TWI408006B - 沸石觸媒及其製法以及沸石觸媒之應用 - Google Patents
沸石觸媒及其製法以及沸石觸媒之應用 Download PDFInfo
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- TWI408006B TWI408006B TW095127161A TW95127161A TWI408006B TW I408006 B TWI408006 B TW I408006B TW 095127161 A TW095127161 A TW 095127161A TW 95127161 A TW95127161 A TW 95127161A TW I408006 B TWI408006 B TW I408006B
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- zeolite
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 168
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000010457 zeolite Substances 0.000 title claims abstract description 73
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 34
- 239000011574 phosphorus Substances 0.000 claims abstract description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims abstract description 27
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 20
- 230000029936 alkylation Effects 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000002168 alkylating agent Substances 0.000 claims abstract description 5
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 3
- -1 phosphorus compound Chemical class 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 195
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 238000010438 heat treatment Methods 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 238000005004 MAS NMR spectroscopy Methods 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 6
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 41
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000004738 31P MAS NMR Methods 0.000 abstract 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 57
- 238000007069 methylation reaction Methods 0.000 description 42
- 230000011987 methylation Effects 0.000 description 33
- 239000008096 xylene Substances 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 238000002002 phosphorus-31 magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000010455 vermiculite Substances 0.000 description 4
