TW201538705A - Process for selective cascade deasphalting - Google Patents
Process for selective cascade deasphalting Download PDFInfo
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- TW201538705A TW201538705A TW103142018A TW103142018A TW201538705A TW 201538705 A TW201538705 A TW 201538705A TW 103142018 A TW103142018 A TW 103142018A TW 103142018 A TW103142018 A TW 103142018A TW 201538705 A TW201538705 A TW 201538705A
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- 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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
- C10G53/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step including only extraction steps, e.g. deasphalting by solvent treatment followed by extraction of aromatics
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- 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
- C10G21/003—Solvent de-asphalting
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- 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
- C10G21/02—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately
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- 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
- C10G21/12—Organic 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
- 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
- C10G21/12—Organic compounds only
- C10G21/14—Hydrocarbons
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- 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
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
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- 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
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- 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
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
Description
本發明係關於原油處理領域。更具體而言，本發明係關於藉由液體/液體萃取對重進料、具體而言原油殘餘物選擇性串聯脫瀝青之新穎方法。 This invention relates to the field of crude oil processing. More specifically, the present invention relates to a novel process for selective deasphalting of heavy feeds, in particular crude oil residues, by liquid/liquid extraction.
原油殘餘物之特徵在於極性及分子量遞增之分子結構連續，該等分子結構一般可分組集合為四個家族：- 飽和烴家族，其包含具有飽和及不飽和特徵之烴且不含芳香族環且極性在四個家族中最小，- 芳香族烴家族，其基本上包含一般含硫及/或含氮之芳香族及/或雜原子及/或聚芳香族環。此家族之極性大於飽和烴家族。 The crude oil residue is characterized by a continuous molecular structure with increasing polarity and molecular weight. The molecular structures can generally be grouped into four families: a family of saturated hydrocarbons containing hydrocarbons having saturated and unsaturated characteristics and containing no aromatic rings. The smallest of the four families, the aromatic hydrocarbon family, consists essentially of aromatic and/or heteroatoms and/or polyaromatic rings which generally contain sulfur and/or nitrogen. This family is more polar than the saturated hydrocarbon family.
- 樹脂家族，其基本上包含一般含硫及/或含氮及/或含金屬且具有諸如鎳及釩等金屬之雜原子芳香族環。此家族亦包含聚芳香族及/或雜原子聚芳香族環。此家族之極性甚至大於芳香族烴家族。 A family of resins which essentially comprise a heteroatom aromatic ring which is generally sulfur-containing and/or nitrogen-containing and/or metal-containing and which has metals such as nickel and vanadium. This family also contains polyaromatic and/or heteroatom polyaromatic rings. This family is even more polar than the aromatic hydrocarbon family.
- 瀝青質家族，其包含該連續中極性最大之分子結構，其係雜原子聚芳香族類型。瀝青質主要係富含與諸如鎳及釩等金屬錯合之含硫及/或含氮及/或含氧雜質之化合物。 - an asphaltene family comprising the most polar molecular structure in the continuous, which is a heteroatom polyaromatic type. Asphaltenes are mainly rich in compounds containing sulfur and/or nitrogen-containing and/or oxygen-containing impurities that are mismatched with metals such as nickel and vanadium.
樹脂含於沸點一般高於300℃之石油餾分中，而瀝青質主要集中於具有一般高於500℃之高沸點之餾分中。 The resin is contained in a petroleum fraction having a boiling point generally higher than 300 ° C, and the asphaltene is mainly concentrated in a fraction having a high boiling point generally higher than 500 ° C.
在現有方法中，原油殘餘物可經受熟習此項技術者熟知之脫瀝 青預處理。脫瀝青之原理係基於藉由沈澱將石油殘餘物分離為兩個相：i)稱作「脫瀝青油」之相，亦稱為「油基質」或「油相」或DAO(脫瀝青油)，其可藉助各種精煉方法升級回收(upcycle)；及ii)稱作「瀝青(asphalt)」或有時稱作「瀝青(pitch)」之相，其含有上述抗拒性分子結構。由於瀝青之次等品質及其端視溫度條件可自固體變為糊狀且最終變為液相之可變狀態，其係對精煉系統有害之產物，應被減至最少。事實上，升級回收並轉化重進料之方法之性能遇到主要由含於瀝青中之該等所謂抗拒性分子結構之存在控制之限制。 In the prior methods, the crude oil residue can be subjected to the leaching well known to those skilled in the art. Green pretreatment. The principle of deasphalting is based on the separation of petroleum residues into two phases by precipitation: i) the phase known as "deasphalted oil", also known as "oil matrix" or "oil phase" or DAO (deasphalted oil) It can be upgraded by various refining methods; and ii) a phase called "asphalt" or sometimes referred to as "pitch", which contains the above-mentioned resistant molecular structure. Since the inferior quality of the bitumen and its end-point temperature conditions can change from a solid to a paste and eventually to a liquid state, the product which is harmful to the refining system should be minimized. In fact, the performance of upgrading the process of recovering and converting heavy feed encounters limitations that are primarily controlled by the presence of such so-called resistive molecular structures contained in the bitumen.
此脫瀝青在下文中稱為習用脫瀝青，其一般係使用石蠟型溶劑來實施。 This deasphalting is hereinafter referred to as conventional deasphalting, which is generally carried out using a paraffin type solvent.
專利US 7,857,964闡述脫瀝青方法中所用石蠟型溶劑對殘餘物之加氫處理之性能的影響。 Patent US 7,857,964 describes the effect of paraffinic solvents used in the deasphalting process on the performance of the hydrotreating of the residue.
專利US 4,305,812及US 4,455,216闡述呈逆流萃取形式之脫瀝青，其係在塔中用若干種在塔不同高度注入之極性遞增之溶劑實施。 The deasphalting in the form of a countercurrent extraction is described in U.S. Patent No. 4,305,812 and U.
專利US 2008/149534涉及串聯(具體而言在兩個階段中)脫瀝青之方法。使用具有5或7個碳原子(C5或C7)之第一石蠟型溶劑來萃取瀝青。然後用含有較少碳(C3或C4)之另一種石蠟型溶劑處理所收集脫瀝青油DAO以自油基質分離包含樹脂之餾分。然而，此方法具有與使用石蠟型溶劑有關之脫瀝青油DAO之產率低之缺點。 Patent US 2008/149534 relates to a method of deasphalting in series, in particular in two stages. The asphalt is extracted using a first paraffinic solvent having 5 or 7 carbon atoms (C5 or C7). The collected deasphalted oil DAO is then treated with another paraffinic solvent containing less carbon (C3 or C4) to separate the fraction containing the resin from the oil matrix. However, this method has the disadvantage of a low yield of the deasphalted oil DAO associated with the use of a paraffinic solvent.
先前技術中提出之解決方案皆係基於習用脫瀝青，其由於其原理而在關於針對石油殘餘物設想之升級回收之產率及靈活性方面受限。在習用脫瀝青中使用石蠟型溶劑或溶劑混合物限制脫瀝青油DAO之產率，該產率隨溶劑(至多C6/C7溶劑)之分子量而增加，然後在每一進料及每一溶劑之特定臨限值處達到平穩。 The solutions proposed in the prior art are based on conventional deasphalting, which is limited by its principle in terms of yield and flexibility with respect to upgrade recovery envisaged for petroleum residues. The use of a paraffinic solvent or solvent mixture in conventional deasphalting limits the yield of the deasphalted oil DAO, which increases with the molecular weight of the solvent (up to C6/C7 solvent) and is then specific to each feed and each solvent. The threshold is stable.
本發明使得可消除先前所述之限制。其使得可改良分離靈活性以及可升級回收產物之產率。此一方法之實施包含至少兩個串聯脫瀝 青階段且使得可提高分離進料之選擇性。其使得可獲得更多樣化之分子結構餾分。本發明脫瀝青階段中之至少一者係藉助至少一種極性溶劑及至少一種非極性溶劑之混合物來實施，該極性溶劑及該非極性溶劑之比例係根據進料之性質、根據每一脫瀝青階段之目標、根據瀝青之期望產率及/或根據期望DAO餾分之品質來調節，該等脫瀝青階段係在溶劑混合物之次臨界條件下實施。 The present invention makes it possible to eliminate the limitations previously described. It makes it possible to improve the separation flexibility and the yield of upgradeable recovered products. The implementation of this method comprises at least two tandem deleaching The cyan phase makes it possible to increase the selectivity of the separated feed. It makes it possible to obtain a more diverse molecular structure fraction. At least one of the deasphalting stages of the present invention is carried out by means of a mixture of at least one polar solvent and at least one non-polar solvent, the ratio of the polar solvent to the non-polar solvent being based on the nature of the feed, according to each deasphalting stage The target, adjusted according to the desired yield of the bitumen and/or according to the desired quality of the DAO fraction, is carried out under subcritical conditions of the solvent mixture.
本發明方法之目標係藉由獲得先前使用習用脫瀝青無法獲得之多種分離選擇性，在進料之處理中容許更大靈活性。本發明方法容許在殘餘物進料之升級回收期間對其中之可升級回收餾分之性質的更具選擇性之調節，同時使該方法之脫瀝青油DAO之所有不同分離餾分之最終產率最大化。 The object of the process of the present invention is to allow for greater flexibility in the processing of the feed by obtaining a plurality of separation selectivity previously not available with conventional deasphalting. The process of the present invention allows for a more selective adjustment of the nature of the upgradeable fractions during the upgrade recovery of the residue feed while maximizing the final yield of all of the different separated fractions of the deasphalted oil DAO of the process. .
