TW396151B - Process for aromatzatioon of hydrocarbons - Google Patents
Process for aromatzatioon of hydrocarbons Download PDFInfo
- Publication number
- TW396151B TW396151B TW086116556A TW86116556A TW396151B TW 396151 B TW396151 B TW 396151B TW 086116556 A TW086116556 A TW 086116556A TW 86116556 A TW86116556 A TW 86116556A TW 396151 B TW396151 B TW 396151B
- Authority
- TW
- Taiwan
- Prior art keywords
- feed stream
- scope
- hydrocarbons
- item
- aromatization
- Prior art date
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 41
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title abstract description 4
- 239000010457 zeolite Substances 0.000 claims abstract description 36
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 33
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 238000009835 boiling Methods 0.000 claims abstract description 5
- 239000003245 coal Substances 0.000 claims description 23
- 238000004939 coking Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 230000002079 cooperative effect Effects 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 150000007857 hydrazones Chemical group 0.000 claims description 3
- 239000013043 chemical agent Substances 0.000 claims 4
- 150000003961 organosilicon compounds Chemical group 0.000 claims 3
- 125000000304 alkynyl group Chemical group 0.000 claims 2
- 150000001409 amidines Chemical class 0.000 claims 2
- 229910052787 antimony Inorganic materials 0.000 claims 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 31
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 13
- 239000000571 coke Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 26
- 238000002386 leaching Methods 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229910052704 radon Inorganic materials 0.000 description 3
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 ethylene, propylene Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000445924 Epiphyllum <angiosperm> Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
- B01J31/124—Silicones or siloxanes or comprising such units
-
- 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
- B01J29/40—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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/949—Miscellaneous considerations
- Y10S585/95—Prevention or removal of corrosion or solid deposits
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
