JPH10216526A - Catalyst composition for fluid catalytic cracking of hydrocarbon - Google Patents
Catalyst composition for fluid catalytic cracking of hydrocarbonInfo
- Publication number
- JPH10216526A JPH10216526A JP9037157A JP3715797A JPH10216526A JP H10216526 A JPH10216526 A JP H10216526A JP 9037157 A JP9037157 A JP 9037157A JP 3715797 A JP3715797 A JP 3715797A JP H10216526 A JPH10216526 A JP H10216526A
- Authority
- JP
- Japan
- Prior art keywords
- catalytic cracking
- catalyst composition
- catalyst
- fluid catalytic
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 31
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 31
- 238000004231 fluid catalytic cracking Methods 0.000 title claims abstract description 28
- 239000004215 Carbon black (E152) Substances 0.000 title abstract description 9
- 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 54
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 claims abstract description 45
- 239000010457 zeolite Substances 0.000 claims abstract description 33
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 31
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 26
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052670 petalite Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 25
- 239000002184 metal Substances 0.000 abstract description 25
- 239000003502 gasoline Substances 0.000 abstract description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- 239000000356 contaminant Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 5
- 150000003464 sulfur compounds Chemical class 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229910011763 Li2 O Inorganic materials 0.000 abstract 1
- 238000004523 catalytic cracking Methods 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 230000000694 effects Effects 0.000 description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 10
- 150000001342 alkaline earth metals Chemical class 0.000 description 10
- 239000000571 coke Substances 0.000 description 9
- 229910044991 metal oxide Inorganic materials 0.000 description 9
- 150000004706 metal oxides Chemical class 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 229910052720 vanadium Inorganic materials 0.000 description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 8
- 229910018068 Li 2 O Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011268 mixed slurry Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 239000012798 spherical particle Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052815 sulfur oxide Inorganic materials 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 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 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910005965 SO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910010100 LiAlSi Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、炭化水素流動接触分解
用触媒組成物に関し、さらに詳しくは、炭化水素、特に
ニッケル、バナジウムなどの金属汚染物と硫黄化合物を
含有する重質炭化水素の流動接触分解に使用して、耐メ
タル性、硫黄酸化物捕捉能に優れ、高活性でガソリン選
択性に優れ、しかもオクタン価（ＲＯＮ）の低下の少な
い炭化水素流動接触分解用触媒組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst composition for fluid catalytic cracking of hydrocarbons, and more particularly, to the flow of hydrocarbons, especially heavy hydrocarbons containing metal contaminants such as nickel and vanadium and sulfur compounds. The present invention relates to a catalyst composition for hydrocarbon fluid catalytic cracking, which is used for catalytic cracking, has excellent metal resistance and sulfur oxide trapping ability, is highly active, has excellent gasoline selectivity, and has a small decrease in octane number (RON).
【０００２】[0002]
【従来技術およびその問題点】従来、ニッケル、バナジ
ウムなどの金属汚染物を含有する重質炭化水素の接触分
解では、触媒上に沈着したバナジウムが活性成分である
結晶性アルミノシリケートゼオライトの結晶構造を破壊
し、触媒の著しい活性低下をもたらすことが知られてお
り、そして、触媒上に沈着したバナジウムなどの金属汚
染物を不活性化するために、種々の化合物を金属捕捉剤
として含有させ、耐メタル性を向上させた触媒も種々提
案されている（例えば、特開昭６１−１４９２４１号、
特開昭６２−３８２４２号）。2. Description of the Related Art Conventionally, in the catalytic cracking of heavy hydrocarbons containing metal contaminants such as nickel and vanadium, the crystal structure of crystalline aluminosilicate zeolite in which vanadium deposited on a catalyst is an active component is used. Various compounds are included as metal scavengers to destroy and deactivate metal contaminants such as vanadium deposited on the catalyst, which are known to cause a significant decrease in the activity of the catalyst. Various catalysts having improved metal properties have also been proposed (for example, JP-A-61-149241,
JP-A-62-38242).
【０００３】しかし、アルカリ土類金属化合物は金属汚
染物を不活性化する優れた効果を有するものの、これを
金属捕捉剤として無機酸化物マトリックス中に分散させ
た触媒組成物では、アルカリ土類金属が接触分解反応使
用中に移動して、結晶アルミノシリケートゼオライトの
熱安定性を低下させ、結晶構造を破壊するため触媒の活
性が低下したり、あるいは、結晶性アルミノシリケート
ゼオライトにアルカリ土類金属がイオン交換して組込ま
れるため、接触分解反応で得られるガソリン生成物のオ
クタン価（ＲＯＮ）が低下する、などの問題があった。[0003] However, although the alkaline earth metal compound has an excellent effect of inactivating metal contaminants, a catalyst composition in which this is dispersed in an inorganic oxide matrix as a metal scavenger has been used. Moves during use of the catalytic cracking reaction, lowering the thermal stability of the crystalline aluminosilicate zeolite, destroying the crystal structure and reducing the activity of the catalyst, or adding an alkaline earth metal to the crystalline aluminosilicate zeolite. Since it is incorporated by ion exchange, there is a problem that the octane value (RON) of the gasoline product obtained by the catalytic cracking reaction is reduced.
【０００４】さらに、金属捕捉剤のアルカリ土類金属の
種類によっては、これを無機酸化物マトリックス前駆物
質と混合した際にそのアルカリ土類金属が溶出して、結
晶性アルミノシリケートゼオライトにイオン交換した
り、あるいは無機酸化物マトリックス前駆物質と反応す
る、などして、得られる触媒組成物の性状に悪影響を及
ぼす問題があった。Further, depending on the kind of alkaline earth metal as a metal scavenger, when the alkaline earth metal is mixed with an inorganic oxide matrix precursor, the alkaline earth metal is eluted and ion-exchanged into a crystalline aluminosilicate zeolite. There is a problem that the properties of the obtained catalyst composition are adversely affected by, for example, reacting with the inorganic oxide matrix precursor.
【０００５】本出願人は、これらの問題点を解消するた
め、触媒内にアルミナをブロック状に存在させたり（特
開昭６１−２２７８４３号公報）、触媒製造時に触媒を
リン酸イオン含有水溶液で処理する（特開平４−２００
７４４号公報）ことにより、金属捕捉剤としてのアルカ
リ土類金属のもつ長所をそこなうことなく、アルカリ土
類金属のもつ欠点を改良した炭化水素接触分解用触媒組
成物の製造方法を提案している。また触媒内に粒子状の
マンガン化合物を分散させた炭化水素接触分解用触媒組
成物を提案している（特開平７−３２３２２９）。In order to solve these problems, the present applicant has proposed that alumina is present in a block form in the catalyst (Japanese Patent Application Laid-Open No. 61-227843), or that the catalyst is prepared using an aqueous solution containing phosphate ions during the production of the catalyst. Processing (JP-A-4-200)
No. 744) proposes a method for producing a catalyst composition for catalytic cracking of hydrocarbons, which does not impair the advantages of alkaline earth metals as metal scavengers and improves the disadvantages of alkaline earth metals. . In addition, a catalyst composition for catalytic cracking of hydrocarbons in which a particulate manganese compound is dispersed in a catalyst has been proposed (JP-A-7-323229).
