JP6666437B2 - 石油から金属を除去する方法 - Google Patents
石油から金属を除去する方法 Download PDFInfo
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- JP6666437B2 JP6666437B2 JP2018519392A JP2018519392A JP6666437B2 JP 6666437 B2 JP6666437 B2 JP 6666437B2 JP 2018519392 A JP2018519392 A JP 2018519392A JP 2018519392 A JP2018519392 A JP 2018519392A JP 6666437 B2 JP6666437 B2 JP 6666437B2
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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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/08—Inorganic compounds only
-
- 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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
-
- 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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
-
- 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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/10—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for with the aid of centrifugal force
-
- 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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
図2に示す構成による実験的規模のプラントにおいて、超臨界水の存在下で石油供給原料を脱金属するためのプロセスを実施した。石油供給原料105は、体積流量0.2リットル/時間(L/時間)の全範囲アラビア軽質原油であった。石油供給原料105の温度は21℃であった。圧力を石油ポンプ5内で圧力25MPaまで上げ、加圧供給原料110を生成した。加圧供給原料110の温度を石油予熱器10内で50℃まで上げ、圧力25MPaのまま加熱供給原料135を生成した。水流115は、温度17℃で体積流量0.6L/時間であった。これを水ポンプ15内で圧力25MPaまで上げ、加圧水120を生成した。加圧水120を水予熱器20内で温度480℃まで加熱し、加熱水流130を生成した。加熱水流130および加熱供給原料135を混合装置30に供給して、混合流140を生成した。次いで、直列の超臨界水反応器40および超臨界水反応器40Aを有する超臨界水ユニットに、混合流140を供給した。超臨界水反応器40の内容積は0.16リットル、流体の滞留時間は1.6分であった。超臨界水反応器40Aの内容積は1.0リットル、流体の滞留時間は9.9分であった。超臨界水反応器40および超臨界水反応器40Aのいずれも温度420℃および圧力25MPaに保持した。2つの反応器を使用すると、混合流140の混合が進んだ。超臨界水反応器40Aの直径に対する長さの比によって激しい乱流が生じ、超臨界水反応器40内を流れる流れの混合が促進された。反応器流出物150が超臨界水ユニットを出るときに温度420℃および25MPaになるように反応条件を保持した。反応器流出物150を冷却装置50に供給し、ここで温度を50℃に下げて、冷却流160を生じさせた。冷却流160を減圧装置70に供給し、ここで圧力を大気圧まで下げて、減圧流172を生じさせた。減圧流172を気液分離器80に供給して、減圧流172を気体生成物202と液相流192に分離した。気液分離器80は500mlの容器であった。次いで、液相流192をバッチ式遠心分離ユニットである油水分離器90に供給し、ここで液相流192を液相石油212と水生成物222に分離した。液相石油212は、液相石油および金属不純物の両方を含んでいた。抽出器92内で10:1のn−ペンタン対石油生成物体積比を用いて、液相石油212をn−ペンタンで抽出した。