JPH0374491A - Method for increasing the degree of conversion of vacuum residue - Google Patents
Method for increasing the degree of conversion of vacuum residueInfo
- Publication number
- JPH0374491A JPH0374491A JP15175690A JP15175690A JPH0374491A JP H0374491 A JPH0374491 A JP H0374491A JP 15175690 A JP15175690 A JP 15175690A JP 15175690 A JP15175690 A JP 15175690A JP H0374491 A JPH0374491 A JP H0374491A
- Authority
- JP
- Japan
- Prior art keywords
- vacuum
- solvent
- unconverted
- conversion
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 26
- 239000010426 asphalt Substances 0.000 claims abstract description 19
- 239000006184 cosolvent Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 230000002950 deficient Effects 0.000 claims abstract description 4
- 238000000605 extraction Methods 0.000 claims abstract description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000013049 sediment Substances 0.000 claims description 14
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012465 retentate Substances 0.000 claims 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 2
- 230000003134 recirculating effect Effects 0.000 claims 1
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CCPHAMSKHBDMDS-UHFFFAOYSA-N Chetoseminudin B Natural products C=1NC2=CC=CC=C2C=1CC1(SC)NC(=O)C(CO)(SC)N(C)C1=O CCPHAMSKHBDMDS-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
- C10G67/049—The hydrotreatment being a hydrocracking
Abstract
Description
【発明の詳細な説明】
本発明は、水素化分解法での真空蒸留残（真空残）の転
換方法に関する。より詳細には、真空残米処理原料の転
換（率）を増大するため、未転換の真空残を処理して大
部分の望ましくないアスファルトン（アスファルト）系
物質をそれから除去することに関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for converting a vacuum distillation residue (vacuum residue) in a hydrocracking process. More particularly, the present invention relates to treating unconverted vacuum residue to remove most of the undesirable asphalt-based materials therefrom in order to increase the conversion of the vacuum residue processing feedstock.
例えば水素化分解法において、重質真空類を転換する際
に、良好を、あるいは、より良い転換率を得るにあたっ
ての問題は、水素を欠くとともに微量金属（ｔｒａｃｅ
ｍｅｔａｌｓ）を高い含有量で有するアルファルトも
しくはアスファルト系物質の量である。より水素が欠乏
しているアスファルトの大部分を沸点１００Ｇ下以上の
物質から選択的に除去することにより、元来の真空残仕
込み原料の転換だけでなく、沸点１０００゜Ｆ以上の物
質の効率的な転換を大幅に改善することができる。For example, in hydrocracking processes, the problem with obtaining good or even better conversion rates when converting heavy vacuums is the lack of hydrogen and trace metals.
The amount of alphalt or asphalt-based material that has a high content of metals. By selectively removing most of the asphalt, which is more deficient in hydrogen, from substances with boiling points below 100G or higher, it is possible to not only convert the original vacuum residual feedstock, but also to efficiently convert substances with boiling points of 1000°F or higher. conversion can be significantly improved.
したがって、本発明の目的は、未転換の真空釜残を処理
して未処理の真空残の最適な転換率を得るための手段を
提供することである。It is therefore an object of the present invention to provide a means for processing unconverted vacuum bottoms to obtain an optimal conversion rate of the unconverted vacuum bottoms.
米国特許再発行第３２．２６５号は、少なくとも一つの
流動接触工程及び、水素化重質液の再循環物質を用いる
水素化方法を開示している。この重質液を３５０〜６０
０ ゜Ｆの温度に冷却してトルエン及びヘプタンに不溶
であるコークス先駆物質を再循環前に分離する。この分
離は、遠心分離、ろ過又は粒子状物質、例えば焼成コー
クスの床の使用によって改善することができる。U.S. Pat. 350~60% of this heavy liquid
Cooling to a temperature of 0°F separates coke precursors that are insoluble in toluene and heptane before recycling. This separation can be improved by centrifugation, filtration or the use of beds of particulate matter, such as calcined coke.
