不被矽選擇性活化。
本發明的一個目的為提供一種製造適用於乙
苯的轉化和二甲苯的異構化之觸媒系統的簡單且可重複方法,其避免先前技術有關因環飽和度之二甲苯損失及有關硫毒害和操作條件之嚴重程度的穩固性之問題。
參考下列詳細說明、較佳具體實例、實例,和所附申請專利範圍,這些及其他目的、特徵和優點將變得顯而易見。
在附圖中,在幾個視圖中,一樣的標號用於表示相同的部件。
圖1-4為比較根據本發明的雙金屬觸媒之性能的繪圖。
根據本發明,有一種適用於藉由乙苯之脫烷作用和二甲苯類之異構化作用從對二甲苯-耗乏C8芳族烴進料流製造二甲苯類之雙金屬觸媒系統、一種製造該雙金屬觸媒系統之方法,和其中所使用之觸媒系統。在具體實例中,本發明提供根據較高乙烯飽和度和較低二甲苯損
失之至少一者的改良選擇性、減少對因為進料流雜質的毒害之敏感性、在較不嚴格條件下操作的能力,及易於製備該觸媒系統。
觸媒系統為一種具有下列之二床系統:第一床,包含適用於乙苯之脫烷作用的觸媒和第二床,包含適用於異構化作用之觸媒。各床可在分開反應器或在同一反應器中串聯。分開之觸媒不混合。
藉由參考下列詳細實例(包括比較根據本發明觸媒與先前技術之商業觸媒的實驗)可較佳地理解本發明。實例應被視為本發明的代表且不對其限制。
以下所使用之術語和技術應為熟練技術人員所熟知的,且除非本文中另有具體定義取自先前技術中,特別是在該等於背景或下文中所討論的參考文獻中所找到之定義。否則,應在參考其他無關的來源之前先參照The Handbook of Petroleum Refining Processes,第三版,Robert Meyers,編者;McGraw-Hill,©2004。然而,為了避免混淆,提供下列某些術語之說明。
初濕(IW)技術為將金屬合併於材料中之眾所周知的方法;參見,例如,美國專利第4,302,359和7,271,118號。同樣地,競爭性離子交換是一種眾所周知的方法,諸如前述美國專利7,271,118中所討論者。
研磨係指混合材料與足夠液體以形成糊狀物且其中混合係伴隨著所得混合物之剪切進行。可使用市售研磨器。參見,例如,美國專利7,335,802。
選擇性活化(selectivation)-就地矽選擇性活化係討論於例如美國專利5,475,179中;易地矽選擇性活化討論於例如美國專利5,625,103中。其他增加對對二甲苯之觸媒選擇性的選擇性活化劑(諸如一氧化碳)為已知;參見例如美國專利7,902,414。術語“選擇性活化之觸媒”如使用於本文中表示觸媒已以在該技術中本身為已知的裝置藉由就地矽選擇性活化或藉由易地矽選擇性活化。在本發明中該第一床含有已被選擇性活化之觸媒,及該第二床含有未被選擇性活化之觸媒。
混合煅燒本身表示在所要溫度及具有逐步減少氮和逐漸增加空氣之空氣和氮固定總流下煅燒。在混合煅燒結束時,大部分的流為空氣。
α值為眾所周知的酸活性之測量且給予每單位時間之每單位體積觸媒的正常己烷轉化之速率的相對速率常數。參見,例如,美國專利8,057,664。
“對-耗乏”是指具有對二甲苯存在量低於平衡值之C8芳族烴類的混合物,該平衡值以總二甲苯類為基準計為約23至24重量%對二甲苯。二甲苯類之對-耗乏混合物係例如產自對二甲苯藉由吸附分離方法諸如藉由透過ParexTM
或EluxylTM
吸附分離單元之處理,或藉由其中利用C8芳族異構物之凝固點的差之結晶方法的較佳移除。術語“對-耗乏”本身在該技術中為已知的。
製造根據本發明之二床觸媒系統。所有頂床(或第一床)觸媒係使用矽-選擇性活化之H-ZSM-5作為基
底和藉由初濕(IW)技術添加金屬製備。當使用二種金屬時,金屬溶液包含二種金屬來源。使用四胺硝酸鉑作為所有觸媒之鉑來源。在周圍空氣中乾燥後,所有觸媒在660℉下於在N2
中的40%空氣(~8.4% O2
)中煅燒3小時。頂床觸媒α值(己烷裂解活性)一般為~450。底(或第二床)觸媒不被矽-選擇性活化。無可否認的,名稱“第二床”假設為待處理的流先接觸“第一床”及然後接觸第二床;同樣地,名稱“底”床和“頂”床假設向下流動,頂-至-底,雖然向下流動不是強制性且一般技藝人士可以設想其他配置。
底床(或第二床)觸媒係藉由擠壓80% H-ZSM-5與20% LaRoche氧化鋁VersalTM
300製造。在研磨期間添加全部金屬溶液和水。關於除AG外的所有觸媒,添加至研磨器之順序為添加晶體且研磨以分佈,接著添加氧化鋁並研磨,接著添加金屬溶液並研磨,及最後加水並研磨。關於觸媒AG,添加之順序為添加晶體且研磨以分佈,接著添加金屬溶液並研磨,接著添加氧化鋁並研磨,及最後加水並研磨。將觸媒擠壓成1/16”圓柱體。擠壓之後,將擠出物乾燥,然後在1000℉下混合煅燒6小時
(80%空氣,~16.8%O2
),和最終於950℉下蒸汽處理4小時。底床觸媒α(己烷裂解活性)一般為~95。
如下所述,接著進行初始雙床篩選。
在固定床的微單元中進行測試觸媒。將總計2克觸媒(如上所述製造,“原樣”)裝入反應器內:頂床0.5
克和底床1.5克。反應器壓力為225psig(1551kPa)和H2