1‧‧‧進料/導管 1‧‧‧Feed/catheter
2‧‧‧非極性溶劑 2‧‧‧Non-polar solvent
3‧‧‧極性溶劑 3‧‧‧Polar solvent
4‧‧‧補給槽 4‧‧‧Supply tank
5‧‧‧補給槽 5‧‧‧Supply tank
6‧‧‧導管 6‧‧‧ catheter
7‧‧‧導管 7‧‧‧ catheter
10‧‧‧混合器 10‧‧‧ Mixer
11‧‧‧導管 11‧‧‧ catheter
12‧‧‧導管 12‧‧‧ catheter
13‧‧‧萃取器 13‧‧‧ extractor
14‧‧‧導管 14‧‧‧ catheter
15‧‧‧導管 15‧‧‧ catheter
16‧‧‧瀝青 16‧‧‧Asphalt
17‧‧‧分離器 17‧‧‧Separator
18‧‧‧導管 18‧‧‧ catheter
19‧‧‧汽提塔/非極性溶劑 19‧‧‧Stripper/non-polar solvent
20‧‧‧導管/分離器 20‧‧‧Tube/separator
21‧‧‧導管/極性溶劑 21‧‧‧catheter/polar solvent
22‧‧‧溶劑混合物或溶劑混合物中所含非極性溶劑/導管 22‧‧‧Non-polar solvents/conduit contained in solvent mixtures or solvent mixtures
23‧‧‧管線/汽提塔 23‧‧‧Line/Stripper
24‧‧‧密度計或折射計/導管 24‧‧‧Densometer or refractometer/catheter
25‧‧‧靜態型混合器/導管 25‧‧‧Static mixer/catheter
26‧‧‧非極性溶劑/管線 26‧‧‧Non-polar solvent/pipeline
27‧‧‧極性溶劑 27‧‧‧Polar solvent
28‧‧‧補給槽 28‧‧‧Supply tank
29‧‧‧補給槽 29‧‧‧Supply tank
34‧‧‧混合器 34‧‧‧ Mixer
37‧‧‧第二萃取器 37‧‧‧Second extractor
38‧‧‧稱作輕DAO之輕脫瀝青油餾分/第二萃取器 38‧‧‧Light deasphalted oil fraction/second extractor called light DAO
39‧‧‧稱作重DAO之重脫瀝青油餾分 39‧‧‧Re-de-asphalt oil fraction called heavy DAO
40‧‧‧分離器 40‧‧‧Separator
41‧‧‧稱作輕DAO之輕脫瀝青油 41‧‧‧Light deasphalting oil called light DAO
42‧‧‧汽提塔 42‧‧‧Stripper
43‧‧‧導管 43‧‧‧ catheter
44‧‧‧導管 44‧‧‧ catheter
45‧‧‧本發明溶劑 45‧‧‧Solvent of the invention
46‧‧‧管線 46‧‧‧ pipeline
47‧‧‧密度計或折射計 47‧‧‧densitometer or refractometer
48‧‧‧靜態型混合器 48‧‧‧Static mixer
49‧‧‧分離器 49‧‧‧Separator
50‧‧‧稱作重DAO之重脫瀝青油 50‧‧‧Re-de-asphalt oil called heavy DAO
51‧‧‧汽提塔 51‧‧‧Stripper
52‧‧‧導管 52‧‧‧ catheter
53‧‧‧非極性溶劑或本發明溶劑或溶劑混合物中所含非極性溶劑 53‧‧‧Non-polar solvent or non-polar solvent contained in the solvent or solvent mixture of the invention
54‧‧‧導管 54‧‧‧ catheter
圖1代表本發明脫瀝青之圖解。 Figure 1 represents an illustration of the deasphalting of the present invention.
圖2代表納入兩個分離器並使溶劑個別再循環至其各別槽中之脫瀝青之圖解。 Figure 2 represents an illustration of deasphalting incorporating two separators and recycling the solvent individually into their respective tanks.
在下文及上文中，表述「本發明溶劑混合物」應理解為意指本發明之至少一種極性溶劑及至少一種非極性溶劑之混合物。 In the following and the above, the expression "solvent mixture of the invention" is understood to mean a mixture of at least one polar solvent of the invention and at least one non-polar solvent.
本發明方法包含至少兩個對欲處理進料串聯實施之脫瀝青階段，其使得可分離至少一種瀝青餾分、至少一種稱作重DAO之重脫瀝青油餾分及至少一種稱作輕DAO之輕脫瀝青油餾分，該等脫瀝青階段中之至少一者係藉助溶劑混合物來實施，該等脫瀝青階段係在所用溶劑混合物之次臨界條件下實施。 The process of the invention comprises at least two deasphalting stages carried out in series on the feed to be treated, which makes it possible to separate at least one bitumen fraction, at least one heavy deasphalted oil fraction called heavy DAO and at least one lightly called light DAO The bituminous oil fraction, at least one of the deasphalting stages is carried out by means of a solvent mixture which is carried out under subcritical conditions of the solvent mixture used.
溶劑之選擇以及該極性溶劑及該非極性溶劑在溶劑混合物中之比例一方面係根據欲處理進料之性質及根據瀝青之產率及/或重DAO及輕DAO之期望脫瀝青餾分之品質來調節，且另一方面係根據針對每 一餾分設想之後續升級回收方法(例如加氫裂解、加氫處理、加氫轉化、催化裂解、熱裂解等)之規範來調節。此導致分離性能方面之顯著增益，從而端視其中包括本發明方法之系統之目標，改良及/或優化分離餾分之產率及品質。 The choice of solvent and the ratio of the polar solvent and the non-polar solvent in the solvent mixture are adjusted on the one hand depending on the nature of the feed to be treated and on the quality of the bitumen and/or the desired deasphalted fraction of the heavy DAO and light DAO. And on the other hand A fraction is contemplated to be regulated by subsequent upgrade recovery methods (eg, hydrocracking, hydrotreating, hydroconversion, catalytic cracking, thermal cracking, etc.). This results in a significant gain in separation performance, thereby improving and/or optimizing the yield and quality of the separated fractions, depending on the objectives of the system in which the process of the invention is included.
由於特定脫瀝青條件，本發明方法端視進料之性質，但亦端視在進料處理下游之所設想升級回收系統，容許進料處理之更大靈活性。本發明之脫瀝青條件使得可克服如在習用脫瀝青中因使用石蠟型溶劑所造成之對脫瀝青油DAO之產率之限制。由於特定脫瀝青條件，本發明方法使得可在維持重質樹脂及瀝青質之全部或一些極性結構在油基質中之溶解方面更進一步，該等重質樹脂及瀝青質在習用脫瀝青情形中係瀝青相之主要成份。本發明由此使得可選擇何種類型之極性結構在DAO油基質中保持溶解。在本發明脫瀝青期間所萃取瀝青對應於在轉化及精煉方法中基本上由抗拒性最強之聚芳香族及/或雜原子分子結構組成之最終瀝青。此導致改良脫瀝青油之總產率。 Due to the particular deasphalting conditions, the process of the present invention respects the nature of the feed, but also dictates the upgraded recovery system envisioned downstream of the feed treatment, allowing for greater flexibility in the feed treatment. The deasphalting conditions of the present invention make it possible to overcome the limitation on the yield of the deasphalted oil DAO caused by the use of a paraffinic solvent in conventional deasphalting. Due to the specific deasphalting conditions, the process of the present invention makes it possible to further maintain the dissolution of all or some of the polar structures of the heavy resin and the asphaltenes in the oil matrix, which are in the case of conventional deasphalting. The main component of the asphalt phase. The invention thus allows the selection of which type of polar structure to remain dissolved in the DAO oil matrix. The bitumen extracted during the deasphalting of the present invention corresponds to the final bitumen which consists essentially of the most resistant polyaromatic and/or hetero atom molecular structure in the conversion and refining process. This results in an improved overall yield of the deasphalted oil.
因此，本發明使得可獲得至少三種餾分：瀝青餾分、稱作重DAO之重脫瀝青油餾分及稱作輕DAO之輕脫瀝青油餾分，且在優化每一所獲得餾分之產率及/或品質方面靈活性大於習用脫瀝青情形。 Thus, the present invention makes it possible to obtain at least three fractions: a bitumen fraction, a heavy deasphalted oil fraction called heavy DAO, and a light deasphalted oil fraction called light DAO, and in optimizing the yield of each obtained fraction and/or The flexibility in terms of quality is greater than that in the case of conventional deasphalting.
根據本發明，所用進料選自原油型石油源進料或源自原油之殘餘餾分(例如源自所謂常規原油(API度>20°)、重質原油(API度包含於10°與20°之間)或超重原油(API度<10°)之常壓殘餘物或真空殘餘物)。該進料亦可係源自該等原油中之一者或該等常壓殘餘物中之一者或該等真空殘餘物中之一者之任何預處理或轉化階段(例如加氫裂解、加氫處理、熱裂解、加氫轉化)之殘餘餾分。該進料亦可係源自不管使用何種方法，使用或不使用氫、使用或不使用觸媒之直接煤液化(常壓或真空殘餘物)之殘餘餾分，亦或源自單獨或呈與煤及/或殘餘石油餾分之混合物之木質纖維素生質的不管使用何種方法，使用或不使用 氫、使用或不使用觸媒之直接液化之殘餘餾分。 According to the invention, the feed used is selected from a crude oil type petroleum source feed or a residual fraction derived from crude oil (for example derived from so-called conventional crude oil (API degree > 20°), heavy crude oil (API degree is included in 10° and 20°) Between) or overweight crude oil (API degree <10 °) atmospheric residue or vacuum residue). The feed may also be derived from any of the pre- or conversion stages of one of the crude oils or one of the atmospheric residues or one of the vacuum residues (eg hydrocracking, addition) Residual fractions of hydrogen treatment, thermal cracking, hydroconversion). The feed may also be derived from residual fractions of direct coal liquefaction (atmospheric or vacuum residues) with or without the use of hydrogen, with or without catalyst, or from alone or in combination. Whether or not to use lignocellulosic biomass of a mixture of coal and/or residual petroleum fraction, with or without Hydrogen, residual fraction of direct liquefaction with or without catalyst.
根據本發明方法之進料之沸點一般高於300℃，較佳高於400℃，更佳高於450℃。 The boiling point of the feed according to the process of the invention is generally above 300 ° C, preferably above 400 ° C, more preferably above 450 ° C.
進料可具有不同地理及地球化學來源(I型、II型、IIS型或III型)，亦及不同成熟及生物降解程度。 The feed can have different geographic and geochemical sources (type I, type II, type IIS or type III), as well as different degrees of maturation and biodegradation.
根據本發明方法之進料之硫含量可大於0.5% m/m(表示為硫質量相對於進料質量之百分比)，較佳大於1% m/m，更佳大於2% m/m，甚至更佳大於4% m/m；金屬含量大於20ppm(表示為金屬質量相對於進料質量之百萬分率)，較佳大於70ppm，較佳大於100ppm，更佳大於200ppm；C7瀝青質含量大於1% m/m(表示為C7瀝青質質量相對於進料質量之百分比，根據NF T60-115方法來量測)，較佳大於3% m/m，較佳大於8% m/m，更佳大於14% m/m；康拉遜碳(Conradson carbon，亦稱為CCR)含量大於5% m/m(表示為CCR質量相對於進料質量之百分比)，較佳大於7% m/m，較佳大於14% m/m，更佳大於20% m/m。有利地，C7瀝青質之含量包含於1重量%與40重量%之間且較佳介於2重量%與30重量%之間。 The sulphur content of the feed according to the process of the invention may be greater than 0.5% m/m (expressed as a percentage of sulphur mass relative to the feed mass), preferably greater than 1% m/m, more preferably greater than 2% m/m, or even More preferably greater than 4% m/m; metal content greater than 20 ppm (expressed as a mass fraction of metal relative to the mass of the feed), preferably greater than 70 ppm, preferably greater than 100 ppm, more preferably greater than 200 ppm; C7 asphaltene content greater than 1% m/m (expressed as the percentage of C7 asphaltene mass relative to the feed mass, measured according to the NF T60-115 method), preferably greater than 3% m/m, preferably greater than 8% m/m, more Preferably greater than 14% m/m; Conradson carbon (also known as CCR) content greater than 5% m/m (expressed as a percentage of CCR mass relative to feed mass), preferably greater than 7% m/m Preferably, it is greater than 14% m/m, more preferably greater than 20% m/m. Advantageously, the C7 asphaltene content is comprised between 1% and 40% by weight and preferably between 2% and 30% by weight.