- 229910052902 vermiculite Inorganic materials 0.000 description 4
- 235000019354 vermiculite Nutrition 0.000 description 4
- 239000012690 zeolite precursor Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- SBMYBOVJMOVVQW-UHFFFAOYSA-N 2-[3-[[4-(2,2-difluoroethyl)piperazin-1-yl]methyl]-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCN(CC1)CC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SBMYBOVJMOVVQW-UHFFFAOYSA-N 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- WWFZRAYTGNKUQC-UHFFFAOYSA-H [Al+3].[Y+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Al+3].[Y+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WWFZRAYTGNKUQC-UHFFFAOYSA-H 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- LGZQQMXQPAHRIH-UHFFFAOYSA-N dimethylphosphinothioyl-dimethyl-sulfanylidene-$l^{5}-phosphane Chemical compound CP(C)(=S)P(C)(C)=S LGZQQMXQPAHRIH-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005206 flow analysis Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- RYIOLWQRQXDECZ-UHFFFAOYSA-N phosphinous acid Chemical compound PO RYIOLWQRQXDECZ-UHFFFAOYSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
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
- B01J29/82—Phosphates
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
-
- 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
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
-
- 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
-
- 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
- B01J2229/37—Acid treatment
-
- 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
- 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
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
大體而言,本發明係關於芳香族化合物之烷化及用於此等反應之觸媒以及其製備。
對二甲苯為有價值之經取代芳香族化合物,因為將其氧化成對苯二甲酸之需求頗大,對苯二甲酸係形成聚酯纖維及樹脂之主要成分。在商業上,對二甲苯可從輕油(naphtha,或稱石油腦)之氫化處理(觸媒重組),輕油或汽油(gas oil)之蒸氣裂解或甲苯之不對稱化反應(disproportionation)而製造。
甲苯以甲醇烷化,亦稱為甲苯甲基化,曾於實驗室研究中用於製造對二甲苯。已知甲苯甲基化可在酸性觸媒(尤其沸石或沸石型觸媒)存在下發生。更特定而言,ZSM-5型沸石、β沸石及矽鋁磷酸鹽(silicaaluminophosphate,SAPO)觸媒已被使用於此方法中。一般而言,鄰(o)-、間(m)-及對(p)-二甲苯之熱動力平衡組合物從甲苯之甲基化形成,如下列反應式所示。