【０００６】一方、硫黄化合物を含有する炭化水素を接
触分解するに際し、流動接触分解（ＦＣＣ）装置の再生
塔から排出される燃焼ガス中のＳＯｘ成分を減少する方
法（特公昭５６−９１９６号公報）および、触媒組成物
（特開昭５６−１１１０４７号公報）についても提案さ
れている。On the other hand, when catalytically cracking a hydrocarbon containing a sulfur compound, a method for reducing the SOx component in the combustion gas discharged from a regeneration tower of a fluid catalytic cracking (FCC) apparatus (Japanese Patent Publication No. 56-9196) ) And a catalyst composition (JP-A-56-111047).
【０００７】重質炭化水素中の硫黄化合物は、コークと
共に触媒に付着し、ＦＣＣ装置の再生塔では次の反応に
より、ＳＯｘとなり、ついで金属酸化物と反応して触媒
中に捕捉される。[0007] The sulfur compound in the heavy hydrocarbons adheres to the catalyst together with coke, and becomes SOx by the following reaction in the regeneration tower of the FCC unit, and then reacts with the metal oxide to be captured in the catalyst.
【化１】コーク中のＳ＋Ｏ2 → ＳＯ2＋ＳＯ3 ２ＳＯ2＋Ｏ2 → ２ＳＯ3 金属酸化物（ＭＯ）＋ＳＯ3 → ＭＳＯ4 Embedded image S + O 2 in coke → SO 2 + SO 3 2SO 2 + O 2 → 2SO 3 metal oxide (MO) + SO 3 → MSO 4
【０００８】反応塔においては、次の反応により[0008] In the reaction tower, the following reaction
【化２】 ２ＭＳＯ4＋８Ｈ2 → ＭＳ＋ＭＯ＋Ｈ2Ｓ＋７Ｈ2Ｏ ストリッパーにおいては、次の反応によりEmbedded image In a 2MSO 4 + 8H 2 → MS + MO + H 2 S + 7H 2 O stripper, the following reaction is carried out.
【化３】ＭＳ＋Ｈ2Ｏ → ＭＯ＋Ｈ2Ｓ いずれも硫化水素に変換して分離回収し、燃焼ガス中の
ＳＯｘ成分を減少させている。MS + H 2 O → MO + H 2 S All are converted to hydrogen sulfide, separated and recovered, and the SOx component in the combustion gas is reduced.
【０００９】従来、アルカリ金属、アルカリ土類金属
は、硫黄酸化物捕捉能を有することは知られているが、
アルカリ金属成分、アルカリ土類金属成分を含有する溶
液と触媒とを接触（含浸あるいはイオン交換を含む）さ
せる方法で触媒中に担持した触媒組成物では、アルカリ
金属やアルカリ土類金属が触媒組成物の接触分解反応使
用中あるいは触媒調製中にゼオライトの細孔などに移動
して、結晶性アルミノシリケートゼオライトにイオン交
換して組込まれるため接触分解反応で得られるガソリン
生成物のオクタン価（ＲＯＮ）が低下するなどの問題が
あった。Conventionally, it has been known that alkali metals and alkaline earth metals have a sulfur oxide trapping ability.
In a catalyst composition supported in a catalyst by a method of contacting (including impregnation or ion exchange) a solution containing an alkali metal component and an alkaline earth metal component with a catalyst, the alkali metal or the alkaline earth metal contains the catalyst composition. During the catalytic cracking reaction during use or during catalyst preparation, it migrates to the pores of the zeolite and is ion-exchanged into the crystalline aluminosilicate zeolite to reduce the octane number (RON) of the gasoline product obtained by the catalytic cracking reaction There were problems such as doing.
【００１０】[0010]
【発明が解決しようとする課題】本発明の目的は、耐メ
タル性に優れ、高活性でガソリン選択性が高く、しかも
生成ガソリンのオクタン価（ＲＯＮ）の低下が少なく、
さらに硫黄酸化物捕捉能に優れた炭化水素流動接触分解
用触媒組成物を提供する点にある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a gasoline with excellent metal resistance, high activity, high gasoline selectivity, and low decrease in octane number (RON) of gasoline produced.
It is still another object of the present invention to provide a catalyst composition for fluid catalytic cracking of hydrocarbons having excellent sulfur oxide trapping ability.
【００１１】[0011]
【課題を解決するための手段】本発明は、結晶性アルミ
ノシリケートゼオライトおよびリチウムアルミノシリケ
ートが無機酸化物マトリックス中に分散していることを
特徴とする炭化水素流動接触分解用触媒組成物に関す
る。SUMMARY OF THE INVENTION The present invention relates to a catalyst composition for fluid catalytic cracking of hydrocarbons, comprising crystalline aluminosilicate zeolite and lithium aluminosilicate dispersed in an inorganic oxide matrix.
【００１２】[0012]
【発明の具体的説明】以下に本発明について具体的に説
明する。本発明に係る炭化水素流動接触分解用触媒組成
物は、結晶性アルミノシリケートゼオライトを５〜５０
重量％、好ましくは５〜４０重量％、リチウムアルミノ
シリケートを０．１〜５０重量％、好ましくは０．５〜
２０重量％、およびこれら以外の無機酸化物マトリック
スを２０〜９４．９重量％。好ましくは３０〜９０重量
％の範囲で含有することが望ましい。DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. The catalyst composition for fluid catalytic cracking of hydrocarbons according to the present invention comprises a crystalline aluminosilicate zeolite in an amount of 5 to 50.
%, Preferably 5 to 40% by weight, lithium aluminosilicate 0.1 to 50% by weight, preferably 0.5 to 50% by weight.
20% by weight, and 20 to 94.9% by weight of the other inorganic oxide matrix. Preferably, it is contained in the range of 30 to 90% by weight.
【００１３】リチウムアルミノシリケートの含有量が
０．１重量％未満では所望の効果が得られないことがあ
り、また５０重量％を越えて高くなると耐摩耗性（Ａｔ
ｔ．Ｒｅｓ．）が低下する傾向にあるので好ましくな
い。If the content of lithium aluminosilicate is less than 0.1% by weight, the desired effect may not be obtained, and if it exceeds 50% by weight, the abrasion resistance (At)
t. Res. ) Is not preferred because it tends to decrease.
