JPWO2013147219A1 - 水素化異性化触媒の製造方法及び潤滑油基油の製造方法 - Google Patents
水素化異性化触媒の製造方法及び潤滑油基油の製造方法 Download PDFInfo
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- JPWO2013147219A1 JPWO2013147219A1 JP2013515450A JP2013515450A JPWO2013147219A1 JP WO2013147219 A1 JPWO2013147219 A1 JP WO2013147219A1 JP 2013515450 A JP2013515450 A JP 2013515450A JP 2013515450 A JP2013515450 A JP 2013515450A JP WO2013147219 A1 JPWO2013147219 A1 JP WO2013147219A1
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- zeolite
- oil
- hydroisomerization
- producing
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- UYVTYBDVUSLCJA-UHFFFAOYSA-N 1-methyl-3-propan-2-ylimidazol-1-ium Chemical compound CC(C)[N+]=1C=CN(C)C=1 UYVTYBDVUSLCJA-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7484—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
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- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract
Description
本発明の水素化異性化触媒は、特定の方法によって製造されることでその特徴が付与される。以下、本発明の水素化異性化触媒について、その好ましい製造の態様に沿って説明する。
VZ=Vc/Mz×100
次に、本発明に係る潤滑油基油の製造方法について説明する。本実施形態の潤滑油基油の製造方法は、水素の存在下、炭素数10以上のノルマルパラフィンを含有する炭化水素原料油と、上記本発明に係る水素化異性化触媒とを接触させる工程を備える。
式(I)中、Cnは、接触前の炭化水素原料油中に含まれる炭素数10以上のノルマルパラフィンのうちで最小の炭素数を示す。
(製造例1)
<ZSM−22ゼオライトの製造>
Si/Al比が45である結晶性アルミノシリケートからなるZSM−22ゼオライト(以下、「ZSM−22」ということがある。)を以下の手順で水熱合成により製造した。
溶液A:1.94gの水酸化カリウムを6.75mLのイオン交換水に溶解したもの。
溶液B:1.33gの硫酸アルミニウム18水塩を5mLのイオン交換水に溶解したもの。
溶液C:4.18gの1,6−ヘキサンジアミン(有機テンプレート)を32.5mLのイオン交換水にて希釈したもの。
溶液D:18gのコロイダルシリカ(Grace Davison社製Ludox AS−40)を31mLのイオン交換水にて希釈したもの。
上記で得られたZSM−22について、以下の操作によりアンモニウムイオンを含む水溶液でイオン交換処理を行った。
上記で得たNH4型ZSM−22と、バインダーであるアルミナとを質量比7:3にて混合し、ここに少量のイオン交換水を添加して混錬した。得られた粘ちょうな流体を押出成型機に充填、成型し、直径約1.6mm、長さ約10mmの円筒状の成型体を得た。この成型体を、空気雰囲気下、400℃にて3時間加熱して、担体前駆体を得た。
テトラアンミンジニトロ白金[Pt(NH3)4](NO3)2を、担体前駆体のあらかじめ測定した吸水量に相当するイオン交換水に溶解して含浸溶液を得た。この溶液を、上記の担体前駆体に初期湿潤法により含浸し、ZSM−22ゼオライトの質量に対して、0.3質量%の白金量となるように担持を行った。次に、得られた含浸物(触媒前駆体)を60℃の乾燥中で一晩乾燥した後、空気流通下、400℃で3時間焼成して、水素化異性化触媒E−1を得た。
<ZSM−48ゼオライトの製造>