在反應溫度約500℃時,從鄰(o)-、間(m)-及對(p)-二甲
苯形成之熱力動力平衡組成分別為25、50及25莫耳%。然而,此種甲苯甲基化可在廣大之溫度範圍發生。副產物諸如C9+及其他芳香族產物可藉由二甲苯產物之二次烷基化而產生。
對二甲苯可藉由吸附及異構物化之循環而從混合之二甲苯分離。因為在平衡混合物中異構物濃度低,該循環可重覆數次。為了氧化成對苯二甲酸,對二甲苯宜為高純度等級(99+%)。然而,此種高純度等級之對二甲苯之製造成本將變得很高。可使用採用結晶技術之不同方法,該方法較不昂貴,在該法中對二甲苯在初期二甲苯產物中之濃度為約80%或80%以上。因此,可期望得到高於平衡濃度之對二甲苯。
如果觸媒具有形狀選擇性質,則在甲苯甲基化反應中可得到明顯較高量之對二甲苯。藉由沸石孔隙尺寸之縮小,沸石外表面之去活性化或沸石酸性之控制而改質之沸石觸媒可得到形狀選擇性質。甲苯甲基化可在改質之ZSM-5或ZSM-5型沸石觸媒存在下進行,得到含有明顯高於熱力學平衡濃度之對二甲苯之二甲苯產物。
遺憾地,要讓甲苯甲基化在商業化上成功仍有許多障礙需要加以改善。此等障礙之例子如觸媒之快速去活性化及低甲醇選擇性。
為更能了解本發明,請參考下文說明及隨附之圖式。
ZSM-5沸石為用於烴轉化之最多態樣之觸媒之一。其為一種含有由10-員氧環所形成之互通二維孔隙結構之多孔性物質。具有此種10-員氧環孔隙結構之沸石物質通常被歸類為中孔隙(medium-pore)沸石。已證實將ZSM-5-型沸石觸媒用含磷化合物改質能提供觸媒形狀選擇性質,當該經磷改質之ZSM-5-型沸石觸媒用於甲苯甲基化時,與未經改質之觸媒相較,可得到顯然比熱力學平衡值大量之對二甲苯。此種改質顯示能提供大於80%之對二甲苯選擇率。雖然此種經磷-處理之ZSM-5觸媒對於對二甲苯具有高選擇率,但傾向於以極快速率去活化;例如該觸媒可在一天之內損失其最初活性之50%以上。其原因可能是由於觸媒上有焦碳沉積(coke deposition)。
本文中所使用之術語「ZSM-5-型」意指與ZSM-5沸石具有同等結構之沸石。再者,術語「ZSM-5」及「ZSM-5-型」在本文中可交替使用且包含彼此而無限定之意。在本文中,「觸媒活性」以「經轉化之甲苯於甲苯進料莫耳數中所佔之莫耳%」表示,並由下述公式界定:甲苯轉化率(莫耳%)=[(Ti-To)/Ti]×100 (2)
[其中,Ti為甲苯進料之莫耳數,To為未反應甲苯之莫耳數]。在本文中,「混合二甲苯選擇率」可用下式表示:混合二甲苯選擇率(莫耳%)=[Xtx(Ti-To)]×100 (3)
[其中,Xtx為該產物中混合之(鄰-、間-或對-)二甲苯之莫耳數]。
在本文中,「對二甲苯選擇率」可用下式表示:
對二甲苯選擇率(莫耳%)=Xp/Xtx×100 (4)
[其中,Xp為對二甲苯之莫耳數]。
在本文中,「甲醇轉化率」可用下式表示:甲醇轉化率(莫耳%)=[(Mi-Mo)/Mi]×100 (5)
[其中,Mi為甲醇進料之莫耳數,Mo為未反應之甲醇之莫耳數]。
在本文中,「甲苯甲基化之甲醇選擇率」可用下式表示:甲醇選擇率(莫耳%)=[Xtx/(Mi-Mo)]×100 (6)
[其中,Xtx為混合之(鄰-、間-或對-)二甲苯之莫耳數,Mi為甲醇進料之莫耳數,Mo為未反應之甲醇莫耳數]。
ZSM-5沸石觸媒及其製備記載於美國專利第3,702,886號,該專利以參考方式納入本文。在本發明中ZSM-5沸石觸媒可包括改質之前矽石/礬土莫耳比率為200或以上,尤其約250至約500者。起始之ZSM-5可為NH4 +或H+形式,並可包括微量之其他陽離子。
ZSM-5可藉由用含磷化合物處理而改質。該含磷化合物可包括(但不限定於)膦酸、亞膦酸(phosphinous acid)、亞磷酸及磷酸,此等酸之鹽或酯以及鹵化磷。尤其可用磷酸(H3PO4)及磷酸氫銨((NH4)2HPO4)做為含磷化合物,以賦予用於甲苯甲基化之觸媒形狀選擇性,而增加對二甲苯選擇率。此等經改質觸媒所含之磷(P)量為約0.01至約0.15g P/g沸石,其中以約0.02至約0.13g P/g沸石為較佳,以約0.07g P/g沸石至約0.12g P/g沸石為更佳,以約0.09g P/g沸石至
約0.11g P/g沸石為特佳。磷處理之後,可將經磷處理之沸石乾燥。
先前已發現磷處理後,將經P-改質之沸石加熱至300℃或更高溫度,繼而用適當黏結劑(如下文所述)黏結時,可使芳香族烷化(尤其甲苯烷化)之對位選擇率增加。該加熱導致在沸石中產生各種磷之物種。該加熱亦可加速磷處理後之觸媒乾燥。溫度300℃、400℃或更高溫度在提高對位選擇率上特別有用。該磷處理後之加熱之適當溫度範圍為約300℃至約600℃。此種加熱可進行0.5小時或以上。
