JP7178829B2 - Fluid catalytic cracking catalyst for hydrocarbon oil - Google Patents
Fluid catalytic cracking catalyst for hydrocarbon oil Download PDFInfo
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- JP7178829B2 JP7178829B2 JP2018160535A JP2018160535A JP7178829B2 JP 7178829 B2 JP7178829 B2 JP 7178829B2 JP 2018160535 A JP2018160535 A JP 2018160535A JP 2018160535 A JP2018160535 A JP 2018160535A JP 7178829 B2 JP7178829 B2 JP 7178829B2
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- 239000003054 catalyst Substances 0.000 title claims description 234
- 238000004231 fluid catalytic cracking Methods 0.000 title claims description 34
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 32
- 229930195733 hydrocarbon Natural products 0.000 title claims description 32
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 32
- 239000011148 porous material Substances 0.000 claims description 138
- 239000010457 zeolite Substances 0.000 claims description 65
- 229910021536 Zeolite Inorganic materials 0.000 claims description 60
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- 239000011230 binding agent Substances 0.000 claims description 47
- 238000009826 distribution Methods 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 238000004523 catalytic cracking Methods 0.000 claims description 27
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 24
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- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 238000011067 equilibration Methods 0.000 claims description 20
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- 239000000377 silicon dioxide Substances 0.000 claims description 15
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
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- 238000005342 ion exchange Methods 0.000 description 2
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
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- HNQGTZYKXIXXST-UHFFFAOYSA-N calcium;dioxido(oxo)tin Chemical compound [Ca+2].[O-][Sn]([O-])=O HNQGTZYKXIXXST-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
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- 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
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- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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Description
本発明は、重質留分の低減やコーク生成の抑制に有効で、ガソリンや液化石油ガス（ＬＰＧ）を高い収率で得る際に有効な炭化水素油の流動接触分解触媒に関する。 TECHNICAL FIELD The present invention relates to a fluidized catalytic cracking catalyst for hydrocarbon oils that is effective in reducing heavy fractions and suppressing coke formation, and is effective in obtaining high yields of gasoline and liquefied petroleum gas (LPG).
一般に接触分解用触媒は、常圧蒸留残油などの重質炭化水素油に対する分解能力（「ボトム分解能」ともいう）が高いこと、あるいは、触媒表面に析出するコークの析出量が少ないことなど、種々の観点で高い性能を発揮できるものが求められる。この点に関し、従来、炭化水素油の流動接触分解にあたっては、コークの収率を低くして、ガソリンや中間留分（軽油および灯油）などの収率をあげるために、異なる二種の触媒が混合して用いる方法などが提案されている。 In general, catalytic cracking catalysts have high cracking ability (also called "bottom decomposition") for heavy hydrocarbon oil such as atmospheric distillation residue, or have a small amount of coke deposited on the catalyst surface. There is a demand for materials that can exhibit high performance from various viewpoints. In this regard, conventionally, in the fluidized catalytic cracking of hydrocarbon oils, two different catalysts are used in order to reduce the yield of coke and increase the yield of gasoline and middle distillates (light oil and kerosene). A method of mixing and using them has been proposed.
例えば、特許文献１には、炭化水素油の流動接触分解に用いられる触媒について、二種の触媒を１：９～９：１の割合で物理的に混合してなるクラッキング触媒につき、一方の触媒をゼオライト含有クラッキング触媒とし、他方の触媒を２０～２００Å（２～２０ｎｍ）の細孔直径範囲において、同じ細孔直径範囲における一方の触媒より高い平均細孔体積を有するとともにＭ４１Ｓ物質を含まない触媒としたものが開示されている。
For example,
また、特許文献２には、ゼオライトと、活性マトリックス成分および不活性マトリックス成分からなる無機酸化物マトリックスとを含有する触媒を２種以上混合してなる炭化水素油の流動接触分解触媒であって、各触媒のゼオライトの含有量を変えることを特徴とする炭化水素油の流動接触分解触媒が開示されている。 Further, Patent Document 2 discloses a fluidized catalytic cracking catalyst for hydrocarbon oil obtained by mixing two or more catalysts containing zeolite and an inorganic oxide matrix composed of an active matrix component and an inactive matrix component, Fluid catalytic cracking catalysts for hydrocarbon oils are disclosed which feature varying zeolite content in each catalyst.
そして、特許文献３には、ゼオライトおよび結合剤として１０～３０質量％のシリカ系バインダーを含む触媒と、ゼオライトおよび結合剤として１０～３０質量％のアルミニウム化合物バインダーを含む触媒とを、質量比が１０：９０～９０：１０の範囲内で混合してなる流動接触分解触媒が開示されている。これにより、低コークとボトム（重質留分）分解能に優れたものになるとしている。 Patent Document 3 discloses a catalyst containing zeolite and 10 to 30% by mass of a silica-based binder as a binder, and a catalyst containing 10 to 30% by mass of an aluminum compound binder as a zeolite and a binder. Fluid catalytic cracking catalysts are disclosed which are mixed in the range of 10:90 to 90:10. This will result in excellent low coke and bottoms (heavy fraction) resolution.
しかしながら、従来の前記流動接触分解触媒については、実際には、低重質留分、低コークを十分に達成し、かつ、高付加価値製品（ガソリンやＬＰＧ）を高収率で得る触媒になっていないという問題があった。 However, the conventional fluid catalytic cracking catalyst actually achieves sufficient low-heavy fractions and low coke, and is a catalyst for obtaining high value-added products (gasoline and LPG) at high yields. There was a problem that it was not.
本発明は、従来材が抱えている前記事情に鑑みてなされたものであって、重質留分の低減やコーク生成の抑制に有効な、かつ、ガソリンやＬＰＧを高い収率で得るのに有効な炭化水素油の流動接触分解触媒を提供することを目的とする。 The present invention has been made in view of the above-mentioned circumstances of conventional materials, and is effective for reducing heavy fractions and suppressing coke formation, and for obtaining gasoline and LPG at high yields. It is an object of the present invention to provide an effective fluid catalytic cracking catalyst for hydrocarbon oils.
このような技術的背景のもと、発明者らは、上記課題を解決すべく鋭意検討した結果、特定の細孔分布（細孔径―細孔容積分布）をもつ流動接触分解触媒ではコークの生成が効果的に抑制される一方、それとは異なる細孔分布（細孔径―細孔容積分布）をもつものでは高い重質油分解能を示すことを見出した。 Based on this technical background, the inventors have made intensive studies to solve the above problems, and found that a fluid catalytic cracking catalyst having a specific pore size distribution (pore diameter - pore volume distribution) produces coke. was effectively suppressed, while those with a different pore distribution (pore diameter - pore volume distribution) showed high heavy oil decomposition.
そして、それらの触媒を適正な比率で混合することで、重質留分を低減しつつ、コーク生成を抑制して、高付加価値製品の収率を上げることを知見し、本発明を開発するに至った。 Then, by mixing these catalysts in an appropriate ratio, it is possible to suppress coke formation while reducing the heavy fraction, and to increase the yield of high value-added products, and develop the present invention. reached.
前記課題を解決し上記の目的を実現するため開発した本発明は、下記のとおりのものである。すなわち、本発明は、第一に、他の触媒に配合して用いられる炭化水素油用流動接触分解触媒であって、
擬平衡化を施した後の細孔分布において、（ａ）細孔径が４ｎｍ以上５０ｎｍ以下である細孔容積（ＰＶ１）の、細孔径が５０ｎｍより大きい細孔容積（ＰＶ２）に対する割合（ＰＶ１／ＰＶ２）が０．８以上で、かつ、（ｂ）細孔径が４ｎｍより大きい細孔容積（ＰＶ３）に対する、細孔径が３０ｎｍ以上１００ｎｍ以下の細孔容積（ＰＶ４）の割合（ＰＶ４／ＰＶ３）が０．２未満であることを特徴とする重質油分解性能に優れる炭化水素油用流動接触分解触媒である。
The present invention developed to solve the above problems and achieve the above objects is as follows. That is, the present invention is firstly a fluidized catalytic cracking catalyst for hydrocarbon oil that is used by blending with another catalyst,
In the pore distribution after pseudo-equilibration, (a) the ratio of the pore volume (PV1) having a pore diameter of 4 nm or more and 50 nm or less to the pore volume (PV2) having a pore diameter larger than 50 nm (PV1/ PV2) is 0.8 or more, and (b) the ratio of the pore volume (PV4) with a pore diameter of 30 nm or more to 100 nm or less to the pore volume (PV3) with a pore diameter of more than 4 nm (PV4/PV3) is It is a fluid catalytic cracking catalyst for hydrocarbon oils, characterized by having a polynomial ratio of less than 0.2, which is excellent in heavy oil cracking performance.
なお、本発明に係る上記重質油分解性能に優れる炭化水素油用流動接触分解触媒については、
（１）前記触媒は、ゼオライトと、結合剤としてアルミニウム化合物バインダーを含み、触媒組成基準で、前記ゼオライトを１５～６０質量％、前記アルミニウム化合物バインダーを５～３０質量％含むこと、
（２）前記アルミニウム化合物バインダーは、下記（ａ）～（ｃ）から選ばれるいずれか少なくとも１種を含むこと、（ａ）塩基性塩化アルミニウム、（ｂ）重リン酸アルミニウム、（ｃ）アルミナゾル、
（３）前記触媒に含まれるゼオライトは、ＦＡＵ型（フォージャサイト型）、ＭＦＩ型、ＣＨＡ型、およびＭＯＲ型のいずれか１種又は２種以上であること、
（４）前記ＦＡＵ型のゼオライトは、水素型Ｙ型ゼオライト（ＨＹ）、超安定化Ｙ型ゼオライト（ＵＳＹ）、レアアース交換Ｙ型ゼオライト（ＲＥＹ）、およびレアアース交換超安定化Ｙ型ゼオライト（ＲＥＵＳＹ）のいずれかであること、
（５）前記触媒は、前記ゼオライトおよび前記結合剤の他に、粘土鉱物を含むこと、
などがより好ましい解決手段になり得るものと考えられる。
Regarding the fluidized catalytic cracking catalyst for hydrocarbon oils having excellent heavy oil cracking performance according to the present invention,
(1) The catalyst contains zeolite and an aluminum compound binder as a binder, and contains 15 to 60% by mass of the zeolite and 5 to 30% by mass of the aluminum compound binder, based on the catalyst composition;
(2) The aluminum compound binder contains at least one selected from the following (a) to (c): (a) basic aluminum chloride, (b) aluminum biphosphate, (c) alumina sol,
(3) the zeolite contained in the catalyst is one or more of FAU type (faujasite type), MFI type, CHA type, and MOR type;
(4) The FAU-type zeolite includes hydrogen-type Y-type zeolite (HY), ultra-stabilized Y-type zeolite (USY), rare-earth-exchanged Y-type zeolite (REY), and rare-earth-exchanged ultra-stabilized Y-type zeolite (REUSY). be either
(5) the catalyst contains a clay mineral in addition to the zeolite and the binder;
etc. is considered to be a more preferable solution.
