JP6105753B2 - 超低レベルの有機硫黄化合物を有するディーゼル燃料を生成するための、気相酸化脱硫及び水素化脱硫を統合する、標的とした脱硫プロセス及び装置 - Google Patents
超低レベルの有機硫黄化合物を有するディーゼル燃料を生成するための、気相酸化脱硫及び水素化脱硫を統合する、標的とした脱硫プロセス及び装置 Download PDFInfo
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- JP6105753B2 JP6105753B2 JP2015552618A JP2015552618A JP6105753B2 JP 6105753 B2 JP6105753 B2 JP 6105753B2 JP 2015552618 A JP2015552618 A JP 2015552618A JP 2015552618 A JP2015552618 A JP 2015552618A JP 6105753 B2 JP6105753 B2 JP 6105753B2
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- oxidation catalyst
- sulfur
- hydrodesulfurization
- hydrocarbon
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/16—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural parallel stages only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Description
本出願は、2013年1月14日に出願された、米国特許出願番号第13/741,101号の利益を主張し、参照によりその全体が本明細書に組み込まれる。
本発明は、効率的に炭化水素の硫黄含有量を減少させるために、統合された気相接触酸化脱硫プロセスに関する。
処理中の硫黄化合物の大気中への排出及び、硫黄含有原粗油由来の石油製品の最終用途は、健康及び環境問題を提起する。輸送用及び他の燃料製品に適用可能な厳しく減少された硫黄仕様は、製油業へ影響を及ぼし、100万分の10重量部(ppmw)以下へ軽油中の硫黄分を大幅に低減するために、製油業者は設備投資をする必要がある。米国、日本、欧州連合諸国などの先進国では、輸送用燃料のための製油所は、既に、環境的にクリーンな輸送用燃料を製造することが求められている。例えば、2007年に米国環境保護庁は、高速道路のディーゼル燃料の硫黄含有量を、500ppmw(低硫黄ディーゼル)から15ppmw(超低硫黄ディーゼル)へ、97%減少させることを課した。欧州連合は更に厳しい基準を制定しており、2009年に販売されたディーゼル及びガソリン燃料は、10ppmw未満の硫黄を含有することが求められている。他の国々は、米国及び欧州連合(EU)の足跡を追いかけており、超低硫黄レベルの輸送用燃料を生産する製油所を必要とする規制を進めている。
不安定な有機硫黄化合物を除去するための燃料流の穏やかな水素化脱硫、及び不応性有機硫黄化合物を除去するための標的画分の気相酸化的脱硫による、不応性の及び不安定な有機硫黄化合物の両方を含む炭化水素原料の脱硫のための装置及びプロセスにより、上記の目的及び他の利点が提供されている。
有機硫黄化合物の超低レベルの炭化水素燃料を生成するために、統合された脱硫プロセスが設けられている。プロセスは以下のステップを含む:
a.二つの画分を得るために、約300℃〜約360℃、好ましくは約340℃の標的カット点温度で、炭化水素原料をフラッシングする(Flashing)ステップ。水素化脱硫及び酸化的脱硫プロセスへ供された場合、二つの画分は、異なる反応性を有する有機硫黄化合物の異なるクラスを含む。