金属含有留分214を濾過して取り出した後、残った液体をロータリーエバポレーターにかけ、ここでn−ペンタンが除去されて石油生成物210が残った。金属含有留分214は0.9重量%の液相石油212であった。ここでn−ペンタンを含まない石油生成物210のバナジウム含有量は0.5重量ppmであった。石油生成物210中のバナジウム含有量は、残留バナジウムが金属含有留分214に濃縮されたことを示す。油水分離器90内の油/水分離ステップの間に生じた液体の損失を伴い、100%から金属含有留分214を差し引いた石油生成物210の液収率は99.5重量%と測定された。この実施例は、本発明のプロセスが、約75重量%の低い液収率を有する従来の溶剤脱れきプロセスよりも良い液収率を与えることを示す。石油供給原料105および液相石油212の特性を表1に示す。
実施例2は、図3および実施例1を参照して説明した構成にしたがって実施した実験的規模のシミュレーションであった。実施例2では、活性炭対液体生成物重量比1:200で活性炭を液体生成物192に加えた(0.5重量%のカーボンブラックを液体生成物192に加えた)。超音波発生装置96内で混合物に超音波を15分間照射した。次に、混合物を50℃で撹拌した。撹拌した後、油水分離器90内で混合物を遠心分離して、水生成物222および石油212を生成した。試験は、活性炭が水生成物222中にあることを示した。液収率は99重量%であった。石油212のバナジウム含有量は0.4重量ppmであった。実施例2の結果は、リジェクタ(この実施例では、遠心分離機を使用して、遠心分離管の底にスラッジを濃縮した。)および吸着材が、石油供給原料から金属不純物を除去できることを示す。
Claims (17)
- 発電プロセスにおいて使用するための石油供給原料から金属不純物を除去する方法であって、
前記金属不純物を含み、150℃の供給原料温度および水の臨界圧よりも高い供給原料圧力まで加熱された加熱供給原料と、水の臨界温度を上回る水温および水の臨界圧を上回る水圧まで加熱される加熱水流と、を混合装置内で混合して、混合流を生成するステップであって、
前記混合流が、アスファルテンと樹脂部分、炭化水素部分および超臨界水部分を含む、ステップと、
外部から供給された水素および外部から供給された酸化剤がない状態で、前記混合流を超臨界水反応器に導入して、精製石油部分およびある量の固体コークスを含む反応器流出物を生成するステップであって、脱金属反応により、前記金属不純物を、金属酸化物、金属水酸化物、有機金属化合物、またはこれらの組み合わせを含む変換金属に変換し、アップグレーディング、脱硫、脱窒、脱酸素、クラッキング、異性化、アルキル化、縮合、二量体化、加水分解、水和、またはこれらの組み合わせからなる群から選択される変換反応により、前記超臨界水部分の存在下で前記炭化水素部分を精製して前記精製石油部分を生成するステップと、
前記反応器流出物を冷却装置内で冷却して冷却流を生成するステップと、
前記アスファルテンと樹脂部分および前記変換金属を含むスラッジ留分を前記冷却流から分離して、脱スラッジ流を生じるように構成された、リジェクタ温度を有するリジェクタに、前記冷却流を供給するステップと、
減圧装置内の前記脱スラッジ流の圧力を低下させて、減圧生成物を生成するステップと、
気液分離器内の前記減圧生成物を分離して、気相生成物および液体生成物を生成するステップと、
油水分離器内の前記液体生成物を分離して、ある液収率を有し、前記石油供給原料と比べてアスファルテン含有量が減少し、金属不純物の濃度が低下し、かつ硫黄が減少した石油生成物と、水生成物とを生成するステップと
を含む方法。 - 前記石油供給原料が、全範囲原油、抜頭原油、燃料油、製油所流、製油所流からの残油、原油精製所からの分解生成物流、常圧残油流、減圧残油流、石炭由来の炭化水素、液化石炭、ビチューメン、バイオマス由来の炭化水素および他の石油化学プロセスからの炭化水素流からなる群から選択される石油系炭化水素である、請求項1に記載の方法。
- 前記金属不純物が、バナジウム、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、請求項1または2に記載の方法。
- 前記金属不純物が金属ポルフィリンを含む、請求項1〜3のいずれか一項に記載の方法。
- 前記リジェクタがリジェクタ吸着材を含む、請求項1〜4のいずれか一項に記載の方法。
- 前記リジェクタがリジェクタ溶剤を含む、請求項1〜5のいずれか一項に記載の方法。
- 前記リジェクタが、サイクロン型容器、管状型容器、CSTRおよび遠心分離機からなる群から選択される、請求項1〜6のいずれか一項に記載の方法。
- 前記反応器流出物中の固体コークスの量が、石油供給原料の1.5重量%未満である、請求項1〜7のいずれか一項に記載の方法。