另外發現在上述初始加熱步驟之後,將經P-處理之ZSM-5(P/ZSM-5)與適當之黏結劑組合,可進一步增加芳香族烷化之產物選擇率。更特定而言,P/ZSM-5於加熱及用適當黏結劑黏結時,該觸媒與使用於相似條件之甲苯甲基化之未經黏結的相同觸媒相較,可提高至少5%之對二甲苯選擇率。適當之黏結劑物質可包括無機氧化物。此等物質之例子包括礬土、黏土、磷酸鋁及矽石-礬土。尤其,礬土或黏土類黏結劑或其等之組合特別有用。經黏結觸媒可含有佔經黏結觸媒總重之約1%至99%之黏結劑,而以含有佔經黏結觸媒總重之約10%至50%之黏結劑為較佳。
為形成經黏結之觸媒,可將黏結劑物質與經磷處理之沸石組合,以形成可擠製之混合物。該用黏結劑黏結之經P處理之沸石可在400℃或以上之溫度,較佳500℃與700℃間之溫度煅燒或加熱。該加熱可進行0.5小時或以上,以形成經黏結之觸媒。現已發現將經P-處理之ZSM-5在約
300℃或以上之溫度加熱,繼而將該沸石用適當之上述黏結劑黏結,可導致在經黏結之沸石中呈現多種P-物種,此可由31P MAS NMR之峰顯示。
特定而言,經黏結之沸石觸媒呈現至少兩個於約0ppm至約-55ppm具有最大值之峰。更特定而言,該經黏結之沸石觸媒呈現一個於約0ppm至約-25ppm,尤其是約-5ppm至約-20ppm具有最大值之31P MAS NMR峰,而另一者於約-40ppm至約-50ppm具有最大值之峰。此等峰為各種磷物種之指標。尤其,在約-44ppm具有最大值之31P MAS NMR峰可能表示聚磷酸鹽物種。在約0ppm至約-25ppm具有最大值之峰可能表示藉由框架外(extra-framework)鋁或無定形之礬土而黏結之磷。磷酸鋁(AlPO4)及磷酸矽鋁(SAPO)可藉由在約-28ppm至約-35ppm具有最大值之峰表示。游離磷酸鹽可藉由在約0ppm具有最大值之峰表示。
對照於經黏結之經P-改質之沸石觸媒曾在300℃或以上之溫度被煅燒或加熱,未黏結之經P-改質之沸石先質未接受相同溫度之加熱處理。此種經黏結之經P-改質之沸石觸媒顯示只呈現一個31P MAS NMR峰。此顯示黏結劑與磷物種間交互作用之差異係取決於未黏結之經P-改質之沸石先質之加熱溫度。
經P-改質之ZSM-5觸媒(無論是經黏結或未經黏結)可在將該觸媒使用於任何反應之前,於300℃或以下之溫度溫和地進行蒸氣處理。該蒸氣處理可在反應器內部當場(in-situ)處理,亦可在反應器之外(ex-situ)處理。使用蒸氣
在溫和溫度下處理觸媒記載於同屬審查中之美國專利申請案號第11/122,919號中(申請日2005年5月5日),該案之標題為「經磷-改質之沸石觸媒之水性熱處理(hydrothermal treatment)」,該案以參考方式納入本文。
經P-改質之ZSM-5觸媒(無論經黏結或未經黏結)可在烷化反應條件下與適當之芳香烴進料及烷化劑接觸,以進行芳香族烷化。該觸媒在利用甲苯/甲醇進料進行甲苯甲基化時特別有用。亦可使用氣體共進料(cofeed)。該共進料氣體可包括氫氣或惰性氣體。在本文中使用之術語「烷化進料」意指包含芳香族化合物及烷化劑。在本文中使用之術語「甲基化進料」意欲包含甲苯及甲醇進料。
除任何共進料氣體之外,亦可將水(其可為水蒸氣形式)做為共進料而與烷化進料一起導入反應器中。甲烷化反應所用之水或水蒸氣可在烷化反應開始階段或開始階段之後,連同或不連同做為烷化進料之共進料之氫氣或惰性氣體引進反應器中。在任一種情況,均可添加液態水並在其與共進料氣體(若存在)及烷化進料混合前蒸氣化。水共進料之使用記載於美國專利申請案公開公報第US2005/0070749 A1號中,該案公開日為2005年3月31日,標題「甲苯甲基化方法」,該案以參考方式納入本文。
甲苯甲基化或其他芳香族烷化之反應器壓力可改變,但通常在約10至約1000psig之範圍。反應器溫度可改變,但典型地為約400至約700℃之範圍。當將進料導入反應器時,可將該觸媒床之溫度調整至選定之反應溫度,以獲
得期望之轉化率。該溫度可以約1℃/min至約10℃/min之速率逐漸增加,以提供期望之最後反應器溫度。在實施例中,反應器溫度意指從反應器之觸媒床入口量測到之溫度。
該反應可在通常用於進行芳香族烷化反應之各種不同反應器中進行。單反應器或串聯及/或並聯之多反應器均適於進行該芳香族烷化。