經濟部中央標準局員工消費合作社印製 A7 _____ B7五、發明説明（1 ) 發明之昔吾 本發明係關於在沸石物質之存在下，將非芳族烴轉化為 芳族烴之方法。更特別地’本發明亦關於在沸石物質之存 在下之烴之芳化時，焦煤形成速率之降低，因而增強此滩 石物質之安定力。 已知在含沸石（如ZSM-5)之觸媒之存在下’可將非芳族汽 油彿點範圍fe催化地裂解成低碳錦:烴（如乙浠與丙蟑）及芳 族烴（如苯、甲苯、與二甲苯），如Ν. γ Chen等人之工業與 工程化學製程設計與發展，第25卷，1986年，第15丨_155頁 之文章所述。此催化裂解處理之反應產物含多種烴：未轉 化Cs+烷屬烴、低碳烷屬烴（甲烷、乙烷、丙烷）、低碳缔 屬fe (乙婦與丙浠）、Ce -〇8芳族烴（苯、甲苯、二甲苯、與 乙基苯）、及c9+芳族烴。 在汽油沸騰範圍之烴成為芳族烴與低碳烯烴之轉化中， 使用沸石觸媒之顧慮為轉化反應時焦煤之過度產生。在烴 之沸石催化芳化時形成之焦煤趨於沉積於沸石之表面，因 而造成去活化。希望藉由在此芳化反應方法時減少形成之 焦煤量而改良烴之芳化方法。 發明之概要 本發明之目的為將含於汽油中之烴至少部份地轉化為乙 烯、丙烯與BTX(苯、甲苯、二甲苯與乙基苯）芳族化合 物。 本發明之另一個目的為提供改良之烴之芳也方法，其中 在此烴之芳化時之焦煤形成速率降低至低於先行技藝芳化 -4- 本紙張尺度適用中國國家標率（CNS )八4規格（21()>< 297公瘦） - (請先閱讀背面之注意事項再填寫本頁)
,1T 五、發明説明（2 A7 B7 經濟部中央標準局員工消費合作.杜印褽 方法之焦煤形成速率。 本發明方法提供低碳㈣與芳族由煙進㈣之製造，其 在轉化反應時之焦煤.形成速率低於其他類似轉化方法。含 ^油:騰範圍烴之進料流藉由在芳化反應條件下以酸歷滤 ::物質接觸進料流而進行芳化步驟。其條件為接觸酸瀝 滤滞石物質之進料流為—定濃度切燒化劑。 本發明之其他目的與㈣由詳細說明與所 圍變為明顯的。 曼上月之詳細說明 含在非芳族成為芳族之轉化中為有效的之潍石之任何觸 媒可用於本發明方法之接觸步驟。較佳為，觸媒之滞石成 刀”有、0 0.4至約12，車父佳為約2_9範圍之強制指數（如美國 專利4:M7,3 67所定義）。通常，滞石結晶框架中〜…對 2 3之莫耳比例為至少约5 ·‘ 1而且範圍可達無限大。較佳 為，沸石框架中Si〇jiA12〇3之莫耳比例為約8 ·〗至約2〇〇: 1，更佳為約12 : i至約60 : i。較佳沸石包括ZSM_5、 ZSM-8、ZSM_U、ZSM]2、ZSM 35、zsm_38、及其混合 物。—些這種沸石亦已知為"MFI"或，，Pentasil，，滩石。使用 含硼及/或至少—種選自包括Ga、In、Zn、Cr、Ge與S l金屬在本發明之範圍内。目前較佳之沸石為ZSM-5。 觸媒通常亦可含無機黏合劑（亦稱為基質物質），其較佳 為選自包括氧化鋁、矽石、氧化鋁-矽石、磷酸鋁、黏土 (略土）及其混合物。視情況地，其他金屬氧化物，如 氧鎮氧化鈽、氧化叙、氧化鈥、氧化錯、氧化給、氧 η (請先閱讀背面之注意事項再填寫本頁) 訂 -5 本紙張尺纽巧( 297公釐）
化in昆合物，亦可存在於觸媒中，其增強觸媒組合物 請 先 閲 讀 背 ιέ 注 意 再 填 寫 本 頁 ;=4=為，觸媒本質上應無如一，與其 屬，Ag、M°'w等之氳化促進劑(即， 这皂金屬之總量應低於約重量％)。 量，而=中沸石成份之含量為約1-99(較佳為約5-8°)重 二二上列無機黏合劑與金屬氧化物之含量為 觸媒之滞石成份已與黏合劑化合繼 而成形（如藉片化、擠製或錠化 ⑽,平方米/克，Μ粒度為約MG毫米媒《表面積為 訂 適合進科’其包含鍵燒煙（燒屬煙）及/或缔烴 (浠屬fe)及/或茶（環燒屬烴），其中這些烴每個分子各冬5-=個碳原子，可作為本發明接觸步驟之進料。這些進料你 :=二=。適合’可得進料之非限制實例包括得自催 tFCC)方法之汽油、得自_例如，@ t 熱解汽油、石油精、製氣油、重组油等。較佳 為適口作為至少-種汽油摻合物原科之汽油沸騰範 ㈣_21()t之弗點。通常，鍵㈣ 合=超過缔烴 '環燒屬烴與芳族化合物（如果存在）之组 經濟部中央樣_局員工消費合作社印製 之可藉任何適合之方法接觸含於本發明反應區内 ===_。接觸步驟可如分批方法步驟，或較佳 操作。在後者操作中，可使用固體觸媒 媒床或流體化觸媒床。任何之這些操作模式具 …、缺點，而且熟悉此技藝者可選擇最適合之特定進 本紐尺度 -6· A7五、發明説明（4 )
泛、媒：不需將大量氫氣隨進料引入接觸步驟之反應 ' ’即、，％全無H2或僅不重大地影響方法之殘量之h “例 如’低於約1 PPmH2)自外部來源引入這些反應器。 本發月之 <固重要狀態為氮進料流中—定濃度之石夕燒化 劑之提供，其接觸含於本發明反應區内之㈣觸媒。已發 現在-定濃度之㈣化劑存在^進料時，烴進料之滞石催 化芳化時之焦煤形成速率戲劇性地降低。核化劑在芳化 反應條件下接觸沸石觸媒時存在於烴進料中對本發明為重 要的。已在作為芳化觸媒前先时燒化劑改性之滞石之使 用不提供此種焦煤形成速率之降低，其由在芳化反應條件 下接觸滞石觸媒之㈣料内使㈤__定濃度之錢化劑生 成。 用於本發明方法之矽烷化劑為在適合烴之芳化之反應條 件下時，加入接觸沸石之烴進料時有效降低焦煤形成速率 之任何適合之含矽化合物。更特別地，矽烷化劑為選自具 有以下分子式之化合物之有機矽化合物： SiRyX4-y與（Rwx3.wSi)2_Z (請先閲讀背面之注意事項再填寫本頁) 訂 其中 f ! 經濟部中央標準局員工消费合作社印装 y = 1 至 4 ; w=1至3 ; R =烷基、芳基、Η、烷氧基、芳烷基 具有1至10個碳原子； X =鹵化物；及 Ζ =氧或ΝΗ或經取代之胺或醯胺。
及其中F -7- 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） 經濟部中央樣準局員工消費合作社印裝 A7 B7