また、本発明は、第二に、２種の流動接触分解触媒を混合してなる炭化水素油用流動接触分解触媒であって、
一の触媒は、擬平衡化を施した後の細孔分布において、細孔径が４ｎｍ以上５０ｎｍ以下である細孔容積（ＰＶ１）の、細孔径が５０ｎｍより大きい細孔容積（ＰＶ２）に対する割合（ＰＶ１／ＰＶ２）が０．８未満である触媒（Ａ）であり、
他の触媒は、擬平衡化を施した後の細孔分布において、（ａ）細孔径が４ｎｍ以上５０ｎｍ以下である細孔容積（ＰＶ１）の、細孔径が５０ｎｍより大きい細孔容積（ＰＶ２）に対する割合（ＰＶ１／ＰＶ２）が０．８以上で、かつ、（ｂ）細孔径が４ｎｍより大きい細孔容積（ＰＶ３）に対する、細孔径が３０ｎｍ以上１００ｎｍ以下の細孔容積（ＰＶ４）の割合（ＰＶ４／ＰＶ３）が０．２未満である触媒（Ｂ）であり、
前記触媒（Ａ）を１００質量部に対して、前記触媒（Ｂ）を１０～２００質量部混合してなることを特徴とする製品収率に優れる炭化水素油用流動接触分解触媒である。
Secondly, the present invention is a fluid catalytic cracking catalyst for hydrocarbon oil, which is obtained by mixing two kinds of fluid catalytic cracking catalysts,
One catalyst has a pore volume (PV1) with a pore diameter of 4 nm or more and 50 nm or less in the pore distribution after pseudo-equilibration, the ratio of the pore volume (PV2) with a pore diameter of more than 50 nm ( A catalyst (A) in which PV1/PV2) is less than 0.8,
Other catalysts have a pore volume (PV2) with a pore diameter of greater than 50 nm in the pore distribution after pseudo-equilibration: (a) the pore volume (PV1) having a pore diameter of 4 nm or more and 50 nm or less (PV1/PV2) is 0.8 or more, and (b) the ratio of the pore volume (PV4) with a pore diameter of 30 nm or more to 100 nm or less to the pore volume (PV3) with a pore diameter of more than 4 nm ( A catalyst (B) in which PV4/PV3) is less than 0.2,
A fluidized catalytic cracking catalyst for hydrocarbon oil having excellent product yield, characterized by mixing 10 to 200 parts by mass of the catalyst (B) with 100 parts by mass of the catalyst (A).
なお、本発明に係る上記製品収率に優れる炭化水素油用流動接触分解触媒については、
（１）前記触媒（Ａ）は、ゼオライトと、結合剤としてシリカ系バインダーを含み、触媒組成基準で、前記ゼオライトを１５～６０質量％、前記シリカ系バインダーを５～３０質量％含むこと、
（２）前記シリカ系バインダーは、シリカゾル、水ガラス、および酸性ケイ酸液のいずれか１又は２以上であること、
（３）前記触媒（Ｂ）は、ゼオライトと、結合剤としてアルミニウム化合物バインダーを含み、触媒組成基準で、前記ゼオライトを１５～６０質量％、前記アルミニウム化合物バインダーを５～３０質量％含むこと、
（４）前記アルミニウム化合物バインダーは、下記（ａ）～（ｃ）から選ばれるいずれか少なくとも１種を含むこと、（ａ）塩基性塩化アルミニウム、（ｂ）重リン酸アルミニウム、（ｃ）アルミナゾル、
（５）前記触媒（Ａ）および前記触媒（Ｂ）に含まれるゼオライトは、ＦＡＵ型（フォージャサイト型）、ＭＦＩ型、ＣＨＡ型、およびＭＯＲ型のいずれか１種又は２種以上であること、
（６）前記ＦＡＵ型のゼオライトは、水素型Ｙ型ゼオライト（ＨＹ）、超安定化Ｙ型ゼオライト（ＵＳＹ）、レアアース交換Ｙ型ゼオライト（ＲＥＹ）、およびレアアース交換超安定化Ｙ型ゼオライト（ＲＥＵＳＹ）のいずれかであること、
（７）前記触媒（Ａ）および前記触媒（Ｂ）は、前記ゼオライトおよび前記結合剤の他に、粘土鉱物を含むこと、
などがより好ましい解決手段になり得るものと考えられる。
In addition, regarding the fluid catalytic cracking catalyst for hydrocarbon oil excellent in product yield according to the present invention,
(1) The catalyst (A) contains zeolite and a silica-based binder as a binder, and contains 15 to 60% by mass of the zeolite and 5 to 30% by mass of the silica-based binder, based on the catalyst composition;
(2) the silica-based binder is one or more of silica sol, water glass, and acidic silicic acid liquid;
(3) The catalyst (B) contains zeolite and an aluminum compound binder as a binder, and contains 15 to 60% by mass of the zeolite and 5 to 30% by mass of the aluminum compound binder, based on the catalyst composition;
(4) The aluminum compound binder contains at least one selected from the following (a) to (c): (a) basic aluminum chloride, (b) aluminum biphosphate, (c) alumina sol,
(5) The zeolite contained in the catalyst (A) and the catalyst (B) is one or more of FAU type (faujasite type), MFI type, CHA type, and MOR type. ,
(6) The FAU-type zeolite includes hydrogen-type Y-type zeolite (HY), ultra-stabilized Y-type zeolite (USY), rare-earth-exchanged Y-type zeolite (REY), and rare-earth-exchanged ultra-stabilized Y-type zeolite (REUSY). be either
(7) the catalyst (A) and the catalyst (B) contain a clay mineral in addition to the zeolite and the binder;
etc. is considered to be a more preferable solution.
以上説明したように、本発明によれば、細孔分布の異なる２種の流動接触分解触媒、その一方を重質油分解性能に優れる流動接触分解触媒として混合した炭化水素油用流動接触分解触媒とすることにより、重質留分を低減しつつ、コーク収率も低くでき、特に高付加価値製品であるガソリンの収率やＬＰＧの収率を高くすることができるようになる。 As described above, according to the present invention, two types of fluid catalytic cracking catalysts with different pore distributions, one of which is mixed as a fluid catalytic cracking catalyst having excellent heavy oil cracking performance, are mixed. As a result, the coke yield can be lowered while the heavy fraction is reduced, and in particular, the yield of gasoline and LPG, which are high value-added products, can be increased.
本発明の流動接触分解触媒では、擬平衡化の処理が施された後の細孔分布の異なる、炭化水素油用流動接触分解触媒を２種混合して調整する。以下、それぞれの触媒について、詳しく説明する。 The fluid catalytic cracking catalyst of the present invention is prepared by mixing two kinds of fluid catalytic cracking catalysts for hydrocarbon oil, which have different pore distributions after being subjected to pseudo-equilibration treatment. Each catalyst will be described in detail below.
上掲のいずれの触媒も炭化水素油用流動接触分解触媒として機能する必要があり、まず共通する事項について説明する。 Any of the catalysts listed above must function as a fluidized catalytic cracking catalyst for hydrocarbon oils, and common items will be explained first.
＜触媒の構成＞
ａ．構成成分について
バインダー成分として、シリカゾルなどのシリカ系バインダーや、塩基性塩化アルミニウム等のアルミニウム化合物バインダーを用いることができる。そのうちシリカ系バインダーとしては、シリカゾルの他に、ナトリウム型、リチウム型、酸型等のコロイダルシリカも使用することができる。これらのうちシリカゾルが好適である。アルミニウム化合物バインダーとしては、塩基性塩化アルミニウムの他に、重リン酸アルミニウム溶液、ジブサイト、バイアライト、ベーマイト、ベントナイト、結晶性アルミナなどを酸溶液中に溶解させた粒子や、ベーマイトゲル、無定形のアルミナゲルを水溶液中に分散させた粒子、あるいはアルミナゾルも使用することができる。これらは単独で、もしくは混合して、または複合して用いることができる。
<Structure of catalyst>
a. Constituent Components Silica-based binders such as silica sol and aluminum compound binders such as basic aluminum chloride can be used as binder components. Among them, as the silica-based binder, in addition to silica sol, sodium-type, lithium-type, acid-type colloidal silica, and the like can also be used. Of these, silica sol is preferred. In addition to basic aluminum chloride, aluminum compound binders include particles of aluminum biphosphate solution, gibbsite, bayerite, boehmite, bentonite, crystalline alumina, etc. dissolved in an acid solution, boehmite gel, amorphous Particles obtained by dispersing alumina gel in an aqueous solution, or alumina sol can also be used. These can be used alone, mixed or combined.
増量剤として、カオリンやベントナイト、カオリナイト、ハロイサイト、モンモリロナイト等の粘土鉱物を用いることができる。 Clay minerals such as kaolin, bentonite, kaolinite, halloysite and montmorillonite can be used as bulking agents.
その他の成分として、活性マトリックス成分や、ゼオライト、金属捕捉剤（メタルトラップ剤）を含有させることができる。 As other components, an active matrix component, zeolite, and a metal trapping agent (metal trapping agent) can be contained.
活性マトリックス成分として、活性アルミナやシリカ－アルミナ、シリカ－マグネシア、アルミナ－マグネシア、シリカ－マグネシア－アルミナなどの固体酸を有する物質を含むものを用いることができる。なお、固体酸とは、触媒が使用される温度領域において固体酸性を示すものであり、固体酸性の確認は、アンモニアを用いた昇温脱離法や、アンモニア又はピリジンを用いる in situ ＦＴＩＲ（フーリエ変換赤外線吸収スペクトル）法によりなされる。 As the active matrix component, those containing substances having a solid acid such as activated alumina, silica-alumina, silica-magnesia, alumina-magnesia, silica-magnesia-alumina can be used. The solid acid indicates solid acidity in the temperature range where the catalyst is used, and the solid acidity can be confirmed by the temperature programmed desorption method using ammonia, or the in situ FTIR (Fourier IR) method using ammonia or pyridine. conversion infrared absorption spectrum) method.