本文中所述之經P-改質之ZSM-5沸石觸媒在從甲苯及甲醇進料製備二甲苯產物之甲苯甲基化上具有特殊之用途。該觸媒在使用於甲苯甲基化時,可提供較高之對二甲苯選擇率。尤其,該觸媒在使用於甲苯甲基化時,可提供高於85%、90%甚至95%之對二甲苯選擇率。再者,在某些情況,可達到大於95%之總二甲苯選擇率。
再者,本文所述之P/ZSM-5觸媒(無論經黏結或未經黏結)可在適當之反應條件下,對於甲苯甲基化提供穩定的觸媒活性及選擇率達25日、30日、60日或60日以上之期間。在進行此種具有穩定觸媒性能之反應時,可將該觸媒於適當溫度下與甲基化進料及氣體共進料接觸,以得到期望之甲苯轉化率。在以下討論之實施例中,使用含有甲苯/甲醇(莫耳比約4.5)之甲基化進料時,期望之甲苯轉化率為理論上最大甲苯轉化率之63%。在測試期間,該反應係在,恆定反應器溫度下進行。
下述實施例將更充分地說明本發明。
製備不含黏結劑之經P-改質之ZSM-5(P/ZSM-5)。起始沸石粉末為所具SiO2/Al2O3莫耳比為280之NH4-ZSM-5。在2公升燒杯中製備含有700g之NH4-ZSM-5沸石及700ml水之漿液。將燒杯放置在熱板上,並使用機械(頂垂式)攪拌器以250-300rpm之速率攪拌該漿液。將該漿液之溫度緩慢地升高至約80-85℃。將含有319g磷酸(Aldrich,85重量%水溶液)之磷酸溶液緩慢加入漿液中。將該漿液溫度進一步提高至95-100℃,持續加熱直至所有液體蒸發。繼而將經磷酸改質之沸石依照下列加溫方式:90℃至120℃歷3小時,340℃至360℃歷3小時,510℃至530℃(空氣中)歷10小時,在對流烘箱中於空氣存在下加熱。繼而將得到之經熱處理之沸石(觸媒A)壓碎,使用20及40號篩網篩分出適用於觸媒反應者,或者用80號篩網篩分出適合用黏結劑黏結之沸石。
藉由X-射線螢光儀(XRF)分析觸媒A之Si、Al及P,並藉由N2吸附測定觸媒A之BET表面積及總孔隙體積。如表1所示,觸媒A含有35.73重量%之Si,0.28重量%之Al,9.01重量%之P,並具有BET表面積160m2/g及總孔隙體積0.12ml/g。觸媒A之X-射線繞射圖形係在Philips(X’Pert型)繞射分析儀上,於5-55°之範圍,掃描速度每分鐘2°,使用CuKα1射線進行記錄。其結果示於表2。
使用400MHz光度計(27Al於104.5MHz)在室溫記錄觸媒A之固體狀態魔角旋轉(Magic Angle Spinning;MAS)NMR光譜(27Al MAS NMR)。將樣本充填在氮化矽轉子(Si3N4)並於13至KHz將樣本旋轉(約800000rpm)。使用10度尖頭,且再循環延遲0.5秒以防止飽和。累積約4000至10000掃描數,以求出信號平均值並改進信號/雜音比。未使用質子去偶合(proton decoupling)。所有光譜均以在化
學位移標尺上氯化鋁六水合物(在試管中分開進行)為0.0ppm做為參考基準。由此得到基於氮化鋁(氮化矽轉子中之小量雜質)峰之內部參考值104.85ppm。觸媒A在50-55ppm區域呈現弱峰,此歸因於呈四面體結構之鋁。該四面體鋁之峰嚴重變形,顯示存在著巢狀矽烷醇(silanol),該巢狀矽烷醇係由於移去框架上之一些鋁時結構中之空洞所造成。相鄰峰(30-40ppm)歸因於嚴重變形但仍留在框架上之鋁原子,該鋁原子以氧3或5配位(coordination)。出現在-14ppm之光譜最大峰係歸因於呈八面體配位之鋁原子,該呈八面體配位之鋁原子係當用上述之磷酸鹽改質方法將呈四面體配位之框架鋁從沸石框架上移除時而形成。
使用400MHz光度計(31P於161.7MHz)在室溫記錄觸媒A之固體狀態魔角旋轉(MAS)NMR光譜(31P MAS NMR)。將樣本充填在氮化矽轉子(Si3N4)並於13至KHz將樣本旋轉(約800000rpm)。使用30度尖頭,且再循環延遲15秒以防止飽和。累積約4000至10000次掃描,以求出信號平均值並改進信號/雜音比。未使用質子去偶合(proton decoupling)。所有光譜均以在化學位移標尺上四甲基二膦二硫化物為37.8ppm及85%磷酸(在試管中分開進行)為0.0ppm做為雙重參考基準。
第一圖表示P/ZSM-5沸石(觸媒A)之31P MAS NMR光譜。該觸媒A之31P MAS NMR光譜顯示在0、-11、-31及-44ppm之峰屬於各種P-物種,例如游離磷及結合於(經由氧)Si及Al之磷。
將經熱處理之經P-改質之ZSM-5(如上述記載之觸媒A)用20重量%礬土黏結劑黏結。將19.18gm礬土(擬薄水鋁石(pseudobohemite)型,得自Alcoa,HiQ-40品級)用無機酸(例如HNO3)膠化(peptized),繼而與57.44gm之P/ZSM-5沸石粉末(通過80號篩)混合。噴水添加以形成柔軟之糊狀物。使用與上述觸媒A相同之溫度調控方式,將觸媒糊在510℃至530℃煅燒或加熱(為不規則塊或形成圓柱形狀)。將得到之觸媒B壓碎,並使用20及40號篩網篩分,以進行觸媒測試。