五、發明説明L ，佳义矽烷化劑選自四烷基正矽酸酯（Si(〇R)4)及聚（烷基） 矽氧烷。最佳之矽烷化劑為四烷基正矽酸酯與聚（苯基甲基 梦氧娱；。 在芳化反應區内接觸沸石觸媒之烴進料之矽烷化劑濃度 應足以降低焦煤形成速率至低於進料中並無矽燒化劑時之 焦煤形成速率。烴進料中之矽烷化劑之有效濃度可為使得 存在之矽量基於烴之總重量達約5 〇重量％矽之範圍。較佳 為’碎之濃度可為約〇·01重量％至約8〇重量％，而且最佳 為〇，1重量％10重量％之範圍。 ‘ 接觸步驟在含沸石觸媒之芳化反應區内，及在適當地促 進烴進料中至少一部份烴之芳化之反應條件下進行。接觸 步驟之反應溫度更特別是在約40〇t：至約8〇(rc，較佳為約 450 C至約750°C，而且最佳為500°C至700°C之範圍《接觸 壓力範圍為大氣壓力至達約500 psia，較佳為約20 pSia至約 450 psia，而且最佳為 50 psia至 400 psia。 烴進料裝入芳化反應之流速為提供超過〇小時-1至高達約 1000小時·ι之重量小時空間速度（"WHSV”）。在此使用之名 詞π重量小時空間速度”表示烴進料以每小時磅數裝入反應 區之速率除以含於裝烴反應區之觸媒磅數之數量比例。接 觸區之進料之較佳WHS V可為約0.25小時-1至約25〇小時-1 ’而且最佳為0_5小時-1至100小時-1之範圍。本發明之特 佳具體實施例為在接觸含一定濃度之矽烷化劑之烴進料之 前已接受酸處理步驟之沸石觸媒之使用。任何適合之方法 可用以酸處理沸石觸媒，但是較佳為沸石藉此技藝已知之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)
Γ A7 B7 396151 五、發明説明（6 ) ^可適^方法以酸溶液浸料石，以㈣石與此酸溶液接 。酸溶視《酸可為適當地提供铭原子由滞石結晶結構歷 遽之任何酸。酸溶液較佳為水性氫氯酸1石浸於酸溶液 約0.25小時至約1 〇小時之時胡守，主 守疋時間。汉潰後，沸石清洗至無酸 然後乾燥及視情況烺燒。 提出以下實例以進一步描被太恭BE) t „ . 歹獨迷本弩明而且不應視為不當地 限制其範圍。
實例I 此實例敘述兩種用於實例丨〗之芳化反應進行之沸石製 品。 商業可得ZSM-5觸媒（聯合觸媒公司，L〇uisville，肯德基 州，以產品代號"T-4480”提供）藉酸瀝濾處理。為了酸瀝 遽，觸媒在約90 C之固定溫度浸於具有1 9重量％ HC1濃度 之水性HC1溶液中兩小時。浸潰後，自酸溶液分離觸媒而 且以水完全清洗及乾燥。酸浸潰、清洗與乾燥觸媒在約5〇〇 °C之溫度烺燒四小時。此酸瀝濾zsm-5觸媒用於如下所述 之芳化反應進行以決定有關其使用.之焦煤速率。 上述之酸瀝濾ZSM-5沸石藉由使用初期濕潤技術以梦炫 化劑處理，而以聚（甲基苯基）矽氧烷於環己垸作為溶液之 5 0重量％溶液浸潰之。浸潰、酸瀝濾ZSM-5乾燥兩小時繼 而在530°C烺燒6小時。此矽烷化與烺燒酸瀝濾ZSM_5觸媒 用於下述之芳化反應進行以決定有關其使用之焦煤速率。 實例11 此實例描述由以沸石觸媒含一定濃度之矽龙化劑之烴進 9- 本纸張尺度適用中國國家標隼（CNS ) M規格（210X297公廣） (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作.杜印装 396151 A7 B7__五、發明説明（7 ) 料之本發明方法生成之降低焦煤形成速率之益處。實例I之 兩種沸石製品用於芳化反應進行，其結果歸納於表I。酸瀝 濾沸石及矽烷化、酸瀝濾沸石為基本情形沸石觸媒，以其 比較本發明之結果。 對於各反應試驗進行，5克特定沸石觸媒製品混合約5cc 之10-20篩目氧化鋁之樣品置於不銹鋼管反應器中（長度： 1 8英吋；内徑：約0.5英吋）。得自煉油廠之催化裂解單元 之汽油在約600°C之溫度及大氣壓力（約0 psig)，以約1 5毫 升/小時之流速通過反應器。形成之反應產物離開反應器管 及通過許多冰冷閘。液體部份保留在這些閘中並且稱重， 而離開閘之氣態部份之體積以”濕試驗計"測量。定期地收 集液體與氣態產物樣品及藉氣相層析儀分析。反應進行完 成後，藉由測量沉積於觸媒表面上之焦煤量測定焦煤速 率。在本發明進行中，使用酸瀝濾沸石觸媒。裝於反應器 之起初進料含對各2體積份之正矽酸四甲酯（TEOS)為5體積 份之汽油進料，並且以約1 2毫升/小時之速率進料2小時。 繼而，無TEOS之汽油進料以1 4毫升/小時之速率裝於反應 器6小時。 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裝 表I 觸媒 焦煤速率 Wt%hr 酸瀝濾沸石 1.74 矽烷化，酸酸瀝濾沸石 0.46 加入以酸瀝濾沸石接觸之進料之TEOS 0.17 -10- 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） 396151五、發明説明（8 A7 B7 如由表I所示之焦煤速率數據所見到，ί夕燒化酸瀝遽沸石 在烴之芳化中之使用生成比酸瀝濾沸石低之焦煤速率。此 外，矽烷化劑對芳化時接觸酸瀝濾沸石之烴進料之加成比 使用矽烷化、酸瀝濾沸石提供更大之焦煤速率降低。 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 -11 - 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）
Claims (1)
