JP2012502876A - 超メソ多孔性yゼオライト - Google Patents
超メソ多孔性yゼオライト Download PDFInfo
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- JP2012502876A JP2012502876A JP2011527821A JP2011527821A JP2012502876A JP 2012502876 A JP2012502876 A JP 2012502876A JP 2011527821 A JP2011527821 A JP 2011527821A JP 2011527821 A JP2011527821 A JP 2011527821A JP 2012502876 A JP2012502876 A JP 2012502876A
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- zeolite
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- 239000010457 zeolite Substances 0.000 title claims abstract description 330
- 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 296
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 290
- 239000011148 porous material Substances 0.000 claims abstract description 182
- 238000000034 method Methods 0.000 claims abstract description 100
- 230000008569 process Effects 0.000 claims abstract description 52
- 238000005504 petroleum refining Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims description 78
- 239000012690 zeolite precursor Substances 0.000 claims description 46
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 21
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 10
- 238000004523 catalytic cracking Methods 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 230000029936 alkylation Effects 0.000 claims description 4
- 238000005804 alkylation reaction Methods 0.000 claims description 4
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 4
- 238000006384 oligomerization reaction Methods 0.000 claims description 4
- 150000002910 rare earth metals Chemical group 0.000 claims description 4
- 238000006317 isomerization reaction Methods 0.000 claims description 3
- 238000002407 reforming Methods 0.000 claims description 3
- 230000002035 prolonged effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 238000003795 desorption Methods 0.000 description 46
- 230000007774 longterm Effects 0.000 description 30
- 230000009849 deactivation Effects 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000011734 sodium Substances 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 12
- 238000005342 ion exchange Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 230000001186 cumulative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000002336 sorption--desorption measurement Methods 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 230000036961 partial effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 6