有機テンプレートを含むSi/Al比が45であるZSM−48型ゼオライト(以下、「ZSM−48」ということもある。)は、Applied Catalysis A:General vol.299(2006)167−174に基づき合成した。
試薬E:2.97gの水酸化ナトリウム。
試薬F:0.80gの硫酸アルミニウム18水塩。
試薬G:26.2gの1,6−ヘキサンジアミン(有機テンプレート)。
試薬H:0.9mlの98%硫酸溶液
試薬I:75gのコロイダルシリカ(Grace Davison社製Ludox AS−40)水溶液(SiO2濃度は40%)。
次に、180mgのイオン交換水に上記の試薬E、F、G、H、Iを加え、常温で2時間攪拌して完全に溶解させた。
有機テンプレートを含有するZSM−22に代えて上記にて得られた有機テンプレートを含有するZSM−48を用いた以外は、実施例1のZSM−22のイオン交換と同様の操作により、イオン交換されたNH4型ZSM−48を得た。
<SSZ−32ゼオライトの製造>
JP2006−523136号公報に記載の方法に準拠して、以下の手順で水熱合成により、SSZ−32ゼオライト(以下、「SSZ−32」ということもある。)を製造した。
SiO2/Al2O3=35、
イソブチルアミンとN−メチル−N'−イソプロピル−イミダソリウムカチオンの合計量がSiO2の0.2倍
有機テンプレートを含有するZSM−22に代えて上記にて得られた有機テンプレートを含有するSSZ−32を用いた以外は、製造例1のZSM−22のイオン交換と同様の操作により、イオン交換されたNH4型SSZ−32を得た。
製造例1における担体前駆体の焼成条件を、N2雰囲気下、300℃にて3時間加熱したこと以外は製造例1と同様にして、水素化異性化触媒E−4を得た。
製造例1におけるZSM−22を得る工程までは同様にして、その後、上記で得たZSM−22と、バインダーであるアルミナとを質量比7:3にて混合し、ここに少量のイオン交換水を添加して混錬した。得られた粘ちょうな流体を押出成型機に充填、成型し、直径約1.6mm、長さ約10mmの円筒状の成型体を得た。この成型体を、空気雰囲気下、400℃にて3時間加熱して、成形体ZSM−22を得た。
製造例1における担体前駆体を得るための焼成条件を、N2雰囲気下、300℃にて3時間加熱したこと、触媒前駆体の焼成条件を、空気流通下、350℃にて3時間加熱したこと以外は製造例1と同様にして、水素化異性化触媒E−6を得た。
上記で得られた触媒をそれぞれ用い、ワックスの脱蝋及び潤滑油基油留分の分離・回収を行った。
水素化異性化触媒E−1を使用してワックスの脱蝋を行った。脱蝋処理前に、まず下記のコーキング処理を実施した。
内径15mm、長さ380mmのステンレス鋼製反応管に成形触媒を100ml充填し、触媒層平均温度350℃、水素流通下(水素分圧3MPa)で12時間還元処理を行った。その後、原料として石油系スラックワックス(炭素数分布C10〜C40、150ニュートラルのスラックワックス、組成を図1に示す)を、反応温度320℃、水素分圧3MPa、LHSV 0.5h−1、水素/油比500NL/Lの条件にて通油して、コーキング処理を開始し、100時間後に処理を終了した。なお、図1中、Aは非ノルマルパラフィン量を示し、Bはノルマルパラフィン量を示す。
コーキング処理後の触媒に含まれるカーボン量、及び、コーキング処理前後の触媒について、触媒に含有されるゼオライトの単位質量当たりのミクロ細孔容積を以下の方法で測定した。
VZ=Vc/Mz×100
式中、Vcは水素化異性化触媒の単位質量当りのミクロ細孔容積を示し、Mzは触媒に含有されるゼオライトの含有割合(質量%)を示す。
異性化脱蝋処理の反応温度Tc(℃)を求めるために、予め、同じ触媒(E−1)を用いた下記の予備実験を行った。内径15mm、長さ380mmのステンレス鋼製反応管に成形触媒を100ml充填し、触媒層平均温度350℃、水素流通下(水素分圧3MPa)で12時間還元処理を行った。その後、上記原料を、反応温度310−330℃、水素分圧3MPa、LHSV 1.0h−1、水素/油比500NL/Lの条件にて通油して、水素化異性化脱蝋反応による脱蝋処理を開始した。72時間反応後、反応生成物を採取、分析した。
その後、水素分圧、LHSV、水素/油比はそのままに、反応温度を段階的に約350℃まで高め、原料油転化率を増加させた。それぞれの反応温度にて72時間反応し、安定化したところでそれぞれの反応生成物の採取、分析を行った。
