JP7419289B2 - 舶用重質燃料油組成物 - Google Patents
舶用重質燃料油組成物 Download PDFInfo
- Publication number
- JP7419289B2 JP7419289B2 JP2021065338A JP2021065338A JP7419289B2 JP 7419289 B2 JP7419289 B2 JP 7419289B2 JP 2021065338 A JP2021065338 A JP 2021065338A JP 2021065338 A JP2021065338 A JP 2021065338A JP 7419289 B2 JP7419289 B2 JP 7419289B2
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- Prior art keywords
- marine
- fuel oil
- sulfur
- hmfo
- heavy
- Prior art date
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 134
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/343—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances the substance being a gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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Description
概説:パイロット試験運転の目的は、特定の条件で市販の触媒を充填した反応器によってHMFO原料を処理して、HMFOから環境汚染物、特に硫黄等の汚染物を除去することにより、MARPOLに適合したHMFO製品を製造することが可能であること、すなわち低硫黄の舶用重質燃料油(LS-HMFO)又は超低硫黄の舶用重質燃料油(USL-HMFO)の製造を実証することである。
パイロット設備のセットアップ:以下の点を変更した他は上述した実施例1と同様にしてパイロット設備をセットアップした。第一反応器には、原料に接する第一(上)層として70体積%のAlbemarle KFR20シリーズ水素化脱金属触媒と、第二(下)層として30体積%のAlbemarle KFR30シリーズ水素化遷移触媒とを充填した。第二反応器には、第一(上)層として20%のAlbemarle KFR30シリーズ水素化遷移触媒と、第二(下)層として80体積%の水素化脱硫触媒とを充填した。当業者に周知の方法によりジメチルジスルフィド(DMDS)で触媒を硫化して触媒を活性化した。
上記実施例2で用いたパイロット反応器への原料を、環境汚染物(すなわち硫黄(3.3重量%))が多いが適商性のある市販のISO8217:2017RMK-500適合HMFOに変更した。RMK-500高硫黄HMFO原料の他のバルク性質を以下に示す。
Claims (15)
- 100%水素化処理した高硫黄舶用重質燃料油から本質的になる低硫黄舶用重質燃料油であって、
上記高硫黄舶用重質燃料油は、水素化処理前、ISO8217:2017に適合するが、硫黄の含有量が0.5重量%を超えるものであり、バナジウム、ナトリウム、アルミニウム、ケイ素、カルシウム、亜鉛、リン、ニッケル、鉄、およびこれらの組み合わせからなる群から選択される特定汚染物を含み、
上記低硫黄舶用重質燃料油は、ISO8217:2017に適合し、舶用残渣燃料油として適商品質を有し、硫黄の含有量が0.5重量%未満であり、
バナジウムの含有量が450mg/kg未満、またはアルミニウムおよびケイ素の合計含有量が60mg/kg以下である、
低硫黄舶用重質燃料油。 - 低硫黄舶用重質燃料油の硫黄含有量がISO14596又はISO8754により決定され、
特定汚染物の濃度は下記基準:
バナジウムはIP501、IP470、またはISO14597、
ナトリウムはIP501、またはIP470、
アルミニウムはIP501、IP470、またはISO10478、
ケイ素はIP501、IP470、またはISO10478、
カルシウムはIP501、IP470、またはISO500、
亜鉛はIP501、IP470、またはISO500、
リンはISO500、
ニッケルはIP501、またはIP470、
鉄はIP501、またはIP470
により決定される、請求項1に記載の低硫黄舶用重質燃料油。 - 上記高硫黄舶用重質燃料油の硫黄含有量(ISO14596又はISO8754)は1.0重量%~5.0重量%の範囲であり、50℃の動粘度(ISO3104)が180mm2/秒~700mm2/秒の範囲であり、15℃の密度(ISO3675)が991.0kg/m3~1010.0kg/m3の範囲であり、CCAIが780~870の範囲であり、引火点(ISO2719)が60.0℃以上である、請求項1または2に記載の低硫黄舶用重質燃料油。
- 多量の100%水素化処理した高硫黄舶用重質燃料油と、少量の希釈材とから本質的になる低硫黄炭化水素燃料組成物であって、
上記高硫黄舶用重質燃料油は、水素化処理前、ISO8217:2017に適合するが、硫黄の含有量が0.5重量%を超えるものであり、バナジウム、ナトリウム、アルミニウム、ケイ素、カルシウム、亜鉛、リン、ニッケル、鉄、およびこれらの組み合わせからなる群から選択される特定汚染物を含み、
上記低硫黄炭化水素燃料組成物は、ISO8217:2017に適合し、舶用残渣燃料油として適商品質を有し、硫黄含有量(ISO14596又はISO8754)が0.5重量%未満であり、バナジウムの含有量が450mg/kg未満、またはアルミニウムおよびケイ素の合計含有量が60mg/kg以下であり、
上記希釈材は、炭化水素材料、非炭化水素材料、固体材料及びこれらの組合せからなる群より選択される、低硫黄炭化水素燃料組成物。 - 硫黄含有量がISO14596又はISO8754により決定され、
特定汚染物の濃度は下記基準:
バナジウムはIP501、IP470、またはISO14597、