將經熱處理之經P-改質之ZSM-5(上述記載之觸媒A)用20%矽石黏結劑黏結。將8.19gm之Aerosil-200與5.05gm之Ludox-HS-40(膠體性矽石)混合,並於攪拌中緩慢將20.0ml之0.2N NH4OH加入其中。將20.02gm之P/ZSM-5粉末(通過80號篩)加入該矽石混合物中並充分攪拌。噴水製成糊狀,並使用與上述觸媒A相同之溫度調控方式將該糊於510℃至530℃煅燒。將得到之觸媒C壓碎,並使用20及40號篩網篩分以使用於觸媒測試。
將觸媒A用20%磷酸鋁黏結。依照對觸媒B所述之相同步驟將觸媒A用做為黏結劑之磷酸鋁黏結,該磷酸鋁得自Aldrich Chemical公司。將得到之觸媒D壓碎,並使用20及40號之篩網篩分以使用於觸媒測試。
將觸媒A用20%高嶺土黏結。依照對觸媒B所述之相同步驟,將P/ZSM-5用做為黏結劑之高嶺土黏結。使用得自Aldrich Chemical公司之高嶺土(矽酸鋁氫氧化物)。將得到之觸媒E壓碎,並使用20及40號之篩網篩分以使用於觸媒測試。
在實施例1-5中,於甲苯甲基化中使用觸媒A-E。反應各在固定床、連續流動型反應器中進行。在每一情況,將5.4ml觸媒(觸媒尺寸:通過20-40號篩)裝載於反應器中。該觸媒藉由在氫氣流(50cc/min)下,將觸媒床溫度緩慢地(約5℃/min)升高至200℃而乾燥至少一小時。該觸媒藉由於200℃導入水蒸氣(2.2 mmole/min)及H2載體氣體(459cc/min)而進行蒸氣處理隔夜。將預混合之甲苯及甲醇進料(莫耳比4.5)加入200℃之反應器中,並將觸媒床入口溫度增高至約550℃。將液體每小時空間速度(LHSV)(以甲基化進料為基準)維持在約2hr-1,以及饋入共進料H2氣體,並使H2/甲基化進料之莫耳比維持約7-8。再者,亦添加水至反應器中做為共進料,並在導入反應器之前將其蒸氣化。H2O/甲基化進料之莫耳比為約0.8,反應器壓力為約20psig。分析反應器流體以計算轉化率及選擇率。使用觸媒A-E之甲苯甲基化反應之液體產物流分析以及轉化率及選擇率如下表3所示。
使用對觸媒A所述之步驟,將所具SiO2/Al2O3莫耳比為280之NH4-ZSM-5用H3PO4處理。繼而將該經H3PO4處理之ZSM-5於510-530℃加熱約10小時。使用得到之P/ZSM-5粉末與做為黏結劑之10重量%礬土(Alcoa HiQ40)製備三種經礬土黏結之觸媒,並將其各個進一步於不同之最高溫度進行煅燒或加熱,形成觸媒F-H。觸媒F係在最
高溫度400℃加熱。觸媒G係在最高溫度510℃加熱。觸媒H係在最高溫度600℃加熱。將此等觸媒使用實施例1-5所述之條件測試甲苯甲基化。表4列出實施例6-8中於使用觸媒F-H下,液體產物流之分析以及轉化率及選擇率。
使用對觸媒A所述之步驟,將具有SiO2/Al2O3莫耳比為280之NH4-ZSM-5用H3PO4處理。繼而將該經H3PO4
處理之ZSM-5於不同溫度90℃、250℃及320℃加熱。繼而將該經加熱處理之經P-改質之ZSM-5沸石粉末與20重量%礬土(Alcoa HiQ40)混合,隨後進行對觸媒B所述之相同步驟,並於最高溫度510至530℃進行煅燒或加熱。將此等經黏結之觸媒(被命名為觸媒I、J及K)使用實施例1-5所述之條件測試甲苯甲基化。觸媒I及K之31P MAS NMR光譜如第二圖所示。觸媒I之31P MAS NMR光譜顯示只有在約-30ppm具有含長尾之單峰(第二圖之光譜a)。由於對於P/ZSM-5(用礬土黏結之前)之加熱溫度提高至約300℃或以上,因此最後生成之經黏結觸媒顯示峰數增加,包括在約-44ppm(參考例如第二圖之光譜b及第三圖之光譜b)之峰。表5簡述未經黏結之P/ZSM-5之最初加熱溫度及經黏結觸媒I至K之觸媒測試結果。再者,從表3複製之觸媒B數據亦呈現於表5中做為對照。此等由經P-改質之ZSM-5沸石於300℃或以上之溫度加熱,繼而用適當黏結劑加以黏結而製得之觸媒,顯示對甲苯甲基化具有90%或以上之對二甲苯選擇率。
為了比較,將表5中所示之轉化率及選擇率數據分別加以平均,並將對觸媒I所觀察到之值定為1.00,繼而與其他觸媒以相對尺度比較。如表6所示,在將沸石與黏結劑混合之前,隨著經磷-處理之ZSM-5之第一次加熱溫度增高,對二甲苯選擇率增高而甲苯轉化率降低。