:HC比為1:1。總進料流率,表示為每小時每克觸媒之進料克數(WHSV),為12hr-1。觸媒之活性係根據反應器溫度(660至730℉或349至388℃)函數而測定。溫度範圍允許橫跨乙苯轉化率之範圍的比較,從約55至85重量%。至反應器之進料主要是含有C8芳族烴類與約16%乙苯。進料之詳細分析顯示於表3中。在引入進料之前將觸媒在氫中於400℃下還原1小時。未進行硫化。使用線上GC-FID與60-M DB-WAX管柱進行產物分析。產物中之飽和物(重量%)用於指示不同觸媒系統的相對環飽和活性。
測試具有Pt對第二金屬之1:1莫耳比的觸媒。所有金屬組合僅顯示超越Pt之一些改良。銦和錫顯示飽和物之最大減少,接著Cu、Ag、Rh和Ru。各種二金屬系統之研究結果係顯示於圖1中。
然後如下所述進行二次雙床測試。
在根據本發明製造之包括Pt-Sn、Pt-Ag和Pt-Cu觸媒的選擇觸媒系統上進行第二系列之固定床微單元測試。將第二GC管柱(DB-1)加至GC配置以容許更詳細的分析,包括透過乙烷/乙烯比定量乙烯飽和活性,和產率計算。將總計2克的所指定之的觸媒(“原樣”)裝入反應器內。使用雙金屬:頂床0.5克和底床1.5克。反應器壓力為225psig(1551kPa)和H2
:HC比為1:1。所有觸媒之總進料流率,表示為每小時每克觸媒之進料克數(WHSV),為12hr-1
。觸媒之活性係如同反應器溫度函數而測定。至反應器之進料主要是含有C8芳族烴類與約16%乙苯。進料之詳細分析顯示於表4中。觸媒不進行硫化。在移動到640/650℉至745/755℉的溫度掃描之前,將所有待測試之觸媒於430℃、0.9:1之H2
:HC比和壓力185psig(1275kPa)去邊(de-edged)經歷24小時。使用線上GC-FID與60-M DB-WAX管柱和DB-1管柱(各指定管柱,DB-WAX和DB-1,本身在該技藝中為已知且市售的)分析產物。一般乙苯轉化率(“EBC”)之所要程度為>70%。
本發明具有1:1 Pt:M觸媒(M=Ag、Cu和Sn)之某些二金屬系統的比較係顯示於圖2-4中;特別是關於環損失相對於乙苯轉化率(圖2)、環損失相對於溫度(圖3)和莫耳C2比(乙烷/乙烯比;圖4)。
所有觸媒具有低環損失(低芳烴飽和度)和高C2/C2=莫耳比(高乙烯飽和度)。
實例1. 頂床觸媒製備:0.1重量% Pt和1:0 Pt/Ag莫耳比
頂床觸媒製備所使用之觸媒為1/16”(約16cm)於圓柱形擠出物之形式的具有35%二氧化矽黏合劑之H-ZSM-5。H-ZSM-5係在金屬浸漬之前用矽氧(silicone)選擇性活化三次。將用1.41g的四胺硝酸鉑溶液(具有3.55重量%Pt之水溶液)和16.7g的去離子(DI)水製造的浸漬液緩慢加至50g的觸媒。將混合物徹底翻轉,直至完全鬆散。將混合物首先在周圍條件下然後在250℉下空氣乾燥四小時。將混合物在660℉(352℃)下用40%空氣和60%氮之混合物以5vol/vol/min之流率煅燒3小時。
實例2. 頂床觸媒製備:0.1重量% Pt和1:1 Pt/Ag莫耳比
採用實例1中所述相同的步驟,除了浸漬液用下述組成物製造之外:1.41g的四胺硝酸鉑溶液(具有3.55重量% Pt之
水溶液)
0.0446g的化學級硝酸銀,固體
16.7g的DI水
實例3. 頂床觸媒製備:0.1重量% Pt和1:2 Pt/Ag莫耳比
採用實例1中所述相同的步驟,除了所使用之觸媒為100g和浸漬液用下述組成物製造之外:2.83g的四胺硝酸鉑溶液(具有3.55重量% Pt之水溶液)
0.175g的化學級硝酸銀,固體
26.2g的DI水
實例4. 頂床觸媒製備:0.1重量% Pt和1:3 Pt/Ag莫耳比
採用實例3中所述相同的步驟,除了浸漬液用下述組成物製造之外:2.83g的四胺硝酸鉑溶液(具有3.55重量% Pt之水溶液)
0.265g的化學級硝酸銀,固體
26.2g的DI水
實例5. 頂床觸媒製備:0.1重量% Pt和1:4 Pt/Ag莫耳比
採用實例3中所述相同的步驟,除了浸漬液用下述組成物製造之外:2.83g的四胺硝酸鉑溶液(具有3.55重量% Pt之
水溶液)
0.36g的化學級硝酸銀,固體
27.5g的DI水
實例6. 底床觸媒製備:0.115重量% Pt和1:0 Pt/Ag莫耳比
擠壓:將400g之H-ZSM-5結晶和100g Versal 300的混合物在研磨器中徹底研磨。將271g的DI水加至混合物中同時研磨。將用下列組成物製造之浸漬液加至混合物中同時研磨。
16.22g的四胺硝酸鉑溶液(具有3.55重量% Pt之水溶液)
120g的DI水
混合物用1/16”圓筒模頭板將金屬浸漬的混合物擠出。將擠出物在250℉下乾燥。
煅燒:將擠出物在流動氮(5vol/vol/min)中以150℉/h加熱至900℉(482℃),保持於900℉經3hr。同時在900℉下,將氣體混合物改變至0.25vol/vol/min空氣+4.75vol/vol/min氮,保持30min;0.50vol/vol/min空氣+4.50vol/vol/min氮,保持30min;1.0vo1/vol/min空氣+4.0vol/vol/min氮,保持30min;2.0vol/vol/min空氣+3.0vol/vol/min氮,保持30min。將溫度以150℉/h(83.3℃/h)增加至1000℉(538℃)。一旦穩定1000℉,將氣體混合物改變至4vol/vol/min空氣+1vol/vol/min氮和保持6小時。冷卻到周圍條件和