b.標的カット点温度以下で沸騰する画分中の有機硫黄化合物は主に不安定な有機硫黄化合物であり、スルフィド、ジスルフィド、メルカプタンなどの脂肪族分子、チオフェン及びチオフェンのアルキル誘導体などの特定の芳香族化合物を含む。有機硫黄化合物を除去するために、穏やかな操作条件下で、水素化脱硫反応領域において、この画分を水素化脱硫触媒と接触させる。
c.標的カット点温度またはそれ以上で沸騰する画分中の有機硫黄化合物は、主に不応性有機硫黄化合物であり、特定のベンゾチオフェン(例えば、長鎖アルキル化ベンゾチオフェン)、ジベンゾチオフェン及びアルキル誘導体、例えば、4,6−ジメチルジベンゾチオフェンなどの芳香族分子を含む。硫黄を含まない炭化水素及びSOXへ有機硫黄化合物を変換するために、気相触媒酸化反応領域において、この画分を酸化触媒上でガス状の酸化剤と接触させる。
d.気液分離器及び/又はストリッパー及び/又は蒸留カラム及び/又は膜を含む装置により、副生成物のSOXは、その後、液体生成物から分離領域において除去される。
e.水素化脱硫反応領域から得られる流及び分離領域からの低硫黄流を、例えばフルレンジディーゼル燃料生成物などの超低硫黄レベル炭化水素生成物を生成するために、再結合することができる。
実施例1
気相酸化的脱硫触媒材料を作るための方法(2〜12)及び、それらの触媒を用いた試験(13)を記載する実施例2〜13を提供する。
37.5gのCu(NO3)2(0.2モル)、13.3gのZn(NO3)2(0.07モル)及び50.1gのAl(NO3)3(0.235モル)を、500mLの蒸留水中に溶かし、以下で「溶液A」と呼ばれるものを形成した。溶液のpHは2.3であった。
溶液Aの500mLのサンプルを、実施例2の手順に従って調製した。
500mLの溶液Aのサンプルを、実施例2の手順に従って調製した。
実施例2のステップに従ったが、沈殿物を熱濾過し、熟成しなかった。詳細された組成物は、40.2重量%の元素Cu、9.7重量%の元素Zn、17.2重量%の元素Al、及び0.22重量%の元素Naを含んでいた。Cu:Zn:Alの原子比は、4.2:1:4.3であった。比表面積は75m2/gであり、細孔容積は0.29cm3/gであった。平均孔直径は、12.5nmであった。相組成物は高度に分散した、CuO、ZnO及びAl2O3の結晶相であった。
本実施例において、0.18gのCe(NO3)3(5.5×10−4モル)も溶液Aの調製の際に加えることを除き、実施例3に従った。沈殿が形成した後、55℃で6時間熟成させた。焼成した組成物の分析は、20.9重量%の元素Cu、17.1重量%の元素Zn、23.9重量%の元素Al及び0.5重量%の元素Ceを示した。Cu:Zn:Ce:Alの原子比は、3.0:1:0.01:3.8であった。組成物は、83m2/gの比表面積、0.20cm3/gの細孔容積、及び10.0nmの平均孔直径を有していた。それは、Cu0.5Zn0.5Al2O4の組成を有するX−線アモルファス酸化物相及び高度に分散された結晶相を示し、これは、60%未満のCu及び、また5nmを超えない粒径を有するCe相を含んでいた。
本実施例は、Ce(NO3)3の量を、3.1g(9.5×10−3モル)へ増加させることを除き、実施例6に従った。沈殿物形成及び濾過を、6時間65℃で行った。
本実施例において「溶液A」は、9.4gのCu(NO3)2(0.05モル)、13.3gのZn(NO3)2(0.07モル)及び27.7gのAl(NO3)2(0,13モル)を、500mLの蒸留水中に含んでいた。溶液Aは、2.6のpHを有していた。溶液Bは、53.0gのNa2CO3(0.5モル)及び18gのNaOH(0.45モル)を600mLの水中に含んでいた。溶液Bは、13.7のpHを有していた。
本実施例において、実施例3における溶液と同じ方法で、溶液A及びCを調製した。
本実施例において、溶液Aは、9.4gのCu(NO3)2(0.05モル)、3.8gのZn(NO3)2(0.02モル)及び95.8gのAl(NO3)2(0.45モル)を、500mLの蒸留水中に溶かした。溶液Aは、2.25のpHを有していた。