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- RNAMYOYQYRYFQY-UHFFFAOYSA-N 2-(4,4-difluoropiperidin-1-yl)-6-methoxy-n-(1-propan-2-ylpiperidin-4-yl)-7-(3-pyrrolidin-1-ylpropoxy)quinazolin-4-amine Chemical compound N1=C(N2CCC(F)(F)CC2)N=C2C=C(OCCCN3CCCC3)C(OC)=CC2=C1NC1CCN(C(C)C)CC1 RNAMYOYQYRYFQY-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- -1 alkaline earth metal cation Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000008684 selective degradation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- B01J35/69—
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
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- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
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- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
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- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/22—After treatment, characterised by the effect to be obtained to destroy the molecular sieve structure or part thereof
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
Description
a)Na−Yゼオライトをアンモニウム交換して約2〜約5重量%のNa2O含有率のゼオライト前駆体を得る工程と;
b)このゼオライト前駆体を、約1200°F〜約1500°Fの温度での高温水蒸気か焼(カ焼又は焼成)にかける工程であって、ゼオライト前駆体の温度が、5分未満で高温水蒸気か焼温度の50°F内にある工程と
を含む、超メソ多孔性ゼオライトの製造方法であり、
このゼオライトが少なくとも約0.03cm3/gの大きなメソ孔容積および約0.15cm3/g未満の小さなメソ孔ピークを有する方法である。
a)石油精製プロセス(又は方法)で、炭化水素含有供給原料をYゼオライトと接触させる工程と;
b)炭化水素含有供給原料より低い平均分子量を有する少なくとも1つの生成物流れを生成する工程と
を含む、炭化水素含有供給原料の転化のための超メソ多孔性ゼオライトの使用方法であって、
このゼオライトが少なくとも約0.03cm3/gの大きなメソ孔容積および約0.15cm3/g未満の小さなメソ孔ピークを有する方法である。
a)石油精製プロセスで炭化水素含有供給原料をYゼオライトと接触させる工程と;
b)炭化水素含有供給原料より低い平均分子量を有する少なくとも1つの生成物流れを生成する工程と
を含む、炭化水素含有供給原料の転化プロセスであって、
ゼオライトが少なくとも約0.03cm3/gの大きなメソ孔容積および約0.15cm3/g未満の小さなメソ孔ピークを有するプロセスに利用される。
低いナトリウム含有率の市販のアンモニウム交換Yゼオライト(ZeolystTMからのCBV−300(登録商標)、SiO2/Al2O3モル比=5.3、Na2O 無水ベースで3.15重量%)を、1000°Fの温度でおよび50%水蒸気+50%N2の流れにある水平か焼炉で1時間水蒸気処理した。生じた生成物は、超安定Y(USY)ゼオライトであり、77.35°Kでの窒素吸着/脱着による細孔径分布特性を測定するためにMicromeritics(登録商標)Tristar 3000(登録商標)分析器で分析した。本明細書に記載されるようなBJH法をN2吸着/脱着等温線に適用してゼオライトの細孔径分布を得た。dV/dlogD対平均孔径のプロットを図1に示す。
((62.8−50.0)/(62.8−41.5)×0.0032)+0.0085=0.0104cm3/g
((5.3−5.0)/(5.3−4.6)×0.0031)+0.0286=0.0299cm3/g
0.0299cm3/g−0.0104cm3/g=0.0195cm3/g
小さなメソ多孔性容積(範囲:3.0nm〜5.0nm):0.0193cm3/g
大きなメソ多孔性容積(範囲:5.0nm〜50.0nm):0.0195cm3/g
(大きなメソ孔容積)/(小さなメソ孔容積)の比:1.01
小さなメソ孔ピーク(3.9nmでのdV/dlogD):0.20cm3/g
小さなメソ多孔性容積(範囲:3.0nm〜5.0nm):0.0112cm3/g
大きなメソ多孔性容積(範囲:5.0nm〜50.0nm):0.1211cm3/g
(大きなメソ孔容積)/(小さなメソ孔容積)の比:10.85
小さなメソ孔ピーク(3.9nmでのdV/dlogD):0.19cm3/g
この実施例では、超メソ多孔性Y(「EMY」)ゼオライトの実施形態を次の通り調製した:
小さなメソ多孔性容積(範囲:3.0nm〜5.0nm):0.0109cm3/g
大きなメソ多孔性容積(範囲:5.0nm〜50.0nm):0.0740cm3/g
(大きなメソ孔容積)/(小さなメソ孔容積)の比:6.79