卸料。
蒸汽處理:將煅燒觸媒在流動氮(5vol/vol/min)中以150℉/h加熱至900℉,保持於900℉經30min。切換到蒸汽處理經30分鐘期間。以150℉/h將溫度增加至950℉(510℃),和然後在100%蒸汽中保持4小時。在空氣中冷卻和卸料。
實例7. 底床觸媒製備:0.115重量% Pt和1:1 Pt/Ag莫耳比
採用實例6中所述的三階段步驟,除了浸漬液用下述組成物製造之外:16.22g的四胺硝酸鉑溶液(具有3.55重量% Pt之水溶液)
0.502g的化學級硝酸銀,固體
120g的DI水
實例8. 底床觸媒製備:0.115重量% Pt和1:2 Pt/Ag莫耳比
採用實例6中所述的三階段步驟,除了浸漬液用下述組成物製造之外:16.22g的四胺硝酸鉑溶液(具有3.55重量% Pt之水溶液)
1.004g的化學級硝酸銀,固體
120g的DI水
實例9. 底床觸媒製備:0.1重量% Pt和1:
3 Pt/Ag莫耳比
採用實例6中所述的三階段步驟,除了浸漬液用下述組成物製造之外:14.10g的四胺硝酸鉑溶液(具有3.55重量% Pt之水溶液)
1.310g的化學級硝酸銀,固體
120g的DI水
實例10. 底床觸媒製備:0.1重量% Pt和1:4 Pt/Ag莫耳比
採用實例6中所述的三階段步驟,除了浸漬液用下述組成物製造之外:14.10g的四胺硝酸鉑溶液(具有3.55重量% Pt之水溶液)
1.746g的化學級硝酸銀,固體
120g的DI水
於下描述在固定床微單元中之觸媒評估。
實例11. 具有1:0 Pt/Ag之Pt/ZSM-5觸媒的評估
將具有3/8”外徑之固定床反應器中使用於評估。將反應器配備1/8”直徑熱井以在觸媒床的中心監測反應器的溫度。根據下表中提供的觸媒資訊將圓柱形1/16”擠出物形狀之觸媒裝入反應器中。
反應器壓力設定於225psig與於92cc/min之H2
穩定流。將反應器溫度以0.833℃/min增加至200℃,且於200℃保持16小時。將溫度以0.833℃/min進一步增加至380℃,並於380℃保持3小時。以27.6cc/hr(12 WHSV)引入進料。在整個運作中保持此進料速率。進料組成物係顯示於下表中。進料密度為0.87g/cc。
然後將反應器壓力減少至185psig,將H2
流減少至82cc/min,及將反應器溫度以0.833℃/min增加至430℃,並於430℃下保持24小時。
將反應器壓力增加至225psig,將H2
流增加至92cc/min,及將反應器溫度減少至340℃,並於340℃下保持12小時,用於藉由線上GC分析的數據收集。連續將反應器溫度以0.833℃/min進一步增加至355、370、385和400℃並於各溫度設定下保持12小時,用於藉由線上GC分析的數據收集。將結果與討論段中的其餘觸媒比較。
實例12. 具有1:1 Pt/Ag之Pt/ZSM-5觸媒的評估
採用實例1中所述之相同步驟以評估下表中所述之第二組觸媒。將結果與討論段中的其餘觸媒相比較。
實例13. 具有1:2 Pt/Ag之Pt/ZSM-5觸媒的評估
採用實例1中所述之相同步驟以評估下表中所述之第三組觸媒。將結果與討論段中的其餘觸媒相比較。
實例14.具有1:3 Pt/Ag之Pt/ZSM-5觸媒的評估
採用實例1中所述之相同步驟以評估下表中所述之第四組觸媒。將結果與討論段中的其餘觸媒相比較。
實例15. 具有1:4 Pt/Ag之Pt/ZSM-5觸媒的評估
採用實例1中所述之相同步驟以評估下表中所述之第五組觸媒。將結果與討論段中的其餘觸媒相比較。
表5顯示於EB轉化率約75%之微單元結果。當相較於無Ag觸媒時,所有含Ag-觸媒已減少C5
-、C6 +
非芳烴和C9 +
芳烴之產生以及較低二甲苯損失和環損失。所有含Ag-觸媒與EB比較也具有高的苯選擇性。
雖然已用特性描述本發明之說明性具體實例,應了解:各種其他的修正對於熟習項技藝者是顯而易知且可在卻不偏離本發明之精神及範圍下容易地進行。
在本文中所用之商品名以TM
符號或®符號指示,其指示該等名稱可受某種商標權保護,例如,彼等可以各種權限註冊商標。在本文中所引證之所有的專利、專利申請案、測試步驟(諸如ASTM方法、UL方法、等等)及其他本文中所引用之文件以該揭示內容不抵觸本發明且其中允許該併入的所有權限之範圍的引用方式完全併入。當本文中列舉數值下限及數值上限時,將任何下限至任何上限之範圍都考慮進去。
Claims (9)
- 一種觸媒系統,其包含:第一床,其包括分散在ZSM-5上的至少一種選自第7-10族之第一金屬及至少一種選自銀、銅、釕、銦和錫之第二金屬,及第二床,其包括分散在ZSM-5上的至少一種選自第7-10族之第一金屬及至少一種選自銀、銅、釕、銦和錫之第二金屬,進一步特徵在於第一床中之ZSM-5被矽選擇性活化(silicon-selectivated)及第二床中之ZSM-5不被矽選擇性活化。