コーキング処理した後に、水素分圧、水素/油比はそのままに、上記の方法にて得られた反応温度Tc=325℃、LHSV 1.0h−1の条件にて通油して、水素化異性化反応による脱蝋処理を開始した。
10時間および100時間反応後、反応生成物を採取し、潤滑油基油留分1及び2の収率を算出した。
反応温度350℃、LHSV 0.5h−1で触媒E−1をコーキング処理した以外は実施例1と同様にして、潤滑油基油留分1及び2の収率を算出した。
反応温度320℃、LHSV 0.1h−1で触媒E−1をコーキング処理した以外は実施例1と同様にして、潤滑油基油留分1及び2の収率を算出した。
触媒E−1に代えて触媒E−4を用いたこと以外は実施例1と同様にコーキング処理及び脱蝋処理を行い、潤滑油基油留分1及び2の収率を算出した。
触媒E−1に代えて触媒E−4を用い、反応温度315℃、LHSV 0.1h−1でコーキング処理した以外は実施例1と同様にして、潤滑油基油留分1及び2の収率を算出した。
触媒E−1に代えて触媒E−2を用い、反応温度310℃、LHSV 0.1h−1でコーキング処理し、反応温度Tc=320℃とした以外は実施例1と同様にして、潤滑油基油留分1及び2の収率を算出した。
触媒E−1に代えて触媒E−3を用い、反応温度315℃、LHSV 0.1h−1でコーキング処理した以外は実施例1と同様にして、潤滑油基油留分1及び2の収率を算出した。
触媒E−1に代えて触媒E−5を用い、反応温度310℃、LHSV0.1h−1でコーキング処理した以外は実施例1と同様にして、潤滑油基油留分1及び2の収率を算出した。
触媒E−1に代えて触媒E−6を用い、反応温度310℃、LHSV0.1h−1でコーキング処理した以外は実施例1と同様にして、潤滑油基油留分1及び2の収率を算出した。
コーキング処理を行わず、還元後すぐに異性化脱蝋を開始したこと以外は実施例1と同様にして、潤滑油基油留分1及び2の収率を算出した。
コーキング処理を行わず、還元後すぐに異性化脱蝋を開始したこと以外は実施例6と同様にして、潤滑油基油留分1及び2の収率を算出した。
コーキング処理を行わず、還元後すぐに異性化脱蝋を開始したこと以外は実施例7と同様にして、潤滑油基油留分1及び2の収率を算出した。
コーキング処理を行わず、還元後すぐに異性化脱蝋を開始したこと以外は実施例8と同様にして、潤滑油基油留分1及び2の収率を算出した。
Claims (8)
- 10員環一次元状細孔構造を有するゼオライトを含む担体と、該担体に担持された周期表第8〜10族に属する金属、Mo及びWからなる群より選択される少なくとも一種の金属と、を有する被処理触媒を用意する第1工程と、
前記被処理触媒に炭素含有化合物によるコーキング処理を施すことにより、触媒に含まれるカーボン量が0.4〜2.5質量%である水素化異性化触媒を得る第2工程と、
を有することを特徴とする水素化異性化触媒の製造方法。 - 前記第2工程において、触媒の単位質量当たりのミクロ細孔容積が0.02〜0.11cc/gであり、触媒に含有される前記ゼオライトの単位質量当りのミクロ細孔容積が0.04〜0.12cc/gである水素化異性化触媒を得ることを特徴とする請求項1に記載の水素化異性化触媒の製造方法。
- 前記ゼオライトが、ZSM−22ゼオライト、ZSM−23ゼオライト、SSZ−32ゼオライト及びZSM−48ゼオライトからなる群より選択される少なくとも一種であることを特徴とする請求項1又は2に記載の水素化異性化触媒の製造方法。
- 請求項1〜3のいずれか一項に記載の水素化異性化触媒の製造方法により得られることを特徴とする水素化異性化触媒。
- 水素の存在下、炭素数10以上のノルマルパラフィンを含有する炭化水素原料油と、請求項4に記載の水素化異性化触媒と、を接触させることを特徴とする潤滑油基油の製造方法。
- 前記水素化異性化触媒が、前記炭素含有化合物として前記炭化水素原料油を用い、前記炭化水素原料油を水素化異性化する反応温度よりも低い温度で前記被処理触媒に前記コーキング処理を施すことにより得られることを特徴とする請求項5に記載の潤滑油基油の製造方法。
- 前記炭化水素原料油を前記水素化異性化触媒に接触させた後、更に水素化仕上げし、減圧蒸留することを特徴とする請求項5又は6に記載の潤滑油基油の製造方法。
- 前記炭化水素原料油が、常圧残油、減圧残油、減圧軽油、スラックワックス、及びフィッシャー・トロプシュ合成ワックスからなる群より選択される少なくとも一種であることを特徴とする請求項5〜7のいずれか一項に記載の潤滑油基油の製造方法。
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