- ^ 398151 第86116556號專利申請案 申請專利範圍f if本年？ )一種含非芳族烴之進料流之烴之芳化方法，該方法包含 在該進料流中提供矽烷化劑，及在芳化反應條件下以酸 瀝濾沸石接觸具有生成濃度之該矽燒化劑之該進料流， 其中石夕燒化劑為選自由聚燒基石夕氧燒、聚（苯基甲基）石夕 氧娱:及具有以下分子式之化合物所組成之有機矽化合 物： S i RyX4-4 ( RwX3.wSi)2_z 其中 經濟部中央梯準局員工消費合作社印製 1至4 ; w = 1 至 3 ; R =燒基、芳基、Η、娱•氧基 具有1至10個碳_原子； X =鹵化物；及 Ζ=氧或ΝΗ或經取代之胺或醯胺；及 其中該芳化反應條件包含反應溫度為4 〇 〇它至8 〇 〇。匚及反 應壓力為大氣壓力至500 psia。 2.根據申請專利範圍第1項之方法’其中該進料流中之烴 之沸騰範圍為30。(：至210°C。 3·根據申請專利範圍第1項之方法’其中該進料流中該矽 娱•化劑之漢度在該進料流之烴之芳化時有效降低焦煤形 成速率。 4_根據申請專利範圍第1項之方法，其中該進料流中該石夕 ’元化劑之;辰度為使得存在之梦之量為高達該進料流之垣 之50重量％之範圍。 y 芳烷基，及其中R (請先閲讀背面之注意Ϋ項再填寫本f) -、tr 锑 本紙張尺度逋用中國國家標準（CNS〉八4洗格（210X297公嫠） ^ 398151 第86116556號專利申請案 申請專利範圍f if本年？ )一種含非芳族烴之進料流之烴之芳化方法，該方法包含 在該進料流中提供矽烷化劑，及在芳化反應條件下以酸 瀝濾沸石接觸具有生成濃度之該矽燒化劑之該進料流， 其中石夕燒化劑為選自由聚燒基石夕氧燒、聚（苯基甲基）石夕 氧娱:及具有以下分子式之化合物所組成之有機矽化合 物： S i RyX4-4 ( RwX3.wSi)2_z 其中 經濟部中央梯準局員工消費合作社印製 1至4 ; w = 1 至 3 ; R =燒基、芳基、Η、娱•氧基 具有1至10個碳_原子； X =鹵化物；及 Ζ=氧或ΝΗ或經取代之胺或醯胺；及 其中該芳化反應條件包含反應溫度為4 〇 〇它至8 〇 〇。匚及反 應壓力為大氣壓力至500 psia。 2.根據申請專利範圍第1項之方法’其中該進料流中之烴 之沸騰範圍為30。(：至210°C。 3·根據申請專利範圍第1項之方法’其中該進料流中該矽 娱•化劑之漢度在該進料流之烴之芳化時有效降低焦煤形 成速率。 4_根據申請專利範圍第1項之方法，其中該進料流中該石夕 ’元化劑之;辰度為使得存在之梦之量為高達該進料流之垣 之50重量％之範圍。 y 芳烷基，及其中R (請先閲讀背面之注意Ϋ項再填寫本f) -、tr 锑 本紙張尺度逋用中國國家標準（CNS〉八4洗格（210X297公嫠） as 396151 ll D8 六、申請專利範圍 5. 根據申請專利範圍第1項之方法，其中該有機矽化合物 為正矽酸四烷酯。 6. 根據申請專利範圍第5項之方法，其中該正矽酸四烷酯 為正矽酸四乙酯。 (請先聞讀背面之注意事項再填寫本頁) 經濟部中央標隼局員工消費合作社印製 -2 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公嫠）
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| US08/745,527 US5800696A (en) | 1996-11-12 | 1996-11-12 | Method for inhibiting the rate of coke formation during the zeolite catalyzed aromatization of hydrocarbons |
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| US (2) | US5800696A (zh) |
| EP (1) | EP0841387B1 (zh) |
| JP (1) | JPH10147543A (zh) |
| KR (1) | KR19980042252A (zh) |
| CN (1) | CN1068373C (zh) |
| AU (1) | AU689414B1 (zh) |
| BR (1) | BR9705454A (zh) |
| CA (1) | CA2218763C (zh) |
| DE (1) | DE69725409T2 (zh) |
| ES (1) | ES2208804T3 (zh) |
| ID (1) | ID19065A (zh) |
| NO (1) | NO975182L (zh) |
| TW (1) | TW396151B (zh) |
| ZA (1) | ZA9710218B (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5942443A (en) | 1996-06-28 | 1999-08-24 | Caliper Technologies Corporation | High throughput screening assay systems in microscale fluidic devices |
| US5945364A (en) * | 1996-06-26 | 1999-08-31 | Phillips Petroleum Company | Catalyst composition comprising acid-base leached zeolites |
| US5800696A (en) * | 1996-11-12 | 1998-09-01 | Phillips Petroleum Company | Method for inhibiting the rate of coke formation during the zeolite catalyzed aromatization of hydrocarbons |
| US5873994A (en) * | 1997-07-15 | 1999-02-23 | Phillips Petroleum Company | Process for aromatization of a cracked gasoline feedstock using a catalyst containing an acid leached zeolite and tin |
| WO2000015338A1 (en) * | 1998-09-16 | 2000-03-23 | Phillips Petroleum Company | An improved zeolite |