【００１４】本発明におけるリチウムアルミノシリケー
トとはリチウム、アルミニウム、ケイ素を主成分とする
無機酸化物を言い、リチウムアルミノシリケートとして
は、通常Ｌｉ2Ｏ・ｘＡｌ2Ｏ3・ｙＳｉＯ2の形で表した
時のｘが０．８〜１．５、ｙが１．０〜２０の範囲にあ
るものが好ましい。ｘが０．８未満または１．５を越え
て高い場合はリチウムアルミノシリケートの熱的安定性
が低くメタル捕捉能が低下して耐メタル性に対する効果
が充分発現しないことがあるので好ましくない。ｙが
１．０未満の場合も同様にリチウムアルミノシリケート
の熱的安定性が低くメタル捕捉能が低下するため耐メタ
ル性に対する効果が充分発現しないことがあるので好ま
しくなく、２０を越えて高い場合はリチウムアルミノシ
リケートの量を増やす必要が生じ触媒の耐摩耗性が低下
することがあるので好ましくない。In the present invention, the lithium aluminosilicate refers to an inorganic oxide containing lithium, aluminum and silicon as main components, and the lithium aluminosilicate is usually expressed in the form of Li 2 O.xAl 2 O 3 .ySiO 2 . It is preferable that x is in the range of 0.8 to 1.5 and y is in the range of 1.0 to 20. When x is less than 0.8 or higher than 1.5, the thermal stability of lithium aluminosilicate is low, and the metal-capturing ability is reduced, so that the effect on the metal resistance may not be sufficiently exhibited. Similarly, when y is less than 1.0, the thermal stability of lithium aluminosilicate is low, and the metal-capturing ability is lowered, so that the effect on metal resistance may not be sufficiently exhibited. Is not preferable because the amount of lithium aluminosilicate needs to be increased and the wear resistance of the catalyst may decrease.
【００１５】また、本発明におけるリチウムアルミノシ
リケートとしては、該リチウムアルミノシリケートに含
まれるリチウムが強固に保持されていること、すなわ
ち、触媒内でリチウムがゼオライトに移動しないことが
好ましく、触媒製造時の水性スラリー中あるいは高温固
相（本発明触媒を用いる反応は４００〜６００℃である
が、触媒再生工程においては８００℃を超える場合があ
り、とくにその場合Ｈ2Ｏが存在するので、一層リチウ
ムが移動しやすい条件になる）中でリチウムが容易に脱
離したり、他のカチオンと容易にイオン交換するような
リチウムアルミノシリケート、例えばリチウム交換した
結晶性アルミノシリケートゼオライト等はオクタン価が
低下することがあるので好ましくない。The lithium aluminosilicate used in the present invention is preferably one in which lithium contained in the lithium aluminosilicate is firmly retained, that is, lithium does not move to the zeolite in the catalyst. In an aqueous slurry or a high-temperature solid phase (the reaction using the catalyst of the present invention is at 400 to 600 ° C., but in the catalyst regeneration step, the temperature may exceed 800 ° C. In particular, in this case, since H 2 O is present, lithium is further reduced. The octane number of lithium aluminosilicate, which easily desorbs lithium or easily exchanges ions with other cations in such a condition that the lithium is exchanged, for example, lithium-exchanged crystalline aluminosilicate zeolite may be reduced. It is not preferable.
【００１６】典型的なリチウムアルミノシリケートの例
としては、Ｌｉ2Ｏ・Ａｌ2Ｏ3・２ＳｉＯ2（ＬｉＡｌＳ
ｉＯ4と標記されることもある）、Ｌｉ2Ｏ・Ａｌ2Ｏ3・
４ＳｉＯ2（ＬｉＡｌＳｉ2Ｏ6と標記されることもあ
る）、Ｌｉ2Ｏ・Ａｌ2Ｏ3・８ＳｉＯ2（ＬｉＡｌＳｉ4
Ｏ10と標記されることもある）などのように近似的に表
される無機酸化物粒子を挙げることができる。特にＸ線
的に検知可能なリチウムアルミノシリケートは触媒性能
面で優れた効果を示し好適である。なかでも天然に産す
るペタライト鉱（ペタル石とも呼ばれる）を粉砕して得
られる粒子状のリチウムアルミノシリケートは安価な点
においても好ましい。[0016] Examples of typical lithium aluminosilicate, Li 2 O · Al 2 O 3 · 2SiO 2 (LiAlS
iO 4 ), Li 2 O.Al 2 O 3.
4SiO 2 (sometimes be labeled as LiAlSi 2 O 6), Li 2 O · Al 2 O 3 · 8SiO 2 (LiAlSi 4
Inorganic oxide particles approximately represented as O 10 ). In particular, lithium aluminosilicate which can be detected by X-ray is preferable because it shows an excellent effect in terms of catalytic performance. Among them, particulate lithium aluminosilicate obtained by pulverizing naturally occurring petalite ore (also referred to as petalite) is preferable in that it is inexpensive.
【００１７】本発明のリチウムアルミノシリケートは、
粒子状であることが好ましい。リチウムアルミノシリケ
ートが粒子状の場合は、リチウムアルミノシリケートが
触媒粒子内にプロック状に存在するために結晶性アルミ
ノシリケートゼオライトに悪影響を及ぼすことなくメタ
ル捕捉能、脱ＳＯｘ能を高めることが出来るので好まし
い。The lithium aluminosilicate of the present invention comprises
It is preferably in the form of particles. In the case where the lithium aluminosilicate is in the form of particles, the lithium aluminosilicate is present in the form of a block in the catalyst particles, so that the metal capturing ability and the SOx removal ability can be increased without adversely affecting the crystalline aluminosilicate zeolite. .
【００１８】粒子状のリチウムアルミノシリケートの平
均粒子径は６０μｍ以下であることが好ましい。さらに
好ましい平均粒子径の範囲は０．１〜３０μｍである。
平均粒子径が小さすぎる場合は捕捉されるバナジウム等
の金属汚染物が触媒粒子内に分散するため、金属汚染物
の不活性化が充分されないことがある。また平均粒子径
が６０μｍを上廻ると、最終的に得られる触媒組成物の
平均粒子径との関係で、流動床用の触媒としては望まし
くない。The average particle size of the particulate lithium aluminosilicate is preferably 60 μm or less. A more preferable range of the average particle diameter is 0.1 to 30 μm.
If the average particle diameter is too small, trapped metal contaminants such as vanadium disperse in the catalyst particles, and thus the metal contaminants may not be sufficiently deactivated. On the other hand, if the average particle size exceeds 60 μm, it is not desirable as a catalyst for a fluidized bed because of the relationship with the average particle size of the finally obtained catalyst composition.