米国特許第４．４１１．７６８号は、沸騰させた触媒床
中で高沸点炭化水素物質をより低沸点の貴重な炭化水素
物質へと改質する方法であって、改質された生成物から
再循環物が回収されると、この再循環物の少なくとも２
５容量％が生成物の沸点９５０Ｔ以上の成分となる方法
において、比較的高率の転換を開示している。再循環流
を３５０７〜７００″Ｆの温度に冷却して、水素化域へ
と再び循環させる前に、粒子状固体の床上でコークス先
駆物質をこの再循環流から分離する。U.S. Pat. No. 4,411,768 discloses a process for reforming high boiling hydrocarbon materials into lower boiling valuable hydrocarbon materials in a boiled catalyst bed, the method comprising: When the recycle is collected, at least two
A relatively high conversion rate is disclosed in a process in which 5% by volume is a component of the product with a boiling point above 950T. The recycle stream is cooled to a temperature of 3507-700''F and the coke precursor is separated from the recycle stream over a bed of particulate solids before being recycled back to the hydrogenation zone.
米国特許第４．３０５．８１４号は、高温及び高圧下で
溶媒を用いる。炭化水素系物質を多様な留分へと分離す
るための、エネルギー効率の優れた方法を開示している
。溶媒の組成は、３〜９個の炭素原子を含むパラフィン
系炭化水素類、４〜８個の炭素原子を含むモノオレフィ
ン炭化水素類、約３５０下未満の通常の沸点を有する芳
香族炭化水素類及び３〜９個の炭素原子を含むアルコー
ル類からなる群から選択される少なくヒも一種を含む、
優れた再循環特性を有する脱歴された油状物を得るため
に除去すべきアスファルト又は沈降物の具体的な量は開
示されていない。US Pat. No. 4,305,814 uses a solvent at high temperature and pressure. An energy-efficient method for separating hydrocarbon-based materials into various fractions is disclosed. The composition of the solvent is paraffinic hydrocarbons containing 3 to 9 carbon atoms, monoolefinic hydrocarbons containing 4 to 8 carbon atoms, aromatic hydrocarbons having a normal boiling point below about 350 and at least one selected from the group consisting of alcohols containing 3 to 9 carbon atoms,
The specific amount of asphalt or sediment that must be removed to obtain a deasphalted oil with excellent recycling properties is not disclosed.
米国特許第４，５０２．９４４号は、油状物、樹脂及び
アスファルトからなる加工物を少なくとも三種の留分へ
と分離する方法を開示している。この方法は、高温及び
高圧の条件下、軽質有機溶媒（少なくとも約３：ｌの溶
媒／加工物の比率において好ましくは３〜８個の炭素原
子を有するパラフィン系炭化水素類）を用いる。米国特
許第４．３０５．Ｉ！１１４号におけるように、優れた
再循環特性を有する脱歴された油状物を得るために除去
すべきアスファルト又は沈降物の具体的な量は開示され
ていない。U.S. Pat. No. 4,502,944 discloses a process for separating a workpiece consisting of oils, resins and asphalt into at least three fractions. This method uses light organic solvents (paraffinic hydrocarbons preferably having 3 to 8 carbon atoms in a solvent/workpiece ratio of at least about 3:1) under conditions of high temperature and pressure. U.S. Patent No. 4.305. I! As in No. 114, the specific amount of asphalt or sediment to be removed to obtain a deasphalted oil with excellent recycling properties is not disclosed.
米国特許第３．４１２．０１０号は、水素化分解能中の
真空残の転換を、６８０〜９７５″Ｆでの留分及び９７
５下以上での残を反応容器へと再循環させることによっ
て改善することを開示している。再循環流中のコークス
先駆物質又はアスファルトの除去については言及してい
ない。U.S. Pat.
It is disclosed that the improvement is achieved by recycling the residue below 5 to the reaction vessel. There is no mention of removal of coke precursors or asphalt in the recycle stream.
米国特許第３．９０Ｓ、８９２号は、真空残を水素化分
解するための方法であって、脱歴した後に、沸点９７５
７以上の生成物を再循環させることができる方法を開示
している。後者を部分的に酸化させ、水素化分解容器用
の補給水素を提供するための水素を生じさせる。脱歴さ
れた油状物を再循環させる際の生成物の収率に対する脱
歴条件の効果は開示されていない。U.S. Pat.
A method is disclosed in which more than 7 products can be recycled. The latter is partially oxidized to produce hydrogen to provide make-up hydrogen for the hydrocracking vessel. The effect of deasphalting conditions on product yield when recycling deasphalted oil is not disclosed.