ゼオライトとして、通常、炭化水素油の接触分解触媒に使用されるゼオライトを用いることができる。例えば、ＦＡＵ型（フォージャサイト型。例えば、Ｙ型ゼオライト、Ｘ型ゼオライト等）、ＭＦＩ型（例えば、ＺＳＭ－５、ＴＳ－１等）、ＣＨＡ型(例えば、チャバサイト、ＳＡＰＯ－３４等)、およびＭＯＲ型（例えば、モルデナイト、Ｃａ－Ｑ等）のいずれか１又は２以上であり、特にＦＡＵ型が好適である。なお、フォージャサイト型のゼオライトとしては、水素型Ｙ型ゼオライト（ＨＹ）、超安定化Ｙ型ゼオライト（ＵＳＹ）や、ＨＹおよびＵＳＹにそれぞれ希土類金属をイオン交換等により担持させたレアアース交換Ｙ型ゼオライト（ＲＥＹ）、あるいはレアアース交換超安定化Ｙ型ゼオライト（ＲＥＵＳＹ）が例示される。 As zeolites, zeolites that are usually used for catalytic cracking catalysts for hydrocarbon oils can be used. For example, FAU type (faujasite type, e.g., Y-type zeolite, X-type zeolite, etc.), MFI type (e.g., ZSM-5, TS-1, etc.), CHA type (e.g., chabasite, SAPO-34, etc.) , and MOR type (eg, mordenite, Ca—Q, etc.), and the FAU type is particularly preferred. The faujasite-type zeolite includes hydrogen-type Y-type zeolite (HY), ultra-stabilized Y-type zeolite (USY), and rare earth-exchanged Y-type in which HY and USY each carry a rare earth metal by ion exchange or the like. Zeolite (REY) or rare earth-exchanged ultra-stabilized Y-type zeolite (REUSY) is exemplified.
金属捕捉剤として、アルミナ粒子やリン－アルミナ粒子、結晶性カルシウムアルミネート、セピオライト、チタン酸バリウム、スズ酸カルシウム、チタン酸ストロンチウム、酸化マンガン、マグネシア、マグネシア－アルミナなどを用いることができる。
また、メタルトラップ剤原料として、酸化雰囲気で焼成することによりアルミナなどとなるベーマイトなどの前駆体物質を用いることができる。
Alumina particles, phosphorus-alumina particles, crystalline calcium aluminate, sepiolite, barium titanate, calcium stannate, strontium titanate, manganese oxide, magnesia, magnesia-alumina, and the like can be used as metal scavengers.
Also, a precursor substance such as boehmite which becomes alumina or the like by firing in an oxidizing atmosphere can be used as a raw material for the metal trapping agent.
本発明触媒には、希土類金属（Ｒａｒｅ Ｅａｒｔｈ：ＲＥ）をイオン交換したものを含有させてもよい。その希土類金属としては、例えば、セリウム（Ｃｅ）、ランタン（Ｌａ）、プラセオジウム（Ｐｒ）、およびネオジム（Ｎｄ）などの使用が可能である。これらは単独ないし２種以上の金属酸化物としてもよい。なおこれらは、ゼオライトをイオン交換したものでもよく、それは希土類金属を含むことで、ゼオライトの耐水熱性が向上するからである。 The catalyst of the present invention may contain an ion-exchanged rare earth metal (Rare Earth: RE). Examples of rare earth metals that can be used include cerium (Ce), lanthanum (La), praseodymium (Pr), and neodymium (Nd). These may be single or two or more metal oxides. These zeolites may be ion-exchanged zeolites, because the hydrothermal resistance of the zeolites is improved by containing rare earth metals.
ｂ．成分組成について
前記バインダー成分は、５～３０質量％含有することが好ましい。より好ましくは１０～２５質量％である。その理由は、バインダー成分が５質量％より少ないと接触分解活性が高くなるものの、触媒のアトリッション（摩耗）強度が十分に保てない。一方、３０質量％より多いと、十分な接触分解活性が得られないおそれがある。
b. Concerning Component Composition The binder component is preferably contained in an amount of 5 to 30% by mass. More preferably, it is 10 to 25% by mass. The reason for this is that if the binder component is less than 5% by mass, the catalytic cracking activity increases, but the attrition (wear) strength of the catalyst cannot be sufficiently maintained. On the other hand, if it is more than 30% by mass, there is a possibility that sufficient catalytic cracking activity cannot be obtained.
前記ゼオライトは、１５～６０質量％が好ましい。より好ましくは２０～５０質量％である。さらに好ましくは２０～４０質量％である。その理由は、触媒に対するゼオライトの含有量が、１５％未満では接触分解活性が低くなる傾向があり、また、６０質量％を超えると接触分解活性が高くなりすぎてコークの析出量が多くなり、また、嵩密度が高くなると共に強度が低くなるためである。 The zeolite is preferably 15 to 60% by mass. More preferably 20 to 50% by mass. More preferably, it is 20 to 40% by mass. The reason for this is that if the zeolite content of the catalyst is less than 15%, the catalytic cracking activity tends to be low, and if it exceeds 60% by mass, the catalytic cracking activity becomes too high and the amount of coke deposition increases. This is also because the strength decreases as the bulk density increases.
前記希土類金属を用いる場合、ＲＥ２Ｏ３として、１０．０質量％以下、好ましくは０．５～５．０質量％となるように含有させる。ここで、触媒としては、ＲＥ２Ｏ３／ゼオライト質量比が一定となるように、ＲＥ２Ｏ３の添加を調整する。 When the rare earth metal is used, the content of RE 2 O 3 is 10.0% by mass or less, preferably 0.5 to 5.0% by mass. Here, as a catalyst, addition of RE 2 O 3 is adjusted so that the mass ratio of RE 2 O 3 /zeolite is constant.
さらに、各触媒には、粘土鉱物（増量剤）を１５～４５質量％含むことができる。その理由は、粘土鉱物が１５質量％未満では、活性成分が多くなるため、コーク生成が過剰となり十分な性能を示さない場合があるためであり、一方、４５質量％を超えると触媒中の固体酸量が少なくなりすぎて触媒活性が低下する恐れがある。また、各触媒が金属捕捉剤を含む場合、その含有量は、各触媒中に０．１～１０質量％、好ましくは０．１～５質量％の範囲内とすることが望ましい。 In addition, each catalyst may contain 15 to 45% by weight of clay mineral (extending agent). The reason for this is that if the clay mineral content is less than 15% by mass, the amount of active components increases, resulting in excessive coke formation and insufficient performance. There is a possibility that the amount of acid becomes too small, resulting in a decrease in catalytic activity. Moreover, when each catalyst contains a metal scavenger, the content thereof is desirably within the range of 0.1 to 10% by mass, preferably 0.1 to 5% by mass in each catalyst.
＜擬平衡化処理＞
炭化水素油の流動接触分解触媒の性能を実験室の反応装置で評価する際には、前処理として擬平衡化と呼ばれる処理を行う。その擬平衡化は、流動接触分解触媒にＶやＮｉ等のメタルを担持してスチーム処理を行うことで、活性を平衡触媒と同等のレベルまで低下させる処理である。この擬平衡化の処理により、平衡触媒の性状を再現することは、より精度の高い活性評価を得るためには重要である。
<Pseudo-equilibration processing>
When evaluating the performance of fluid catalytic cracking catalysts for hydrocarbon oils in laboratory reactors, a process called pseudo-equilibration is performed as a pretreatment. The quasi-equilibration is a process in which metals such as V and Ni are supported on a fluidized catalytic cracking catalyst and subjected to steam treatment to lower the activity to a level equivalent to that of the equilibrium catalyst. It is important to reproduce the properties of the equilibrium catalyst by this pseudo-equilibration process in order to obtain a more accurate activity evaluation.
＜比表面積の測定＞
擬平衡化した触媒は、ＢＥＴ法、例えば、ＭＯＵＮＴ ＥＣＨ社製Ｍａｃｓｏｒｂ ＨＭ ｍｏｄｅｌ―１２００を用いて、比表面積を測定する。また、マトリックス成分の比表面積は、例えば、日本ベル製ベルソープｍｉｎｉ―ＩＩ型を用いて、窒素の吸着等温線を測定し、得られた吸着側の等温線からＶａ－ｔプロットにより求める。なお、全体の比表面積からマトリックス成分の比表面積を差し引くことでゼオライト成分の比表面積を求めることができる。本発明では、触媒全体の比表面積（ＳＡ）は、１００～２００ｍ２／ｇの範囲にあることが好ましい。マトリックス成分の比表面積は４５ｍ２／ｇ以上が好ましく、さらに５０ｍ２／ｇ以上であることがより好ましい。
<Measurement of specific surface area>
The specific surface area of the pseudo-equilibrated catalyst is measured using the BET method, for example, Macsorb HM model-1200 manufactured by MOUNT ECH. In addition, the specific surface area of the matrix component is obtained by measuring the adsorption isotherm of nitrogen using, for example, Bell Soap Mini-II, manufactured by Nippon Bell Co., Ltd., and calculating the Va-t plot from the obtained isotherm on the adsorption side. The specific surface area of the zeolite component can be obtained by subtracting the specific surface area of the matrix component from the total specific surface area. In the present invention, the specific surface area (SA) of the entire catalyst is preferably in the range of 100-200 m 2 /g. The specific surface area of the matrix component is preferably 45 m 2 /g or more, more preferably 50 m 2 /g or more.
＜細孔径－細孔容積分布の測定＞
擬平衡化した触媒は水銀圧入法により、細孔径－細孔容積分布を測定する。測定装置としては、例えば、Ｑｕａｎｔａ ｃｈｒｏｍｅ社製Ｐｏｒｅ Ｍａｓｔｅｒ－６０ＧＴを用いて、細孔径－細孔容積分布を測定する。細孔径は、水銀の表面張力４８０ｄｙｎｅ／ｃｍ、接触角１５０°を用いて計算した値である。また、各細孔径範囲の細孔容積（ＰＶｎ）は、水銀圧入法により測定した各細孔直径範囲における細孔容積の積算値である。本発明では、触媒の全細孔容積（ＰＶ）は、０．１５ｍｌ／ｇ以上、さらに好ましくは０．２０～０．４０ｍｌ／ｇの範囲にあることが好ましい。
<Measurement of pore diameter-pore volume distribution>
The pore diameter-pore volume distribution of the pseudo-equilibrated catalyst is measured by mercury porosimetry. As a measuring device, for example, Pore Master-60GT manufactured by Quanta chrome is used to measure the pore diameter-pore volume distribution. The pore diameter is a value calculated using a mercury surface tension of 480 dyne/cm and a contact angle of 150°. Also, the pore volume (PVn) in each pore diameter range is the integrated value of the pore volume in each pore diameter range measured by mercury porosimetry. In the present invention, the total pore volume (PV) of the catalyst is preferably 0.15 ml/g or more, more preferably in the range of 0.20-0.40 ml/g.