【００１９】本発明で使用する結晶性アルミノシリケー
トゼオライトには、Ｘ型ゼオライト、Ｙ型ゼオライト、
モルデナイト、ＺＳＭ型ゼオライトおよび天然ゼオライ
トなどを使用することができ、これは通常の接触分解用
触媒組成物の場合と同様、水素、アンモニウム及び多価
金属から選ばれるカチオンでイオン交換された形で使用
される。Ｙ型ゼオライトはガソリン選択性が高く、特に
超安定性Ｙ型ゼオライトは耐水熱安定性にも優れている
ので好適である。The crystalline aluminosilicate zeolite used in the present invention includes X-type zeolite, Y-type zeolite,
Mordenite, ZSM-type zeolite, natural zeolite, and the like can be used, which are used in the form of ion-exchanged with cations selected from hydrogen, ammonium and polyvalent metals, as in the case of ordinary catalytic cracking catalyst compositions. Is done. Y-type zeolites are preferred because they have high gasoline selectivity, and particularly ultra-stable Y-type zeolites have excellent hydrothermal stability.
【００２０】使用する結晶性アルミノシリケートゼオラ
イトの量は５〜５０重量％の範囲が好ましい。５重量％
未満では活性が低くガソリン収率が低いことがある。ま
た５０重量％を越えて高い場合は活性が高すぎてガス、
コークの生成量が増加するためにガソリン収率が低いこ
とがある。The amount of the crystalline aluminosilicate zeolite used is preferably in the range of 5 to 50% by weight. 5% by weight
If it is less than the above, the activity may be low and the gasoline yield may be low. If the content is higher than 50% by weight, the activity is too high and the gas,
Gasoline yield may be low due to increased coke production.
【００２１】また、本発明の無機酸化物マトリックスと
しては、シリカ、シリカ−アルミナ、アルミナ、シリカ
−マグネシア、アルミナ−マグネシア、リン−アルミ
ナ、シリカ−ジルコニア、シリカ−マグネシア−アルミ
ナなど結合剤としても作用する通常の接触分解用触媒に
使用されるマトリックス成分が使用可能である。このよ
うなマトリックス成分には、リチウムアルミノシリケー
ト以外の無機酸化物、例えば、カオリン、ハロイサイ
ト、モンモリロナイトなどをも使用することができる。The inorganic oxide matrix of the present invention also acts as a binder such as silica, silica-alumina, alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica-zirconia, silica-magnesia-alumina. Matrix components used in conventional catalytic cracking catalysts can be used. As such a matrix component, inorganic oxides other than lithium aluminosilicate, for example, kaolin, halloysite, montmorillonite and the like can also be used.
【００２２】前記無機酸化物マトリックスの成分中に
は、とくにアルミナ粒子を含有させておくことが好まし
い（この場合は、本出願人の出願にかかる特開昭６１−
２２７８４３号公報記載の機能も発揮する）。アルミナ
粒子を含有させることにより、つぎのような効果がさら
に増大される。脱ＳＯx能力が向上する。活性を高
める。耐水熱性が向上する。金属捕捉能が向上す
る。前記〜の効果を有するので、選択性が向上
し、ガソリン収率などが高まる。It is preferred that alumina particles are particularly contained in the components of the inorganic oxide matrix (in this case, Japanese Patent Application Laid-Open No. Sho 61-61 filed by the present applicant).
No. 227843). By including alumina particles, the following effects are further enhanced. The ability to remove SO x is improved. Increase activity. Hydrothermal resistance is improved. The metal capturing ability is improved. With the above-mentioned effects, selectivity is improved, and gasoline yield and the like are increased.
【００２３】また、本発明の炭化水素流動接触分解用触
媒組成物は、従来のメタル捕捉剤を併用して含有せしめ
ることもできる。Further, the catalyst composition for fluid catalytic cracking of hydrocarbons of the present invention can be contained in combination with a conventional metal scavenger.
【００２４】本発明の触媒組成物は、結晶性アルミノシ
リケートゼオライトおよびリチウムアルミノシリケート
を無機酸化物マトリックス前駆物質と混合し、噴霧乾燥
することによって製造することができる。The catalyst composition of the present invention can be produced by mixing a crystalline aluminosilicate zeolite and a lithium aluminosilicate with an inorganic oxide matrix precursor and spray drying.
【００２５】さらに具体的に説明すると、本発明の触媒
組成物は前述の無機酸化物マトリックスの前駆物質、例
えばシリカヒドロゾル、シリカ−アルミナヒドロゲルな
どに結晶性アルミノシリケートゼオライトおよびリチウ
ムアルミノシリケートを加えて均一に分散させ、得られ
た混合物スラリーを常法通り噴霧乾燥することによって
製造することができる。そして、噴霧乾燥された粒子は
必要に応じて洗浄され、洗浄後は再び乾燥又は乾燥、焼
成される。More specifically, the catalyst composition of the present invention is obtained by adding a crystalline aluminosilicate zeolite and a lithium aluminosilicate to a precursor of the above-mentioned inorganic oxide matrix, for example, silica hydrosol, silica-alumina hydrogel or the like. It can be manufactured by uniformly dispersing and spray-drying the resulting mixture slurry as usual. Then, the spray-dried particles are washed as necessary, and after the washing, they are dried or dried and fired again.
【００２６】本発明の触媒組成物は、硫黄化合物および
ニッケル、バナジウムなどの金属汚染物含有重質炭化水
素の接触分解で使用するのに特に好適であるが、金属汚
染物を含有しない炭化水素の接触分解にも使用可能であ
り、該触媒組成物を使用した接触分解は、通常の接触分
解条件が採用される。The catalyst composition of the present invention is particularly suitable for use in the catalytic cracking of sulfur compounds and heavy hydrocarbons containing metal contaminants such as nickel, vanadium, etc. The catalyst can be used for catalytic cracking, and the catalytic cracking using the catalyst composition employs ordinary catalytic cracking conditions.
【００２７】本発明の触媒組成物は、灯・軽油から高沸
点の脱れき油にいたるまでの広範囲の石油留分の接触分
解に利用することができる。The catalyst composition of the present invention can be used for the catalytic cracking of a wide range of petroleum fractions from kerosene / light oil to high boiling deoiled oil.
【００２８】[0028]
【実施例】以下に実施例を示して本発明を説明するが、
本発明はこれにより何ら限定されるものではない。The present invention will be described below with reference to examples.
The present invention is not limited thereby.