- 根據申請專利範圍第1項之觸媒系統,其中該第一床及該第二床之至少一者進一步包含獨立地選自氧化鋁、二氧化矽、鋁矽酸鹽、黏土、及其組合之至少一者的載體。
- 根據申請專利範圍第1項之觸媒系統,進一步特徵在於包括:第一床,其包含如下製造之觸媒:藉由以初濕技術將至少一種選自第7-10族之第一金屬及至少一種選自銀、銅、釕、銦和錫之第二金屬加至矽選擇性活化(silicone-selectivated)之ZSM-5,接著乾燥和煅燒,及第二床,其包含如下製造之觸媒:藉由組合包含至少一種選自第7-10族之第一金屬及至少一種選自銀、銅、釕、銦和錫之第二金屬和水的金屬溶液及非選擇性活化ZSM-5分子篩並與載體一起研磨,接著擠壓、乾燥、煅燒和蒸汽處理。
- 根據申請專利範圍第1項之觸媒系統,其中該第一床包含至少一種選自鉑、錸、及其混合物之第一金屬, 及至少一種選自銀、銅、錫、及其混合物之第二金屬,及該第二床包含至少一種選自鉑、錸、及其混合物之第一金屬,及至少一種選自銀、銅、錫、及其混合物之第二金屬。
- 根據申請專利範圍第1項之觸媒系統,其中該第一床包含至少一種選自鉑、錸、及其混合物之第一金屬,及至少一種選自銀、錫、及其混合物之第二金屬,及該第二床包含至少一種選自鉑、錸、及其混合物之第一金屬,及至少一種選自銀、錫、及其混合物之第二金屬。
- 根據申請專利範圍第1項之觸媒系統,其中在該第一床中之該第一金屬為錸及在該第二床中之該第一金屬為錸。
- 根據申請專利範圍第1項之觸媒系統,其中在該第一床中之該第二金屬為銀及在該第二床中之該第二金屬為銀。
- 根據申請專利範圍第1項之觸媒系統,其中在該第一床中之該第二金屬為錫及在該第二床中之該第二金屬為錫。
- 一種方法,其包含使包括乙苯和二甲苯異構物的對二甲苯-耗乏之C8芳族烴進料與前述申請專利範圍中任一項之觸媒系統接觸,以提供一種包含當與該進料比較時對二甲苯量增加和乙苯量減少的最終產物。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261604926P | 2012-02-29 | 2012-02-29 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201410319A TW201410319A (zh) | 2014-03-16 |
TWI469829B true TWI469829B (zh) | 2015-01-21 |
Family
ID=49003593
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW102103735A TWI469829B (zh) | 2012-02-29 | 2013-01-31 | 雙金屬觸媒及彼於製造二甲苯上之用途 |
Country Status (3)
Country | Link |
---|---|
US (2) | US9018121B2 (zh) |
TW (1) | TWI469829B (zh) |
WO (1) | WO2013130194A1 (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10988421B2 (en) | 2013-12-06 | 2021-04-27 | Exxonmobil Chemical Patents Inc. | Removal of bromine index-reactive compounds |
MY178976A (en) | 2014-04-30 | 2020-10-26 | Exxonmobil Chemical Patents Inc | Method of improving metal-impregnated catalyst performance |
US10035140B2 (en) | 2016-09-20 | 2018-07-31 | King Fahd University Of Petroleum And Minerals | Process for producing xylene using a metal-doped zeolite catalyst |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5689027A (en) * | 1994-11-18 | 1997-11-18 | Mobil Oil Corporation | Selective ethylbenzene conversion |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55129232A (en) | 1979-03-29 | 1980-10-06 | Teijin Yuka Kk | Isomerization of xylenes |
US4899011A (en) * | 1986-01-15 | 1990-02-06 | Mobil Oil Corporation | Xylene isomerization process to exhaustively convert ethylbenzene and non-aromatics |