ナトリウムはIP501、またはIP470、
アルミニウムはIP501、IP470、またはISO10478、
ケイ素はIP501、IP470、またはISO10478、
カルシウムはIP501、IP470、またはISO500、
亜鉛はIP501、IP470、またはISO500、
リンはISO500、
ニッケルはIP501、またはIP470、
鉄はIP501、またはIP470
により決定される、請求項4に記載の低硫黄炭化水素燃料組成物。 - 上記高硫黄舶用重質燃料油の硫黄含有量(ISO14596又はISO8754)は1.0重量%~5.0重量%の範囲であり、50℃の動粘度(ISO3104)が180mm2/秒~700mm2/秒の範囲であり、15℃の密度(ISO3675)が991.0kg/m3~1010.0kg/m3の範囲であり、CCAIが780~870の範囲であり、引火点(ISO2719)が60.0℃以上である、請求項4または5に記載の低硫黄炭化水素燃料組成物。
- ISO8217:2017に適合し、舶用残渣燃料油として適商品質を有し、硫黄含有量(ISO14596又はISO8754)が0.5重量%未満である、舶用重質燃料油の製造方法であって、
下記工程a)~f)を含む方法:
a)所定量の舶用重質燃料油原料を所定量の活性化ガスと混合して原料混合物を得る工程であって、
上記舶用重質燃料油原料は、ISO8217:2017に適合するバルク物性を有するが、硫黄の含有量が0.5重量%を超えるものであり、バナジウム、ナトリウム、アルミニウム、ケイ素、カルシウム、亜鉛、リン、ニッケル、鉄、およびこれらの組み合わせからなる群から選択される特定汚染物を含む、工程
b)原料混合物を所定の温度及び圧力条件で処理し、加熱され加圧された原料混合物を得る工程、
c)加熱され加圧された原料混合物を、少なくとも1つの反応容器中で、
沸騰床担持遷移金属不均一触媒、固定床担持遷移金属不均一触媒、及び、沸騰床担持遷移金属不均一触媒と固定床担持遷移金属不均一触媒との組合せからなる群より選択される1種以上の触媒システムと、プロセス条件下で接触させることにより、
プロセス混合物を得る工程であって、
プロセス混合物は、バルク気体成分、残留気体成分、副産物炭化水素成分、および舶用重質燃料油製品成分を含む、工程
d)プロセス混合物を、少なくとも1つの反応容器から取り除き、1種以上の触媒システムと接触した状態から解放し、
プロセス混合物のバルク気体成分を、プロセス混合物の残留気体成分、副産物炭化水素成分、および舶用重質燃料油製品成分から分離するために、プロセス混合物を少なくとも1つの反応容器から少なくとも1つの第二容器へと流体連通によって送る工程、
e)プロセス混合物の残留気体成分、副産物炭化水素成分、および舶用重質燃料油製品成分を、流体連通によって少なくとも1つの第二容器から少なくとも1つの第三の反応容器に送り、残留気体成分、および副産物炭化水素成分を、舶用重質燃料油製品成分から取り除いて舶用重質燃料油製品を得る工程、
f)少なくとも1つの第三の反応容器から、舶用重質燃料油製品を排出する工程。 - さらに、工程f)で排出された多量の舶用重質燃料油製品を、炭化水素系材料、非炭化水素系材料、固体材料、およびこれらの組み合わせからなる群から選択される少量の希釈材と混合する工程を含む、
請求項7に記載の舶用重質燃料油の製造方法。 - 舶用重質燃料油原料の硫黄含有量がISO14596又はISO8754により決定され、
特定汚染物の濃度は下記基準:
バナジウムはIP501、IP470、またはISO14597、
ナトリウムはIP501、またはIP470、
アルミニウムはIP501、IP470、またはISO10478、
ケイ素はIP501、IP470、またはISO10478、
カルシウムはIP501、IP470、またはISO500、
亜鉛はIP501、IP470、またはISO500、
リンはISO500、
ニッケルはIP501、またはIP470、
鉄はIP501、またはIP470
により決定される、請求項7または8に記載の舶用重質燃料油の製造方法。 - 舶用重質燃料油原料の硫黄含有量(ISO14596又はISO8754)は1.0重量%~5.0重量%の範囲であり、50℃の動粘度(ISO3104)が180mm2/秒~700mm2/秒の範囲であり、15℃の密度(ISO3675)が991.0kg/m3~1010.0kg/m3の範囲であり、CCAIが780~870の範囲であり、引火点(ISO2719)が60.0℃以上である、請求項7~9のいずれかに記載の舶用重質燃料油の製造方法。
- 触媒システムが、アルミナ、アルミナ/ボリア担体、金属含有アルミノシリケートを含む担体、アルミナ/リン担体、アルミナ/アルカリ土類金属化合物担体、アルミナ/チタニア担体及びアルミナ/ジルコニア担体からなる群より選択される多孔質無機酸化物触媒担体を含み、
触媒の遷移金属成分は、周期表の6族、8族、9族及び10族からなる群より選択される1種以上の金属である、
請求項7~10のいずれかに記載の舶用重質燃料油の製造方法。 - 触媒システムが固定床担持遷移金属不均一触媒を含み、
担持遷移金属不均一触媒が、多孔質アルミナ酸化物触媒担体、及びNi-Mo、Co-Mo、Ni-W、及びNi-Co-Moからなる群から選択される遷移金属触媒からなる、
請求項7~11のいずれかに記載の舶用重質燃料油の製造方法。 - 活性化ガスの量と舶用重質燃料油原料の量との比は、舶用重質燃料油原料に対してガスが2500scf ガス/bbl~4500scf ガス/bblの範囲である、
請求項7~12のいずれかに記載の舶用重質燃料油の製造方法。 - 反応容器において、
温度のプロセス条件が650°F~850°Fであり、
圧力のプロセス条件が1000psig~2500psigであり、
液空間速度のプロセス条件が0.08(油)/時間/m3(触媒)~0.5(油)/時間/m3(触媒)である、
請求項7~13のいずれかに記載の舶用重質燃料油の製造方法。 - 反応容器において、水理的能力速度は、舶用重質燃料油原料が5,000bbl/日~45,000bbl/日である、
請求項13に記載の舶用重質燃料油の製造方法。
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