【００２９】参考例：リチウムアルミノシリケートの性
状 以下の実施例には市販のリチウムアルミノシリケート
（ペタライト粉）を使用した。このペタライト粉はリチ
ウムをＬｉ2Ｏとして４．１重量％、アルミニウムをＡ
ｌ2Ｏ3として１６．５重量％、ケイ素をＳｉＯ2として
７６．５重量％と他に少量のＮａ2ＯとＫ2Ｏを含有して
おり、その組成式はＬｉ2Ｏ・１．２Ａｌ2Ｏ・９．３Ｓ
ｉＯ2であり、その平均粒子径は９μｍであった。また
このペタライト粉のＸ線回折パターンを図１に示した。Reference Example: Properties of lithium aluminosilicate A commercially available lithium aluminosilicate (petalite powder) was used in the following examples. This petalite powder contains 4.1% by weight of lithium as Li 2 O and aluminum as A
It contains 16.5% by weight as l 2 O 3 and 76.5% by weight as silicon as SiO 2 and a small amount of Na 2 O and K 2 O. Its composition formula is Li 2 O · 1.2Al 2 O ・ 9.3S
iO 2 and the average particle size was 9 μm. FIG. 1 shows the X-ray diffraction pattern of this petalite powder.
【００３０】実施例１ 水硝子を硫酸に加えて調製した１２．５重量％のＳｉＯ
2を含むシリカヒドロゾル４０００ｇにカオリンクレー
１０００ｇ（乾燥基準）、活性アルミナ１００ｇ（乾燥
基準）、交換率９０％でアンモニウムイオン交換された
Ｙ型結晶性アルミノシリケート（ＮＨ4Ｙゼオライト）
８２５ｇ（乾燥基準）、および参考例のリチウムアルミ
ノシリケート（ペタライト粉）７５ｇ（乾燥基準）を加
えて混合スラリーを調製し、この混合スラリーを噴霧乾
燥して微小球状粒子を得た。ついでこの微小球状粒子を
洗浄し、乾燥して本発明の接触分解用触媒組成物を得
た。この接触分解用触媒組成物は、活性アルミナ４重量
％、ＮＨ4Ｙゼオライト３３重量％、リチウムアルミノ
シリケート３重量％を含有し、その平均粒子径は６４μ
ｍであった。この接触分解用触媒組成物をＡとする。触
媒の性状は表１に示した。Example 1 12.5% by weight SiO 2 prepared by adding water glass to sulfuric acid
1000 g (dry basis) of kaolin clay and 100 g (dry basis) of activated alumina in 4000 g of silica hydrosol containing 2 , Y-type crystalline aluminosilicate (NH 4 Y zeolite) exchanged with ammonium ion at an exchange rate of 90%
825 g (dry basis) and 75 g (dry basis) of lithium aluminosilicate (Petalite powder) of Reference Example were added to prepare a mixed slurry, and this mixed slurry was spray-dried to obtain fine spherical particles. Then, the fine spherical particles were washed and dried to obtain a catalytic cracking catalyst composition of the present invention. The catalytic cracking catalyst composition contains 4% by weight of activated alumina, 33% by weight of NH 4 Y zeolite, and 3% by weight of lithium aluminosilicate, and has an average particle diameter of 64 μm.
m. This catalytic cracking catalyst composition is designated as A. The properties of the catalyst are shown in Table 1.
【００３１】実施例２ 水硝子を硫酸に加えて調製した１２．５重量％のＳｉＯ
2を含むシリカヒドロゾル４０００ｇにカオリンクレー
８２５ｇ（乾燥基準）、活性アルミナ１００ｇ（乾燥基
準）、交換率９０％でアンモニウムイオン交換されたＹ
型結晶性アルミノシリケート（ＮＨ4Ｙゼオライト）８
２５ｇ（乾燥基準）、および参考例のリチウムアルミノ
シリケート（ペタライト粉）２５０ｇ（乾燥基準）を加
えて混合スラリーを調製し、この混合スラリーを噴霧乾
燥して微小球状粒子を得た。ついでこの微小球状粒子を
洗浄し、乾燥して本発明の接触分解用触媒組成物を得
た。この接触分解用触媒組成物は、活性アルミナ４重量
％、ＮＨ4Ｙゼオライト３３重量％、リチウムアルミノ
シリケート１０重量％を含有し、その平均粒子径は６４
μｍであった。この接触分解用触媒組成物をＢとする。
触媒の性状は表１に示した。Example 2 12.5% by weight SiO 2 prepared by adding water glass to sulfuric acid
825 g of kaolin clay (dry basis), 100 g of activated alumina (dry basis), and ammonium ion-exchanged Y at an exchange rate of 90% are added to 4000 g of silica hydrosol containing 2
-Type crystalline aluminosilicate (NH 4 Y zeolite) 8
A mixed slurry was prepared by adding 25 g (dry basis) and 250 g (dry basis) of lithium aluminosilicate (petalite powder) of Reference Example, and the mixed slurry was spray-dried to obtain fine spherical particles. Then, the fine spherical particles were washed and dried to obtain a catalytic cracking catalyst composition of the present invention. The catalytic cracking catalyst composition contains 4% by weight of activated alumina, 33% by weight of NH 4 Y zeolite, and 10% by weight of lithium aluminosilicate, and has an average particle diameter of 64%.
μm. This catalytic composition for catalytic cracking is referred to as B.
The properties of the catalyst are shown in Table 1.
【００３２】比較例１ 水硝子を硫酸に加えて調製した１２．５重量％のＳｉＯ
2を含むシリカヒドロゾル４０００ｇにカオリンクレー
１０７５ｇ（乾燥基準）、活性アルミナ１００ｇ（乾燥
基準）、交換率９０％でアンモニウムイオン交換された
Ｙ型結晶性アルミノシリケート（ＮＨ4Ｙゼオライト）
８２５ｇ（乾燥基準）を加えて混合スラリーを調製し、
この混合スラリーを噴霧乾燥して微小球状粒子を得た。
ついでこの微小球状粒子を洗浄し、乾燥して接触分解用
触媒組成物を得た。この接触分解用触媒組成物は、活性
アルミナを４重量％、ＮＨ4Ｙゼオライトを３３重量％
含有し、その平均粒子径は６４μｍであった。この接触
分解用触媒組成物をＣとする。触媒の性状は表１に示し
た。Comparative Example 1 12.5% by weight of SiO 2 prepared by adding water glass to sulfuric acid
1075 g (dry basis) of kaolin clay, 100 g (dry basis) of activated alumina, and Y-type crystalline aluminosilicate (NH 4 Y zeolite) exchanged with ammonium at a conversion rate of 90% in 4000 g of silica hydrosol containing 2
825 g (dry basis) was added to prepare a mixed slurry,
This mixed slurry was spray-dried to obtain fine spherical particles.
Then, the fine spherical particles were washed and dried to obtain a catalytic cracking catalyst composition. This catalytic cracking catalyst composition comprises 4% by weight of activated alumina and 33% by weight of NH 4 Y zeolite.
Contained, and the average particle size was 64 μm. This catalytic cracking catalyst composition is designated as C. The properties of the catalyst are shown in Table 1.