| WO2000024509A1 (en) * | 1998-10-27 | 2000-05-04 | Phillips Petroleum Company | Method of making a zeolite catalyst and using the catalyst in a hydrocarbon conversion process |
| US6066770A (en) * | 1998-11-05 | 2000-05-23 | Phillips Petroleum Company | Selectivated zeolitic hydrocarbon conversion catalyst |
| CN1298425C (zh) * | 2004-12-01 | 2007-02-07 | 中国石油化工集团公司 | 一种芳构化催化剂及其制备方法和应用 |
| US20060219598A1 (en) * | 2005-01-10 | 2006-10-05 | Cody Ian A | Low energy surfaces for reduced corrosion and fouling |
| US20130237734A1 (en) * | 2012-03-07 | 2013-09-12 | Chevron Phillips Chemical Company Lp | Aromatization Catalyst and Methods of Preparing Same |
| JP7239100B2 (ja) * | 2018-09-03 | 2023-03-14 | Ｅｎｅｏｓ株式会社 | 炭素数６～８の単環芳香族炭化水素の製造方法 |
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| US3980586A (en) * | 1974-08-28 | 1976-09-14 | Mobil Oil Corporation | Modified solid catalyst materials |
| US4097367A (en) * | 1977-07-25 | 1978-06-27 | Mobil Oil Corporation | Conversion of olefinic naphtha |
| US4390414A (en) * | 1981-12-16 | 1983-06-28 | Exxon Research And Engineering Co. | Selective dewaxing of hydrocarbon oil using surface-modified zeolites |
| US4548914A (en) * | 1983-08-26 | 1985-10-22 | Mobil Oil Corporation | Zeolite catalysts of improved activity and para-selectivity |
| US4677094A (en) * | 1986-09-22 | 1987-06-30 | Uop Inc. | Trimetallic reforming catalyst |
| US4983274A (en) * | 1986-12-04 | 1991-01-08 | Mobil Oil Corp. | Shape selective crystalline silicate zeolite containing intermetallic component and use as catalyst in hydrocarbon conversions |
| US4849386A (en) * | 1987-04-08 | 1989-07-18 | Taiwan Styrene Monomer Corporation | Novel silicon-modified catalyst Si/HZSM-5 preparation |
| US4835336A (en) * | 1987-12-31 | 1989-05-30 | Mobil Oil Corporation | Method for suppressing hydrogenolysis of noble metal/low acidity zeolites |
| US4985135A (en) * | 1988-12-30 | 1991-01-15 | Exxon Research And Engineering Company | Surface silylated zeolite cataysts, and processes for the preparation, and use of said catalysts in the production of high octane gasoline |
| US4950835A (en) * | 1989-10-24 | 1990-08-21 | Taiwan Styrene Monomer Corporation | Novel silicon-modified catalyst Si/HZSM-5, it's preparation, and a process for synthesizing high purity p-dialkyl benzene from monoalkyl benzene by using said catalyst |
| GB8924410D0 (en) * | 1989-10-30 | 1989-12-20 | Exxon Chemical Patents Inc | Zeolite l |