本發明方法之脫瀝青階段可在萃取塔或萃取器中、較佳在混合器-沉降器中實施。較佳地，將本發明溶劑混合物在兩個不同位凖引入萃取塔或混合器-沉降器中。較佳地，將本發明溶劑混合物在單一引入位凖引入萃取塔或混合器-沉降器中。 The deasphalting stage of the process of the invention can be carried out in an extraction column or extractor, preferably in a mixer-settler. Preferably, the solvent mixture of the invention is introduced into the extraction column or mixer-settler at two different positions. Preferably, the solvent mixture of the invention is introduced into the extraction column or mixer-settler at a single introduction point.
根據本發明，脫瀝青階段之液體/液體萃取係在該溶劑混合物之次臨界條件下、即在低於溶劑混合物之臨界溫度之溫度下實施。在利用單一溶劑、較佳非極性溶劑時，脫瀝青階段係在該溶劑之次臨界條件下、即在低於該溶劑之臨界溫度之溫度下實施。萃取溫度有利地包含於50℃與350℃之間，較佳介於90℃與320℃之間，更佳介於100℃與310℃之間，甚至更佳介於120℃與310℃之間，甚至更佳介於150℃ 與310℃之間，且壓力有利地包含於0.1MPa與6MPa之間，較佳介於2MPa與6MPa之間。 According to the invention, the liquid/liquid extraction of the deasphalting stage is carried out under subcritical conditions of the solvent mixture, i.e. at a temperature below the critical temperature of the solvent mixture. When a single solvent, preferably a non-polar solvent, is utilized, the deasphalting stage is carried out under subcritical conditions of the solvent, i.e., at a temperature below the critical temperature of the solvent. The extraction temperature is advantageously comprised between 50 ° C and 350 ° C, preferably between 90 ° C and 320 ° C, more preferably between 100 ° C and 310 ° C, even more preferably between 120 ° C and 310 ° C, or even more Good between 150 ° C Between 310 ° C and the pressure is advantageously comprised between 0.1 MPa and 6 MPa, preferably between 2 MPa and 6 MPa.
本發明溶劑混合物之體積(極性溶劑之體積+非極性溶劑之體積)對進料質量之比率一般包含於1/1與10/1之間，較佳介於2/1至8/1之間，表示為升/公斤。 The ratio of the volume of the solvent mixture of the present invention (volume of polar solvent + volume of non-polar solvent) to the mass of the feed is generally comprised between 1/1 and 10/1, preferably between 2/1 and 8/1. Expressed as liters / kg.
根據本發明之選擇性脫瀝青階段中之至少一者中所用溶劑混合物係至少一種極性溶劑及至少一種非極性溶劑之混合物。 The solvent mixture used in at least one of the selective deasphalting stages according to the present invention is a mixture of at least one polar solvent and at least one non-polar solvent.
有利地，極性溶劑在極性溶劑及非極性溶劑之混合物中之比例包含於0.1%與99.9%之間，較佳介於0.1%與95%之間，較佳介於1%與95%之間，更佳介於1%與90%之間，甚至更佳介於1%與85%之間，且極佳介於1%與80%之間。 Advantageously, the proportion of polar solvent in the mixture of polar solvent and non-polar solvent is comprised between 0.1% and 99.9%, preferably between 0.1% and 95%, preferably between 1% and 95%, more preferably Preferably between 1% and 90%, even better between 1% and 85%, and preferably between 1% and 80%.
有利地，根據本發明方法，本發明溶劑混合物中極性溶劑之沸點係高於非極性溶劑之沸點。 Advantageously, according to the process of the invention, the boiling point of the polar solvent in the solvent mixture of the invention is higher than the boiling point of the non-polar solvent.
本發明方法中所用極性溶劑可選自純芳香族或環烷烴-芳香族溶劑、包含雜元素之極性溶劑或其混合物。芳香族溶劑有利地選自單獨或呈混合物之單芳香族烴，較佳係苯、甲苯或二甲苯；雙環芳香烴或多環芳香烴；環烷烴-芳香族烴，例如四氫萘或二氫茚；雜原子芳香族烴(含氧、含氮、含硫)或極性強於飽和烴之任何其他家族之化合物，例如二甲亞碸(DMSO)、二甲基甲醯胺(DMF)、四氫呋喃(THF)。本發明方法中所用極性溶劑可係富含芳香族化合物之餾分。本發明之富含芳香族化合物之餾分可係(例如)源自FCC(流體催化裂解)之餾分(例如重汽油或LCO(LCO(輕循環油))或源自精煉廠之石油化學單元之餾分。亦可提及在使用或不使用氫、使用或不使用觸媒之熱化學轉化後視情況具有殘餘石油進料之衍生自煤、生質或生質/煤混合物之餾分。較佳地，所用極性溶劑係純淨或呈與芳香族烴之混合物之單芳香族烴。 The polar solvent used in the process of the invention may be selected from the group consisting of a pure aromatic or cycloalkane-aromatic solvent, a polar solvent comprising a hetero element or a mixture thereof. The aromatic solvent is advantageously selected from mono-aromatic hydrocarbons, alone or in mixtures, preferably benzene, toluene or xylene; bicyclic aromatic hydrocarbons or polycyclic aromatic hydrocarbons; cycloalkane-aromatic hydrocarbons such as tetrahydronaphthalene or dihydrogen a compound of a heteroatom aromatic hydrocarbon (oxygen, nitrogen, sulfur) or any other family that is more polar than a saturated hydrocarbon, such as dimethyl hydrazine (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF). The polar solvent used in the process of the present invention may be a fraction rich in aromatic compounds. The aromatic-rich fraction of the present invention may be, for example, a fraction derived from FCC (fluid catalytic cracking), such as heavy gasoline or LCO (LCO (light cycle oil)) or a fraction derived from a petrochemical unit of a refinery. It is also possible to mention a fraction derived from coal, biomass or biomass/coal mixture having residual petroleum feed, optionally with or without the use of hydrogen, with or without the use of a catalyst. The polar solvent used is pure or a single aromatic hydrocarbon in a mixture with an aromatic hydrocarbon.
本發明方法中所用之非極性溶劑較佳係由碳原子數大於或等於2、較佳介於2與9之間之飽和烴構成之溶劑。該等溶劑係以純淨或混合物形式(例如：烷烴及/或環烷烴之混合物或石腦油型之輕石油餾分)使用。 The non-polar solvent used in the process of the present invention is preferably a solvent composed of a saturated hydrocarbon having a carbon number of 2 or more, preferably 2 and 9. These solvents are used neat or as a mixture (for example, a mixture of alkanes and/or naphthenes or a light petroleum fraction of naphtha type).
與本發明萃取之溫度及壓力條件組合，在至少一個脫瀝青階段中之溶劑性質之選擇、非極性/極性溶劑組合之選擇使得可獲得最少兩個串聯調節關鍵點，其可經調節且其使得可獲得先前使用習用脫瀝青無法獲得之多種選擇性。在本發明情形中，兩個調節關鍵點之優化使得可將進料分離為三種餾分：稱作最終瀝青之瀝青餾分，其富集雜質及抵抗升級回收之化合物；稱作重DAO之重脫瀝青油相，其富集無抗拒性之最小極性樹脂及瀝青質之結構；及稱作輕DAO之輕脫瀝青油相，其不含樹脂及瀝青質，且一般不含雜質(金屬、雜原子)。 In combination with the temperature and pressure conditions of the extraction of the present invention, the choice of solvent properties in at least one deasphalting stage, the selection of the non-polar/polar solvent combination allows a minimum of two series adjustment key points to be obtained, which can be adjusted and which A variety of selectivities not previously available with conventional deasphalting are available. In the context of the present invention, the optimization of the two adjustment points makes it possible to separate the feed into three fractions: a bitumen fraction called final bitumen, which is enriched with impurities and resistant to upgrade recovery; a heavy deasphalting called heavy DAO The oil phase, which is enriched in the structure of the least polar resin and asphaltene with no resistance; and the light deasphalted oil phase called light DAO, which is free of resin and asphaltenes and generally contains no impurities (metals, heteroatoms). .
根據本發明方法，溶劑性質及/或極性溶劑在溶劑混合物中之比例及/或固有極性可根據期望在第一脫瀝青階段期間或在第二脫瀝青階段期間萃取瀝青來調節。 According to the process of the invention, the solvent nature and/or the proportion of polar solvent in the solvent mixture and/or the inherent polarity can be adjusted as desired during the first deasphalting stage or during the second deasphalting stage.
在第一實施例中，本發明方法係以稱作具有降低極性之構形來實施，即在第一脫瀝青階段期間所用溶劑混合物之極性大於在第二脫瀝青階段期間所用溶劑或溶劑混合物之極性。此構形使得可在第一脫瀝青階段期間萃取稱作最終瀝青之瀝青相餾分及稱作完全DAO之完全脫瀝青油餾分；該兩種稱作重脫瀝青油及輕脫瀝青油之餾分係在第二脫瀝青階段期間自稱作完全DAO之完全脫瀝青油萃取。 In a first embodiment, the process of the invention is carried out in a configuration referred to as having a reduced polarity, i.e., the polarity of the solvent mixture used during the first deasphalting stage is greater than the solvent or solvent mixture used during the second deasphalting stage. polarity. This configuration makes it possible to extract a bitumen fraction referred to as final bitumen and a fully deasphalted oil fraction called complete DAO during the first deasphalting stage; the two are referred to as re-de-asphalt oil and light de-asphalt oil. Complete deasphalted oil extraction referred to as full DAO during the second deasphalting stage.
在第二實施例中，本發明方法係以稱作具有增加極性之構形實施，即在第一脫瀝青階段期間所用溶劑或溶劑混合物之極性小於在第二脫瀝青階段期間所用溶劑混合物之極性。在此一構形中，在第一階段期間萃取稱作輕DAO之脫瀝青油餾分及包含油相及瀝青相之流出物；該流出物經受第二脫瀝青階段以萃取瀝青相餾分及稱作重DAO之 重脫瀝青油相餾分。 In a second embodiment, the process of the invention is carried out in a configuration referred to as having increased polarity, i.e., the polarity of the solvent or solvent mixture used during the first deasphalting stage is less than the polarity of the solvent mixture used during the second deasphalting stage. . In this configuration, a deasphalted oil fraction referred to as light DAO and an effluent comprising an oil phase and a bitumen phase are extracted during the first stage; the effluent is subjected to a second deasphalting stage to extract the asphalt phase fraction and is referred to as Heavy DAO The bituminous oil phase fraction is removed.