US5192728A (en) | 1988-06-24 | 1993-03-09 | Mobil Oil Corporation | Tin-colating microporous crystalline materials and their use as dehydrogenation, dehydrocyclization reforming catalysts |
US5705726A (en) * | 1994-11-18 | 1998-01-06 | Mobil Oil Corporation | Xylene isomerization on separate reactors |
US6028238A (en) | 1998-04-14 | 2000-02-22 | Mobil Oil Corporation | Xylene isomerization |
US20010051754A1 (en) * | 1999-08-03 | 2001-12-13 | Daria N. Lissy | Plural stage toluene disproportionation process minimizing ethylbenzene |
EP1511705A1 (en) | 2000-02-22 | 2005-03-09 | ExxonMobil Chemical Patents Inc. | Process for producing para-xylene |
TWI263630B (en) | 2003-07-08 | 2006-10-11 | Toray Industries | Conversion catalyst for ethylbenzene containing xylenes and process for converting ethylbenzene containing xylenes by using catalyst |
US7247762B2 (en) | 2003-09-12 | 2007-07-24 | Exxonmobil Chemical Patents Inc. | Process for xylene isomerization and ethylbenzene conversion |
EP1699556A2 (en) | 2003-12-30 | 2006-09-13 | Uop Llc | Process and catalyst for c8 alkylaromatic isomerization |
US20050143614A1 (en) * | 2003-12-30 | 2005-06-30 | Leon-Escamilla E. A. | Process and catalyst for C8 alkylaromatic isomerization |
US7271118B2 (en) * | 2004-07-29 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Xylenes isomerization catalyst system and use thereof |
WO2007037866A2 (en) | 2005-09-14 | 2007-04-05 | Uop Llc | Process for the isomerization of xylenes and catalyst therefor |
WO2007127049A2 (en) | 2006-04-25 | 2007-11-08 | Exxonmobil Chemical Patents Inc. | Process for producing para-xylene |
KR101470623B1 (ko) | 2006-11-17 | 2014-12-12 | 에스케이이노베이션 주식회사 | 자일렌 이성화 촉매 및 그 제조방법 |
EP2022564A1 (en) | 2007-07-31 | 2009-02-11 | Shell Internationale Researchmaatschappij B.V. | Catalyst composition, its preparation and use |
RU2010114178A (ru) | 2007-09-10 | 2011-10-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (NL) | Цеолит zsm-5, его получение и применение при деалкилировании этилбензола |
JP5695674B2 (ja) | 2010-02-03 | 2015-04-08 | エクソンモービル・ケミカル・パテンツ・インク | 重質芳香族炭化水素原料のトランスアルキル化 |