| US5382696A (en) * | 1992-10-16 | 1995-01-17 | Mitsui Toatsu Chemicals, Incorporated | Method for preparing methylamines |
| US5300469A (en) * | 1992-12-08 | 1994-04-05 | Engelhard Corporation | Composition for passivating vanadium in catalytic cracking and preparation thereof |
| US5349113A (en) * | 1993-02-25 | 1994-09-20 | Mobil Oil Corp. | Shape selective hydrocarbon conversion over pre-selectivated, activated catalyst |
| US5476823A (en) * | 1993-05-28 | 1995-12-19 | Mobil Oil Corp. | Method of preparation of ex situ selectivated zeolite catalysts for enhanced shape selective applications and method to increase the activity thereof |
| US5800696A (en) * | 1996-11-12 | 1998-09-01 | Phillips Petroleum Company | Method for inhibiting the rate of coke formation during the zeolite catalyzed aromatization of hydrocarbons |
-
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- 1996-11-12 US US08/745,527 patent/US5800696A/en not_active Expired - Fee Related
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1997
- 1997-10-20 CA CA002218763A patent/CA2218763C/en not_active Expired - Fee Related
- 1997-10-29 AU AU43608/97A patent/AU689414B1/en not_active Ceased
- 1997-11-06 TW TW086116556A patent/TW396151B/zh active
- 1997-11-06 ID IDP973617A patent/ID19065A/id unknown
- 1997-11-10 KR KR1019970059006A patent/KR19980042252A/ko active IP Right Grant
- 1997-11-10 BR BR9705454-2A patent/BR9705454A/pt unknown
- 1997-11-11 NO NO975182A patent/NO975182L/no not_active Application Discontinuation
- 1997-11-11 DE DE69725409T patent/DE69725409T2/de not_active Expired - Fee Related
- 1997-11-11 ES ES97119723T patent/ES2208804T3/es not_active Expired - Lifetime
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- 1997-11-12 JP JP9310649A patent/JPH10147543A/ja active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH10147543A (ja) | 1998-06-02 |
| US5800696A (en) | 1998-09-01 |
| MX9708694A (es) | 1998-09-30 |
| NO975182D0 (no) | 1997-11-11 |
| CN1068373C (zh) | 2001-07-11 |
| NO975182L (no) | 1998-05-13 |
| ZA9710218B (en) | 1998-06-03 |
| DE69725409D1 (de) | 2003-11-13 |
| DE69725409T2 (de) | 2004-08-19 |
| CA2218763C (en) | 2001-05-22 |
| EP0841387A3 (en) | 1998-07-29 |
| BR9705454A (pt) | 1999-10-05 |
| EP0841387B1 (en) | 2003-10-08 |
| CA2218763A1 (en) | 1998-05-12 |
| ES2208804T3 (es) | 2004-06-16 |
| KR19980042252A (ko) | 1998-08-17 |
| CN1182117A (zh) | 1998-05-20 |
| AU689414B1 (en) | 1998-03-26 |
| ID19065A (id) | 1998-06-11 |
| EP0841387A2 (en) | 1998-05-13 |
| US5925237A (en) | 1999-07-20 |
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