【００３３】[0033]
【表１】 a)：見掛比重 b)：比表面積[Table 1] a) : apparent specific gravity b) : specific surface area
【００３４】実施例３〈性能試験〉 実施例および比較例で調製した触媒Ａ、Ｂ、Ｃについ
て、触媒循環再生方式のＭｉｄｇｅｔ−２パイロットプ
ラントを用いて性能評価した。Ｍｉｄｇｅｔ−２パイロ
ットプラントは図２にその概略図を示した。図中１は反
応器、２はストリッパー、３は触媒再生装置、４はコン
デンサー、５はフラクショネーター、６はレシーバー、
７はキャットトラップ、８は分離器、９は可動式管、１
０は空冷管、１１はＮ2導入口、１２は原料油導入口、
１３はＮ2，Ｈ2Ｏ排出口、１４はＮ2導入口、１５は空
気導入口、１６は移送管、１７は煙導ガス排出口であ
る。Example 3 <Performance Test> The catalysts A, B, and C prepared in Examples and Comparative Examples were evaluated for performance using a Midget-2 pilot plant of a catalyst circulation regeneration system. The Midget-2 pilot plant is shown schematically in FIG. In the figure, 1 is a reactor, 2 is a stripper, 3 is a catalyst regenerator, 4 is a condenser, 5 is a fractionator, 6 is a receiver,
7 is a cat trap, 8 is a separator, 9 is a movable tube, 1
0 air cooling tube, 11 N 2 inlet, 12 a raw material oil introduction port,
Reference numeral 13 denotes an N 2 and H 2 O outlet, 14 denotes an N 2 inlet, 15 denotes an air inlet, 16 denotes a transfer pipe, and 17 denotes a smoke gas outlet.
【００３５】１の反応器における反応は、The reaction in one reactor is:
【化４】２ＭＳＯ4＋８Ｈ2Ｏ → ＭＳ＋ＭＯ＋Ｈ2Ｓ
＋７Ｈ2Ｏ ２のストリッパーにおける反応は、Embedded image 2MSO 4 + 8H 2 O → MS + MO + H 2 S
The reaction in the + 7H 2 O 2 stripper is:
【化５】ＭＳ＋Ｈ2Ｏ → ＭＯ＋Ｈ2Ｓ ３の触媒再生装置における反応は、The reaction of MS + H 2 O → MO + H 2 S 3 in the catalyst regeneration unit is as follows:
【化６】コーク中のＳ＋Ｏ2 → ＳＯ2＋ＳＯ3 ２ＳＯ2＋Ｏ2 → ２ＳＯ3 金属酸化物（ＭＯ）＋ＳＯ3 → ＭＳＯ4 である。Embedded image In the coke, S + O 2 → SO 2 + SO 3 2SO 2 + O 2 → 2SO 3 metal oxide (MO) + SO 3 → MSO 4 .
【００３６】運転条件は下記の通りである。 原料油 ：脱硫減圧軽油（６０％）と脱硫常圧残渣
油（４０％）の混合油 原料油Ｓ分 ：０．２６ｗｔ％ 重量空間速度：２５ ｈｒ-1 触媒／油 ：７ 重量比 反応温度 ：５３０ ℃ リジェネレーター温度：６８０℃ ストリッピング温度 ：５００℃ 再生触媒上のコーク ：０．０５ｗｔ％The operating conditions are as follows. Feedstock: Mixed oil of desulfurized vacuum gas oil (60%) and desulfurized atmospheric residue (40%) Feedstock S content: 0.26 wt% Weight hourly space velocity: 25 hr -1 Catalyst / oil: 7 Weight ratio Reaction temperature: 530 ° C Regenerator temperature: 680 ° C Stripping temperature: 500 ° C Coke on regenerated catalyst: 0.05 wt%
【００３７】性能を評価するにあたり、各触媒にはバナ
ジウム、ニッケルを各々４０００ｐｐｍ、２０００ｐｐ
ｍ沈着させ、ついでスチーミングして擬平衡化処理（こ
の擬平衡化処理は、触媒内でリチウムや他のアルカリ金
属、アルカリ土類金属などが移動してオクタン価活性を
低下させる環境を充分与えて、触媒の優劣がはっきり表
われるような処理をするためのものである）を行った。
具体的には、各触媒を予め６００℃で１時間焼成した
後、所定量のナフテン酸バナジウム、ナフテン酸ニッケ
ルのトルエン溶液を吸収させ、次いで、１１０℃で乾燥
後、６００℃で１．５時間焼成し、次いで８１０℃で６
時間スチーム処理した後、図２の装置を用い、重質油の
分解性能を評価した。測定結果を表２に示した。また運
転が定常状態に達した後に、再生装置における煙導ガス
排出口１７から放出されたガスについてＳＯ2、ＣＯお
よびＣＯ2を分析した結果を表２に示した。In evaluating the performance, vanadium and nickel were added to each catalyst at 4000 ppm and 2000 pp, respectively.
m, and then steaming to give a pseudo-equilibrium treatment (this pseudo-equilibrium treatment provides a sufficient environment in which lithium, other alkali metals, alkaline earth metals, etc. move in the catalyst to lower the octane number activity. In order to clearly show the superiority of the catalyst).
Specifically, after each catalyst was previously calcined at 600 ° C. for 1 hour, a predetermined amount of a vanadium naphthenate and nickel naphthenate toluene solution was absorbed, and then dried at 110 ° C. and then at 600 ° C. for 1.5 hours. Firing and then 6 hours at 810 ° C
After the time steam treatment, the cracking performance of heavy oil was evaluated using the apparatus of FIG. Table 2 shows the measurement results. Further, Table 2 shows the results of analysis of SO 2 , CO and CO 2 for the gas discharged from the flue gas discharge port 17 in the regenerator after the operation reached a steady state.