本実施例において、溶液Aは46.9gのCu(NO3)2(0.25モル)、13.3gのZn(NO3)2(0.07モル)及び42.6gのAl(NO3)2(0.20モル)を、500mLの蒸留水中に溶かした。溶液Aは、2.3のpHを有していた。溶液Bは、53.0gのNa2CO3(0.5モル)及び12gのNaOH(0.3モル)を、600mLの蒸留水中に含んでいた。溶液Bは、13.3のpHを有していた。
本実施例において、溶液Aは、Al(NO3)3を含まないが、7.5gのCu(NO3)2(0.04モル)、3.8gのZn(NO3)2(0.02モル)及び45.7gのCe(NO3)3(0.14モル)のみが500mLの蒸留水中に溶けていた。溶液Aは4.2のpHを有していた。
実施例2〜12において調製された触媒を、酸化硫黄含有化合物を含む燃料油を脱硫するそれらの能力について試験した。チオフェン、DBT(ジベンゾチオフェン)及び4,6−DMDBTを含有する燃料を調製した。燃料を気体状態へ加熱し、触媒化合物全体を通過させた。以下の表において、触媒(「Cu−Zn−Al」、「Cu−Zn−Al−Ce」又は「Cu−Zn−Ce」)の式は、(1)又は(2)に続く。これは、実施例2〜12の溶液B、C及びDの性質を指し、(1)は、Na含有溶液(溶液B中)を指し、(2)は、アンモニウム含有溶液(溶液C及びD中)を指す。最終的な数は、触媒を製造するためにどの実施例を使用したかを示す。
Claims (32)
- a.低減されたレベルの有機硫黄化合物を含む低沸点画分及び、不応性有機硫黄化合物を有する高沸点画分を提供するために、炭化水素原料をフラッシングすること、
b.水素化処理流出物を生成するために、前記低沸点画分を、水素化脱硫プロセスへ供すること、
c.C−S結合を切断することにより、不応性有機硫黄化合物を、硫黄を含まない炭化水素及びSOxへ変換するために、前記高沸点画分を、ガス状酸化剤及び、式中xは0〜1の範囲である式CuxZn1−xAl2O4を有する酸化触媒と接触させること、
d.硫黄を含まない炭化水素から、分離領域内おいて副生成物SOxを除去すること、および
e.超低硫黄レベル炭化水素生成物を回収すること
を含む、所望ではない有機硫黄化合物を除去するための炭化水素原料を処理する方法であって、前記酸化触媒が、30重量%(wt%)〜45wt%の範囲の量で酸化銅を、12wt%〜20wt%未満の範囲の量で酸化亜鉛を、及び20wt%〜40wt%の範囲の量で酸化アルミニウムを含み、前記酸化触媒がX−線アモルファス酸化物相、及び高度に分散した結晶性ZnO及びCuOを有する、方法。 - ステップ(a)における温度カット点が340℃である、請求項1に記載の方法。
- 前記低沸点画分が、脂肪族有機硫黄化合物を含む、請求項1に記載の方法。
- 前記脂肪族有機硫黄化合物が、スルフィド、ジスルフィド及びメルカプタンを含む、請求項3に記載の方法。
- 前記低沸点画分が更に、チオフェン及びチオフェンのアルキル誘導体を含む、請求項3に記載の方法。
- 前記高沸点画分が、高沸点画分の範囲の沸点を有する、ジベンゾチオフェン、ジベンゾチオフェンのアルキル誘導体及びベンゾチオフェンの長鎖アルキル化誘導体を含む、請求項1に記載の方法。
- 前記炭化水素原料が、180℃〜450℃の範囲で沸騰する直留ガス油である、請求項1に記載の方法。
- 前記水素化脱硫プロセスが、穏やかな操作条件で操作される、請求項7に記載の方法。
- 水素分圧が55bar未満である、請求項8に記載の方法。
- 水素分圧が25bar〜40barである、請求項8に記載の方法。
- 操作温度が300℃〜400℃である、請求項8に記載の方法。
- 操作温度が320℃〜380℃である、請求項8に記載の方法。
- 前記水素化脱硫プロセスステップにおける水素供給速度が、油のリットル当たり100リットルの水素〜油のリットル当たり1000リットルの水素である、請求項8に記載の方法。
- 前記水素化脱硫プロセスステップにおける水素供給速度が、油のリットル当たり200リットルの水素〜油のリットル当たり300リットルの水素である、請求項8に記載の方法。