上記試験により測定した触媒の細孔径－細孔容積分布の一例を図１に示す。横軸に細孔径（ｎｍ）を、縦軸にログ微分細孔容積ｄＶｐ／ｄｌｏｇｄを取っている。後述する実施例に基づき、ａ１は触媒（Ａ）の分布を、ｂ１は触媒（Ｂ）の分布を、Ｒ１はＰＶ４／ＰＶ３が０．２超えの比較例触媒の分布を表す。 An example of the pore diameter-pore volume distribution of the catalyst measured by the above test is shown in FIG. The horizontal axis is the pore diameter (nm), and the vertical axis is the log differential pore volume dVp/dlogd. Based on the examples described later, a1 represents the distribution of catalyst (A), b1 represents the distribution of catalyst (B), and R1 represents the distribution of the comparative example catalyst with PV4/PV3 exceeding 0.2.
流動接触分解触媒の比表面積が小さすぎ、全細孔容積が小さすぎる場合には、所望の分解反応活性が得られないことがある。比表面積の増大の観点からは、径の小さい細孔が多数あることが好ましい。ただし、４ｎｍ未満の細孔径では重質油の接触分解への寄与が小さいので、４ｎｍ以上の細孔径を有することが好ましい。また、炭化水素油の接触分解においては、コーク収率を低減する反応面からは、触媒の細孔は細孔直径が１０ｎｍより大きい方が反応物の拡散性がよくなるので望ましい。一方、細孔直径が１０００ｎｍより大きい細孔は、触媒の耐摩耗性を悪くすることがあるので少ない方が望ましい。 If the specific surface area of the fluid catalytic cracking catalyst is too small and the total pore volume is too small, desired cracking reaction activity may not be obtained. From the viewpoint of increasing the specific surface area, it is preferable that there are a large number of small-diameter pores. However, if the pore size is less than 4 nm, the contribution to catalytic cracking of heavy oil is small, so it is preferable to have a pore size of 4 nm or more. In the catalytic cracking of hydrocarbon oil, it is desirable that the pore diameter of the catalyst is larger than 10 nm from the viewpoint of reducing the yield of coke, since the diffusibility of reactants is improved. On the other hand, pores with a pore diameter larger than 1000 nm may deteriorate the abrasion resistance of the catalyst, so it is desirable that the number of pores is small.
＜触媒（Ａ）の構成＞
触媒（Ａ）は、本発明に係る流動接触分解触媒の主たる構成要素である。以下にその特性等について説明する。
ａ．細孔分布
触媒（Ａ）は、擬平衡化が施された後の細孔分布（細孔径－細孔容積分布）について、細孔径が４ｎｍ以上５０ｎｍ以下の範囲のメソ細孔容積（ＰＶ１）の、細孔径が５０ｎｍより大きい範囲のマクロ細孔容積（ＰＶ２）に対する割合（ＰＶ１／ＰＶ２）が０．８未満を有する。その細孔構造によって、コークの生成が抑制される。
（ＰＶ１／ＰＶ２）が０．８以上では、コークの生成抑制効果が小さくなるので好ましくない。
また、（ＰＶ１／ＰＶ２）が低い、つまり、マクロ細孔を多量に有する場合には、耐摩耗性の低下が懸念されるので、好ましくは、（ＰＶ１／ＰＶ２）が０．４～０．７の範囲である。
<Structure of catalyst (A)>
Catalyst (A) is the main component of the fluid catalytic cracking catalyst according to the present invention. The characteristics and the like will be described below.
a. Pore distribution The catalyst (A) has a mesopore volume (PV1) with a pore diameter in the range of 4 nm or more and 50 nm or less for the pore distribution (pore diameter - pore volume distribution) after being subjected to pseudo-equilibration. , the ratio (PV1/PV2) to the macropore volume (PV2) in the range of pore diameters larger than 50 nm is less than 0.8. Its pore structure inhibits coke formation.
When (PV1/PV2) is 0.8 or more, the effect of suppressing coke formation is reduced, which is not preferable.
In addition, when (PV1/PV2) is low, that is, when it has a large amount of macropores, deterioration of wear resistance is a concern. Therefore, (PV1/PV2) is preferably 0.4 to 0.7. is in the range of
ｂ．各成分
バインダー成分として、コークの生成を抑制する観点から、シリカ系バインダー単独、または、過半を有するバインダーが好ましい。シリカ系バインダーは、本発明触媒（Ａ）の耐摩耗性を向上させる目的のため、および本発明触媒（Ａ）の固体酸量や酸強度を調節する目的のために添加される。
b. Each Component As the binder component, from the viewpoint of suppressing the formation of coke, a silica-based binder alone or a binder containing a majority thereof is preferable. The silica-based binder is added for the purpose of improving the abrasion resistance of the catalyst (A) of the present invention and for the purpose of adjusting the solid acid content and acid strength of the catalyst (A) of the present invention.
＜触媒（Ａ）の製造方法＞
触媒（Ａ）の好適な製造方法の１例を以下に示す。
１．調整工程
前記したシリカゾル（シリカ系バインダーの一例）、カオリン、活性アルミナ粉末をスラリー形成用の液体（例えば純水）に加え、さらに、硫酸にてｐＨを３．９に調整した超安定化Ｙ型ゼオライトスラリーを加えて、混合スラリーを調整する。添加物の組成は、予め、上記細孔分布となるように把握したものを用いる。
<Method for producing catalyst (A)>
One example of a suitable method for producing the catalyst (A) is shown below.
1. Adjustment step Ultra-stable Y type obtained by adding the silica sol (an example of a silica-based binder), kaolin, and activated alumina powder to a slurry-forming liquid (e.g., pure water), and further adjusting the pH to 3.9 with sulfuric acid. Add the zeolite slurry to adjust the mixed slurry. The composition of the additive is determined in advance so as to achieve the above pore distribution.
２．噴霧乾燥、洗浄、乾燥工程
この混合スラリーを噴霧乾燥し球状粒子を得る。得られた球状粒子を洗浄し、さらに希土類金属（ＲＥ）塩化物の水溶液と接触させて、ＲＥ２Ｏ３として０．５～５．０質量％となるようにイオン交換した後、乾燥して、触媒（Ａ）を得る。得られた触媒（Ａ）の平均粒子径は、後述する触媒（Ｂ）と混合できる範囲であれば特に制限されないが、５０～１００μｍ程度である。
2. Spray-drying, washing, and drying steps The mixed slurry is spray-dried to obtain spherical particles. The obtained spherical particles are washed, further brought into contact with an aqueous solution of rare earth metal (RE) chloride, ion-exchanged so that RE 2 O 3 is 0.5 to 5.0% by mass, and then dried. , to obtain catalyst (A). The average particle size of the obtained catalyst (A) is not particularly limited as long as it can be mixed with the catalyst (B) described later, but it is about 50 to 100 μm.
＜触媒（Ｂ）の構成＞
触媒（Ｂ）は、本発明の根幹をなす、重質油分解性能に優れる炭化水素油用流動接触分解触媒であって、触媒（Ａ）に混合することで効果を発揮する。以下、その特性を説明する。
<Structure of catalyst (B)>
Catalyst (B) is a fluidized catalytic cracking catalyst for hydrocarbon oils that forms the basis of the present invention and has excellent heavy oil cracking performance, and exhibits its effect when mixed with catalyst (A). The characteristics are described below.
ａ．細孔分布
触媒（Ｂ）は、擬平衡化が施された後の細孔径－細孔容積分布について、（ａ）細孔径が４ｎｍ以上５０ｎｍ以下の範囲のメソ細孔容積（ＰＶ１）の、細孔径が５０ｎｍより大きい範囲のマクロ細孔容積（ＰＶ２）に対する割合（ＰＶ１／ＰＶ２）が０．８以上であり、かつ、（ｂ）細孔径が４ｎｍより大きい範囲の細孔容積（ＰＶ３）に対する、細孔径が３０ｎｍ以上１００ｎｍ以下の範囲の細孔容積（ＰＶ４）割合（ＰＶ４／ＰＶ３）が０．２未満であり、このような細孔構造をとることによって、高い重質留分の分解能をもつことになる。
その理由は前記（ＰＶ１／ＰＶ２）が０．８未満では重質留分の分解能が十分ではない。（ＰＶ１／ＰＶ２）が高すぎるとコーク生成が増加する恐れがあるので３．０以下とするのが望ましい。（ＰＶ４／ＰＶ３）が０．２以上では触媒（Ａ）との混合による重質留分の分解能が十分ではない。
（ＰＶ４／ＰＶ３）の下限は特に定めないが、触媒に含まれる構成成分のサイズに起因するため０．０３を下回ることは難しい。
好ましくは、（ＰＶ１／ＰＶ２）が１．２～２．８の範囲、（ＰＶ４／ＰＶ３）が０．０８～０．１５の範囲である。
a. Pore distribution The catalyst (B) has a pore size-pore volume distribution after being subjected to pseudo-equilibration: The ratio (PV1/PV2) to the macropore volume (PV2) in the range of pore diameters larger than 50 nm is 0.8 or more, and (b) the pore volume (PV3) in the range of pore diameters larger than 4 nm, The pore volume (PV4) ratio (PV4/PV3) in the pore diameter range of 30 nm or more and 100 nm or less is less than 0.2, and by adopting such a pore structure, it has a high resolution of heavy fractions. It will be.
The reason for this is that if (PV1/PV2) is less than 0.8, the decomposition of heavy fractions is not sufficient. If (PV1/PV2) is too high, coke formation may increase, so it is desirable to make it 3.0 or less. When (PV4/PV3) is 0.2 or more, the decomposition of the heavy fraction by mixing with the catalyst (A) is not sufficient.
Although the lower limit of (PV4/PV3) is not particularly defined, it is difficult to fall below 0.03 due to the sizes of the components contained in the catalyst.
Preferably, (PV1/PV2) is in the range of 1.2 to 2.8, and (PV4/PV3) is in the range of 0.08 to 0.15.
細孔径が３０ｎｍ以上１００ｎｍ以下の範囲の細孔容積を低くすることで、触媒（Ａ）との混合触媒が高い重質油の分解性能を有する理由は明らかではないが、発明者らは次のように考えている。 It is not clear why the mixed catalyst with the catalyst (A) has high heavy oil cracking performance by reducing the pore volume in the range of 30 nm or more and 100 nm or less, but the inventors have the following. I think so.
３０ｎｍ以上１００ｎｍ以下の範囲の細孔が多くなると、中間生成物であるＬＣＯ（Ｌｉｇｈｔ Ｃｙｃｌｅ Ｏｉｌ）留分等の触媒（Ｂ）の粒子内部への拡散が起こりやすくなるため、触媒（Ａ）と混合した時に、ＨＣＯ（Ｈｅａｖｙ Ｃｙｃｌｅ Ｏｉｌ）等のより重質油の分解により生成したＬＣＯ留分等の中間生成物の粒子（触媒（Ｂ））－粒子間（触媒（Ａ））への拡散が低下することで十分な触媒混合による効果が得られない、と考えている。 When the number of pores in the range of 30 nm or more and 100 nm or less increases, diffusion of the intermediate product such as LCO (Light Cycle Oil) fraction into the particles of the catalyst (B) easily occurs. Therefore, it is mixed with the catalyst (A). When this is done, diffusion of intermediate products such as LCO fractions generated by cracking heavier oil such as HCO (heavy cycle oil) between particles (catalyst (B)) and particles (catalyst (A)) is reduced. It is thought that the effect of sufficient catalyst mixing cannot be obtained by doing so.
ｂ．各成分
バインダー成分として、重質留分の分解の観点から、アルミニウム化合物バインダー単独、または、過半を有するバインダーが好ましい。
b. Each Component As the binder component, from the viewpoint of decomposing the heavy fraction, an aluminum compound binder alone or a binder containing a majority thereof is preferable.
アルミニウム化合物バインダーの原料としては、例えば塩基性塩化アルミニウム（［Ａｌ２（ＯＨ）ｎＣｌ６-ｎ］ｍ（但し、０＜ｎ＜６、ｍ≦１０））を用いることができる。塩基性塩化アルミニウムは、ゼオライトなどに含まれるアルミニウムおよびナトリウムやカリウムなどのカチオンの存在下で２００～４５０℃程度の比較的低温で分解する。この結果、塩基性塩化アルミニウムの一部が分解して、水酸化アルミニウムなどの分解物が存在するサイトがゼオライトの近傍に形成されるものと考えられる。さらに分解した塩基性塩化アルミニウムを３００～６００℃の範囲の温度で焼成することにより、アルミナバインダー（アルミナ）が形成される。このとき、ゼオライト近傍の分解物が焼成されてアルミナバインダーになる際に、細孔径が４ｎｍ以上、５０ｎｍ以下の範囲のメソ細孔が比較的多く形成され、本発明に係る触媒（Ｂ）の比表面積を増大させることができると推定される。一方で、耐摩耗性を低下させる要因となる、細孔径が５０ｎｍより大きく、１０００ｎｍ以下の範囲のマクロ孔の形成を抑えることも確認している。 As a raw material for the aluminum compound binder, for example, basic aluminum chloride ([Al 2 (OH) n Cl 6-n ] m (where 0<n<6, m≦10)) can be used. Basic aluminum chloride decomposes at a relatively low temperature of about 200 to 450° C. in the presence of aluminum contained in zeolite and cations such as sodium and potassium. As a result, it is believed that a portion of the basic aluminum chloride decomposes, forming sites near the zeolite where decomposed products such as aluminum hydroxide are present. Further calcination of the decomposed basic aluminum chloride at a temperature in the range of 300-600° C. forms an alumina binder (alumina). At this time, when the decomposition product near the zeolite is calcined to become an alumina binder, a relatively large number of mesopores having a pore diameter in the range of 4 nm or more and 50 nm or less are formed, and the ratio of the catalyst (B) according to the present invention It is presumed that the surface area can be increased. On the other hand, it has also been confirmed that the formation of macropores with a pore diameter greater than 50 nm and 1000 nm or less, which is a factor in reducing wear resistance, is suppressed.
上記測定に係るゼオライト成分の比表面積として、６０～１００ｍ２／ｇが重質留分の分解の点で好ましい。 The specific surface area of the zeolite component for the above measurement is preferably 60 to 100 m 2 /g from the viewpoint of decomposition of heavy fractions.
＜触媒（Ｂ）の製造方法＞
触媒（Ｂ）の製造方法の１例を以下に示す。
１．調整工程
前記した塩基性塩化アルミニウム水溶液（アルミニウム化合物バインダーの一例）を純水で希釈し、カオリン、活性アルミナ粉末および超安定化Ｙ型ゼオライトスラリーを加えて、よく撹拌した後、塩化ランタン溶液を添加し、調合スラリーを調整する。添加物の組成は、予め、上記細孔分布となるように把握したものを用いる。
<Method for producing catalyst (B)>
An example of the method for producing the catalyst (B) is shown below.
1. Preparation step Dilute the basic aluminum chloride aqueous solution (an example of an aluminum compound binder) with pure water, add kaolin, activated alumina powder and ultra-stable Y-type zeolite slurry, stir well, and then add the lanthanum chloride solution. and adjust the blended slurry. The composition of the additive is determined in advance so as to achieve the above pore distribution.
２．噴霧乾燥、焼成、洗浄、乾燥工程
上記の調合したスラリーを噴霧乾燥し球状粒子とする。次に得られた球状粒子の乾燥粉末を焼成し、温水懸濁－脱水濾過後、温水を掛水し、さらに乾燥して、触媒（Ｂ）を得る。得られた触媒（Ｂ）の平均粒子径は、前記触媒（Ａ）と混合できる範囲であれば特に制限されないが、５０～１００μｍ程度である。
2. Spray-drying, calcination, washing, drying process The prepared slurry is spray-dried to form spherical particles. Next, the obtained dry powder of spherical particles is calcined, suspended in warm water, dehydrated and filtered, poured with warm water, and further dried to obtain a catalyst (B). The average particle size of the obtained catalyst (B) is not particularly limited as long as it can be mixed with the catalyst (A), but is about 50 to 100 μm.
＜混合触媒の調整＞
本発明に係る流動接触分解触媒は、まず、擬平衡化が施された後の、細孔径－細孔容積分布の異なる２種の触媒を調製したのち、公知の方法で混合して製造される。このようにして得られた本発明の流動接触分解触媒は、上記触媒（Ａ）の１００質量部に対して、上記触媒（Ｂ）を１０～２００質量部混合したものである。触媒（Ｂ）の配合量が触媒（Ａ）の１００質量部に対し１０質量部未満だと、重質留分の分解能が十分ではなく、ガソリン＋ＬＰＧ収率が向上しない。一方、２００質量部を超えると触媒（Ａ）のコーク生成抑制効果が薄れてしまい、ガソリン＋ＬＰＧ収率が低下する。従って、上記触媒（Ａ）の１００質量部に対して、上記触媒（Ｂ）を１０～２００質量部混合する。好ましくは、触媒（Ａ）の１００質量部に対して、触媒（Ｂ）を４０～１００質量部混合する。なお、触媒（Ａ）と触媒（Ｂ）との混合割合（質量比）は、炭化水素油を本流動接触分解触媒により分解して得られる分解生成物（特に、ガソリン、ＬＰＧ）が所望の組成（収率）となるように決めるのがよい。
<Adjustment of mixed catalyst>
The fluidized catalytic cracking catalyst according to the present invention is produced by first preparing two catalysts with different pore diameter-pore volume distributions after being subjected to pseudo-equilibration, and then mixing them by a known method. . The fluidized catalytic cracking catalyst of the present invention thus obtained is obtained by mixing 10 to 200 parts by mass of the above catalyst (B) with 100 parts by mass of the above catalyst (A). If the amount of catalyst (B) blended is less than 10 parts by mass with respect to 100 parts by mass of catalyst (A), the decomposition of heavy fractions is not sufficient, and the gasoline+LPG yield is not improved. On the other hand, when the amount exceeds 200 parts by mass, the effect of suppressing coke formation by the catalyst (A) is weakened, and the gasoline+LPG yield is lowered. Therefore, 10 to 200 parts by mass of the catalyst (B) is mixed with 100 parts by mass of the catalyst (A). Preferably, 40 to 100 parts by mass of catalyst (B) is mixed with 100 parts by mass of catalyst (A). The mixing ratio (mass ratio) of the catalyst (A) and the catalyst (B) is such that the cracked product (particularly gasoline and LPG) obtained by cracking the hydrocarbon oil with the present fluidized catalytic cracking catalyst has the desired composition. (yield) should be determined.
＜流動接触分解方法＞
本発明に係る流動接触分解触媒を用いる流動接触分解については、通常の炭化水素油の流動接触分解条件を採用することができ、例えば、以下に述べる条件が好適である。
<Fluid catalytic cracking method>
For the fluid catalytic cracking using the fluid catalytic cracking catalyst according to the present invention, normal fluid catalytic cracking conditions for hydrocarbon oils can be employed, and for example, the conditions described below are suitable.
接触分解に使用される原料油としては、通常の炭化水素原料油、例えば、水素化脱硫減圧蒸留軽油（ＤＳＶＧＯ）や、減圧蒸留軽油（ＶＧＯ）を用いることができる他、常圧蒸留残渣油（ＡＲ）、減圧蒸留残渣油（ＶＲ）、脱硫常圧蒸留残渣油（ＤＳＡＲ）、脱硫減圧蒸留残渣油（ＤＳＶＲ）、脱アスファルテン油（ＤＡＯ）等の残渣油も使用することができ、これらの単独又は混合したものも使用できる。なお、本発明に係る流動接触分解触媒においては、ニッケルおよびバナジウムがそれぞれ０．５ｐｐｍ以上含まれている残渣油も処理可能であり、原料油として残渣油を単独で用いる残渣油接触分解装置（Ｒｅｓｉｄ ＦＣＣ。ＲＦＣＣ）にも使用できる。ここで、従来の流動接触分解触媒をＲＦＣＣで使用した場合には、残渣油中のニッケルおよびバナジウムが触媒に付着して活性が低下するが、本発明の流動接触分解触媒では、バナジウムおよびニッケルがそれぞれ０．５ｐｐｍ以上含有している残渣油を処理しても、優れた触媒性能を保持できる。また、本発明の流動接触分解触媒は、バナジウムおよびニッケルがそれぞれ３００ｐｐｍ以上含有されていても触媒性能を保持できる。本発明の流動接触分解触媒に含有されるバナジウムおよびニッケルの上限は、それぞれ１００００ｐｐｍ程度である。 As the feedstock used for catalytic cracking, ordinary hydrocarbon feedstocks such as hydrodesulfurized vacuum distilled gas oil (DSVGO) and vacuum distilled gas oil (VGO) can be used, as well as atmospheric distillation residue oil ( AR), vacuum distillation residue (VR), desulfurization atmospheric distillation residue (DSAR), desulfurization vacuum distillation residue (DSVR), deasphalted oil (DAO) and the like can also be used, and these oils alone can also be used. Or a mixed one can also be used. In addition, in the fluidized catalytic cracking catalyst according to the present invention, it is possible to treat residual oil containing 0.5 ppm or more of nickel and vanadium, respectively, and a residual oil catalytic cracking unit (Resid FCC, RFCC) can also be used. Here, when a conventional fluid catalytic cracking catalyst is used in RFCC, nickel and vanadium in the residual oil adhere to the catalyst and the activity decreases, but in the fluid catalytic cracking catalyst of the present invention, vanadium and nickel are Excellent catalytic performance can be maintained even when residual oil containing 0.5 ppm or more of each is treated. Further, the fluid catalytic cracking catalyst of the present invention can maintain its catalytic performance even if it contains 300 ppm or more of each of vanadium and nickel. The upper limits of vanadium and nickel contained in the fluid catalytic cracking catalyst of the present invention are each about 10000 ppm.
また、前述の炭化水素原料油を接触分解する際の反応温度は４７０～５５０℃の範囲が好適に採用され、反応圧力は一般的にはおよそ１～３ｋｇ／ｃｍ2の範囲が好適であり、触媒／油の質量比（触媒／油比）は２．５～９．０の範囲が好ましく、更に接触時間は１０～６０ｈｒ-1の範囲が好ましい。 In addition, a reaction temperature in the range of 470 to 550° C. is preferably adopted for the catalytic cracking of the hydrocarbon feedstock described above, and a reaction pressure is generally preferably in the range of about 1 to 3 kg/cm 2 , The catalyst/oil mass ratio (catalyst/oil ratio) is preferably in the range of 2.5 to 9.0, and the contact time is preferably in the range of 10 to 60 hr -1 .
《ガソリン＋ＬＰＧ収率Ｇ》
流動接触分解触媒のガソリン＋ＬＰＧ収率Ｇmが、触媒（Ａ）のガソリン＋ＬＰＧ収率ＧＡおよび触媒（Ｂ）のガソリン＋ＬＰＧ収率ＧＢよりも高いのが好ましい。ここで、ガソリン＋ＬＰＧ収率は、前記した方法で原料油を接触分解し、得られたガソリンの質量＋ＬＰＧの質量と、原料油の質量とから計算される。
《Gasoline + LPG yield G》
Preferably, the gasoline+LPG yield Gm of the fluid catalytic cracking catalyst is higher than the gasoline+LPG yield GA of catalyst ( A ) and the gasoline+LPG yield GB of catalyst ( B ). Here, the gasoline+LPG yield is calculated from the mass of gasoline+LPG mass obtained by catalytically cracking the feedstock oil by the above-described method, and the mass of the feedstock oil.
また、本発明の流動接触分解触媒は、触媒（Ａ）および触媒（Ｂ）の単独のものから混合組成に基づき単純平均した値よりも、水素収率、Ｃ１＋Ｃ２収率、ＨＣＯ収率、およびコーク収率が低くなる傾向にある。すなわち、本発明の流動接触分解触媒は、触媒（Ａ）および触媒（Ｂ）の単体よりも、ガソリンやＬＰＧなどの高付加価値製品の収率が増える傾向にあるが、ガスや重質油、コークなどの収率は低くなる傾向にある。 In addition, the fluid catalytic cracking catalyst of the present invention has a hydrogen yield, C1 + C2 yield, HCO yield, and coke Yields tend to be low. That is, the fluidized catalytic cracking catalyst of the present invention tends to increase the yield of high value-added products such as gasoline and LPG, compared to catalyst (A) and catalyst (B) alone, but gas, heavy oil, Yields such as coke tend to be low.
以下、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの実施例に何ら制限されるものではない。
（製造例）
＜触媒ａ１＞
ａ．調合工程
水ガラス（ＳｉＯ２濃度：１７質量％）２９４１ｇと硫酸（硫酸濃度：２５質量％）１０５９ｇを同時に連続的に加えて、ＳｉＯ２濃度が１２．５質量％のシリカゾル（シリカ系バインダーの一例）４０００ｇを調整した。このシリカゾルにカオリン（固形分濃度：８４％質量）８９３ｇ、活性アルミナ粉末（固形分：８１％質量）５５６ｇを加え、さらに、硫酸にてｐＨを３．９に調整した超安定化Ｙ型ゼオライトスラリー（固形分濃度：３３％質量）を２４２４ｇ加えて混合スラリーを調整した。
EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.
(Manufacturing example)
<Catalyst a1>
a. Preparation process 2941 g of water glass ( SiO2 concentration: 17% by mass) and 1059 g of sulfuric acid (sulfuric acid concentration: 25% by mass) are continuously added at the same time to form a silica sol (an example of a silica-based binder) with an SiO2 concentration of 12.5% by mass. ) was adjusted to 4000 g. 893 g of kaolin (solid content concentration: 84% mass) and 556 g of activated alumina powder (solid content: 81% mass) were added to this silica sol, and the pH was further adjusted to 3.9 with sulfuric acid to form an ultra-stable Y-type zeolite slurry. (Solid content concentration: 33% mass) was added to prepare a mixed slurry.
ｂ．噴霧乾燥、洗浄、乾燥工程
前記混合スラリーを液滴として、入口温度が２３０℃、出口温度が１３０℃の噴霧乾燥機で噴霧乾燥し、平均粒径が７０μｍの球状粒子を得た。得られた噴霧乾燥粒子を質量で１０倍量の温水（６０℃）に懸濁し、脱水濾過した。次いで、質量で１０倍量の温水（６０℃）を掛水した後、さらに懸濁し、希土類金属（ＲＥ）塩化物の水溶液（セリウムおよびランタンの塩化物を含む）と接触させて、ＲＥ２Ｏ３として２．１質量％となるようにイオン交換処理した。その後、触媒粒子を雰囲気１３５℃の乾燥機で乾燥して、触媒ａ１を得た。
b. Spray Drying, Washing, and Drying Steps The mixed slurry was made into droplets and spray-dried in a spray dryer having an inlet temperature of 230° C. and an outlet temperature of 130° C. to obtain spherical particles having an average particle size of 70 μm. The resulting spray-dried particles were suspended in warm water (60° C.) of 10 times the mass, and dehydrated and filtered. Then, hot water (60 ° C.) of 10 times the mass is sprinkled, and then suspended and brought into contact with an aqueous solution of rare earth metal (RE) chloride (containing cerium and lanthanum chloride) to obtain RE 2 O. Ion exchange treatment was carried out so that 3 was 2.1% by mass. Thereafter, the catalyst particles were dried in a drier at an atmosphere of 135° C. to obtain catalyst a1.
ｃ．擬平衡化工程
前記のようにして得られた触媒ａ１を予め雰囲気温度６００℃にて２時間焼成した。その後、ニッケルオクチル酸塩およびバナジウムオクチル酸塩をそれぞれ金属換算で１０００ｐｐｍ（ニッケルの質量を触媒の質量で除算している）および２０００ｐｐｍ（バナジウムの質量を触媒の質量で除算している）の量で、焼成した触媒粒子に沈着させた。次いで、触媒を雰囲気温度１１０℃で乾燥した後、雰囲気温度６００℃で１．５時間焼成し、その後、触媒に雰囲気温度７８０℃で１３時間のスチーム処理を施し、触媒ａ１の擬平衡化処理品を得た。
c. Pseudo-Equilibration Step The catalyst a1 obtained as described above was calcined in advance at an ambient temperature of 600° C. for 2 hours. Then, nickel octylate and vanadium octylate are added in amounts of 1000 ppm (weight of nickel divided by weight of catalyst) and 2000 ppm (weight of vanadium divided by weight of catalyst), respectively, in terms of metal. was deposited on the calcined catalyst particles. Next, after drying the catalyst at an atmospheric temperature of 110° C., it is calcined at an atmospheric temperature of 600° C. for 1.5 hours, and then subjected to steam treatment at an atmospheric temperature of 780° C. for 13 hours to obtain a pseudo-equilibrated product of catalyst a1. got
ｄ．細孔径－細孔容積分布の測定
擬平衡化を施した触媒ａ１について、前述の水銀圧入法による細孔径－細孔容積分布測定を行った。擬平衡化を施した触媒ａ１は測定前に空気雰囲気下、６００℃で１時間焼成した。全細孔容積は０．２８ｍｌ／ｇであった。細孔径が４ｎｍ以上５０ｎｍ以下の範囲のメソ細孔容積（ＰＶ１）の、細孔径が５０ｎｍより大きい範囲のマクロ細孔容積（ＰＶ２）に対する割合はＰＶ１／ＰＶ２＝０．５６であった。擬平衡化を施した触媒ａ１の細孔径［ｎｍ］に対するログ微分細孔容積ｄＶ／ｄｌｏｇｄの分布を図１に示す。
d. Measurement of Pore Size--Pore Volume Distribution The pore size--pore volume distribution of the pseudo-equilibrated catalyst a1 was measured by the aforementioned mercury intrusion method. The pseudo-equilibrated catalyst a1 was calcined at 600° C. for 1 hour in an air atmosphere before measurement. Total pore volume was 0.28 ml/g. The ratio of the mesopore volume (PV1) with pore diameters in the range of 4 nm to 50 nm to the macropore volume (PV2) with pore diameters in the range of greater than 50 nm was PV1/PV2=0.56. FIG. 1 shows the distribution of the log differential pore volume dV/dlogd with respect to the pore diameter [nm] of the pseudo-equilibrated catalyst a1.
ｅ．比表面積
擬平衡化した触媒ａ１について、前述の比表面積測定を行ったところ１６９ｍ２／ｇであった。また、マトリックス成分の表面積は４８ｍ２／ｇであり、ゼオライト成分の比表面積は１２１ｍ２／ｇであった。
e. Specific Surface Area The specific surface area of the pseudo-equilibrated catalyst a1 was measured to be 169 m 2 /g. The matrix component had a surface area of 48 m 2 /g, and the zeolite component had a specific surface area of 121 m 2 /g.
＜触媒ｂ１＞
ａ．調合工程
２３．５質量％の塩基性塩化アルミニウム水溶液５３１．９ｇと純水１１３８．０ｇを混合した。次いで、この混合溶液をよく攪拌しながら、カオリン（固形分濃度：８４％質量）４５２．４ｇ、活性アルミナ粉末（固形分濃度：８１％質量）２４６．９ｇおよび超安定化Ｙ型ゼオライト粉末（固形分濃度：７５質量％）３３３．３ｇを順次添加した。その後、塩化ランタン溶液（Ｌａ２Ｏ３濃度：２９．１質量％）を１５４．６ｇ添加し、よく撹拌し、調合スラリーを得た。得られた調合スラリーは、ホモジナイザーを用いて分散処理した結果、固形分濃度は３５質量％、ｐＨは３．８であった。
<Catalyst b1>
a. Preparation Step 531.9 g of a 23.5% by mass aqueous solution of basic aluminum chloride and 1138.0 g of pure water were mixed. Next, while stirring this mixed solution well, 452.4 g of kaolin (solid content concentration: 84% mass), 246.9 g of activated alumina powder (solid content concentration: 81% mass) and ultra-stable Y-type zeolite powder (solid content) concentration: 75% by mass) 333.3 g were sequentially added. After that, 154.6 g of a lanthanum chloride solution (La 2 O 3 concentration: 29.1% by mass) was added and thoroughly stirred to obtain a mixed slurry. As a result of dispersing the obtained mixed slurry using a homogenizer, the solid content concentration was 35% by mass and the pH was 3.8.
ｂ．噴霧乾燥、焼成、洗浄、乾燥工程
前記のようにして得られた調合スラリーを液滴として、入口温度が２３０℃、出口温度が１３０℃の噴霧乾燥機で噴霧乾燥を行い、平均粒子径が７０μｍの球状粒子を得た。この乾燥粉末は電気炉にて空気雰囲気下、４００℃で1時間焼成した後、焼成品に対して質量にて１０倍量の温水（６０℃）に懸濁させ、脱水濾過を施した。さらに、質量で１０倍量の温水（６０℃）を掛水した後、ケーキを回収し、雰囲気温度１４０℃に保持した乾燥機にて１０時間乾燥させて、触媒ｂ１を得た。
b. Spray drying, baking, washing, drying process The prepared slurry obtained as described above is used as droplets and spray-dried with a spray dryer having an inlet temperature of 230 ° C. and an outlet temperature of 130 ° C., and the average particle size is 70 μm. of spherical particles were obtained. The dry powder was calcined in an electric furnace at 400° C. for 1 hour in an air atmosphere, suspended in hot water (60° C.) in an
ｃ．擬平衡化工程
得られた触媒ｂ１は、触媒ａ１と同様の条件で擬平衡化処理を施した。
c. Pseudo-Equilibration Step The obtained catalyst b1 was subjected to a pseudo-equilibration treatment under the same conditions as those for the catalyst a1.
ｄ．細孔径－細孔容積分布の測定
擬平衡化を施した触媒ｂ１について、触媒ａ１と同様に、前述の水銀圧入法による細孔径－細孔容積分布測定を行った。全細孔容積は０．３９ｍｌ／ｇであり、細孔径が４ｎｍ以上５０ｎｍ以下の範囲のメソ細孔容積（ＰＶ１）の、細孔径が５０ｎｍより大きい範囲のマクロ細孔容積（ＰＶ２）に対する割合はＰＶ１／ＰＶ２＝１．５３であった。また、細孔径が４ｎｍより大きい範囲の細孔容積（ＰＶ３）に対する、細孔径が３０ｎｍ以上１００ｎｍ以下の範囲の細孔容積（ＰＶ４）割合は、ＰＶ４／ＰＶ３＝０．１１であった。擬平衡化を施した触媒ｂ１の細孔径［ｎｍ］に対するログ微分細孔容積ｄＶ／ｄｌｏｇｄの分布を図１に示す。
d. Measurement of Pore Diameter-Pore Volume Distribution For the pseudo-equilibrated catalyst b1, the pore diameter-pore volume distribution was measured by the aforementioned mercury intrusion method in the same manner as for the catalyst a1. The total pore volume is 0.39 ml / g, and the ratio of the mesopore volume (PV1) with a pore diameter in the range of 4 nm to 50 nm to the macropore volume (PV2) with a pore diameter in the range of greater than 50 nm is It was PV1/PV2=1.53. Moreover, the ratio of the pore volume (PV4) in the pore diameter range of 30 nm or more to 100 nm or less to the pore volume (PV3) in the pore diameter range of 4 nm or more was PV4/PV3=0.11. FIG. 1 shows the distribution of the log differential pore volume dV/dlogd with respect to the pore diameter [nm] of the pseudo-equilibrated catalyst b1.
ｅ．比表面積
擬平衡化した触媒ｂ１について、前述の比表面積測定を行ったところ１６６ｍ２／ｇであった。マトリックス成分の表面積は９０ｍ２／ｇであり、計算されるゼオライト成分の比表面積は７６ｍ２／ｇであった。
e. Specific surface area The above-mentioned specific surface area measurement of the pseudo-equilibrated catalyst b1 was 166 m 2 /g. The surface area of the matrix component was 90 m 2 /g and the calculated specific surface area of the zeolite component was 76 m 2 /g.
＜ブレンド触媒ａ１ｂ１＞
得られた触媒ａ１の固形分１００質量部に対し、触媒ｂ１を固形分４２．９質量部および１００質量部混合し、本発明に係るブレンド触媒ａ１ｂ１を得た。
<Blend catalyst a1b1>
42.9 parts by mass and 100 parts by mass of solids content of catalyst b1 were mixed with 100 parts by mass of solid content of catalyst a1 thus obtained to obtain blended catalyst a1b1 according to the present invention.
（比較例）
＜触媒Ｒ１＞
ａ．調合工程
２３．５質量％の塩基性塩化アルミニウム水溶液５３１．９ｇと純水２９９．３ｇを混合した。次いで、この混合溶液をよく攪拌しながら、カオリン（固形分濃度：８４％質量）４５２．４ｇ、活性アルミナ粉末（固形分濃度：８１％質量）６１．７ｇ、事前に硫酸を用いてｐＨを３．１に調整した活性アルミナスラリー（ベーマイトゲルスラリー。固形分濃度：１０質量％）１５００ｇおよび超安定化Ｙ型ゼオライト粉末（固形分濃度：７５質量％）３３３．３ｇを順次添加した。その後、塩化ランタン溶液（Ｌａ２Ｏ３濃度：２９．１質量％）を１５４．６ｇ添加し、よく撹拌し、調合スラリーを得た。得られた調合スラリーは、ホモジナイザーを用いて分散処理を行い、固形分濃度が３０質量％、ｐＨが３．４であった。
(Comparative example)
<Catalyst R1>
a. Preparation Step 531.9 g of a 23.5% by mass aqueous solution of basic aluminum chloride and 299.3 g of pure water were mixed. Next, while thoroughly stirring this mixed solution, 452.4 g of kaolin (solid content concentration: 84% mass), 61.7 g of activated alumina powder (solid content concentration: 81% mass), and pH 3 using sulfuric acid in advance. 1500 g of activated alumina slurry (boehmite gel slurry, solid content concentration: 10% by mass) and 333.3 g of ultra-stable Y-type zeolite powder (solid content concentration: 75% by mass) adjusted to .1 were sequentially added. After that, 154.6 g of a lanthanum chloride solution (La2O3 concentration: 29.1% by mass) was added and thoroughly stirred to obtain a mixed slurry. The resulting prepared slurry was subjected to dispersion treatment using a homogenizer, and had a solid content concentration of 30% by mass and a pH of 3.4.
ｂ．噴霧乾燥、焼成、洗浄、乾燥工程
調合スラリーを液滴として、入口温度が２３０℃、出口温度が１３０℃の噴霧乾燥機で噴霧乾燥を行い、平均粒子径が６８μｍの球状粒子を得た。この乾燥粉末は電気炉にて空気雰囲気下、４００℃で1時間焼成した後、焼成品に対して質量にて１０倍量の温水（６０℃）に懸濁させ、脱水濾過を施した。さらに、質量で１０倍量の温水（６０℃）を掛水した後、ケーキを回収し、雰囲気温度１４０℃に保持した乾燥機にて１０時間乾燥させ、触媒Ｒ１を得た。
b. Spray Drying, Firing, Washing, and Drying Steps The prepared slurry was made into droplets and spray-dried in a spray dryer with an inlet temperature of 230° C. and an outlet temperature of 130° C. to obtain spherical particles with an average particle size of 68 μm. The dry powder was calcined in an electric furnace at 400° C. for 1 hour in an air atmosphere, suspended in hot water (60° C.) in an
ｃ．擬平衡化工程
得られた触媒Ｒ１は、触媒ａ１と同様の条件で擬平衡化処理を施した。
c. Pseudo-Equilibration Process The obtained catalyst R1 was subjected to a pseudo-equilibration treatment under the same conditions as those for the catalyst a1.
ｄ．細孔径－細孔容積分布の測定
擬平衡化を施した触媒Ｒ１について、触媒ａ１と同様に、前述の水銀圧入法による細孔径－細孔容積分布測定を行った。全細孔容積は０．３１ｍｌ／ｇであり、細孔径が４ｎｍ以上５０ｎｍ以下の範囲のメソ細孔容積（ＰＶ１）の、細孔径が５０ｎｍより大きい範囲のマクロ細孔容積（ＰＶ２）に対する割合はＰＶ１／ＰＶ２＝１．１４であった。また、細孔径が４ｎｍより大きい範囲の細孔容積（ＰＶ３）に対する、細孔径が５０ｎｍ以上１００ｎｍ以下の範囲の細孔容積（ＰＶ４）割合は、ＰＶ４／ＰＶ３＝０．２５であった。擬平衡化を施した触媒Ｒ１の細孔径［ｎｍ］に対するログ微分細孔容積ｄＶ／ｄｌｏｇｄの分布を図１に示す。
d. Measurement of Pore Diameter-Pore Volume Distribution For the pseudo-equilibrated catalyst R1, the pore diameter-pore volume distribution was measured by the aforementioned mercury intrusion method in the same manner as for the catalyst a1. The total pore volume is 0.31 ml / g, and the ratio of the mesopore volume (PV1) with a pore diameter in the range of 4 nm to 50 nm to the macropore volume (PV2) with a pore diameter in the range of greater than 50 nm is It was PV1/PV2=1.14. Moreover, the ratio of the pore volume (PV4) in the pore diameter range of 50 nm or more to 100 nm or less to the pore volume (PV3) in the pore diameter range of more than 4 nm was PV4/PV3=0.25. FIG. 1 shows the distribution of the log differential pore volume dV/dlogd with respect to the pore diameter [nm] of the pseudo-equilibrated catalyst R1.
ｅ．比表面積
擬平衡化した触媒Ｒ１について、前述の比表面積測定を行ったところ１６０ｍ２／ｇであった。マトリックス成分の表面積は８７ｍ２／ｇであり、計算されるゼオライト成分の比表面積は７３ｍ２／ｇであった。
e. Specific surface area The above-mentioned specific surface area measurement of the pseudo-equilibrated catalyst R1 was 160 m 2 /g. The surface area of the matrix component was 87 m 2 /g and the calculated specific surface area of the zeolite component was 73 m 2 /g.
＜ブレンド触媒ａ１Ｒ１＞
得られた触媒ａ１の固形分１００質量部に対し、触媒Ｒ１を固形分４２．９質量部混合し、比較例のブレンド触媒ａ１Ｒ１を得た。
<Blend catalyst a1R1>
42.9 parts by mass of solid content of catalyst R1 was mixed with 100 parts by mass of solid content of catalyst a1 thus obtained to obtain blended catalyst a1R1 of Comparative Example.