- 前記石油生成物中の金属不純物の濃度が2重量ppm未満である、請求項1〜8のいずれか一項に記載の方法。
- 前記石油生成物の前記液収率が96%よりも高い、請求項1〜9のいずれか一項に記載の方法。
- 発電プロセスにおいて使用するための石油供給原料から金属不純物を除去する方法であって、
前記金属不純物を含み、150℃の供給原料温度および水の臨界圧よりも高い供給原料圧力まで加熱された加熱供給原料と、水の臨界温度を上回る水温および水の臨界圧を上回る水圧まで加熱される加熱水流と、を混合装置内で混合して混合流を生成するステップであって、
前記混合流が、アスファルテンと樹脂部分、炭化水素部分および超臨界水部分を含む、ステップと、
外部から供給された水素および外部から供給された酸化剤がない状態で、前記混合流を超臨界水反応器に導入して、精製石油部分を含む反応器流出物を生成するステップであって、脱金属反応により、前記金属不純物を、金属酸化物、金属水酸化物、有機金属化合物、またはこれらの組み合わせを含む変換金属に変換し、アップグレーディング、脱硫、脱窒、脱酸素、クラッキング、異性化、アルキル化、縮合、二量体化、加水分解、水和、またはこれらの組み合わせからなる群から選択される変換反応により、前記超臨界水部分の存在下で前記炭化水素部分を精製して前記精製石油部分を生成するステップと、
前記反応器流出物を冷却装置内で冷却して冷却流を生じるステップと、
減圧装置内の前記冷却流の圧力を低下させて、前記精製石油部分、アスファルテン留分、水留分および気相生成物留分を含む減圧流を生成するステップと、
気液分離器内の前記減圧流を分離して、気体生成物および液相流を生成するステップと、
油水分離器内の前記液相流を分離して、液相石油流および水相流を生成するステップと、
前記液相石油流を溶剤抽出器に供給するステップと、
前記石油供給原料と比べてアスファルテン含有量が減少し、金属不純物の濃度が低下し、かつ硫黄が減少した石油生成物を、前記溶剤抽出器内の前記液相石油流から抽出して、金属含有留分を残すステップと
を含む方法。 - 前記石油供給原料が、全範囲原油、抜頭原油、燃料油、製油所流、製油所流からの残油、原油精製所からの分解生成物流、常圧残油流、減圧残油流、石炭由来の炭化水素、液化石炭、ビチューメン、バイオマス由来の炭化水素および他の石油化学プロセスからの炭化水素流からなる群から選択される石油系炭化水素である、請求項11に記載の方法。
- 前記金属不純物が、バナジウム、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、請求項11または12に記載の方法。
- 前記金属不純物が金属ポルフィリンを含む、請求項11〜13のいずれか一項に記載の方法。
- 前記溶剤抽出器において溶剤脱れきプロセスが実施される、請求項11〜14のいずれか一項に記載の方法。
- 前記反応器流出物中の固体コークスの量が、石油供給原料の1.5重量%未満である、請求項11〜15のいずれか一項に記載の方法。
- 前記石油生成物中の金属不純物の濃度が2重量ppm未満である、請求項11〜16のいずれか一項に記載の方法。
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JP2020097756A (ja) | 2020-06-25 |
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EP3374470A1 (en) | 2018-09-19 |
JP2018534396A (ja) | 2018-11-22 |
KR20200045007A (ko) | 2020-04-29 |
WO2017066269A1 (en) | 2017-04-20 |
US20180171240A1 (en) | 2018-06-21 |
KR102105575B1 (ko) | 2020-04-29 |
WO2017066269A8 (en) | 2018-05-24 |
EP3374470B1 (en) | 2019-09-18 |
EP3567089A1 (en) | 2019-11-13 |
KR102233862B1 (ko) | 2021-03-30 |
CN110607190A (zh) | 2019-12-24 |
US9926497B2 (en) | 2018-03-27 |
EP3567089B1 (en) | 2020-07-22 |
CN108291155A (zh) | 2018-07-17 |
KR20180066222A (ko) | 2018-06-18 |
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