根據此實施例，本發明方法至少包含：a)第一脫瀝青階段，其包含使進料與至少一種極性溶劑及至少一種非極性溶劑之混合物接觸，該極性溶劑及該非極性溶劑之比例經調節以獲得至少一種瀝青相餾分及一種稱作完全DAO之完全脫瀝青油相餾分；及b)第二脫瀝青階段，其包含使源自階段a)之稱作完全DAO之完全脫瀝青油相中之至少一部分與非極性溶劑或至少一種極性溶劑及至少一種非極性溶劑之混合物接觸，該極性溶劑及該非極性溶劑在該混合物中之比例經調節以獲得至少一種輕脫瀝青油餾分及一種重脫瀝青油餾分，脫瀝青階段a)及b)係在所用溶劑或溶劑混合物之次臨界條件下實施。 According to this embodiment, the method of the invention comprises at least: a) a first deasphalting stage comprising contacting the feed with a mixture of at least one polar solvent and at least one non-polar solvent, the ratio of the polar solvent to the non-polar solvent being adjusted Obtaining at least one bitumen phase fraction and a fully deasphalted oil phase fraction referred to as complete DAO; and b) a second deasphalting stage comprising a fully deasphalted oil phase derived from stage a) referred to as complete DAO At least a portion of which is contacted with a non-polar solvent or a mixture of at least one polar solvent and at least one non-polar solvent, the ratio of the polar solvent and the non-polar solvent in the mixture being adjusted to obtain at least one light deasphalted oil fraction and a re-offset The bituminous oil fraction, the deasphalting stages a) and b) are carried out under subcritical conditions of the solvent or solvent mixture used.
對於給定進料，極性溶劑在溶劑混合物中之比例及/或固有極性愈大，脫瀝青油之產率愈高，進料之一部分極性結構保持溶解及/或分散於脫瀝青油DAO相中。減小極性溶劑在混合物中之比例具有增加所收集瀝青質相數量之效應。 For a given feed, the greater the ratio and/or the inherent polarity of the polar solvent in the solvent mixture, the higher the yield of the deasphalted oil, and the polar structure of one of the feeds remains dissolved and/or dispersed in the DAO phase of the deasphalted oil. . Reducing the proportion of polar solvent in the mixture has the effect of increasing the amount of asphaltene phase collected.
因此，第一脫瀝青階段使得可選擇性地以適於每一進料之最佳方式萃取稱作最終瀝青之瀝青餾分，其富集雜質及抵抗升級回收之化合物，同時在完全DAO油基質中保持溶解，對於最小極性重質樹脂及瀝青質之全部或部分極性結構而言，其不抵抗下游升級回收階段。因此，端視非極性/極性溶劑比例，可顯著改良脫瀝青油DAO之產率並由此使瀝青之產率降至最低。瀝青產率可介於0.1%至50%範圍內且更具體而言介於0.1%至25%範圍內。此係所關注點，已知瀝青(有害餾分)之升級回收始終構成包括此類方法之系統之真實限制。 Thus, the first deasphalting stage makes it possible to selectively extract a bitumen fraction known as final bitumen in an optimum manner suitable for each feed, which enriches impurities and resists upgrading of the recovered compounds, while in the complete DAO oil matrix. Keeping dissolved, it does not resist the downstream upgrade recovery stage for all or part of the polar structure of the minimum polarity heavy resin and asphaltenes. Thus, by looking at the non-polar/polar solvent ratio, the yield of the deasphalted oil DAO can be significantly improved and thus the yield of the asphalt can be minimized. The bitumen yield can range from 0.1% to 50% and more specifically from 0.1% to 25%. In this regard, it is known that upgrading and recycling of bitumen (hazardous fractions) has always constituted a real limitation of the system including such methods.
在第一萃取階段期間至少部分經本發明溶劑混合物萃取之源自階段a)之稱作完全DAO之完全脫瀝青油較佳經受至少一個分離階段，其中稱作完全DAO之完全脫瀝青油與本發明溶劑混合物分離；或經受至少一個分離階段，其中稱作完全DAO之完全脫瀝青油僅與非極性溶劑分離。 The fully deasphalted oil referred to as the complete DAO derived from stage a) at least partially extracted by the solvent mixture of the invention during the first extraction stage is preferably subjected to at least one separation stage, wherein the complete deasphalted oil referred to as complete DAO and the invention The solvent mixture is separated; or subjected to at least one separation stage, wherein the fully deasphalted oil referred to as complete DAO is only separated from the non-polar solvent.
在該方法之變體中，至少部分經本發明溶劑混合物萃取之源自階段a)之稱作完全DAO之完全脫瀝青油經受至少兩個連續分離階段，使得可在每一階段中個別分離該等溶劑。因此，例如，在第一分離階段中，非極性溶劑與稱作完全DAO之完全脫瀝青油及極性溶劑之混合物分離；且在第二分離階段中，極性溶劑與稱作完全DAO之完全脫瀝青油分離。 In a variant of the process, the fully deasphalted oil from stage a), referred to as complete DAO, which is at least partially extracted by the solvent mixture of the invention, is subjected to at least two successive stages of separation such that the individual separations can be carried out in each stage. Solvent. Thus, for example, in the first separation stage, the non-polar solvent is separated from the mixture of fully deasphalted oil and polar solvent known as complete DAO; and in the second separation stage, the polar solvent is completely deasphalted and called complete DAO. Oil separation.
分離階段係在超臨界或次臨界條件下實施。 The separation stage is carried out under supercritical or subcritical conditions.
在分離階段結束時，有利地將與本發明溶劑混合物分離之完全脫瀝青油DAO發送至至少一個汽提塔中，之後發送至第二脫瀝青階段。 At the end of the separation stage, the fully deasphalted oil DAO separated from the solvent mixture of the invention is advantageously sent to at least one stripper and then sent to the second deasphalting stage.
有利地使極性及非極性溶劑之混合物或個別分離之溶劑再循環。在該方法之變體中，僅使非極性溶劑再循環至其各別補給槽中。當再循環溶劑呈混合物時，線上檢驗非極性/極性比例並視需要經由個別含有極性及非極性溶劑之補給槽再調節。在個別分離溶劑時，使該等溶劑個別再循環至該等各別補給槽中。 It is advantageous to recycle a mixture of polar and non-polar solvents or individually separated solvents. In a variation of this method, only non-polar solvents are recycled to their respective make-up tanks. When the recycled solvent is a mixture, the non-polar/polar ratio is checked on-line and re-adjusted via separate feed tanks containing polar and non-polar solvents as needed. When the solvents are separately separated, the solvents are individually recycled to the respective supply tanks.
第一脫瀝青階段中經分離之瀝青相較佳呈液態且一般至少部分經一部分本發明溶劑混合物稀釋，該部分混合物之數量可介於所抽出瀝青體積之至多200%範圍內，較佳介於30%與80%之間。在萃取階段結束時，至少部分經極性及非極性溶劑之混合物萃取之瀝青可與至少一種熔劑混合以更易於抽出。所用熔劑可為可溶解或分散瀝青之任何溶劑或溶劑混合物。熔劑可為選自以下之極性溶劑：單芳香族烴，較 佳係苯、甲苯或二甲苯；二芳香族化合物或多芳香族化合物；環烷烴-芳香族烴，例如四氫萘或二氫茚；雜原子芳香族烴；分子量對應於包含於(例如)200℃與600℃之間之沸點之極性溶劑，例如LCO(來自FCC之輕循環油)、HCO(來自FCC之重循環油)、FCC漿料、HCGO(重焦化瓦斯油)或自油鏈萃取之芳香族萃取物或非芳香族餾分、源自殘餘餾分及/或煤及/或生質之轉化之VGO餾分。確定熔劑體積對瀝青質量之比率使得混合物可易於抽出。 The separated bitumen phase in the first deasphalting stage is preferably in a liquid state and is generally at least partially diluted with a portion of the solvent mixture of the present invention, and the amount of the portion of the mixture may be in the range of up to 200% of the volume of the extracted bitumen, preferably between 30. Between % and 80%. At the end of the extraction stage, at least a portion of the bitumen extracted by the mixture of polar and non-polar solvents can be mixed with at least one flux to facilitate extraction. The flux used may be any solvent or solvent mixture that dissolves or disperses the asphalt. The flux may be a polar solvent selected from the group consisting of monoaromatic hydrocarbons. Preferred are benzene, toluene or xylene; diaromatic or polyaromatic compounds; cycloalkane-aromatic hydrocarbons such as tetrahydronaphthalene or indoline; heteroatom aromatic hydrocarbons; molecular weight corresponding to, for example, 200 Polar solvent with a boiling point between °C and 600 °C, such as LCO (light cycle oil from FCC), HCO (recycled oil from FCC), FCC slurry, HCGO (re-coking gas oil) or self-oil chain extraction An aromatic extract or a non-aromatic fraction, a VGO fraction derived from the conversion of residual fractions and/or coal and/or biomass. The ratio of flux volume to asphalt mass is determined such that the mixture can be easily withdrawn.
可在至少一種極性溶劑及至少一種非極性溶劑之混合物存在下，在所用溶劑混合物之次臨界條件下，對源自第一脫瀝青階段之稱作完全DAO之完全脫瀝青油之至少一部分、較佳全部實施第二脫瀝青階段。亦可在非極性溶劑存在下，在所用溶劑之次臨界條件下，對源自第一脫瀝青階段之稱作完全DAO之完全脫瀝青油之至少一部分、較佳全部實施第二脫瀝青階段。該溶劑或溶劑混合物之極性較佳小於第一脫瀝青階段中所用溶劑混合物之極性。實施此萃取以獲得沈澱的稱作重DAO之重脫瀝青油相，其主要包含最小極性樹脂及瀝青質家族；及稱作輕DAO之輕脫瀝青油相，其不含樹脂及瀝青質，且一般不含雜質(金屬、雜原子)。稱作輕DAO之輕脫瀝青油相主要包含飽和烴家族及芳香族烴家族。 At least a portion of the fully deasphalted oil referred to as the complete DAO derived from the first deasphalting stage, in the presence of a mixture of at least one polar solvent and at least one non-polar solvent, under subcritical conditions of the solvent mixture used All of them implement the second deasphalting stage. At least a portion, preferably all, of the fully deasphalted oil referred to as the complete DAO derived from the first deasphalting stage may also be subjected to a second deasphalting stage in the presence of a non-polar solvent under subcritical conditions of the solvent employed. The polarity of the solvent or solvent mixture is preferably less than the polarity of the solvent mixture used in the first deasphalting stage. This extraction is carried out to obtain a precipitated heavy deasphalted oil phase called heavy DAO, which mainly comprises a family of least polar resins and asphaltenes; and a light deasphalted oil phase called light DAO, which is free of resin and asphaltenes, and Generally free of impurities (metals, heteroatoms). The light deasphalted oil phase called light DAO mainly comprises a saturated hydrocarbon family and an aromatic hydrocarbon family.