［触媒活性評価試験］
＜性能評価試験＞
前記した製造例、比較例に係る各触媒単体および各ブレンド触媒について、ＡＣＥ－ＭＡＴ（Advanced Cracking Evaluation-Micro Activity Test）を用い、同一原油、同一反応条件下で触媒の性能評価試験を行った。ただし、評価にあたって、すべて、前記の擬平衡化処理を施したものを用いた。
性能評価試験における運転条件は以下の通りである。
反応温度：５２０℃
再生温度：７００℃
原料油：脱硫常圧残渣油（ＤＳＡＲ）５０％：水素化脱硫減圧蒸留軽油（ＤＳＶＧＯ）５０％
触媒／油比：３．７５，５．０
但し、
・転化率（質量％）＝（Ａ－Ｂ）／Ａ×１００
Ａ：原料油の重量
Ｂ：生成油中の２１６℃以上の留分の重量
・水素（質量％）＝Ｃ／Ａ×１００
Ｃ：生成ガス中の水素の重量
・Ｃ１＋Ｃ２（質量％）＝Ｄ／Ａ×１００
Ｄ：生成ガス中のＣ１（メタン）、Ｃ２（エタン、エチレン）の重量
・ＬＰＧ（液化石油ガス、質量％）＝Ｅ／Ａ×１００
Ｅ：生成ガス中のプロパン、プロピレン、ブタン、ブチレンの重量
・ガソリン（質量％）＝Ｆ／Ａ×１００
Ｆ：生成油中のガソリン（沸点範囲：Ｃ５～２１６℃）の重量
・ＬＣＯ（質量％）＝Ｇ／Ａ×１００
Ｇ：生成油中のライトサイクルオイル（沸点範囲：２１６～３４３℃）の重量
・ＨＣＯ（質量％）＝Ｈ／Ａ×１００
Ｈ：生成油中のヘビーサイクルオイル（沸点範囲：３４３℃以上）の重量
・コーク（質量％）＝Ｉ／Ａ×１００
Ｉ：触媒混合物上に析出したコーク重量
[Catalytic activity evaluation test]
<Performance evaluation test>
Using the ACE-MAT (Advanced Cracking Evaluation-Micro Activity Test), a catalyst performance evaluation test was performed on each catalyst unit and each blend catalyst according to the production examples and comparative examples under the same crude oil and under the same reaction conditions. However, in the evaluation, all the samples were subjected to the pseudo-equilibration treatment described above.
The operating conditions in the performance evaluation test are as follows.
Reaction temperature: 520°C
Regeneration temperature: 700°C
Raw material oil: Desulfurized atmospheric residual oil (DSAR) 50%: Hydrodesulfurized vacuum distilled light oil (DSVGO) 50%
Catalyst/oil ratio: 3.75, 5.0
however,
・ Conversion rate (mass%) = (AB) / A × 100
A: Weight of feedstock oil
B: Weight of fraction of 216 ° C. or higher in produced oil Hydrogen (mass%) = C / A × 100
C: Weight of hydrogen in generated gas C1 + C2 (% by mass) = D/A x 100
D: Weight of C1 (methane) and C2 (ethane, ethylene) in generated gas LPG (liquefied petroleum gas, mass%) = E/A x 100
E: Weight of propane, propylene, butane, and butylene in generated gas Gasoline (mass%) = F/A x 100
F: Weight of gasoline (boiling range: C5-216°C) in produced oil LCO (mass%) = G/A x 100
G: Weight of light cycle oil (boiling range: 216-343°C) in produced oil HCO (mass%) = H/A x 100
H: Weight of heavy cycle oil (boiling range: 343°C or higher) in produced oil Coke (mass%) = I/A
I: Weight of coke deposited on the catalyst mixture
上記で調整した触媒ａ１、ｂ１およびＲ１単体の触媒活性評価試験の結果を表１に示す。 Table 1 shows the results of the catalytic activity evaluation test of the catalysts a1, b1 and R1 prepared above.
上記で調整した本発明に係る混合触媒ａ１ｂ１（ａ１：ｂ１の質量比７０：３０および５０：５０）、比較例の混合触媒ａ１Ｒ１（ａ１：Ｒ１の質量比７０：３０）の触媒活性評価試験の結果を表２に示す。 The catalyst activity evaluation test of the mixed catalyst a1b1 according to the present invention (a1:b1 mass ratio of 70:30 and 50:50) and the mixed catalyst a1R1 of the comparative example (a1:R1 mass ratio of 70:30) prepared above Table 2 shows the results.
触媒ａ１とｂ１との混合比率が高付加価値品であるガソリン＋ＬＰＧ収率に与える影響を図４に示す。混合触媒は単体より高付加価値品であるガソリン＋ＬＰＧ収率が向上しており、特に混合触媒全体に対するｂ１の比率９質量％～６６質量％（触媒ａ１の１００質量部に対し、ｂ１を１０～２００質量部）であれば、触媒単体より高付加価値品（製品）の収率が高いことがわかる。 FIG. 4 shows the influence of the mixing ratio of catalysts a1 and b1 on the yield of gasoline+LPG, which is a high value-added product. The mixed catalyst has improved gasoline + LPG yield, which is a high value-added product, compared to the single catalyst. 200 parts by mass), the yield of the high value-added product (product) is higher than that of the single catalyst.
触媒ａ１とｂ１との混合比率がコーク＋ＨＣＯ収率に与える影響を図５に示す。混合触媒では明らかに触媒単体より、コーク＋ＨＣＯ収率が低下しており、重質留分を高付加価値品であるガソリンやＬＰＧに転化する性能が高い。 FIG. 5 shows the effect of the mixing ratio of catalysts a1 and b1 on coke+HCO yield. The coke + HCO yield of the mixed catalyst is clearly lower than that of the single catalyst, and the performance of converting heavy fractions to gasoline and LPG, which are high value-added products, is high.
以上説明したように、本発明によれば、重質留分を低減しつつ、コーク収率も低くでき、特に高付加価値製品であるガソリンの収率やＬＰＧの収率を高くすることができる。
As described above, according to the present invention, the yield of coke can be lowered while the heavy fraction is reduced, and the yield of gasoline and LPG, which are high value-added products, can be increased. .
Claims (6)
一の触媒は、擬平衡化を施した後の細孔分布において、細孔径が４ｎｍ以上５０ｎｍ以下である細孔容積（ＰＶ１）の、細孔径が５０ｎｍより大きい細孔容積（ＰＶ２）に対する割合（ＰＶ１／ＰＶ２）が０．８未満である触媒（Ａ）であり、前記触媒（Ａ）は、ゼオライトと、結合剤としてシリカ系バインダーを含み、触媒組成基準で、前記ゼオライトを１５～６０質量％、前記シリカ系バインダーを５～３０質量％含み、
他の触媒は、擬平衡化を施した後の細孔分布において、（ａ）細孔径が４ｎｍ以上５０ｎｍ以下である細孔容積（ＰＶ１）の、細孔径が５０ｎｍより大きい細孔容積（ＰＶ２）に対する割合（ＰＶ１／ＰＶ２）が０．８以上で、かつ、（ｂ）細孔径が４ｎｍより大きい細孔容積（ＰＶ３）に対する、細孔径が３０ｎｍ以上１００ｎｍ以下の細孔容積（ＰＶ４）の割合（ＰＶ４／ＰＶ３）が０．２未満である触媒（Ｂ）であり、前記触媒（Ｂ）は、ゼオライトと、結合剤としてアルミニウム化合物バインダーを含み、触媒組成基準で、前記ゼオライトを１５～６０質量％、前記アルミニウム化合物バインダーを５～３０質量％含み、
前記触媒（Ａ）を１００質量部に対して、前記触媒（Ｂ）を１０～２００質量部混合してなり、
ここで、擬平衡化は、触媒を、予め雰囲気温度６００℃にて２時間焼成した後、ニッケルオクチル酸塩およびバナジウムオクチル酸塩をそれぞれ触媒の質量で除算した質量基準の金属換算で１０００ｐｐｍおよび２０００ｐｐｍの量で、焼成した触媒粒子に沈着させ、次いで、触媒を雰囲気温度１１０℃で乾燥した後、雰囲気温度６００℃で１．５時間焼成し、その後、触媒に雰囲気温度７８０℃で１３時間のスチーム処理を施す、ことを特徴とする炭化水素油用流動接触分解触媒。 A fluid catalytic cracking catalyst for hydrocarbon oil, which is obtained by mixing two kinds of fluid catalytic cracking catalysts,
One catalyst has a pore volume (PV1) with a pore diameter of 4 nm or more and 50 nm or less in the pore distribution after pseudo-equilibration, the ratio of the pore volume (PV2) with a pore diameter of more than 50 nm ( A catalyst (A) having a PV1/PV2) of less than 0.8, wherein the catalyst (A) contains zeolite and a silica-based binder as a binder, and the zeolite is contained in an amount of 15 to 60% by mass based on the catalyst composition. , containing 5 to 30% by mass of the silica-based binder,
Other catalysts have a pore volume (PV2) with a pore diameter of greater than 50 nm in the pore distribution after pseudo-equilibration: (a) the pore volume (PV1) having a pore diameter of 4 nm or more and 50 nm or less (PV1/PV2) is 0.8 or more, and (b) the ratio of the pore volume (PV4) with a pore diameter of 30 nm or more to 100 nm or less to the pore volume (PV3) with a pore diameter of more than 4 nm ( A catalyst (B) in which PV4/PV3) is less than 0.2, wherein the catalyst (B) contains zeolite and an aluminum compound binder as a binder, and the zeolite is contained in an amount of 15 to 60% by mass based on the catalyst composition. , containing 5 to 30% by mass of the aluminum compound binder,
10 to 200 parts by mass of the catalyst (B) is mixed with 100 parts by mass of the catalyst (A),
Here, pseudo-equilibration is performed by calcining the catalyst in advance at an ambient temperature of 600 ° C. for 2 hours, and then dividing nickel octylate and vanadium octylate by the mass of the catalyst, respectively, to 1000 ppm and 2000 ppm in terms of metal on a mass basis. is deposited on the calcined catalyst particles, then the catalyst is dried at an ambient temperature of 110° C. and then calcined at an ambient temperature of 600° C. for 1.5 hours, after which the catalyst is steamed at an ambient temperature of 780° C. for 13 hours. A fluid catalytic cracking catalyst for hydrocarbon oil, characterized in that it is treated.
（ａ）塩基性塩化アルミニウム。
（ｂ）重リン酸アルミニウム。
（ｃ）アルミナゾル。 The fluid catalytic cracking catalyst for hydrocarbon oil according to claim 1 or 2 , wherein the aluminum compound binder contains at least one selected from the following (a) to (c).
(a) basic aluminum chloride;
(b) aluminum biphosphate;
(c) alumina sol;
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| JP2017087204A (en) | 2015-11-11 | 2017-05-25 | 日揮触媒化成株式会社 | Catalyst for residual oil decomposition active fluid catalytic cracking and manufacturing method therefor |
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