從表6可見到將P/ZSM-5沸石加熱至溫度約300℃或以上,繼而用礬土黏結,隨後於500℃或以上之溫度煅燒或加熱而得者顯示形狀選擇性增加,致使甲苯甲基化時選擇性地產生對二甲苯。藉由將P/ZSM-5於300℃或以下之溫度加熱,並用礬土黏結,以及在500℃或以上煅燒或加熱,可得到具有較高活性但對位選擇率降低之觸媒。
使用對觸媒A所述之步驟,將NH4-ZSM-5沸石(SiO2/Al2O3莫耳比為280)用H3PO4處理,繼而於最高溫度550℃加熱。經P-處理之ZSM-5沸石粉末之分析,以分析觸媒A之方法進行,結果示於表7及8中。P/ZSM-5沸石之31P MAS NMR如第三圖(光譜a)所示。該P/ZSM-5呈現與觸媒A類似之性質。將P/ZSM-5沸石用20%礬土(擬薄水鋁石(pseudobohemite)型)黏結並壓出以製造1/16-吋圓柱型觸媒。分別將美國鋁業公司(Alcoa)之礬土品級HiQ-40及HiQ-10使用於觸媒L及M。將觸媒L及M於最高溫度
510℃及530℃煅燒或加熱。第三圖顯示經礬土黏結之觸媒-觸媒M之31P MAS NMR光譜(光譜b)。該觸媒M之31P MAS NMR光譜在約-13ppm(寬峰)及-44ppm呈現兩個強峰。此明顯地與第二圖(光譜a)所示之觸媒I之31P MAS NMR光譜不同。
測試觸媒L及M於甲苯甲基化中之性能。反應器、觸
媒進料、觸媒乾燥及蒸氣處理步驟與實施例1-5所述者相同,以及反應條件與實施例1-5相同。使用觸媒L及M時,反應器液體產物流之分析以及轉化率及選擇率分別如表9及10所示。在甲苯甲基化所用之反應條件下,觸媒L及M呈現初期甲苯轉化率為14%(係理論最大值之63%),及混合二甲苯選擇率大於98%及對二甲苯選擇率大於96%。
進一步測試觸媒L在甲苯甲基化反應中之觸媒安定性。反應器及進料條件與實施例1-5中所述者相同。在將觸媒於200℃乾燥後,將觸媒進行200℃之蒸氣處理隔夜。將預混合之甲苯及甲醇進料(莫耳比4.5)於200℃加入反應器中。將液體每小時空間速度(LHSV)(以甲基化進料為基準)維持在約2hr-1,饋入為共進料之H2氣體並使H2/甲基化進料莫耳比維持約7-8。除H2之外,亦將水蒸氣加入反應器
中做為共進料。H2O/甲基化進料之莫耳比為約0.8,以及反應器壓力為約20psig。將觸媒床入口溫度經一段期間緩慢增加至約510℃以得到甲苯轉化率約14%,在637小時(26日)測試期間內,未再調整反應器溫度。甲苯轉化率及混合二甲苯、對二甲苯及甲醇之選擇率如第四圖及第五圖所示。
使用觸媒M進一步證明甲苯甲基化反應中觸媒性能穩定。反應器、觸媒進料、觸媒乾燥及蒸氣處理步驟與實施例1-5所述者相同。在將觸媒於200℃乾燥後,將觸媒進行200℃之蒸氣處理隔夜。將預混合之甲苯及甲醇進料(莫耳比4.5)加入200℃之反應器中。將液體每小時空間速度(LHSV)(以甲基化進料為基準)維持在約2hr-1,饋入為共進料之H2氣體並使H2/甲基化進料之莫耳比維持約7-8。除H2之外,亦添加水蒸氣至反應器中做為共進料。H2O/甲基化進料莫耳比為約0.8,反應器壓力為約20psig。將觸媒床入口溫度經一段期間緩慢增加至約535℃以得到甲苯轉化率約14%,在測試期間1560小時(64日)內未再調整反應器溫度。甲苯轉化率及混合二甲苯、對二甲苯及甲醇之選擇率如第六圖及第七圖所示。
測試觸媒A在甲苯甲基化中之活性穩定性。反應器、進料組成、觸媒乾燥及蒸氣處理條件與實施例1-5中所述者相同。在將觸媒於200℃乾燥後,將觸媒於200℃進行蒸
氣處理隔夜。將預混合之甲苯及甲醇進料(莫耳比4.5)於200℃加入反應器中。將液體每小時空間速度(LHSV)(以甲基化進料為基準)維持在約2hr-1,饋入為共進料之H2氣體並將使H2/甲基化進料之莫耳比維持約7-8。再者,亦添加水至反應器中做為共進料,並在導入反應器之前將其蒸氣化。H2O/甲基化進料莫耳比為約0.8,反應器壓力為約20psig。當得到甲苯轉化率約14%時,將觸媒床入口溫度緩慢升高至約492℃,且在測試期間內未再調整反應器溫度。分析反應器蒸氣以計算轉化率及選擇率。第八圖顯示穩定之甲苯轉化率,其為時間之函數。未黏結之P/ZSM-5觸媒(觸媒A)在測試期間726小時(30日)中呈現穩定之性能。表11顯示觸媒A、L及M之平均甲苯轉化率、甲醇選擇率、混合二甲苯選擇率及對二甲苯選擇率。與未黏結之P/ZSM-5(觸媒A)相較,經礬土黏結之觸媒顯示對二甲苯選擇率至少增加5%。
第一圖顯示經磷改質之ZSM-5沸石觸媒A之31P MAS-NMR光譜。
第二圖顯示觸媒I之31P MAS-NMR光譜(光譜a)及觸媒K之31P MAS-NMR光譜(光譜b)。
第三圖顯示用於製備觸媒L及M之經磷改質之ZSM-5沸石先質之31P MAS-NMR光譜(光譜a),以及顯示經礬土黏結之經磷改質之ZSM-5沸石--(觸媒M)之31P MAS-NMR光譜(光譜b)。