根據本發明，可藉由藉助混合物中非極性/極性溶劑之性質及比例或非極性溶劑之性質調節溶劑混合物之極性來修改稱作重DAO之重脫瀝青油餾分及輕DAO之輕脫瀝青油餾分之分離選擇性，且由此修改其組成。 According to the present invention, the light deasphalted oil fraction called the heavy DAO and the light deasphalted oil of the light DAO can be modified by adjusting the polarity of the solvent mixture by the nature of the nonpolar/polar solvent in the mixture and the nature of the ratio or the nonpolar solvent. The separation of the fractions is selective and the composition thereof is modified accordingly.
在第二實施例中，本發明方法至少包含：a)第一脫瀝青階段，其包含使進料與非極性溶劑或至少一種極性溶劑及至少一種非極性溶劑之混合物接觸，該極性溶劑及該非極性 溶劑在混合物中之比例經調節以獲得至少一種輕脫瀝青油相餾分及包含油相及瀝青相之流出物；及b)第二脫瀝青階段，其包含使源自階段a)之流出物之至少一部分與至少一種極性溶劑及至少一種非極性溶劑之混合物接觸，該極性溶劑及該非極性溶劑之比例經調節以獲得至少一種瀝青相餾分及重脫瀝青油相餾分，該等脫瀝青階段係在所用溶劑或溶劑混合物之次臨界條件下實施。 In a second embodiment, the process of the invention comprises at least: a) a first deasphalting stage comprising contacting the feed with a non-polar solvent or a mixture of at least one polar solvent and at least one non-polar solvent, the polar solvent and the non-polar solvent polarity The ratio of the solvent in the mixture is adjusted to obtain at least one light deasphalted oil phase fraction and an effluent comprising the oil phase and the asphalt phase; and b) a second deasphalting stage comprising the effluent derived from stage a) At least a portion is contacted with a mixture of at least one polar solvent and at least one non-polar solvent, the ratio of the polar solvent and the non-polar solvent being adjusted to obtain at least one bitumen fraction and a deasphalted oil phase fraction, the deasphalting stages being The solvent or solvent mixture used is carried out under subcritical conditions.
在本實施例中，反轉各類產物之萃取順序：第一脫瀝青階段中所用溶劑或溶劑混合物之極性低於第二脫瀝青階段中所用溶劑混合物之極性。 In this embodiment, the extraction sequence of the various products is reversed: the polarity of the solvent or solvent mixture used in the first deasphalting stage is lower than the polarity of the solvent mixture used in the second deasphalting stage.
因此，第一脫瀝青階段使得可自進料選擇性萃取稱作輕DAO之輕脫瀝青油餾分以及包含油相及瀝青相之流出物。亦可如對非極性溶劑及本發明溶劑混合物二者實施第一脫瀝青階段。在所用溶劑或溶劑混合物之次臨界條件下，溶劑混合物中極性溶劑之性質、比例及/或極性經調整以萃取主要包含飽和烴家族及芳香族烴家族之輕脫瀝青油餾分。 Thus, the first deasphalting stage enables self-feeding selective extraction of the light deasphalted oil fraction referred to as light DAO and the effluent comprising the oil phase and the asphalt phase. The first deasphalting stage can also be carried out as for both the non-polar solvent and the solvent mixture of the invention. Under subcritical conditions of the solvent or solvent mixture employed, the nature, ratio and/or polarity of the polar solvent in the solvent mixture is adjusted to extract a light deasphalted oil fraction comprising primarily the saturated hydrocarbon family and the aromatic hydrocarbon family.
來自第一脫瀝青階段之包含稱作重DAO之重脫瀝青油相及萃取瀝青相之流出物可至少部分含有非極性溶劑或本發明溶劑混合物。有利地，根據本發明，該流出物經受至少一個分離階段，其中將其與非極性溶劑或本發明溶劑混合物分離；或經受至少一個分離階段，其中該流出物僅與溶劑混合物中所含之非極性溶劑分離。 The effluent from the first deasphalting stage comprising a heavy deasphalted oil phase known as heavy DAO and an extracted bitumen phase may at least partially contain a non-polar solvent or a solvent mixture of the present invention. Advantageously, according to the invention, the effluent is subjected to at least one separation stage, wherein it is separated from the non-polar solvent or the solvent mixture of the invention; or subjected to at least one separation stage, wherein the effluent is only in combination with the solvent mixture The polar solvent is separated.
在本發明方法之變體中，該流出物可經受至少兩個連續分離階段，使得可在每一分離階段中個別分離溶劑(如本發明之第一實施例中所述)。 In a variant of the process according to the invention, the effluent can be subjected to at least two successive stages of separation such that the solvent can be separated separately in each separation stage (as described in the first embodiment of the invention).
分離階段係在超臨界或次臨界條件下實施。 The separation stage is carried out under supercritical or subcritical conditions.
在分離階段結束時，可將與溶劑或與本發明溶劑混合物分離之包含稱作重DAO之重脫瀝青油相及瀝青相之流出物發送至至少一個汽提塔中，之後發送至第二脫瀝青階段。 At the end of the separation stage, the effluent comprising the heavy deasphalted oil phase and the bitumen phase, referred to as heavy DAO, separated from the solvent or solvent mixture of the present invention, can be sent to at least one stripping column and then sent to the second stripping stage. Asphalt stage.
有利地使極性及非極性溶劑之混合物或個別分離之溶劑再循環。在該方法之變體中，僅使非極性溶劑再循環至其各別的補給槽中。在再循環溶劑呈混合物時，線上檢驗非極性及極性溶劑之比例並視需要經由個別含有該等極性及非極性溶劑之補給槽再調節。在個別分離溶劑時，使該等溶劑個別再循環至該等各別補給槽中。 It is advantageous to recycle a mixture of polar and non-polar solvents or individually separated solvents. In a variation of this method, only non-polar solvents are recycled to their respective supply tanks. When the recycled solvent is a mixture, the ratio of the non-polar and polar solvents is checked on-line and, if necessary, re-adjusted via separate supply tanks containing the polar and non-polar solvents. When the solvents are separately separated, the solvents are individually recycled to the respective supply tanks.
在至少一種極性溶劑及至少一種非極性溶劑之混合物存在下，在所用溶劑混合物之次臨界條件下，對源自第一脫瀝青階段之包含稱作重DAO之重脫瀝青油相及瀝青相之流出物之至少一部分、較佳全部實施第二脫瀝青階段。該溶劑混合物之極性較佳高於第一脫瀝青階段中所用溶劑或溶劑混合物之極性。實施此萃取以自流出物選擇性萃取稱作最終瀝青之瀝青餾分，其富集雜質及抵抗升級回收之化合物，同時在稱作重DAO之重脫瀝青油基質中保持溶解，最小極性樹脂及瀝青質之所有或部分極性結構在習用脫瀝青情形中一般保持含於瀝青餾分中。 In the presence of a mixture of at least one polar solvent and at least one non-polar solvent, under the subcritical conditions of the solvent mixture used, the heavy deasphalted oil phase and the bitumen phase, which are referred to as heavy DAO, originating from the first deasphalting stage At least a portion, preferably all, of the effluent is subjected to a second deasphalting stage. The polarity of the solvent mixture is preferably higher than the polarity of the solvent or solvent mixture used in the first deasphalting stage. This extraction is carried out to selectively extract a bitumen fraction called final bitumen from the effluent, which is enriched with impurities and resistant to upgraded recovered compounds, while remaining dissolved in a heavy deasphalted oil matrix called heavy DAO, minimally polar resin and bitumen All or part of the polar structure of the mass is generally retained in the bitumen fraction in the case of conventional deasphalting.
本發明方法具有容許在先前未經習用脫瀝青探索之整個範圍中顯著改良稱為輕DAO及重DAO之輕脫瀝青油及重脫瀝青油之總產率之優點。對於所獲得輕脫瀝青油及重脫瀝青油之總產率在75%停止增加(在習用脫瀝青中用正庚烷萃取)之給定進料，在本發明中實施之脫瀝青使得可在特定條件下藉由調節極性溶劑及非極性溶劑之比例來涵蓋稱為輕DAO及重DAO之輕脫瀝青油及重脫瀝青油之總產率之75%-99.9%之範圍。 The process of the present invention has the advantage of allowing a significant improvement in the overall yield of light deasphalted oils and heavy deasphalted oils known as light DAO and heavy DAO throughout the previously unexplored deasphalting exploration. For a given feed of the obtained light deasphalted oil and heavy deasphalted oil at a 75% stop increase (extracted with n-heptane in conventional deasphalting), the deasphalting carried out in the present invention allows The range of 75% to 99.9% of the total yield of light deasphalted oil and heavy deasphalted oil called light DAO and heavy DAO is covered by adjusting the ratio of polar solvent and non-polar solvent under specific conditions.
本發明方法由於其分離選擇性及其靈活性，使得可在給定進料之情形中獲得瀝青產率遠低於可藉由習用脫瀝青方法所獲得者之瀝青 餾分。該瀝青產率有利地包含於1%與50%之間，較佳介於1%與25%之間，更佳介於1%與20%之間。 The process according to the invention, thanks to its separation selectivity and its flexibility, makes it possible to obtain a bitumen yield which is much lower than that obtainable by conventional deasphalting processes in the case of a given feed. Distillate. The bitumen yield is advantageously comprised between 1% and 50%, preferably between 1% and 25%, more preferably between 1% and 20%.
本發明具有以下優點：i)改良所處理進料之性質，容許更容易且更有效之升級回收，同時ii)以受控方式限制瀝青產率。 The present invention has the following advantages: i) improving the nature of the treated feed, allowing for easier and more efficient upgrade recovery, while ii) limiting asphalt yield in a controlled manner.
由於兩個關鍵調節點，本發明方法具有在以下方面改良靈活性之優點：- 進料性質：本發明適於處理眾多種進料，- 產物之升級回收：端視所尋找產物之升級回收途徑，本發明使得可朝向獲得在產率及/或化學組成方面優化之稱作重DAO之重脫瀝青油餾分及稱作輕DAO之輕脫瀝青油餾分定向分離選擇性。稱作輕DAO之輕脫瀝青油餾分可(例如)經升級回收作為加氫裂解、FCC(例如，以促進汽油之升級回收)或任何其他精煉處理方法之進料。稱作重DAO之重脫瀝青油餾分可(例如)經升級回收作為加氫處理、加氫轉化或任何其他精煉處理方法之進料，但在某些精煉方法中亦可經再循環。 Due to two key adjustment points, the process of the invention has the advantage of improved flexibility in the following aspects: - Feed properties: The invention is suitable for handling a wide variety of feeds, - Product upgrade recovery: an upgraded recovery route looking for the product sought The present invention makes it possible to obtain a directional separation selectivity towards a heavy deasphalted oil fraction called heavy DAO optimized in terms of yield and/or chemical composition and a light deasphalted oil fraction called light DAO. A light deasphalted oil fraction, referred to as light DAO, can be recovered, for example, as a feedstock for hydrocracking, FCC (e.g., to facilitate upgrade recovery of gasoline) or any other refinery process. The heavy deasphalted oil fraction, referred to as heavy DAO, can be upgraded, for example, as a feed to hydrotreating, hydroconversion or any other refinery process, but can also be recycled in some refining processes.
根據圖1中所述之本發明實施例，將使用爐及/或交換器(未顯示)預先加熱之進料(1)引入萃取器(13)(例如萃取塔，較佳混合器-沉降器)中。極性溶劑(3)與非極性溶劑(2)之混合物係在上游在藉由兩個各自單獨填充有極性溶劑(槽4)及非極性溶劑(槽5)之補給槽給料之混合器(10)中產生。將溶劑混合物(例如)在兩個不同位凖引入萃取器(13)中。經由導管11將至少一部分溶劑混合物以與經由導管1引入之進料之混合物發送至萃取器(13)中。經由導管(12)將至少另一部分之溶劑混合物直接發送至萃取器(13)中，其中在上文所定義之本發明條件下實施萃取。 According to an embodiment of the invention illustrated in Figure 1, a preheated feed (1) using a furnace and/or exchanger (not shown) is introduced into the extractor (13) (e.g., an extraction column, preferably a mixer-settler) )in. The mixture of the polar solvent (3) and the non-polar solvent (2) is upstream of the mixer (10) fed by two supply tanks each filled with a polar solvent (tank 4) and a non-polar solvent (tank 5). Produced in. The solvent mixture, for example, is introduced into the extractor (13) at two different positions. At least a portion of the solvent mixture is sent via conduit 11 to the extractor (13) as a mixture with the feed introduced via conduit 1. At least another portion of the solvent mixture is sent directly to the extractor (13) via conduit (12), wherein the extraction is carried out under the conditions of the invention as defined above.
根據圖1，使用經由導管14發送之熔劑將亦至少部分含有本發明 溶劑混合物之瀝青(16)以液體混合物形式或以分散固體形式自萃取器(13)抽出。然後可將瀝青、本發明溶劑及熔劑之混合物發送至另一分離階段(未顯示)。所分離溶劑或溶劑之一部分或熔劑可在本發明方法中重複使用。 According to Figure 1, the use of a flux sent via conduit 14 will also at least partially comprise the invention. The bitumen (16) of the solvent mixture is withdrawn from the extractor (13) as a liquid mixture or as a dispersed solid. The bitumen, the solvent of the invention and the mixture of fluxes can then be sent to another separation stage (not shown). The separated solvent or a portion of the solvent or flux can be reused in the process of the invention.
在第一萃取階段結束時，將呈與至少部分本發明溶劑混合物之混合物之稱作萃取完全DAO之完全脫瀝青油經由導管15發送至分離器(17)，其中將完全脫瀝青油與溶劑混合物或僅與溶劑混合物中所含非極性溶劑(22)分離。在個別分離溶劑之情形中，則該方法可包含第二分離器(見圖2)。有利地在分離器中在超臨界或次臨界條件下分離溶劑混合物或個別使用之溶劑。然後較佳經由導管(18)將完全脫瀝青油發送至汽提塔(19)中，之後經由導管(20)回收。將源自汽提塔之溶劑經由導管(21)發送至管線(23)。 At the end of the first extraction stage, a fully deasphalted oil, referred to as a fully extracted DAO, in a mixture with at least a portion of the solvent mixture of the invention, is sent via conduit 15 to a separator (17) where the fully deasphalted oil is mixed with the solvent. Or only separated from the non-polar solvent (22) contained in the solvent mixture. In the case of individual separation of solvents, the method may comprise a second separator (see Figure 2). The solvent mixture or the solvent used individually is advantageously separated in a separator under supercritical or subcritical conditions. The fully deasphalted oil is then preferably sent to the stripper (19) via conduit (18) and then recovered via conduit (20). The solvent from the stripper is sent via line (21) to line (23).
有利地在該方法中使源自分離器(17)及汽提塔(19)之溶劑經由管線(23)內部再循環至萃取器(13)。較佳藉由密度計或折射計(24)線上檢驗極性與非極性溶劑之混合物之組成。視需要用分別自補給槽(4)及(5)經由導管(6)及(7)轉運之極性溶劑及非極性溶劑之補給再調節極性溶劑及非極性溶劑之比例。有利地將以此方式再調節之混合物在靜態型混合器(25)中勻漿化，之後發送至混合器(10)中。在個別分離溶劑時，將每一溶劑再循環至其原始槽中。 The solvent from the separator (17) and the stripper (19) is advantageously recycled to the extractor (13) via the line (23) in this process. The composition of the mixture of polar and non-polar solvents is preferably verified by a densitometer or refractometer (24) line. The ratio of the polar solvent to the non-polar solvent is adjusted by replenishing the polar solvent and the non-polar solvent which are transported through the conduits (6) and (7), respectively, from the supply tanks (4) and (5). The mixture reconditioned in this way is advantageously homogenized in a static mixer (25) and then sent to the mixer (10). Each solvent is recycled to its original tank when the solvent is separately separated.
然後將經由導管(20)回收之完全脫瀝青油發送至在本發明條件下利用之第二萃取器(37)中且使得可分離稱作輕DAO之輕脫瀝青油餾分(38)及稱作重DAO之重脫瀝青油餾分(39)。極性溶劑(27)及非極性溶劑(26)之混合物係在上游在藉由兩個各自單獨填充有極性溶劑(槽28)及非極性溶劑(槽29)之補給槽給料之混合器(34)中產生。極性及非極性溶劑可不同於在第一萃取器中所用之彼等。在兩個萃取器中所用極性及非極性溶劑相同之情形中，第二萃取器中所用溶劑混合物可藉由 兩個補給槽(4)及(5)給料。否則，第二萃取器中所用溶劑混合物係藉由兩個補給槽(28)及(29)給料。在另一恰當情形中，可僅利用非極性溶劑(26)。 The fully deasphalted oil recovered via conduit (20) is then sent to a second extractor (37) utilized under the conditions of the present invention and such that the lightly deasphalted oil fraction (38) referred to as light DAO can be separated and referred to as Heavy DAO heavy asphalt oil fraction (39). The mixture of the polar solvent (27) and the non-polar solvent (26) is upstream of the mixer (34) fed by two supply tanks each filled with a polar solvent (tank 28) and a non-polar solvent (tank 29). Produced in. The polar and non-polar solvents may differ from those used in the first extractor. In the case where the polar and non-polar solvents used in the two extractors are the same, the solvent mixture used in the second extractor can be used Two supply tanks (4) and (5) are fed. Otherwise, the solvent mixture used in the second extractor is fed through two supply tanks (28) and (29). In another suitable case, only non-polar solvents (26) may be utilized.
將以與至少部分非極性溶劑或本發明溶劑混合物之混合物萃取之稱作輕DAO之輕脫瀝青油餾分(38)發送至分離器(40)中，其中將稱作輕DAO之輕脫瀝青油(41)部分與本發明溶劑(45)分離或不分離。如上文所述在溶劑混合物情形中，在個別分離溶劑之情形中，該方法可包含第二分離器。有利地在分離器中在超臨界或次臨界條件下分離溶劑混合物或個別使用之溶劑。然後較佳將稱作輕DAO之輕脫瀝青油(41)發送至汽提塔(42)中，之後經由導管(43)回收。將源自汽提塔之溶劑經由導管(44)發送至管線(46)。 A light deasphalted oil fraction (38), referred to as light DAO, extracted with a mixture of at least a portion of the non-polar solvent or the solvent mixture of the present invention, is sent to a separator (40), which will be referred to as light DAO light deasphalted oil. Part (41) is separated or not separated from the solvent (45) of the present invention. In the case of a solvent mixture as described above, in the case of individual separation of the solvent, the method may comprise a second separator. The solvent mixture or the solvent used individually is advantageously separated in a separator under supercritical or subcritical conditions. The light deasphalted oil (41), referred to as light DAO, is then preferably sent to the stripper (42) and then recovered via conduit (43). The solvent from the stripper is sent via line (44) to line (46).
將呈與至少部分非極性溶劑或本發明溶劑混合物之混合物之萃取之稱作重DAO之重脫瀝青油餾分(39)發送至分離器(49)中，其中稱作重DAO之重脫瀝青油(50)與非極性溶劑或與本發明溶劑或僅與溶劑混合物中所含之非極性溶劑(53)分離。有利地在分離器中在超臨界或次臨界條件下分離溶劑混合物或個別使用之溶劑。然後較佳將稱作重DAO之重脫瀝青油(50)發送至汽提塔(51)中，之後經由導管(52)回收。將源自汽提塔之溶劑經由導管(54)發送至管線(46)。 The heavy deasphalted oil fraction (39), referred to as heavy DAO, extracted from a mixture of at least a portion of the non-polar solvent or the solvent mixture of the present invention, is sent to a separator (49), which is referred to as heavy DAO heavy deasphalted oil. (50) Separating from the non-polar solvent or the solvent of the present invention or only the non-polar solvent (53) contained in the solvent mixture. The solvent mixture or the solvent used individually is advantageously separated in a separator under supercritical or subcritical conditions. The heavy deasphalted oil (50), referred to as heavy DAO, is then preferably sent to the stripper (51) and then recovered via conduit (52). The solvent from the stripper is sent via line (54) to line (46).
在該方法中將源自汽提塔(42、51)之分離器(40、49)之溶劑有利地經由管線(46)內部再循環至萃取器(37)。在溶劑混合物情形中，較佳藉由密度計或折射計(47)線上檢驗極性及非極性溶劑之混合物之組成。根據第二萃取器中所用溶劑與第一萃取器中所用溶劑相同或不同視需要用自補給槽(28)及(29)或自補給槽(4)及(5)轉運之極性溶劑及非極性溶劑之補給再調節極性溶劑及非極性溶劑之比例。有利地將以此方式再調節之混合物在靜態型混合器(48)中勻漿化，之後發送至混合器(34)。在個別分離溶劑時，將每一溶劑再循環至其原始槽中。 In this process the solvent from the separator (40, 49) of the stripping column (42, 51) is advantageously recycled internally to the extractor (37) via line (46). In the case of a solvent mixture, the composition of the mixture of polar and non-polar solvents is preferably verified by a densitometer or refractometer (47). According to the solvent used in the second extractor, the same or different solvent used in the first extractor, if necessary, the polar solvent and non-polarity transported by the self-feeding tanks (28) and (29) or from the replenishing tanks (4) and (5) Replenishment of the solvent to adjust the ratio of the polar solvent to the non-polar solvent. The mixture reconditioned in this way is advantageously homogenized in a static mixer (48) and then sent to the mixer (34). Each solvent is recycled to its original tank when the solvent is separately separated.
圖2顯示本發明方法之圖解，該方法納入兩個分離器(17)及(20)，使得可個別分離溶劑並使其個別再循環至其各別槽中。因此，根據圖2，將使用爐及/或交換器(未顯示)預先加熱之進料(1)引入萃取器(13)(例如萃取塔，較佳混合器-沉降器)中。極性溶劑(3)與非極性溶劑(2)之混合物係在上游在藉由兩個各自單獨填充有極性溶劑(槽4)及非極性溶劑(槽5)之補給槽給料之混合器(10)中產生。將溶劑混合物(例如)在兩個不同位凖引入萃取器(13)中。將至少一部分溶劑混合物經由導管(11)以與經由導管(1)引入之進料之混合物發送至萃取器(13)中。將至少另一部分之溶劑混合物經由導管12直接發送至萃取器(13)中，其中在上文所定義之本發明條件下實施萃取。 Figure 2 shows an illustration of the process of the invention incorporating two separators (17) and (20) such that the solvents can be individually separated and individually recycled to their respective tanks. Thus, according to Figure 2, a preheated feed (1) using a furnace and/or exchanger (not shown) is introduced into an extractor (13) (e.g., an extraction column, preferably a mixer-settler). The mixture of the polar solvent (3) and the non-polar solvent (2) is upstream of the mixer (10) fed by two supply tanks each filled with a polar solvent (tank 4) and a non-polar solvent (tank 5). Produced in. The solvent mixture, for example, is introduced into the extractor (13) at two different positions. At least a portion of the solvent mixture is sent to the extractor (13) via a conduit (11) with a mixture of feeds introduced via conduit (1). At least another portion of the solvent mixture is sent directly to the extractor (13) via conduit 12, wherein the extraction is carried out under the conditions of the invention as defined above.
使用經由導管(14)發送之熔劑將至少部分亦含有本發明溶劑混合物之瀝青(16)以液體混合物形式或以分散固體形式自萃取器(13)抽出。瀝青(16)可經受與針對圖1所述相同之處理。 At least a portion of the bitumen (16) also containing the solvent mixture of the present invention is withdrawn from the extractor (13) as a liquid mixture or as a dispersed solid using a flux sent via conduit (14). The bitumen (16) can withstand the same treatment as described for Figure 1.
在第一萃取階段結束時，將呈與至少部分本發明溶劑混合物之混合物之稱作完全DAO之萃取完全脫瀝青油經由導管(15)發送至分離器(17)中，其中稱作完全DAO之完全脫瀝青油較佳與非極性溶劑(19)分離。有利地使非極性溶劑再循環至槽(5)中。然後將呈與極性溶劑之混合物之稱作完全DAO之完全脫瀝青油經由導管(18)發送至第二分離器(20)中，其中稱作完全DAO之完全脫瀝青油與發送至管線(26)之極性溶劑(21)分離。有利地在分離器中在超臨界或次臨界條件下分離溶劑。然後較佳將稱作完全DAO之完全脫瀝青油經由導管(22)發送至汽提塔(23)，之後經由導管(24)回收。將源自汽提塔之溶劑經由導管(25)發送至管線(26)。將源自分離器(20)及汽提塔(23)之極性溶劑經由管線(26)再循環至槽(4)中。 At the end of the first extraction stage, the extracted fully deasphalted oil, referred to as a complete DAO, in a mixture with at least a portion of the solvent mixture of the invention, is sent via conduit (15) to a separator (17), referred to as full DAO. The fully deasphalted oil is preferably separated from the non-polar solvent (19). The non-polar solvent is advantageously recycled to the tank (5). The fully deasphalted oil, referred to as the complete DAO, in a mixture with the polar solvent, is then sent via conduit (18) to a second separator (20) where a fully deasphalted oil called full DAO is sent to the pipeline (26). The polar solvent (21) is separated. The solvent is advantageously separated in a separator under supercritical or subcritical conditions. The fully deasphalted oil, referred to as fully DAO, is then preferably sent to the stripper (23) via conduit (22) and then recovered via conduit (24). The solvent from the stripper is sent via line (25) to line (26). The polar solvent from the separator (20) and the stripper (23) is recycled to the tank (4) via line (26).
然後將經由導管(24)回收之稱作完全DAO之完全脫瀝青油發送至第二萃取器(38)中。分離之脫瀝青油餾分經受與上文在圖1中所述相 同之處理。 The fully deasphalted oil, referred to as complete DAO, recovered via conduit (24) is then sent to the second extractor (38). The separated deasphalted oil fraction is subjected to the phase described above in Figure 1. Same treatment.
實例所選進料係源自加拿大北部阿薩巴斯卡之真空殘餘物。其化學特徵在表1中給出。 The selected feed for the example was derived from the vacuum residue of Athabasca in northern Canada. The chemical characteristics are given in Table 1.
實例1對應於如專利US 2008149534中所述習用二階段脫瀝青之實施。所選進料已經受使用石蠟型溶劑正庚烷之第一脫瀝青，然後所收集脫瀝青油C7 DAO已經受使用正丙烷之第二脫瀝青以獲得重DAO及輕DAO餾分。每一餾分之性質以及萃取產率歸納於表1中。 Example 1 corresponds to the practice of conventional two-stage deasphalting as described in the patent US 2008149534. The selected feed has been subjected to a first deasphalting using a paraffinic solvent, n-heptane, and the collected deasphalted oil C7 DAO has been subjected to a second deasphalting using n-propane to obtain a heavy DAO and a light DAO fraction. The nature of each fraction and the extraction yield are summarized in Table 1.
對於14%之C7瀝青質含量(根據標準NFT60-115量測)，C7 DAO之產率係75%。此顯示，一部分樹脂亦已經C7瀝青質萃取以構成瀝青。 For a 14% C7 asphaltene content (measured according to standard NFT 60-115), the yield of C7 DAO is 75%. This shows that a portion of the resin has also been extracted with C7 asphaltenes to form asphalt.
在此實例中，各種DAO之產率以及品質係藉由在兩個階段中之每一者中使用之石蠟型溶劑之性質來固定。 In this example, the yield and quality of the various DAOs are fixed by the nature of the paraffinic solvent used in each of the two stages.
所選進料經受根據本發明之選擇性二階段脫瀝青。第一萃取階段係用溶劑組合nC3(丙烷)/甲苯(36/65；v/v)在130℃之溫度下實施，溶劑/進料比率為5/1(v/m)。此第一階段已使得可自瀝青餾分選擇性萃取50%之C7瀝青質，同時使其瀝青產率最小化(10% m/m)(見表2)。第一階段使得可升級回收90%之殘餘物(脫瀝青油DAO產率為90%)。進料中之極性最強結構集中於瀝青餾分中。 The selected feed is subjected to selective two-stage deasphalting in accordance with the present invention. The first extraction stage was carried out with a solvent combination of nC3 (propane) / toluene (36/65; v/v) at a temperature of 130 ° C with a solvent/feed ratio of 5/1 (v/m). This first stage has enabled the selective extraction of 50% C7 asphaltenes from the bitumen fraction while minimizing the bitumen yield (10% m/m) (see Table 2). The first stage allows for an upgradeable recovery of 90% of the residue (deasphalted oil DAO yield is 90%). The most polar structure in the feed is concentrated in the bitumen fraction.
然後將源自第一脫瀝青階段之脫瀝青油DAO餾分與本發明之溶劑分離，之後經受第二萃取階段。1號及2號案例端視位於下游之單元之所需規範根據分離餾分之品質或設想產率闡釋方法靈活性。 The deasphalted oil DAO fraction from the first deasphalting stage is then separated from the solvent of the present invention and then subjected to a second extraction stage. Cases Nos. 1 and 2 look at the required specifications for the downstream unit to account for method flexibility based on the quality of the separated fraction or the envisaged yield.
用與實例2之第一階段相同之溶劑丙烷(nC3)及甲苯對源自第一脫瀝青階段之脫瀝青油DAO餾分實施第二萃取階段。在此1號案例中，丙烷(nC3)及甲苯之比例經調節以達成獲得稱作輕DAO之輕脫瀝青油之良好品質餾分之目標。該操作係用溶劑混合物nC3/甲苯(99.5/0.5；v/v)在120℃溫度下且以5/1(v/m)之溶劑/DAO比率來實施。稱作重DAO之重脫瀝青油餾分及稱作輕DAO之輕脫瀝青油餾分分別係以54%及36%之產率獲得(產率係參照初始進料殘餘物來計算)。所有結果皆歸納於表2中。 A second extraction stage was carried out on the deasphalted oil DAO fraction from the first deasphalting stage using the same solvent propane (nC3) and toluene as in the first stage of Example 2. In this case No. 1, the ratio of propane (nC3) and toluene was adjusted to achieve the goal of obtaining a good quality fraction of lightly deasphalted oil called light DAO. This operation was carried out with a solvent mixture nC3/toluene (99.5/0.5; v/v) at a temperature of 120 ° C and a solvent/DAO ratio of 5/1 (v/m). The heavy deasphalted oil fraction, referred to as heavy DAO, and the light deasphalted oil fraction, referred to as light DAO, were obtained in 54% and 36%, respectively (yield was calculated with reference to the initial feed residue). All results are summarized in Table 2.
*na：無法分析。 * na: Unable to analyze.
應注意，實例1中獲得之輕脫瀝青油餾分之品質與在根據本發明之輕脫瀝青油中所獲得者極為接近，且根據本發明之輕脫瀝青油之產率相同。 It should be noted that the quality of the lightly deasphalted oil fraction obtained in Example 1 is very close to that obtained in the light deasphalted oil according to the present invention, and the yield of the light deasphalted oil according to the present invention is the same.
根據本發明獲得之稱作重DAO之重脫瀝青油餾分係與最小極性樹脂及瀝青質一起富集。此餾分具有顯著芳香族性質及較稱作輕DAO之輕脫瀝青油餾分高之雜質(金屬、雜原子)濃度。若比較此餾分之性質與實例1之重脫瀝青油之性質，則應注意，其富含更多重結構但可升級回收，與實例1不同，在實例1中該等結構保持未升級回收，如同其含於瀝青餾分中一般。所產生可升級回收之稱作重DAO之重脫瀝青油之產率顯著改良(54%，與之相比，在實例1之習用SDA情形中為41%)。 The heavy deasphalted oil fraction referred to as heavy DAO obtained in accordance with the present invention is enriched with the least polar resin and asphaltenes. This fraction has significant aromatic properties and a higher concentration of impurities (metals, heteroatoms) than the light deasphalted oil fraction referred to as light DAO. If the properties of this fraction are compared with those of the heavy deasphalted oil of Example 1, it should be noted that it is rich in more heavy structures but can be upgraded and recycled. Unlike Example 1, in Example 1, the structures are not upgraded and recovered. As it is contained in the asphalt fraction. The yield of the re-de-asphalt oil produced by the upgradeable recovery, called heavy DAO, was significantly improved (54% compared to 41% in the case of the conventional SDA of Example 1).
用與實例2之第一階段相同之溶劑丙烷(nC3)及甲苯對源自第一脫瀝青階段之DAO實施第二萃取階段。在此2號案例中，丙烷(nC3)及甲苯之比例經調節以達成以高產率獲得稱作輕DAO之輕脫瀝青油之目標。該方法之第一階段之萃取條件保持不變。該操作係用溶劑混合物nC3/甲苯(72/28(v/v))來實施。溫度為125℃且溶劑/DAO比率為5/1 (v/m)。 A second extraction stage was carried out on the DAO derived from the first deasphalting stage using the same solvent propane (nC3) and toluene as in the first stage of Example 2. In this case No. 2, the ratio of propane (nC3) and toluene was adjusted to achieve the goal of obtaining a light deasphalted oil called light DAO in high yield. The extraction conditions of the first stage of the process remain unchanged. This operation was carried out with a solvent mixture of nC3/toluene (72/28 (v/v)). Temperature is 125 ° C and solvent / DAO ratio is 5 / 1 (v/m).
表3中所示結果顯示，稱作輕DAO之輕脫瀝青油餾分係以60%產率獲得，而非1號案例中之36%。另一方面，此脫瀝青油現含有一部分最小極性樹脂。因此，稱作重DAO之重脫瀝青油之產率自54%降低至30%(與1號案例相比)且其集中大部分最小極性瀝青質及極性最強之樹脂。端視其中納入本發明之系統之目標，可再循環並尋找此重脫瀝青油。 The results shown in Table 3 show that the light deasphalted oil fraction called light DAO was obtained in 60% yield, instead of 36% in the case of No. 1. On the other hand, this deasphalted oil now contains a portion of the smallest polar resin. Therefore, the yield of heavy deasphalted oil known as heavy DAO is reduced from 54% to 30% (compared to Case No. 1) and it concentrates most of the smallest polar asphaltenes and the most polar resins. Looking at the objectives in which the system of the invention is incorporated, the re-dewatering oil can be recycled and sought.
使用非極性/極性溶劑組合之優點在於，對於給定進料且對於給定系統之目標，能視需要且無限制地調節並優化源自脫瀝青階段之萃取餾分之產率(與習用脫瀝青不同)、產率/品質關係。溶劑之性質不再如習用脫瀝青情形中一般造成任何限制，此給予方法全面靈活性。 The advantage of using a non-polar/polar solvent combination is that, for a given feed and for a given system target, the yield of the extracted fraction derived from the deasphalting stage can be adjusted and optimized as needed (without deasphalting) Different), yield / quality relationship. The nature of the solvent is no longer as limited as is conventional in the case of conventional deasphalting, and the method of administration is fully flexible.
*na：無法分析。 * na: Unable to analyze.
1‧‧‧進料/導管 1‧‧‧Feed/catheter
2‧‧‧非極性溶劑 2‧‧‧Non-polar solvent
3‧‧‧極性溶劑 3‧‧‧Polar solvent
4‧‧‧補給槽 4‧‧‧Supply tank
5‧‧‧補給槽 5‧‧‧Supply tank
6‧‧‧導管 6‧‧‧ catheter
7‧‧‧導管 7‧‧‧ catheter
10‧‧‧混合器 10‧‧‧ Mixer
11‧‧‧導管 11‧‧‧ catheter
12‧‧‧導管 12‧‧‧ catheter
13‧‧‧萃取器 13‧‧‧ extractor
14‧‧‧導管 14‧‧‧ catheter
15‧‧‧導管 15‧‧‧ catheter
16‧‧‧瀝青 16‧‧‧Asphalt
17‧‧‧分離器 17‧‧‧Separator
18‧‧‧導管 18‧‧‧ catheter
19‧‧‧汽提塔 19‧‧‧Stripper
20‧‧‧導管 20‧‧‧ catheter
21‧‧‧導管 21‧‧‧ catheter
22‧‧‧溶劑混合物或溶劑混合物中所含非極性溶劑 22‧‧‧Non-polar solvents contained in solvent mixtures or solvent mixtures
23‧‧‧管線 23‧‧‧ pipeline
24‧‧‧密度計或折射計 24‧‧‧densitometer or refractometer
25‧‧‧靜態型混合器 25‧‧‧Static mixer
26‧‧‧非極性溶劑 26‧‧‧Non-polar solvents
27‧‧‧極性溶劑 27‧‧‧Polar solvent
28‧‧‧補給槽 28‧‧‧Supply tank
29‧‧‧補給槽 29‧‧‧Supply tank
34‧‧‧混合器 34‧‧‧ Mixer
37‧‧‧第二萃取器 37‧‧‧Second extractor
38‧‧‧稱作輕DAO之輕脫瀝青油餾分 38‧‧‧Light deasphalted oil fraction called light DAO
39‧‧‧稱作重DAO之重脫瀝青油餾分 39‧‧‧Re-de-asphalt oil fraction called heavy DAO
40‧‧‧分離器 40‧‧‧Separator
41‧‧‧稱作輕DAO之輕脫瀝青油 41‧‧‧Light deasphalting oil called light DAO
42‧‧‧汽提塔 42‧‧‧Stripper
43‧‧‧導管 43‧‧‧ catheter
44‧‧‧導管 44‧‧‧ catheter
45‧‧‧本發明溶劑 45‧‧‧Solvent of the invention
46‧‧‧管線 46‧‧‧ pipeline
47‧‧‧密度計或折射計 47‧‧‧densitometer or refractometer
48‧‧‧靜態型混合器 48‧‧‧Static mixer
49‧‧‧分離器 49‧‧‧Separator
50‧‧‧稱作重DAO之重脫瀝青油 50‧‧‧Re-de-asphalt oil called heavy DAO
51‧‧‧汽提塔 51‧‧‧Stripper
52‧‧‧導管 52‧‧‧ catheter
53‧‧‧非極性溶劑或本發明溶劑或溶劑混合物中所含非 53‧‧‧Non-polar solvents or non-containing solvents or solvent mixtures
極性溶劑 Polar solvent
54‧‧‧導管 54‧‧‧ catheter
Claims (15)
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| Application Number | Priority Date | Filing Date | Title |
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| FR1362028A FR3014109B1 (en) | 2013-12-03 | 2013-12-03 | SELECTIVE CASCADE DISASPHALTING METHOD |
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| TW201538705A true TW201538705A (en) | 2015-10-16 |
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| TW103142018A TW201538705A (en) | 2013-12-03 | 2014-12-03 | Process for selective cascade deasphalting |
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| US (1) | US20170029719A1 (en) |
| EP (1) | EP3077482A1 (en) |
| CN (1) | CN105765035B (en) |
| BR (1) | BR112016011247B1 (en) |
| EA (1) | EA201691103A1 (en) |
| FR (1) | FR3014109B1 (en) |
| MY (1) | MY189874A (en) |
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| CN109312239A (en) * | 2016-06-30 | 2019-02-05 | Ifp 新能源公司 | The method of processing hydrocarbon raw material including depitching step and pitch regulating step |
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| DE102016215809A1 (en) | 2016-08-23 | 2018-03-01 | Siemens Aktiengesellschaft | Monitoring a display of a cab of a means of transport |
| JP2020526630A (en) * | 2017-07-14 | 2020-08-31 | エクソンモービル リサーチ アンド エンジニアリング カンパニーＥｘｘｏｎ Ｒｅｓｅａｒｃｈ Ａｎｄ Ｅｎｇｉｎｅｅｒｉｎｇ Ｃｏｍｐａｎｙ | Formation of asphalt fractions from product deasphaltification |
| US10703994B2 (en) * | 2017-09-28 | 2020-07-07 | Uop Llc | Process and apparatus for two-stage deasphalting |
| CN114426778B (en) * | 2020-10-29 | 2022-12-16 | 中国石油化工股份有限公司 | Asphalt composition and preparation method thereof |
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| US3278415A (en) * | 1963-05-15 | 1966-10-11 | Chevron Res | Solvent deasphalting process |
| US3682815A (en) * | 1970-07-27 | 1972-08-08 | Union Oil Co | Duo-sol process with split feed of polar solvent |
| US4278529A (en) * | 1980-06-30 | 1981-07-14 | Kerr-Mcgee Refining Corporation | Process for separating bituminous materials with solvent recovery |
| US4493765A (en) * | 1983-06-06 | 1985-01-15 | Exxon Research And Engineering Co. | Selective separation of heavy oil using a mixture of polar and nonpolar solvents |
| US4686028A (en) * | 1985-04-05 | 1987-08-11 | Driesen Roger P Van | Upgrading of high boiling hydrocarbons |
| US5092983A (en) * | 1986-09-12 | 1992-03-03 | The Standard Oil Company | Process for separating extractable organic material from compositions comprising said extractable organic material intermixed with solids and water using a solvent mixture |
| US4940529A (en) * | 1989-07-18 | 1990-07-10 | Amoco Corporation | Catalytic cracking with deasphalted oil |
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| CN109312239A (en) * | 2016-06-30 | 2019-02-05 | Ifp 新能源公司 | The method of processing hydrocarbon raw material including depitching step and pitch regulating step |
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| CN105765035A (en) | 2016-07-13 |
| BR112016011247B1 (en) | 2020-12-29 |
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| EP3077482A1 (en) | 2016-10-12 |
| FR3014109B1 (en) | 2017-04-07 |
| WO2015082312A1 (en) | 2015-06-11 |
| FR3014109A1 (en) | 2015-06-05 |
| MY189874A (en) | 2022-03-15 |
| CN105765035B (en) | 2018-05-18 |
| EA201691103A1 (en) | 2016-09-30 |
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