小さなメソ孔ピーク(3.9nmでのdV/dlogD):0.09cm3/g
小さなメソ多孔性容積(範囲:3.0nm〜5.0nm):0.0077cm3/g
大きなメソ多孔性容積(範囲:5.0nm〜50.0nm):0.1224cm3/g
(大きなメソ孔容積)/(小さなメソ孔容積)の比:15.97
小さなメソ孔ピーク(3.9nmでのdV/dlogD):0.10cm3/g
この実施例では、実施例1および2でと同じアンモニウム交換した市販のYゼオライトCBV−300(登録商標)を、次の通り異なる高温水蒸気か焼工程にかけ、生じたサンプル3A〜3Fのそれぞれを、実施例1および2と同様なMicromeritics(登録商標)Tristar 3000(登録商標)分析器を用いて分析した。
Claims (38)
- 少なくとも約0.03cm3/gの大きなメソ孔容積および約0.15cm3/g未満の小さなメソ孔ピークを含むYゼオライト。
- 前記ゼオライトの単位格子寸法が約24.37オングストローム〜約24.47オングストロームである、請求項1に記載のゼオライト。
- 少なくとも約4.0の大きな細孔と小さな細孔との容積比を有する、請求項1に記載のゼオライト。
- 前記ゼオライトの前駆体は、約1200°F〜約1500°Fの温度での高温水蒸気か焼工程にかけられ、前記ゼオライト前駆体の温度は、5分未満で高温水蒸気か焼温度の50°F内である、請求項1に記載のゼオライト。
- 前記高温水蒸気か焼工程前の前記ゼオライトの前駆体のNa2O含有率が無水ベースで全前駆体重量の約2〜約5重量%である、請求項4に記載のゼオライト。
- 前記ゼオライトの前記小さなメソ孔容積ピークが約0.13cm3/g未満である、請求項1に記載のゼオライト。
- 前記ゼオライトの前記大きなメソ孔容積が少なくとも約0.05cm3/gである、請求項6に記載のゼオライト。
- 前記ゼオライトの前記大きなメソ孔容積および前記ゼオライトの前記小さなメソ孔ピークが、製造されたままのゼオライトで測定される、請求項1に記載のゼオライト。
- 前記ゼオライトの前記大きなメソ孔容積および前記ゼオライトの前記小さなメソ孔ピークが、前記製造されたままのゼオライトで測定される、請求項7に記載のゼオライト。
- 前記ゼオライトの大きな細孔と小さな細孔との容積比が少なくとも約5.0である、請求項3に記載のゼオライト。
- 前記ゼオライトの単位格子寸法が約24.40オングストローム〜約24.45オングストロームである、請求項10に記載のゼオライト。
- 前記ゼオライト前駆体が、約1250°F〜約1450°Fの温度での高温水蒸気か焼工程にかけられ、前記ゼオライト前駆体の温度が、5分未満で前記高温水蒸気か焼温度の50°F内にある、請求項4に記載のゼオライト。
- 前記高温水蒸気か焼工程前の前記ゼオライトの前駆体の前記Na2O含有率が無水ベースで前記全前駆体重量の約2.3〜約4重量%である、請求項12に記載のゼオライト。
- 希土類元素からなる、請求項1に記載のゼオライト。
- 少なくとも500m2/gのBET表面積を有する、請求項1に記載のゼオライト。
- 1400°Fで16時間長期失活水蒸気処理した後に、前記ゼオライトが、少なくとも約10.0の大きな細孔と小さな細孔との容積比、約0.15cm3/g未満の小さなメソ孔ピーク、および少なくとも0.07cm3/gの大きなメソ孔容積を有する、請求項1に記載のゼオライト。
- 少なくとも約5.0の大きな細孔と小さな細孔との容積比、約0.13cm3/g未満の小さなメソ孔ピーク、および少なくとも0.05cm3/gの大きなメソ孔容積を有する、請求項8に記載のゼオライト。
- 少なくとも約6.0の大きな細孔と小さな細孔との容積比、および約0.11cm3/g未満の小さなメソ孔ピークを有する、請求項17に記載のゼオライト。
- a)Na−Yゼオライトをアンモニウム交換して無水ベースで約2〜約5重量%のNa2O含有率のゼオライト前駆体を得る工程と;
b)前記前ゼオライト駆体を、約1200°F〜約1500°Fの温度での高温水蒸気か焼にかける工程であって、前記ゼオライト前駆体の温度が5分未満で前記高温水蒸気か焼温度の50°F内にある工程と
を含む、Yゼオライトの製造方法であって、
前記ゼオライトが、少なくとも約0.03cm3/gの大きなメソ孔容積、および約0.15cm3/g未満の小さなメソ孔ピークを有する方法。 - 前記ゼオライト前駆体が、前記ゼオライト前駆体を高温水蒸気か焼にかける工程の前に希土類交換される、請求項19に記載の方法。
- 前記ゼオライトが少なくとも約4.0の大きな細孔と小さな細孔との容積比を有する、請求項19に記載の方法。
- 前記ゼオライトの前記大きなメソ孔容積および前記ゼオライトの前記小さなメソ孔ピークが、前記製造されたままのゼオライトで測定される、請求項19に記載の方法。
- 前記ゼオライトの前記大きなメソ孔容積、前記ゼオライトの前記小さなメソ孔ピーク、および前記ゼオライトの前記大きな細孔と小さな細孔との容積比が、前記製造されたままのゼオライトで測定される、請求項21に記載の方法。
- 前記ゼオライトが約24.37オングストローム〜約24.47オングストロームの単位格子寸法を有する、請求項19に記載の方法。
- 前記高温水蒸気か焼の温度が約1250°F〜約1450°Fであり、前記ゼオライト前駆体の温度が2分未満で前記高温水蒸気か焼温度の50°F内にある、請求項21に記載の方法。
- 前記ゼオライト前駆体の前記Na2O含有率が無水ベースで約2.3〜約4重量%である、請求項23に記載の方法。
- 前記ゼオライトが、少なくとも約5.0の大きな細孔と小さな細孔との容積比および約0.13cm3/g未満の小さなメソ多孔性容積ピークを有する、請求項19に記載の方法。
- 前記高温水蒸気か焼の温度が約1250°F〜約1450°Fであり、前記ゼオライト前駆体の温度が2分未満で前記高温水蒸気か焼温度の50°F内にある、請求項27に記載の方法。