-
2013
- 2013-01-23 WO PCT/US2013/022684 patent/WO2013130194A1/en active Application Filing
- 2013-01-23 US US13/747,905 patent/US9018121B2/en not_active Expired - Fee Related
- 2013-01-31 TW TW102103735A patent/TWI469829B/zh not_active IP Right Cessation
-
2015
- 2015-03-26 US US14/669,179 patent/US9096484B1/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5689027A (en) * | 1994-11-18 | 1997-11-18 | Mobil Oil Corporation | Selective ethylbenzene conversion |
Also Published As
Publication number | Publication date |
---|---|
US20130225891A1 (en) | 2013-08-29 |
TW201410319A (zh) | 2014-03-16 |
WO2013130194A1 (en) | 2013-09-06 |
US9018121B2 (en) | 2015-04-28 |
US20150197465A1 (en) | 2015-07-16 |
US9096484B1 (en) | 2015-08-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8134037B2 (en) | Xylene isomerization process and apparatus | |
US7425660B2 (en) | Ethylbenzene conversion and xylene isomerization processes and catalysts therefor | |
KR100531530B1 (ko) | 크실렌 이성질화 | |
TW201202187A (en) | Xylene isomerization process and catalyst therefor | |
JP2006523679A (ja) | エチルベンゼン及びキシレンの異性化 | |
JP2019529511A (ja) | 重質芳香族炭化水素のトランスアルキル化 | |
US7247762B2 (en) | Process for xylene isomerization and ethylbenzene conversion | |
JP6928648B2 (ja) | 重質芳香族炭化水素の脱アルキル化およびトランスアルキル化 | |
US6114592A (en) | Selective aromatics disproportionation process | |
JP2019531298A (ja) | 重質芳香族炭化水素の不均化およびトランスアルキル化 | |
TWI469829B (zh) | 雙金屬觸媒及彼於製造二甲苯上之用途 | |
US7381677B1 (en) | Ethylbenzene conversion and xylene isomerization processes and catalysts therefor | |
US7456125B2 (en) | Ethylbenzene conversion and xylene isomerization processes and catalysts therefor | |
JP4735774B2 (ja) | エチルベンゼンの転化方法及びパラキシレン製造方法 | |
CN108349836B (zh) | 用于二甲苯异构化方法中乙基苯转化的改进催化剂 | |
TWI490035B (zh) | 使用雙催化劑系統之芳香族化合物異構化 | |
WO2009117000A1 (en) | Xylene isomerization process and apparatus | |
CN113663718A (zh) | 乙苯脱烷基型的二甲苯异构化反应催化剂及其制备方法 | |
WO2009116995A1 (en) | Ethylbenzene conversion and xylene isomerization processes and catalysts therefor | |
WO2011061204A1 (en) | Catalyst and isomerisation process | |
MXPA00010008A (es) | Isomerizacion de xileno |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |