JP4394992B2 - Catalyst composition for increasing gasoline octane number and / or lower olefin and fluid catalytic cracking process of hydrocarbons using the same - Google Patents
Catalyst composition for increasing gasoline octane number and / or lower olefin and fluid catalytic cracking process of hydrocarbons using the same Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims description 143
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- 238000004231 fluid catalytic cracking Methods 0.000 title claims description 45
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims description 36
- 150000001336 alkenes Chemical class 0.000 title claims description 31
- 229930195733 hydrocarbon Natural products 0.000 title claims description 29
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 28
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 20
- 239000011148 porous material Substances 0.000 claims description 56
- 239000010457 zeolite Substances 0.000 claims description 40
- 229910021536 Zeolite Inorganic materials 0.000 claims description 39
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 39
- 239000004215 Carbon black (E152) Substances 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 14
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 13
- 238000004523 catalytic cracking Methods 0.000 claims description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004517 catalytic hydrocracking Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 46
- 239000000377 silicon dioxide Substances 0.000 description 20
- 239000002002 slurry Substances 0.000 description 18
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- 239000000843 powder Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 13
- 239000005995 Aluminium silicate Substances 0.000 description 12
- 235000012211 aluminium silicate Nutrition 0.000 description 12
- 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 12
- 235000012239 silicon dioxide Nutrition 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000012013 faujasite Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
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- 239000011973 solid acid Substances 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 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
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
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- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 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
- 238000012986 modification Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、炭化水素を接触分解触媒組成物と接触させて製造されるガソリンのオクタン価及び／又は低級オレフィンを増加させる触媒組成物及びそれを使用した炭化水素の流動接触分解方法に関し、さらに詳しくは、ペンタシル型ゼオライトと無機酸化物マトリックスとからなる触媒組成物であって、特定の細孔構造を有するガソリンのオクタン価及び／又は低級オレフィン増加用触媒組成物及びそれを使用した炭化水素の流動接触分解方法に関する。 The present invention relates to a catalyst composition for increasing the octane number and / or lower olefin of gasoline produced by contacting a hydrocarbon with a catalytic cracking catalyst composition, and a fluid catalytic cracking process for hydrocarbons using the catalyst composition. , A catalyst composition comprising a pentasil-type zeolite and an inorganic oxide matrix, the catalyst composition for increasing octane number and / or lower olefin of gasoline having a specific pore structure, and fluid catalytic cracking of hydrocarbons using the same Regarding the method.
製油所の炭化水素流動接触分解装置（ＦＣＣ装置）では、原料炭化水素を接触分解してガソリン留分を製造することが主目的であり、ガソリンは高オクタン価であることが望まれている。また、製油所によっては、ＦＣＣ装置で原料炭化水素を接触分解してガソリン留分を生成すると同時に石油化学原料である低級オレフィン、特に、プロピレン、ブテンの生産量を高めることが要求される場合がある。
従来、炭化水素を接触分解してガソリンを製造する接触分解触媒組成物としてフォージャサイト型ゼオライトを含有する触媒組成物（フォージャサイト型ゼオライト系触媒組成物）が広く使用されている。フォージャサイト型ゼオライト系触媒組成物は、アモルファス系触媒組成物に比較して炭化水素の分解活性は高いが、得られるガソリンのオクタン価が低く、また、オレフィン量が少ないという問題があった。
In a hydrocarbon fluid catalytic cracking unit (FCC unit) in a refinery, the main purpose is to catalytically crack raw material hydrocarbons to produce a gasoline fraction, and it is desired that gasoline has a high octane number. In some refineries, it is required to increase the production of petrochemical raw materials such as lower olefins, especially propylene and butene, at the same time to produce gasoline fraction by catalytic cracking of raw material hydrocarbons with FCC equipment. is there.
Conventionally, a catalyst composition containing a faujasite type zeolite (a faujasite type zeolite catalyst composition) has been widely used as a catalytic cracking catalyst composition for producing gasoline by catalytic cracking of hydrocarbons. The faujasite-type zeolite catalyst composition has higher hydrocarbon decomposition activity than the amorphous catalyst composition, but has a problem that the obtained gasoline has a low octane number and a small amount of olefin.
そこで、生成ガソリンのオクタン価を改善するために炭化水素のＦＣＣ装置で使用されるフォージャサイト型ゼオライト系流動接触分解触媒組成物に、ＺＳＭ−５などのペンタシル型ゼオライトを含有する触媒組成物（添加剤ということがある）を混合して接触分解する方法が種々提案されている。 Therefore, a catalyst composition containing a pentasil type zeolite such as ZSM-5 (addition) to a faujasite type zeolite fluid catalytic cracking catalyst composition used in a hydrocarbon FCC unit to improve the octane number of the produced gasoline Various methods have been proposed for the catalytic cracking by mixing.
例えば、特許文献１には、炭化水素供給原料のクラッキング方法において、クラッキング触媒を基準として０．０１〜１重量％の量の、１２以上のシリカ／アルミナモル比と１〜１２の制御指数とをもつ粒状の形状選択性促進剤をクラッキング触媒に添加することを特徴とする炭化水素供給原料のクラッキング方法が開示されており、形状選択性促進剤がＺＳＭ−１１、ＺＳＭ−１２、ＺＳＭ−２３、ＺＳＭ−３５、ＺＳＭ−３８及びＺＳＭ−５であることが記載されている。 For example, Patent Document 1 has a silica / alumina molar ratio of 12 or more and a control index of 1 to 12 in an amount of 0.01 to 1% by weight based on the cracking catalyst in a hydrocarbon feedstock cracking method. A method of cracking a hydrocarbon feedstock characterized by adding a particulate shape selectivity promoter to a cracking catalyst is disclosed, wherein the shape selectivity promoter is ZSM-11, ZSM-12, ZSM-23, ZSM -35, ZSM-38 and ZSM-5.
また、特許文献２には、流動接触分解（ＦＣＣ）工程において製造されるガソリンのオクタン価を向上させると同時にガソリン収率の低下を減少させるゼオライト含有触媒が開示されている。該触媒は、ＺＳＭ−１１、ＺＳＭ−１２、ＺＳＭ−３５、ＺＳＭ−３８及びＺＳＭ−５である中程度の孔径のゼオライト添加物を周期律表のＩＡ族、IIＡ族又はIIIＡ族の一種又は多種の元素から選ばれた陽イオンでゼオライト添加物を部分的にイオン交換することを特徴とする。 Patent Document 2 discloses a zeolite-containing catalyst that improves the octane number of gasoline produced in a fluid catalytic cracking (FCC) process and at the same time reduces the decrease in gasoline yield. The catalyst comprises ZSM-11, ZSM-12, ZSM-35, ZSM-38, and ZSM-5 with a medium pore size zeolite additive, one or more of groups IA, IIA or IIIA in the periodic table. The zeolite additive is partially ion-exchanged with a cation selected from these elements.
しかし、従来のガソリンのオクタン価及び／又は低級オレフィンを増加させる触媒組成物の改良は、ゼオライトの変性に重点が置かれ、触媒の細孔構造の改良については注目されていなかった However, the improvement of the catalyst composition that increases the octane number and / or the lower olefin of the conventional gasoline is focused on the modification of the zeolite, and attention has not been paid to the improvement of the pore structure of the catalyst.
一方、本発明者らは、特許文献３において、炭化水素接触分解用触媒組成物における触媒の細孔構造に関して、ボトム分解には触媒のメソ細孔のみならずマクロ細孔をも有することが重要であることを提案した。しかし、該公報には、ガソリンのオクタン価及び／又は低級オレフィンを増加させることに関する記載はない。 On the other hand, in Patent Document 3, regarding the pore structure of the catalyst in the catalyst composition for hydrocarbon catalytic cracking, it is important that the bottom cracking has not only mesopores of the catalyst but also macropores. Proposed to be. However, there is no description in the publication regarding increasing the octane number and / or lower olefin of gasoline.
本発明の目的は、ペンタシル型ゼオライトと無機酸化物マトリックスとからなる特定の細孔構造を有する触媒組成物であって、ＦＣＣ装置内で使用されるフォージャサイト型ゼオライトを含有する炭化水素流動接触分解触媒組成物（ＦＣＣ触媒）に添加剤として添加して、ガソリンのオクタン価及び／又は低級オレフィンを増加させるのに優れた効果を有する触媒組成物及びそれを使用した炭化水素の流動接触分解方法を提供する点にある。 An object of the present invention is a catalyst composition having a specific pore structure composed of a pentasil-type zeolite and an inorganic oxide matrix, and a hydrocarbon fluidized contact containing a faujasite-type zeolite used in an FCC apparatus A catalyst composition having an excellent effect of increasing the octane number and / or lower olefin of gasoline by adding it as an additive to a cracking catalyst composition (FCC catalyst) and a fluid catalytic cracking method of hydrocarbons using the same The point is to provide.
従来、重質炭化水素の接触分解触媒組成物の細孔構造については種々提案されているが、ガソリンのオクタン価及び／又は低級オレフィン増加用触媒組成物の細孔構造に関してはほとんど注目されていなかった。本発明者らは、該触媒組成物においても触媒のメソ細孔のみならずマクロ細孔をも有することが重要であることを見いだし本発明を完成するに至った。 Conventionally, various pore structures of catalytic cracking catalyst compositions of heavy hydrocarbons have been proposed, but little attention has been paid to the pore structure of gasoline octane number and / or catalyst composition for increasing lower olefins. . The present inventors have found that it is important to have not only mesopores of the catalyst but also macropores in the catalyst composition, and have completed the present invention.
即ち、本発明の第１は、ペンタシル型ゼオライトと無機酸化物マトリックスとからなるガソリンのオクタン価及び／又は低級オレフィン増加用触媒組成物であって、該触媒組成物が無水リン酸を含有し、その全細孔容積が０．３０ｍｌ／ｇ以上で、かつ、平均細孔直径が１００±２０ｎｍの範囲にあり、全細孔容積に対する細孔直径１００±２０ｎｍ範囲の細孔容積の占める割合が５０％以上であることを特徴とするガソリンのオクタン価及び／又は低級オレフィン増加用触媒組成物に関する。
本発明の第２は、前記ペンタシル型ゼオライトがＺＳＭ−５であることを特徴とする請求項１記載のガソリンのオクタン価及び／又は低級オレフィン増加用触媒組成物に関する。
本発明の第３は、炭化水素を流動接触分解触媒組成物の存在下に接触分解条件下で流動接触分解する方法において、フォージャサイト型ゼオライトを含有する炭化水素流動接触分解触媒組成物に請求項１または２記載のオクタン価及び／又は低級オレフィン増加用触媒組成物を０．５〜１０重量％の範囲で混合した触媒を使用することを特徴とする炭化水素の流動接触分解方法に関する。
That is, the first invention is a octane and / or a lower olefin increased catalyst composition for gasoline comprising a pentasil-type zeolite and inorganic oxide matrix, said catalyst composition containing phosphoric anhydride, its The total pore volume is 0.30 ml / g or more, the average pore diameter is in the range of 100 ± 20 nm, and the proportion of the pore volume in the pore diameter range of 100 ± 20 nm to the total pore volume is 50 It is related with the catalyst composition for octane number of gasoline and / or a lower olefin increase characterized by being more than%.
The second invention relates to the pentasil type zeolite octane and / or lower olefins increased catalyst composition of gasoline according to claim 1, characterized in that the ZSM-5.
According to a third aspect of the present invention, a hydrocarbon fluid catalytic cracking catalyst composition containing a faujasite-type zeolite in a method of fluid catalytic cracking under the catalytic cracking conditions in the presence of a fluid catalytic cracking catalyst composition. The present invention relates to a fluid catalytic cracking method for hydrocarbons, characterized by using a catalyst in which the catalyst composition for increasing octane number and / or lower olefin according to item 1 or 2 is mixed in the range of 0.5 to 10% by weight.
本発明でのペンタシル型ゼオライトとしては、例えば、ＺＳＭ−５、ＺＳＭ−１１、ＺＳＭ−１２、ＺＳＭ−２２、ＺＳＭ−２３、ＺＳＭ−３５、ＺＳＭ−３８、ＺＳＭ−４８などのゼオライトが例示される。特に、ＺＳＭ−５は酸強度の強い固体酸を有し、高い形状選択性を示すため、ガソリンのオクタン価及び／又は低級オレフィン増加効果が大きいので好適である。 Examples of the pentasil-type zeolite in the present invention include zeolites such as ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, and ZSM-48. . In particular, ZSM-5 is suitable because it has a solid acid with strong acid strength and exhibits high shape selectivity, and therefore has a large effect of increasing gasoline octane number and / or lower olefin.