第四圖為以實施例14之觸媒L進行甲苯甲基化反應時,經時之甲苯轉化率圖。
第五圖為以實施例14之觸媒L進行甲苯甲基化反應時,經時之甲醇選擇率圖(曲線1)、混合二甲苯選擇率圖(曲線2)及對二甲苯選擇率圖(曲線3)。
第六圖為以實施例15之觸媒M進行甲苯甲基化反應時,經時之甲苯轉化率圖。
第七圖為以實施例15之觸媒M進行甲苯甲基化反應時,經時之甲醇選擇率圖(曲線1)、混合二甲苯選擇率圖(曲線2)及對二甲苯選擇率圖(曲線3)。
第八圖為以實施例16之觸媒A進行甲苯甲基化反應時,經時之甲苯轉化率圖。
Claims (11)
- 一種製備沸石觸媒之方法,其包含:將沸石用磷化合物處理以形成經磷-處理之沸石;將該經磷-處理之沸石加熱至300℃至400℃之溫度;將該經磷-處理之沸石與無機氧化物黏結劑材料混合以形成沸石-黏結劑混合物;及將該沸石-黏結劑混合物加熱至400℃或以上之溫度,以形成經黏結之沸石觸媒。
- 如申請專利範圍第1項之方法,其中將該沸石-黏結劑混合物加熱至400℃至700℃之溫度。
- 如申請專利範圍第1項之方法,其中該黏結劑材料之存在量為該經黏結沸石觸媒之1重量%至99重量%。
- 如申請專利範圍第1項之方法,其中該沸石為ZSM-5沸石。
- 如申請專利範圍第4項之方法,其中該黏結劑材料包括礬土、黏土、磷酸鋁及矽石-礬土中之至少一種。
- 如申請專利範圍第4項之方法,其中該經黏結之沸石觸媒呈現至少兩個於0至-55ppm具有最大值之31P MAS NMR峰,其中至少一個峰於-40至-50ppm具有最大值。
- 如申請專利範圍第4項之方法,其進一步包含將該經黏結之沸石於300℃或以下之溫度進行蒸氣處理。
- 如申請專利範圍第4項所述之方法,其中磷含量為每公克沸石具有0.01至0.15公克之磷。
- 如申請專利範圍第4項所述之方法,其中磷-處理之沸石 具有磷含量為每公克沸石具有0.07至0.12公克之磷。
- 一種用於芳香族化合物之烷化之方法,其步驟包含:藉由如申請專利範圍第4至9項任一項所述之方法而製備經黏結的經磷-處理之ZSM-5沸石,且在烷化反應條件下將該觸媒與芳香烴之進料及烷化劑接觸,以進行芳香族烷化。
- 如申請專利範圍第10項所述之方法,其中該芳香烴為甲苯,而該烷化劑為甲醇。
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- 2006-08-03 EP EP06800818A patent/EP1928809A4/en not_active Ceased
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- 2006-08-03 WO PCT/US2006/030582 patent/WO2007019375A2/en active Application Filing
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EP1928809A4 (en) | 2009-11-18 |
SG144162A1 (en) | 2008-07-29 |
SG144161A1 (en) | 2008-07-29 |
JP2009502501A (ja) | 2009-01-29 |
EP1928809A2 (en) | 2008-06-11 |
US20080176736A1 (en) | 2008-07-24 |
US7507685B2 (en) | 2009-03-24 |
US7674942B2 (en) | 2010-03-09 |
WO2007019375A2 (en) | 2007-02-15 |
US20070032690A1 (en) | 2007-02-08 |
TW200806391A (en) | 2008-02-01 |
WO2007019375A3 (en) | 2009-04-23 |
KR20080039967A (ko) | 2008-05-07 |
KR101301890B1 (ko) | 2013-08-29 |
US20080275280A1 (en) | 2008-11-06 |
JP5254789B2 (ja) | 2013-08-07 |
CN101500969A (zh) | 2009-08-05 |
US7368410B2 (en) | 2008-05-06 |
MY144130A (en) | 2011-08-15 |
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