【００３８】[0038]
【表２】 1)転化率：１００−（ＬＣＯ＋ＨＣＯ） 2)ガソリン沸点範囲：Ｃ5〜２１６℃ 3)ＬＣＯ沸点範囲：２１６℃〜３４３℃ 4)ＨＣＯ沸点範囲：３４３℃以上 5)Ｋ（二次反応速度定数）＝転化率／（１００−転化率） 6)水素選択性を表す 7)コーク選択性を表す[Table 2] 1) conversion: 100- (LCO + HCO) 2 ) gasoline boiling range: C 5 ~216 ℃ 3) LCO boiling range: 216 ℃ ~343 ℃ 4) HCO boiling range: 343 ° C. or higher 5) K (secondary reaction rate constant ) = Conversion / (100-conversion) 6) Represents hydrogen selectivity 7) Represents coke selectivity
【００３９】本発明の粒子状のリチウムアルミノシリケ
ート含有触媒ＡおよびＢは、ニッケルおよびバナジウム
を高濃度で含有するにもかかわらず、さらに高温で水熱
処理して擬平衡化を行ったにもかかわらず高い転化率
（活性）を示した。このことは本発明の触媒が通常の触
媒Ｃに比べて耐メタル性と耐水熱性に優れていることを
示している。さらに転化率が高いにもかかわらず水素収
率およびコーク収率は低く、一方ガソリン収率およびガ
ソリンとライトサイクルオイル（ＬＣＯ）を含めた液収
率が高いという結果が得られた。特に粒子状のリチウム
アルミノシリケート含有量の高い触媒Ｂはその傾向が顕
著である。また生成したガソリンのオクタン価は実質的
にほぼ同程度であった。以上のことは粒子状のリチウム
アルミノシリケートがメタルを効果的に捕捉して不動態
化し、メタルの悪影響すなわちゼオライトの破壊による
活性低下、脱水素活性による水素およびコークの生成等
を抑制した結果である。なお、上記をさらに理解するた
めに補足的に付言すると、転化率が高くなるとガス、コ
ーク生成量が増加し、ガソリン、ＬＣＯ収率は増加する
が転化率が高くなりすぎると減少に転じ、またオクタン
価は転化率に比例して高くなるのが本技術分野の常識で
あるが、本発明は、この常識を超える効果を発揮してい
る。Although the particulate lithium aluminosilicate-containing catalysts A and B of the present invention contain nickel and vanadium at a high concentration, they are subjected to hydrothermal treatment at a high temperature to perform pseudo-equilibration. High conversion (activity) was shown. This indicates that the catalyst of the present invention is superior to ordinary catalyst C in metal resistance and hydrothermal resistance. Furthermore, despite the high conversion, the hydrogen yield and coke yield were low, while the gasoline yield and the liquid yield including gasoline and light cycle oil (LCO) were high. In particular, the tendency is remarkable for the catalyst B having a high content of the particulate lithium aluminosilicate. The octane number of the produced gasoline was substantially the same. The above results are the result of the particulate lithium aluminosilicate effectively trapping and passivating the metal, suppressing the adverse effects of the metal, namely, the reduction in activity due to zeolite destruction and the generation of hydrogen and coke due to dehydrogenation activity. . In order to further understand the above, it is additionally added that, when the conversion is high, the amount of gas and coke generated is increased, and the gasoline and LCO yields are increased, but when the conversion is too high, the conversion is reduced, and It is common knowledge in the technical field that the octane number increases in proportion to the conversion, but the present invention has an effect exceeding this common sense.
【００４０】本発明の実施態様を以下に列記する。 （１）結晶性アルミノシリケートゼオライトおよびリチ
ウムアルミノシリケートが無機酸化物マトリックス中に
分散していることを特徴とする炭化水素流動接触分解用
触媒組成物。 （２）前記リチウムアルミノシリケートが粒子状であ
り、その平均粒子径が６０μｍ以下である前項（１）記
載の炭化水素流動接触分解用触媒組成物。 （３）前記リチウムアルミノシリケートが粒子状であ
り、その平均粒子径が０．１〜３０μｍの範囲にある前
項（１）記載の炭化水素流動接触分解用触媒組成物。 （４）前記リチウムアルミノシリケートがＬｉ2Ｏ・ｘ
Ａｌ2Ｏ3・ｙＳｉＯ2として表した時、ｘが０．８〜
１．５、ｙが１．０〜２０の範囲にある無機酸化物であ
る前項（１）、（２）または（３）記載の炭化水素流動
接触分解用触媒組成物。 （５）前記リチウムアルミノシリケートがＸ線的に検知
可能な無機酸化物粒子である前項（１）、（２）、
（３）または（４）記載の炭化水素流動接触分解用触媒
組成物。 （６）前記Ｘ線的に検知可能な無機酸化物粒子がペタラ
イトである前項（５）記載の炭化水素流動接触分解用触
媒組成物。 （７）前記各成分の配合割合が 結晶性アルミノシリケートゼオライト ５〜５０重量％ リチウムアルミノシリケート ０．１〜５０重量％ 無機酸化物マトリックス ２０〜９４．９重量％ である前項（１）、（２）、（３）、（４）、（５）ま
たは（６）記載の炭化水素流動接触分解用触媒組成物。 （８）前記無機酸化物マトリックス成分の１つとしてア
ルミナ粒子を使用するものである前項（７）記載の炭化
水素流動接触分解用触媒組成物。 （９）前記各成分の配合割合において、リチウムアルミ
ノシリケートが０．５〜２０重量％である前項（７）ま
たは（８）記載の炭化水素流動接触分解用触媒組成物。 （１０）前記各成分の配合割合において、結晶性アルミ
ノシリケートゼオライトが５〜４０重量％である前項
（７）、（８）または（９）記載の炭化水素流動接触分
解用触媒組成物。 （１１）前記各成分の配合割合において、無機酸化物マ
トリックスが３０〜９０重量％である前項（７）、
（８）、（９）または（１０）記載の炭化水素流動接触
分解用触媒組成物。The embodiments of the present invention are listed below. (1) A catalyst composition for fluid catalytic cracking of hydrocarbons, wherein crystalline aluminosilicate zeolite and lithium aluminosilicate are dispersed in an inorganic oxide matrix. (2) The catalyst composition for fluid catalytic cracking of hydrocarbons according to the above (1), wherein the lithium aluminosilicate is in the form of particles and has an average particle diameter of 60 μm or less. (3) The catalyst composition for hydrocarbon fluid catalytic cracking according to the above (1), wherein the lithium aluminosilicate is in the form of particles and the average particle diameter is in the range of 0.1 to 30 µm. (4) The lithium aluminosilicate is Li 2 O · x
When expressed as Al 2 O 3 .ySiO 2 , x is 0.8 to
1.5. The catalyst composition for hydrocarbon fluid catalytic cracking according to the above (1), (2) or (3), wherein y is an inorganic oxide in the range of 1.0 to 20. (5) The above items (1), (2), wherein the lithium aluminosilicate is an inorganic oxide particle detectable X-ray.
(3) The catalyst composition for fluid catalytic cracking according to (4) or (4). (6) The catalyst composition for hydrocarbon fluid catalytic cracking according to the above (5), wherein the inorganic oxide particles detectable by X-ray are petalite. (7) The above items (1), (2), wherein the mixing ratio of each component is 5 to 50% by weight of crystalline aluminosilicate zeolite, 0.1 to 50% by weight of lithium aluminosilicate, and 20 to 94.9% by weight of inorganic oxide matrix. ), (3), (4), (5) or (6). (8) The catalyst composition for fluid catalytic cracking of hydrocarbons according to the above (7), wherein alumina particles are used as one of the inorganic oxide matrix components. (9) The catalyst composition for fluid catalytic cracking of a hydrocarbon according to the above (7) or (8), wherein the content of the lithium aluminosilicate is 0.5 to 20% by weight based on the mixing ratio of each component. (10) The catalyst composition for fluid catalytic cracking of hydrocarbons according to the above (7), (8) or (9), wherein the content of the crystalline aluminosilicate zeolite is 5 to 40% by weight in the mixing ratio of the above components. (11) In the compounding ratio of each of the above components, the inorganic oxide matrix is 30 to 90% by weight (7),
(8) The catalyst composition for fluid catalytic cracking according to (9) or (10).