- a)石油精製方法で、炭化水素含有供給原料をYゼオライトと接触させる工程と;
b)前記炭化水素含有供給原料より低い平均分子量を有する少なくとも1つの生成物流れを生成する工程と
を含む、炭化水素含有供給原料の転化方法であって、
前記ゼオライトが、少なくとも約0.03cm3/gの大きなメソ孔容積および約0.15cm3/g未満の小さなメソ孔ピークを有する方法。 - 前記石油精製方法が、接触分解法、流動接触分解法、水素化分解法、水素化脱硫法、改質法、アルキル化法、オリゴマー化法、脱ロウ法、および異性化法から選択される、請求項29に記載の方法。
- 前記石油精製方法が流動接触分解法である、請求項30に記載の方法。
- 前記ゼオライトの前記単位格子寸法が約24.37オングストローム〜約24.47オングストロームである、請求項29に記載の方法。
- 前記ゼオライトが少なくとも約4.0の大きな細孔と小さな細孔との容積比を有する、請求項29に記載の方法。
- 前記ゼオライトの前記小さなメソ孔容積ピークが約0.13cm3/g未満である、請求項29に記載の方法。
- 前記ゼオライトの前記大きなメソ孔容積が少なくとも約0.05cm3/gである、請求項34に記載の方法。
- 前記ゼオライトの前記大きなメソ孔容積および前記ゼオライトの前記小さなメソ孔ピークが、前記製造されたままのゼオライトで測定される、請求項29に記載の方法。
- 前記ゼオライトの前記大きなメソ孔容積および前記ゼオライトの前記小さなメソ孔ピークが、前記製造されたままのゼオライトで測定される、請求項35に記載の方法。
- 前記ゼオライトが少なくとも約5.0の大きな細孔と小さな細孔との容積比を有する、請求項37に記載の方法。
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JP2012513359A (ja) * | 2008-12-22 | 2012-06-14 | トタル・ラフィナージュ・マーケティング | 三峰性結晶内構造を有する改変y型ゼオライト、それを製作する方法、及びその使用 |
US9126183B2 (en) | 2008-12-22 | 2015-09-08 | Centre National De La Recherche Scientifique | Modified Y-type zeolites having a trimodal intracrystalline structure, method for making same, and use thereof |
US9242234B2 (en) | 2008-12-22 | 2016-01-26 | Centre National De La Recherche Scientifique | Modified Y-type zeolites having a trimodal intracrystalline structure, method for making same, and use thereof |
JP2012046376A (ja) * | 2010-08-26 | 2012-03-08 | Tottori Univ | ゼオライト触媒およびその生産方法 |
JP2017530150A (ja) * | 2014-10-02 | 2017-10-12 | モンサント テクノロジー エルエルシー | 2,5−ジクロロフェノールの合成方法 |
JP2018500152A (ja) * | 2014-10-31 | 2018-01-11 | シェブロン ユー.エス.エー. インコーポレイテッド | 高いナノ細孔の安定化yゼオライトを含有する中間留分水素化分解触媒 |
JP2018500151A (ja) * | 2014-10-31 | 2018-01-11 | シェブロン ユー.エス.エー. インコーポレイテッド | 高い酸点分布を有する安定化yゼオライトを高含有する中間留分水素化分解触媒 |
JP2020182947A (ja) * | 2014-10-31 | 2020-11-12 | シェブロン ユー.エス.エー. インコーポレイテッド | 高い酸点分布を有する安定化yゼオライトを高含有する中間留分水素化分解触媒 |
JP2020182946A (ja) * | 2014-10-31 | 2020-11-12 | シェブロン ユー.エス.エー. インコーポレイテッド | 高いナノ細孔の安定化yゼオライトを含有する中間留分水素化分解触媒 |
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BRPI0918452A2 (pt) | 2015-11-24 |
AR073385A1 (es) | 2010-11-03 |
US20100065477A1 (en) | 2010-03-18 |
AU2009292638A1 (en) | 2010-03-25 |
WO2010033202A1 (en) | 2010-03-25 |
TW201029928A (en) | 2010-08-16 |
US20130115162A1 (en) | 2013-05-09 |
US8513150B2 (en) | 2013-08-20 |
US8361434B2 (en) | 2013-01-29 |
JP5847582B2 (ja) | 2016-01-27 |
CA2736386A1 (en) | 2010-03-25 |
TWI478872B (zh) | 2015-04-01 |
CN102159315A (zh) | 2011-08-17 |
EP2342012A1 (en) | 2011-07-13 |
CN102159315B (zh) | 2014-10-29 |
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