- 前記酸化剤が、窒素酸化物、酸素及び空気から成る群から選択される、請求項1に記載の方法。
- ステップ(b)の水素化処理された流出物を回収することを更に含む、請求項1に記載の方法。
- ステップ(b)の流出物及びステップ(e)の流出物を組み合わせることを更に含む、請求項1に記載の方法。
- ステップ(c)において使用される前記酸化触媒が更にCe2O3を含む、請求項1に記載の方法。
- ステップ(c)において使用される前記酸化触媒が、顆粒状である、請求項1に記載の方法。
- ステップ(c)において使用される前記酸化触媒が、円柱、球体、三葉として形成されているか、又は四葉形状を有する、請求項1に記載の方法。
- 前記酸化触媒の粒子が、1mm〜4mmの有効径を有する、請求項20に記載の方法。
- 前記酸化触媒の粒子が、10m2/g〜100m2/gの比表面積を有する、請求項20に記載の方法。
- 前記酸化触媒の粒子が、50m2/g〜100m2/gの比表面積を有する、請求項20に記載の方法。
- 前記酸化触媒の粒子が、8nm〜12nmの有効径の孔を有する、請求項20に記載の方法。
- 前記酸化触媒の粒子が、8nm〜10nmの有効径の孔を有する、請求項20に記載の方法。
- 前記酸化触媒の粒子が、0.1cm3/g〜0.5cm3/gの体積の孔を有する、請求項20に記載の方法。
- ステップ(c)において使用される前記酸化触媒中のxが、0.1〜0.6である、請求項1に記載の方法。
- ステップ(c)において使用される前記酸化触媒中のxが、0.2〜0.5である、請求項1に記載の方法。
- 320℃〜360℃の温度カット点で炭化水素原料をフラッシュするために操作可能なフラッシングカラムであって、前記フラッシングカラムが、
前記炭化水素原料を受け取るための入口、
低沸点画分を排出するための低沸点出口、及び
不応性有機硫黄化合物を含有する高沸点画分を排出するための高沸点出口を含むフラッシングカラム、
前記低沸点出口及び水素化流出物を排出するための出口と流体連通している入口を有する、水素化脱硫領域、及び、
式中xは0〜1の範囲である式CuxZn1−xAl2O4を有する酸化触媒及びガス状酸化剤を含有する気相接触酸化脱硫領域、前記高沸点出口と流体連通する入口を有する気相接触酸化脱硫領域、並びに、低硫黄炭化水素及びSOxの排出用出口
を含む、所望ではない有機硫黄化合物を含有する炭化水素原料を処理するための装置であって、前記酸化触媒が、30重量%(wt%)〜45wt%の範囲の量で酸化銅を、12wt%〜20wt%未満の範囲の量で酸化亜鉛を、及び20wt%〜40wt%の範囲の量で酸化アルミニウムを含み、前記酸化触媒がX−線アモルファス酸化物相、及び高度に分散した結晶性ZnO及びCuOを有する、装置。 - 気相接触酸化脱硫領域操作を気相中で行う、請求項29に記載の装置。
- ステップ(c)を気相中で行う、請求項7に記載の方法。
- Ce2O3は、前記酸化触媒の0.1wt%〜10wt%の範囲の量で、5nm〜10nmの直径の範囲の粒子形態で存在する、請求項18に記載の方法。
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PCT/US2013/023861 WO2014109777A1 (en) | 2013-01-14 | 2013-01-30 | Targeted desulfurization process and apparatus integrating gas phase oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
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US20140197074A1 (en) | 2014-07-17 |
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