【００４１】[0041]
（１）本発明の触媒は耐メタル性および水熱安定性が高
く、高活性でかつ活性低下が小さい。また生成ガソリン
のオクタン価をほとんど低下させることがない。 （２）本発明の触媒を用いると、水素、コーク、ドライ
ガスの生成量が少なくガソリンおよびライトサイクルオ
イル（ＬＣＯ）等の液収率が高い。 （３）本発明の触媒は脱ＳＯｘ能が高く、排ガス中のＳ
Ｏｘ量を低減できる。(1) The catalyst of the present invention has high metal resistance and high hydrothermal stability, high activity, and a small decrease in activity. Further, the octane number of the produced gasoline is hardly reduced. (2) When the catalyst of the present invention is used, the production amount of hydrogen, coke, and dry gas is small, and the liquid yield of gasoline and light cycle oil (LCO) is high. (3) The catalyst of the present invention has a high ability to remove SOx,
Ox amount can be reduced.
【図１】実施例で使用した市販のペタライト粉のＸ線回
折パターンである。FIG. 1 is an X-ray diffraction pattern of a commercially available petalite powder used in Examples.
【図２】本発明触媒の評価試験に用いたミゼット−２パ
イロットプラントの概略図である。FIG. 2 is a schematic diagram of a Midget-2 pilot plant used for an evaluation test of the catalyst of the present invention.
１ 反応器 ２ ストリッパー ３ 触媒再生装置 ４ コンデンサー ５ フラクショネーター ６ レシーバー ７ キャットトラップ ８ 分離器 ９ 可導式管 １０ 空冷管 １１ Ｎ2導入口 １２ 原料油導入口 １３ Ｎ2，Ｈ2Ｏ排出口 １４ Ｎ2導入口 １５ 空気導入口 １６ 移送管 １７ 煙導ガス排出口1 reactor 2 stripper 3 catalyst regeneration apparatus 4 condenser 5 fractionator 6 Receiver 7 Cat trap 8 separator 9 Kashirubeshiki tube 10 cooling tubes 11 N 2 inlet 12 feed oil inlet 13 N 2, H 2 O outlet 14 N 2 inlet 15 Air inlet 16 Transfer pipe 17 Smoke gas outlet
Claims (5)
よびリチウムアルミノシリケートが無機酸化物マトリッ
クス中に分散していることを特徴とする炭化水素流動接
触分解用触媒組成物。1. A catalyst composition for fluid catalytic cracking of hydrocarbons, comprising crystalline aluminosilicate zeolite and lithium aluminosilicate dispersed in an inorganic oxide matrix.
状であり、その平均粒子径が６０μｍ以下である請求項
１記載の炭化水素流動接触分解用触媒組成物。2. The catalyst composition for fluid catalytic cracking of hydrocarbons according to claim 1, wherein the lithium aluminosilicate is in the form of particles and has an average particle diameter of 60 μm or less.
2Ｏ・ｘＡｌ2Ｏ3・ｙＳｉＯ2として表した時、ｘが０．
８〜１．５、ｙが１．０〜２０の範囲にある無機酸化物
粒子である請求項１または２記載の炭化水素流動接触分
解用触媒組成物。3. The method according to claim 1, wherein the lithium aluminosilicate is Li
When expressed as 2 O.xAl 2 O 3 .ySiO 2 , x is 0.
The catalyst composition for fluid catalytic cracking of hydrocarbons according to claim 1 or 2, wherein the catalyst composition is an inorganic oxide particle having a particle size of from 8 to 1.5 and y of from 1.0 to 20.
的に検知可能な無機酸化物粒子である請求項１、２また
は３記載の炭化水素流動接触分解用触媒組成物。4. The catalyst composition for fluid catalytic cracking of hydrocarbons according to claim 1, wherein the lithium aluminosilicate is an inorganic oxide particle that can be detected by X-ray.
物粒子がペタライトである請求項４記載の炭化水素流動
接触分解用触媒組成物。5. The catalyst composition for fluid catalytic cracking of hydrocarbons according to claim 4, wherein the inorganic oxide particles detectable in X-rays are petalite.
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|---|---|---|---|
| JP03715797A JP3563910B2 (en) | 1997-02-05 | 1997-02-05 | Catalyst composition for fluid catalytic cracking of hydrocarbons |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03715797A JP3563910B2 (en) | 1997-02-05 | 1997-02-05 | Catalyst composition for fluid catalytic cracking of hydrocarbons |
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| Publication Number | Publication Date |
|---|---|
| JPH10216526A true JPH10216526A (en) | 1998-08-18 |
| JP3563910B2 JP3563910B2 (en) | 2004-09-08 |
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ID=12489773
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006205141A (en) * | 2005-01-25 | 2006-08-10 | Catalysts & Chem Ind Co Ltd | Catalyst composition for hydrogenating hydrocarbon oil and method for hydrogenating hydrocarbon oil by using the catalyst composition |
| JP2013255902A (en) * | 2012-06-14 | 2013-12-26 | Jgc Catalysts & Chemicals Ltd | Fluid catalytic cracking catalyst and method of producing the same |
| JP2020520798A (en) * | 2017-05-17 | 2020-07-16 | ビーエーエスエフ コーポレーション | Bottom-up grading and low coke fluid catalytic cracking catalyst |
-
1997
- 1997-02-05 JP JP03715797A patent/JP3563910B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006205141A (en) * | 2005-01-25 | 2006-08-10 | Catalysts & Chem Ind Co Ltd | Catalyst composition for hydrogenating hydrocarbon oil and method for hydrogenating hydrocarbon oil by using the catalyst composition |
| JP2013255902A (en) * | 2012-06-14 | 2013-12-26 | Jgc Catalysts & Chemicals Ltd | Fluid catalytic cracking catalyst and method of producing the same |
| JP2020520798A (en) * | 2017-05-17 | 2020-07-16 | ビーエーエスエフ コーポレーション | Bottom-up grading and low coke fluid catalytic cracking catalyst |
| US11471862B2 (en) | 2017-05-17 | 2022-10-18 | Basf Corporation | Bottoms upgrading and low coke fluid catalytic cracking catalyst |
| US11904302B2 (en) | 2017-05-17 | 2024-02-20 | Basf Corporation | Bottoms upgrading and low coke fluid catalytic cracking catalyst |
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| Publication number | Publication date |
|---|---|
| JP3563910B2 (en) | 2004-09-08 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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