本発明での無機酸化物マトリックスには、通常、ゼオライトを含有する炭化水素流動接触分解用触媒組成物に使用される無機酸化物マトリックスが使用可能であリ、例えば、シリカ、アルミナ、シリカ−アルミナ、シリカ−マグネシア、アルミナ−ボリア、チタニア、ジルコニア、シリカ−ジルコニア、珪酸カルシウム、カルシウムアルミネート、などの無機酸化物、カオリン、ベントナイト、ハロイサイトなどの粘土鉱物などを挙げることができる。特に、シリカ、カオリン、含水微粉ケイ酸及びアルミナからなる無機酸化物マトリックスが好適に使用される。 As the inorganic oxide matrix in the present invention, an inorganic oxide matrix usually used for a catalyst composition for hydrocarbon fluid catalytic cracking containing zeolite can be used, for example, silica, alumina, silica-alumina. And inorganic oxides such as silica-magnesia, alumina-boria, titania, zirconia, silica-zirconia, calcium silicate and calcium aluminate, and clay minerals such as kaolin, bentonite and halloysite. In particular, an inorganic oxide matrix composed of silica, kaolin, hydrous finely divided silicic acid and alumina is preferably used.
本発明のオクタン価及び／又は低級オレフィン増加用触媒組成物は、前述の無機酸化物マトリックス中に前述のペンタシル型ゼオライトが１０〜４０重量％の範囲で均一に分散していることが好ましい。該ペンタシル型ゼオライトの量が１０重量％より少ない場合には、該触媒組成物の使用量を多くしないと所望のオクタン価及び／又は低級オレフィン増加効果が得られない場合があり、該触媒組成物の使用量を多くするとＦＣＣ触媒の使用量が少なくなり、炭化水素の分解活性が低下することがある。また、該ペンタシル型ゼオライトの量を４０重量％より多くしても、該ゼオライトの量が４０重量％の場合に比較してオクタン価及び／又は低級オレフィン増加効果が変わらないので経済的でない。該触媒組成物中のペンタシル型ゼオライトの含有量は、更に好ましくは１５〜２０重量％の範囲が望ましい。 In the catalyst composition for increasing octane number and / or lower olefin of the present invention, the above-mentioned pentasil-type zeolite is preferably uniformly dispersed in the above-mentioned inorganic oxide matrix in the range of 10 to 40% by weight. When the amount of the pentasil-type zeolite is less than 10% by weight, the effect of increasing the desired octane number and / or lower olefin may not be obtained unless the amount of the catalyst composition used is increased. When the amount used is increased, the amount of FCC catalyst used is decreased, and the hydrocarbon decomposition activity may be reduced. Further, even if the amount of the pentasil-type zeolite is more than 40% by weight, the effect of increasing the octane number and / or the lower olefin does not change as compared with the case where the amount of the zeolite is 40% by weight, which is not economical. The content of the pentasil-type zeolite in the catalyst composition is more preferably in the range of 15 to 20% by weight.
本発明の触媒組成物の細孔分布は、該触媒組成物を６００℃で１時間前処理した試料を水銀圧入法で水銀の接触角１３０°、表面張力４８０ｄｙｎ／ｃｍの値を用いて細孔直径５．５ｎｍ以上の細孔について測定したものである。該触媒組成物の全細孔容積（ＰＶＴ）は０．３０ｍｌ／ｇ以上である。該触媒組成物の全細孔容積（ＰＶＴ）が０．３０ｍｌ／ｇより小さい場合には、液化石油ガス（ＬＰＧ）やプロピレンなどの生成量の増加割合が少なく、また、ガソリンのオクタン価の増加も小さい。該触媒組成物の全細孔容積（ＰＶＴ）は、好ましくは０．３０〜０．７０ｍｌ／ｇの範囲であることが望ましい。
また、本発明の触媒組成物は、平均細孔直径（ＰＤＡ）が１００±２０ｎｍの範囲にある。なお、平均細孔直径（ＰＤＡ）は、触媒組成物の細孔分布を累積細孔分布曲線で表し、全細孔容積（ＰＶＴ）の５０％に該当する累積細孔分布曲線上の点に対応する細孔直径をいう。
該触媒組成物の平均細孔直径（ＰＤＡ）が８０ｎｍより小さい場合には触媒組成物中のペンタシル型ゼオライトへの反応物の拡散が悪くなり、所望のオクタン価の増加及び／または低級オレフィンの増加が得られない。また、該触媒組成物の平均細孔直径（ＰＤＡ）が１２０ｎｍより大きい場合には触媒組成物の耐摩耗性（Ａｔｔｒｉｔｉｏｎ Ｒｅｓｉｓｔａｎｃｅ）が悪くなるので好ましくない。該触媒組成物の平均細孔直径（ＰＤＡ）は、好ましくは１００±１５ｎｍの範囲にあることが望ましい。
さらに、本発明の触媒組成物は、前記全細孔容積（ＰＶＴ）に対する細孔直径（ＰＤ）１００±２０ｎｍ範囲の細孔容積（ＰＶ）の占める割合〔（ＰＶ）／（ＰＶＴ）〕が５０％以上である。該（ＰＶ）／（ＰＶＴ）の割合が５０％より小さい場合にはプロピレンなどの低級オレフィン生成量の増加割合が小さく、また、ガソリンのオクタン価の増加も小さい。該触媒組成物の（ＰＶ）／（ＰＶＴ）の割合は、好ましくは５２〜９０％の範囲にあることが望ましい。
The pore distribution of the catalyst composition of the present invention was determined by measuring a sample obtained by pretreating the catalyst composition at 600 ° C. for 1 hour using a mercury intrusion method with a mercury contact angle of 130 ° and a surface tension of 480 dyn / cm. This is measured for pores having a diameter of 5.5 nm or more. The total pore volume (PV T ) of the catalyst composition is 0.30 ml / g or more. If the total pore volume of the catalyst composition (PV T) is 0.30 ml / g smaller than, liquefied petroleum gas (LPG) and rate of increase in the amount of propylene is less, and an increase in gasoline octane number Is also small. The total pore volume (PV T ) of the catalyst composition is preferably in the range of 0.30 to 0.70 ml / g.
The catalyst composition of the present invention has an average pore diameter (PD A ) in the range of 100 ± 20 nm. The average pore diameter (PD A ) represents the pore distribution of the catalyst composition as a cumulative pore distribution curve, and is a point on the cumulative pore distribution curve corresponding to 50% of the total pore volume (PV T ). The pore diameter corresponding to.
When the average pore diameter (PD A ) of the catalyst composition is less than 80 nm, the diffusion of the reactant into the pentasil-type zeolite in the catalyst composition becomes worse, and the desired octane number increases and / or the lower olefin increases. Cannot be obtained. Moreover, when the average pore diameter (PD A ) of the catalyst composition is larger than 120 nm, the abrasion resistance of the catalyst composition is deteriorated, which is not preferable. The average pore diameter (PD A ) of the catalyst composition is preferably in the range of 100 ± 15 nm.
Furthermore, the catalyst composition of the present invention has a ratio [(PV) / (PV T )] of the pore volume (PV) in the pore diameter (PD) 100 ± 20 nm range with respect to the total pore volume (PV T ). Is 50% or more. When the ratio of (PV) / (PV T ) is smaller than 50%, the rate of increase in the production of lower olefins such as propylene is small, and the increase in the octane number of gasoline is also small. The ratio of (PV) / (PV T ) of the catalyst composition is preferably in the range of 52 to 90%.
前述のオクタン価及び／又は低級オレフィン増加用触媒組成物は、無水リン酸（Ｐ２Ｏ５）を含有するものである。該触媒組成物中にリン酸を含有させることにより、ＦＣＣ装置で該触媒組成物を使用している間にペンタシル型ゼオライト骨格から脱アルミニウムが生じて固体酸量が減少するのが抑制される。そのため、オクタン価及び／又は低級オレフィン増加効果の低下が抑制される。該触媒組成物中のリン酸の含有量はＰ２Ｏ５として５〜１５重量％の範囲にあることが望ましい。 Octane and / or lower olefins increased catalyst composition described above are those containing phosphorus anhydride (P 2 O 5). By including phosphoric acid in the catalyst composition, it is possible to suppress dealumination of the amount of solid acid caused by dealumination from the pentasil-type zeolite skeleton while the catalyst composition is used in the FCC apparatus. Therefore, the decrease in octane number and / or lower olefin increase effect is suppressed. The content of phosphoric acid in the catalyst composition is preferably in the range of 5 to 15 wt% as P 2 O 5.
本発明のオクタン価及び／又は低級オレフィン増加用触媒組成物は、前述のペンタシル型ゼオライトと、シリカゾル、カオリン、含水微粉ケイ酸及び活性アルミナなどを含有する無機酸化物マトリックス前駆体との水性混合物を噴霧乾燥し、得られた微小球状粒子を洗浄し、乾燥し、焼成して得られる。特に、含水微粉ケイ酸は、該触媒組成物の細孔容積を大きくし、細孔分布を制御するのに重要な成分で、含水微粉ケイ酸自体の細孔容積及び含有量は触媒組成物の細孔分布に影響する。無機酸化物マトリックス前駆体は、無機酸化物マトリックス基準で、シリカゾルをＳｉＯ２として１０〜５０重量％、好ましくは２０〜４０重量％、カオリンを２０〜８０重量％、好ましくは３０〜６０重量％、含水微紛ケイ酸をＳｉＯ２として３〜３０重量％、好ましくは５〜２５重量％、擬ベーマイトアルミナ水和物をＡｌ２Ｏ３として０〜３０重量％、好ましくは５〜２０重量％の範囲で含有することが望ましい。無機酸化物マトリックス前駆体の組成範囲が前述の範囲内であると所望の細孔分布の触媒が得られやすい。なお、該触媒組成物中に無水リン酸を含有させる場合には、前記微小球状粒子を洗浄、乾燥した後にリン酸（Ｈ３ＰＯ４）水溶液を含浸して担持することができる。 The catalyst composition for increasing octane number and / or lower olefin of the present invention sprays an aqueous mixture of the above-mentioned pentasil-type zeolite and an inorganic oxide matrix precursor containing silica sol, kaolin, hydrous finely divided silicic acid, activated alumina and the like. It is obtained by drying, washing the resulting microspherical particles, drying and firing. In particular, hydrous fine powdered silicic acid is an important component for increasing the pore volume of the catalyst composition and controlling the pore distribution. The pore volume and content of the hydrous fine powdered silicic acid itself are the same as those of the catalyst composition. Affects pore distribution. The inorganic oxide matrix precursor is 10 to 50% by weight, preferably 20 to 40% by weight, kaolin 20 to 80% by weight, preferably 30 to 60% by weight, based on the inorganic oxide matrix, with silica sol as SiO 2 . A range of 3 to 30% by weight, preferably 5 to 25% by weight, of hydrated fine silicic acid as SiO 2 and 0 to 30% by weight, preferably 5 to 20% by weight, of pseudoboehmite alumina hydrate as Al 2 O 3 It is desirable to contain. When the composition range of the inorganic oxide matrix precursor is within the aforementioned range, a catalyst having a desired pore distribution is easily obtained. When phosphoric anhydride is contained in the catalyst composition, the fine spherical particles can be washed and dried, and then impregnated with and supported by an aqueous solution of phosphoric acid (H 3 PO 4 ).
次に、本発明の炭化水素の流動接触分解方法について述べる。本発明の方法では、炭化水素をＦＣＣ触媒の存在下に流動接触分解する方法において、前述のオクタン価及び／又は低級オレフィン増加用触媒組成物を、フォージャサイト型ゼオライトを含有するＦＣＣ触媒に混合触媒基準で０．５〜１０重量％の範囲で混合した触媒の存在下で流動接触分解することを特徴とする。
フォージャサイト型ゼオライトを含有するＦＣＣ触媒としては、ＦＣＣ装置で使用される通常のＦＣＣ触媒が使用可能である。この様なＦＣＣ触媒としては、市販のＦＣＣ触媒、例えば、ＨＭＲ、ＳＴＷ、ＤＣＴ、ＡＣＺ、ＣＶＺ〔何れも触媒化成工業（株）製：商品名〕などが例示される。
前述のオクタン価及び／又は低級オレフィン増加用触媒組成物を、フォージャサイト型ゼオライトを含有するＦＣＣ触媒に混合する量が混合触媒基準で０．５重量％より少ない場合には、所望のオクタン価及び／又は低級オレフィン増加効果が得られないことがある。また、該触媒組成物の量が混合触媒基準で１０重量％より多い場合には、ＦＣＣ触媒の量が少なくなるため、炭化水素の分解活性が低下するので好ましくない。該触媒組成物のフォージャサイト型ゼオライトを含有するＦＣＣ触媒に混合する量は、好ましくは１〜５重量％の範囲が望ましい。
Next, the method for fluid catalytic cracking of hydrocarbons of the present invention will be described. In the method of the present invention, in the method of fluid catalytic cracking of hydrocarbon in the presence of an FCC catalyst, the catalyst composition for increasing octane number and / or lower olefin is mixed with the FCC catalyst containing faujasite type zeolite. It is characterized by fluid catalytic cracking in the presence of a catalyst mixed in a range of 0.5 to 10% by weight on the basis.
As the FCC catalyst containing the faujasite type zeolite, a normal FCC catalyst used in an FCC apparatus can be used. Examples of such FCC catalysts include commercially available FCC catalysts such as HMR, STW, DCT, ACZ, and CVZ [all manufactured by Catalyst Kasei Kogyo Co., Ltd .: trade name].
When the amount of the catalyst composition for increasing the octane number and / or the lower olefin added to the FCC catalyst containing the faujasite type zeolite is less than 0.5% by weight based on the mixed catalyst, the desired octane number and / or Alternatively, the effect of increasing the lower olefin may not be obtained. On the other hand, when the amount of the catalyst composition is more than 10% by weight based on the mixed catalyst, the amount of the FCC catalyst is decreased, which is not preferable because the hydrocarbon decomposition activity is lowered. The amount of the catalyst composition mixed with the FCC catalyst containing the faujasite type zeolite is preferably in the range of 1 to 5% by weight.
本発明の炭化水素の流動接触分解方法では、通常のＦＣＣ装置での炭化水素の流動接触分解条件が採用される。 In the fluid catalytic cracking method for hydrocarbons of the present invention, fluid catalytic cracking conditions for hydrocarbons in an ordinary FCC apparatus are employed.
本発明のオクタン価及び／又は低級オレフィン増加用触媒組成物は、全細孔容積が大きく、全細孔容積に対するマクロ細孔の占める細孔容積の割合が大きく、活性成分であるペンタシル型ゼオライが有効に利用されるため、前述のような要望のある製油所のＦＣＣ装置で炭化水素を接触分解する際に、フォージャサイト型ゼオライトを含有する流動接触分解触媒組成物に添加して使用することにより、高オクタン価のガソリンを得ると同時にブテン、プロピレンなどの低級オレフィンを高収率で得ることができる。 The catalyst composition for increasing octane number and / or lower olefin according to the present invention has a large total pore volume, a large proportion of the pore volume occupied by macropores with respect to the total pore volume, and the active component pentasil-type zeolite is effective. Therefore, when hydrocarbons are catalytically cracked in a refinery FCC unit that has the above-mentioned demands, it is added to a fluid catalytic cracking catalyst composition containing faujasite-type zeolite. In addition to obtaining high octane gasoline, it is possible to obtain lower olefins such as butene and propylene in high yield.
以下に実施例を示し本発明を具体的に説明するが、本発明はこれによリ限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
実施例１
ＳｉＯ２濃度２４重量％のＳｉＯ２／Ｎａ２Ｏモル比が３．２０のケイ酸ソーダを希釈してＳｉＯ２濃度４．０重量％の希釈ケイ酸ソーダ溶液１００ｋｇを調製した。該溶液を２００Ｌのスティームジャケット付きタンクに入れ、６００ｒｐｍで攪拌しながら１０００ｇの硫酸ナトリウムを加えた後９０℃まで２０分間で昇温した。次いで、９０℃の温度に保ちながら２５ｗｔ％濃度の硫酸水溶液８．０７ｋｇを５０分間で加えて、ｐＨ７．０のケイ酸スラリーを得た。
該ケイ酸スラリーをフィルターで濾過し、６０℃の温水２００Ｌを掛け水洗浄して副生するＮａ２ＳＯ４を除去した。この洗浄ケーキに純水を加えＳｉＯ２濃度８．０重量％のスラリーを調製した後、ホモジナイザーを通し均質化スラリーにした。このスラリーを入口温度２８０℃、出口温度１５０℃で噴霧乾燥して多孔性シリカ粒子を得た。次いで、該多孔性シリカ粒子をジェットミルにて粉砕し平均粒径８μｍの多孔性シリカ粉（Ｘ）を調製した。なお、この多孔性シリカ粉（Ｘ）を６００℃で２時間焼成した物の性状は、表面積１９０ｍ２／ｇ、細孔容積２．５ｍｌ／ｇ、平均細孔直径５３ｎｍであった。
別途、ＳｉＯ２濃度１７重量％の水ガラスに、濃度２５重量％の硫酸を連続的に加えてｐＨ１．６、温度４０℃、ＳｉＯ２濃度１２．５重量％のシリカヒドロゾルを調製した。触媒組成物基準でのＳｉＯ２含有量が１５重量％となるように、このシリカヒドロゾルを秤量し、このシリカヒドロゾルにカオリン、アルミナ（サソール社製ＣＡＴＡＰＡＬ−Ａ）、前記多孔性シリカ粉（Ｘ）を触媒組成物基準での含有量がそれぞれ５７重量％、５重量％、８重量％となるように加えマトリックス前躯体スラリーを調製した。さらに、平均粒子径１μｍ程度に粉砕されたＺＳＭ−５ゼオライト（東ソー社製８３０ＮＨＡ）を約３０重量％含む水性スラリーを調製し、これを前記マトリックス前躯体スラリーにＺＳＭ−５ゼオライトの含有量がＰ２Ｏ５を含まない触媒組成物基準で１５重量％になるように加えてｐＨ２．６、温度３５℃の混合スラリーを調製した。
この混合スラリーを噴霧乾燥して平均粒径６０μｍの微小球状粒子を調製した後、Ｎａ２Ｏ含有量が０．１重量％以下になるまで５％硫安水溶液で洗浄した後、１３５℃の乾燥機内で乾燥した。乾燥された触媒粒子に対して乾燥基準でＰ２Ｏ５が７．０重量％になるようにＨ３ＰＯ４水溶液を含浸し、１３５℃で一晩乾燥して触媒Ａを得た。
触媒Ａの性状を表１に示す。
Example 1
A diluted sodium silicate solution having a SiO 2 concentration of 4.0 wt% was prepared by diluting sodium silicate having a SiO 2 concentration of 24 wt% and a SiO 2 / Na 2 O molar ratio of 3.20. The solution was placed in a 200 L steam jacketed tank, 1000 g of sodium sulfate was added with stirring at 600 rpm, and the temperature was raised to 90 ° C. over 20 minutes. Next, while maintaining the temperature at 90 ° C., 8.07 kg of a 25 wt% sulfuric acid aqueous solution was added over 50 minutes to obtain a silicic acid slurry having a pH of 7.0.
The silicic acid slurry was filtered through a filter and washed with 200 L of hot water of 60 ° C. to remove by-produced Na 2 SO 4 . Pure water was added to the washed cake to prepare a slurry having a SiO 2 concentration of 8.0% by weight and then passed through a homogenizer to obtain a homogenized slurry. The slurry was spray-dried at an inlet temperature of 280 ° C. and an outlet temperature of 150 ° C. to obtain porous silica particles. Next, the porous silica particles were pulverized by a jet mill to prepare porous silica powder (X) having an average particle diameter of 8 μm. Incidentally, the porous silica powder (X) nature of what was calcined 2 hours at 600 ° C. The a surface area 190 m 2 / g, pore volume 2.5 ml / g, an average pore diameter of 53 nm.
Separately, sulfuric acid having a concentration of 25% by weight was continuously added to water glass having a SiO 2 concentration of 17% by weight to prepare a silica hydrosol having a pH of 1.6, a temperature of 40 ° C., and a SiO 2 concentration of 12.5% by weight. The silica hydrosol was weighed so that the SiO 2 content on the basis of the catalyst composition was 15% by weight, and kaolin, alumina (CAPPAL-A manufactured by Sasol Co.), the porous silica powder ( A matrix precursor slurry was prepared by adding X) such that the content based on the catalyst composition was 57 wt%, 5 wt%, and 8 wt%, respectively. Further, an aqueous slurry containing about 30% by weight of ZSM-5 zeolite (830 NHA manufactured by Tosoh Corporation) pulverized to an average particle size of about 1 μm was prepared, and this was added to the matrix precursor slurry with a ZSM-5 zeolite content of P A mixed slurry having a pH of 2.6 and a temperature of 35 ° C. was prepared by adding 15% by weight based on the catalyst composition not containing 2 O 5 .
The mixed slurry was spray-dried to prepare fine spherical particles having an average particle size of 60 μm, and then washed with a 5% aqueous ammonium sulfate solution until the Na 2 O content was 0.1% by weight or less, and then the inside of a dryer at 135 ° C. And dried. The dried catalyst particles were impregnated with an aqueous H 3 PO 4 solution so that P 2 O 5 was 7.0 wt% on a dry basis, and dried at 135 ° C. overnight to obtain Catalyst A.
Properties of catalyst A are shown in Table 1.
実施例２
実施例１において、Ｐ２Ｏ５を含まない触媒組成物基準で多孔性シリカ粉（Ｘ）の含有量が１０重量％となるように加え、カオリン含有量をバランスとしたこと以外は、実施例１の方法と同様にして触媒Ｂを調製した。
触媒Ｂの性状を表１に示す。
Example 2
In Example 1, except that the content of the porous silica powder (X) is 10% by weight on the basis of the catalyst composition not containing P 2 O 5 and the kaolin content is balanced. Catalyst B was prepared in the same manner as in Method 1.
Properties of catalyst B are shown in Table 1.
実施例３
実施例１において、Ｐ２Ｏ５を含まない触媒組成物基準でＺＳＭ−５ゼオライトの含有量が２０重量％となるように加え、カオリン含有量をバランスとしたこと以外は、実施例１の方法と同様にして触媒Ｃを調製した。
触媒Ｃの性状を表１に示す。
Example 3
The method of Example 1 except that in Example 1, the content of ZSM-5 zeolite was 20% by weight on the basis of the catalyst composition not containing P 2 O 5 and that the kaolin content was balanced. Catalyst C was prepared in the same manner as above.
The properties of catalyst C are shown in Table 1.
実施例４
実施例１において、Ｐ２Ｏ５を含まない触媒組成物基準で多孔性シリカ粉（Ｘ）の含有量が１０重量％、ＺＳＭ−５ゼオライトの含有量が２０重量％となるようにそれぞれを加え、カオリン含有量をバランスとしたこと以外は、実施例１の方法と同様にして触媒Ｄを調製した。
触媒Ｄの性状を表１に示す。
Example 4
In Example 1, the porous silica powder (X) content was 10% by weight and the ZSM-5 zeolite content was 20% by weight on the basis of the catalyst composition not containing P 2 O 5. Catalyst D was prepared in the same manner as in Example 1 except that the kaolin content was balanced.
Properties of catalyst D are shown in Table 1.
比較例１
実施例１において、多孔性シリカ粉（Ｘ）を加えないで、Ｐ２Ｏ５を含まない触媒組成物基準でカオリンの含有量が６５重量％となるようにカオリン量を増やしたこと以外は、実施例１の方法と同様にして触媒Ｅを調製した。
触媒Ｅの性状を表１に示す。
Comparative Example 1
In Example 1, without adding the porous silica powder (X), except that the amount of kaolin was increased so that the content of kaolin was 65% by weight on the basis of the catalyst composition not containing P 2 O 5 , Catalyst E was prepared in the same manner as in Example 1.
Properties of catalyst E are shown in Table 1.
比較例２
実施例１において、多孔性シリカ粉（Ｘ）を加えないで、Ｐ２Ｏ５を含まない触媒組成物基準でカオリンの含有量が６０重量％となるようにカオリン量を増やし、ＺＳＭ−５ゼオライトの含有量が２０重量％となるように加えたこと以外は、実施例１の方法と同様にして触媒Ｆを調製した。
触媒Ｆの性状を表１に示す。
Comparative Example 2
In Example 1, without adding the porous silica powder (X), the amount of kaolin was increased so that the content of kaolin was 60% by weight on the basis of the catalyst composition not containing P 2 O 5 , and ZSM-5 zeolite Catalyst F was prepared in the same manner as in Example 1 except that the content of was added so as to be 20% by weight.
Properties of catalyst F are shown in Table 1.
実施例５
ＳｉＯ２濃度２４重量％のＳｉＯ２／Ｎａ２Ｏモル比が３．２０のケイ酸ソーダを希釈してＳｉＯ２濃度４．０重量％の希釈ケイ酸ソーダ溶液１００ｋｇを調製した。該溶液を２００Ｌのスティームジャケット付きタンクに入れ、６００ｒｐｍで攪拌しながら１０００ｇの硫酸ナトリウムを加えた後９０℃まで２０分間で昇温した。次いで、９０℃の温度に保ちながら２５ｗｔ％濃度の硫酸水溶液８．０７ｋｇを３０分間で加えて、ｐＨ７．０のケイ酸スラリーを得た。
該ケイ酸スラリーをフィルターで濾過し、６０℃の温水２００Ｌを掛け水洗浄して副生するＮａ２ＳＯ４を除去した。この洗浄ケーキに純水を加えＳｉＯ２濃度８．０重量％のスラリーを調製した後、ホモジナイザーを通し均質化スラリーにした。このスラリーを入口温度２８０℃、出口温度１５０℃で噴霧乾燥して多孔性シリカ粒子を得た。次いで、該多孔性シリカ粒子をジェットミルにて粉砕し平均粒径６μｍの多孔性シリカ粉（Ｙ）を調製した。なお、この多孔性シリカ粉（Ｙ）を６００℃で２時間焼成した物の性状は、表面積２１０ｍ２／ｇ、細孔容積２．１ｍｌ／ｇ、平均細孔直径３８ｎｍであった。
実施例２において、前記多孔性シリカ粉（Ｙ）を多孔性シリカ粉（Ｘ）の代わりに用いたこと以外は、実施例２の方法と同様にして触媒Ｇを調製した。
触媒Ｇの性状を表３に示す。
Example 5
A diluted sodium silicate solution having a SiO 2 concentration of 4.0 wt% was prepared by diluting sodium silicate having a SiO 2 concentration of 24 wt% and a SiO 2 / Na 2 O molar ratio of 3.20. The solution was placed in a 200 L steam jacketed tank, 1000 g of sodium sulfate was added with stirring at 600 rpm, and the temperature was raised to 90 ° C. over 20 minutes. Subsequently, while maintaining the temperature at 90 ° C., 8.07 kg of a 25 wt% sulfuric acid aqueous solution was added over 30 minutes to obtain a silicic acid slurry having a pH of 7.0.
The silicic acid slurry was filtered through a filter and washed with 200 L of hot water of 60 ° C. to remove by-produced Na 2 SO 4 . Pure water was added to the washed cake to prepare a slurry having a SiO 2 concentration of 8.0% by weight and then passed through a homogenizer to obtain a homogenized slurry. The slurry was spray-dried at an inlet temperature of 280 ° C. and an outlet temperature of 150 ° C. to obtain porous silica particles. Next, the porous silica particles were pulverized with a jet mill to prepare porous silica powder (Y) having an average particle diameter of 6 μm. Incidentally, the porous silica powder (Y) Properties of what was calcined 2 hours at 600 ° C. The a surface area 210 m 2 / g, pore volume 2.1 ml / g, an average pore diameter of 38 nm.
In Example 2, a catalyst G was prepared in the same manner as in Example 2 except that the porous silica powder (Y) was used instead of the porous silica powder (X).
Properties of catalyst G are shown in Table 3.
比較例３
ＳｉＯ２濃度２４重量％のＳｉＯ２／Ｎａ２Ｏモル比が３．２０のケイ酸ソーダを希釈してＳｉＯ２濃度４．０重量％の希釈ケイ酸ソーダ溶液１００ｋｇを調製した。該溶液を２００Ｌのスティームジャケット付きタンクに入れ６００ｒｐｍで攪拌しながら１０００ｇの硫酸ナトリウムを加え９０℃まで２０分間で昇温した。次いで、９０℃の温度に保ちながら２５ｗｔ％濃度の硫酸水溶液８．０７ｋｇを１０分間で加えて、ｐＨ７．０のケイ酸スラリー得た。
該ケイ酸スラリーをフィルターで濾過し、６０℃の温水２００Ｌを掛け水洗浄して副生するＮａ２ＳＯ４を除去した。この洗浄ケーキに純水を加えＳｉＯ２濃度８．０重量％のスラリーを調製した後、ホモジナイザーを通し均質化スラリーにした。このスラリーを入口温度２８０℃、出口温度１５０℃で噴霧乾燥して多孔性シリカ粒子を得た。次いで、該多孔性シリカ粒子をジェットミルにて粉砕し平均粒径６μｍの多孔性シリカ粉（Ｚ）を調製した。なお、この多孔性シリカ粉（Ｚ）を６００℃で２時間焼成した物の性状は、表面積３５５ｍ２／ｇ、細孔容積１．８ｍｌ／ｇ、平均細孔直径１９ｎｍであった。
実施例２において、前記多孔性シリカ粉（Ｚ）を多孔性シリカ粉（Ｘ）の代わりに用いたこと以外は、実施例２の方法と同様にして触媒Ｈを調製した。
触媒Ｈの性状を表３に示す。
Comparative Example 3
A diluted sodium silicate solution having a SiO 2 concentration of 4.0 wt% was prepared by diluting sodium silicate having a SiO 2 concentration of 24 wt% and a SiO 2 / Na 2 O molar ratio of 3.20. The solution was placed in a 200 L steam jacketed tank, stirred at 600 rpm, 1000 g of sodium sulfate was added, and the temperature was raised to 90 ° C. over 20 minutes. Subsequently, while maintaining the temperature at 90 ° C., 8.07 kg of a 25 wt% sulfuric acid aqueous solution was added over 10 minutes to obtain a silicic acid slurry having a pH of 7.0.
The silicic acid slurry was filtered through a filter and washed with 200 L of hot water of 60 ° C. to remove by-produced Na 2 SO 4 . Pure water was added to the washed cake to prepare a slurry having a SiO 2 concentration of 8.0% by weight and then passed through a homogenizer to obtain a homogenized slurry. The slurry was spray-dried at an inlet temperature of 280 ° C. and an outlet temperature of 150 ° C. to obtain porous silica particles. Next, the porous silica particles were pulverized with a jet mill to prepare porous silica powder (Z) having an average particle diameter of 6 μm. The properties of the porous silica powder (Z) calcined at 600 ° C. for 2 hours were a surface area of 355 m 2 / g, a pore volume of 1.8 ml / g, and an average pore diameter of 19 nm.
In Example 2, Catalyst H was prepared in the same manner as in Example 2, except that the porous silica powder (Z) was used instead of the porous silica powder (X).
Properties of catalyst H are shown in Table 3.
実施例６
本発明に係る実施例の触媒及び比較例の触媒について、触媒循環再生方式のＭｉｄｇｅｔ−２パイロット反応装置を用いて活性評価試験を行った。活性評価試験の触媒は、製油所のＦＣＣ装置で使用されたフォージャサイト型ゼオライト系炭化水素流動接触分解触媒（ＦＣＣ平衡触媒）と実施例及び比較例の擬平衡化したそれぞれの触媒とを一定の割合で混合して行った。実施例及び比較例の触媒の擬平衡化は、それぞれの触媒を７５０℃で１３時間、スチーム１００％雰囲気で処理した。ＦＣＣ平衡触媒に対するそれぞれの擬平衡化した触媒の混合量は、ＦＣＣ平衡触媒２Ｋｇに対して触媒Ａ、触媒Ｂ、触媒Ｅ、触媒Ｇ、触媒Ｈは４重量％、触媒Ｃ、触媒Ｄ、触媒Ｆは３重量％とし、平衡触媒に対するＺＳＭ−５量が一定（０．６ｗｔ％）になるようにした。反応条件は以下の通りであった。
原料油： 脱硫減圧軽油（１００％）
反応温度：５００℃
触媒／原料油比：５ｇ／ｇ、 ７ｇ／ｇ
原料油供給速度：１０ｇ／ｍｉｎ
再生触媒中の炭素量（ＣＲＣ）： ０．０５重量％
なお、生成ガス及び生成油の分析はガスクロマトグラフィーを用いて行ない、ガソリンは沸点範囲２０４〜３４３℃で得られる生成油とした。反応結果からそれぞれ分解率が７０．０ｗｔ％における各生成物の収率及びリサーチ法オクタン価（ＲＯＮ）をグラフから読み取った。活性評価試験結果を表２及び表４に示す。
Example 6
About the catalyst of the Example which concerns on this invention, and the catalyst of a comparative example, the activity evaluation test was done using the Midget-2 pilot reactor of a catalyst circulation reproduction | regeneration system. As the catalyst for the activity evaluation test, the faujasite-type zeolite hydrocarbon fluid catalytic cracking catalyst (FCC equilibrium catalyst) used in the FCC equipment of the refinery and the quasi-equilibrium catalysts of the examples and comparative examples are constant. The mixing was performed at a ratio of In the pseudo-equilibration of the catalysts of Examples and Comparative Examples, each catalyst was treated at 750 ° C. for 13 hours in a 100% steam atmosphere. The amount of each quasi-equilibrium catalyst mixed with the FCC equilibrium catalyst is 4% by weight of Catalyst A, Catalyst B, Catalyst E, Catalyst G, and Catalyst H with respect to 2 kg of FCC equilibrium catalyst, Catalyst C, Catalyst D, and Catalyst F. Was 3 wt% so that the amount of ZSM-5 relative to the equilibrium catalyst was constant (0.6 wt%). The reaction conditions were as follows.
Raw material oil: Desulfurized vacuum gas oil (100%)
Reaction temperature: 500 ° C
Catalyst / raw oil ratio: 5 g / g, 7 g / g
Raw material supply rate: 10 g / min
Carbon content in regenerated catalyst (CRC): 0.05% by weight
In addition, analysis of the product gas and the product oil was performed using gas chromatography, and gasoline was a product oil obtained in a boiling range of 204 to 343 ° C. From the reaction results, the yield of each product and the research method octane number (RON) at a decomposition rate of 70.0 wt% were read from the graph. The activity evaluation test results are shown in Tables 2 and 4.
表１に示したように本発明に係る実施例の触媒Ａ〜Ｄは、比較例の触媒Ｅ、Ｆの全細孔容積０．２１ｍｌ／ｇ及び０．２４ｍｌ／ｇに比べ全細孔容積が０．３１ｍｌ／ｇ以上で大きい事が分かる。
活性評価試験結果、表２、表４から分かるように、全細孔容積の大きい触媒（Ａ〜Ｄ及びＧ）では全細孔容積の小さい触媒（Ｅ、Ｆ）に比較してＣ３＝、Ｃ４＝、ｉｓｏ−Ｃ４の収率とＲＯＮ（リサーチ法オクタン価）が大きく増加した。
また比較例３の触媒Ｈは全細孔容積が０．３０ｍｌ／ｇ以上であるが細孔直径１００±２０ｎｍ範囲の細孔容積の占める割合［ＰＶ／ＰＶＴ］が５０％以下であるため充分な性能が出ていない事が分かる。
As shown in Table 1, the catalysts A to D of the examples according to the present invention have total pore volumes that are 0.21 ml / g and 0.24 ml / g of the total pore volumes of the catalysts E and F of the comparative example. It turns out that it is large at 0.31 ml / g or more.
Activity evaluation test results in Table 2, as can be seen from Table 4, C 3 = as compared to the larger catalyst (to D and G) in small catalyst having a total pore volume of the total pore volume (E, F), C 4 =, the yield of iso-C 4 and RON (research method octane number) were greatly increased.
The catalyst H of Comparative Example 3 has a total pore volume of 0.30 ml / g or more, but the ratio [PV / PV T ] of the pore volume in the pore diameter range of 100 ± 20 nm is 50% or less. It can be seen that the performance is not good.
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