米国特許第４．４５７．８３０号は、アスファルト前駆
体を沈殿及び分解させ、固体類をともに沈殿させるため
の無機酸の使用を開示している。脱歴された油状物が際
循環される場合の、生成物の収量に及ぼす脱歴条件の影
響は開示されていない。US Pat. No. 4,457,830 discloses the use of inorganic acids to precipitate and decompose asphalt precursors and co-precipitate solids. The effect of deasphalting conditions on product yield is not disclosed when the deasphalted oil is recycled.
本発明は、真空残原料を改質し、残る真空残原料から留
出物を回収及び分離し、未転換の真空釜残を改質域へと
再循環させることからなる、水素化分解法での真空残原
料の転換のための方法における改善を提供する。この改
善は、再循環流中のアスファルト含有の未転換真空釜残
を、抽出域中で共溶媒（ｃｏｓｏｌｖｅｎｔ）を用いて
、周囲条件から関連温度（及び共溶媒を液状に維持する
のに充分な圧力）下で処理することによって脱歴し、大
部分の望ましくない水素欠乏のアスファルトを未転換真
空釜残から選択的に除去して真空残原料全体としての転
換率を増大することからなる。The present invention is a hydrocracking process that consists of reforming the vacuum bottoms feedstock, recovering and separating distillate from the remaining vacuum bottoms feedstock, and recycling the unconverted vacuum bottoms to the reforming zone. Provided are improvements in methods for conversion of vacuum residue materials. This improvement utilizes a cosolvent in the extraction zone to move the asphalt-containing unconverted vacuum bottoms in the recycle stream from ambient conditions to the relevant temperature (and sufficient temperature to maintain the cosolvent in liquid form). deasphalting by treatment under pressure) to selectively remove most of the undesired hydrogen-depleted asphalt from the unconverted vacuum bottoms to increase the overall conversion of the vacuum bottoms.
未処理の真空残の有用な生成物への転換を改善するため
の本発明は、未転換の真空残を反応流出液中の分解され
た反応留出物から分離した後、その未転換の真空残を処
理することを考案する。そして、大部分の望□ましくな
い水素欠乏のアスファルト及び大部分の微量金属を比較
的少なく含有する、処理された真空釜残を反応域に再循
環させ、これを追加量の目的留出物、すなわちナフサ、
ディーゼル燃料及び減圧軽油へと転換させる。後者の気
流を流動触媒分解器に仕込むための原料成分として用い
ることにより、さらなるナフサ及びディーゼル燃料を製
造する。The present invention for improving the conversion of unconverted vacuum residues into useful products provides a method for improving the conversion of unconverted vacuum residues into useful products after separating the unconverted vacuum residues from the cracked reaction distillate in the reaction effluent. Come up with a way to deal with the leftovers. The treated vacuum bottoms, which are relatively low in most of the undesirable hydrogen-depleted asphalt and most trace metals, are then recycled to the reaction zone and used to produce an additional amount of target distillate. , i.e. naphtha,
Conversion to diesel fuel and vacuum gas oil. The latter gas stream is used as a feedstock component to feed a fluidized catalytic cracker to produce additional naphtha and diesel fuel.
真空残原料を目的の留出物へと転換する全過程において
、本発明によってもたらされる改善は、未転換の真空釜
残を共溶媒で処理して、不要な水素欠乏のアスファルト
の大部分を、それがさらなる水素化分解のために反応容
器、すなわち反応域へと再循環される前に、真空釜残か
ら選択的に除去することである。In the entire process of converting vacuum residue feedstock to the desired distillate, the improvement brought about by the present invention is that the unconverted vacuum residue is treated with a co-solvent to remove most of the unwanted hydrogen-depleted asphalt. It is selectively removed from the vacuum bottoms before it is recycled to the reaction vessel, ie, reaction zone, for further hydrocracking.
共溶媒での処理の結果、選択的に除去される大部分の望
ましくない水素欠乏のアスファルトの量は、約１０％〜
約２０％の範囲である。The amount of mostly undesirable hydrogen-deficient asphalt selectively removed as a result of treatment with co-solvents ranges from about 10% to
The range is about 20%.
未転換の真空釜残を共溶媒で処理することにおいては、
使用される共溶媒の量は、共溶媒と未転換の真空釜残と
の容量比として定義され、約１：１〜約４０：１の範囲
である。In treating unconverted vacuum pot residue with a co-solvent,
The amount of co-solvent used is defined as the volume ratio of co-solvent to unconverted vacuum bottoms and ranges from about 1:1 to about 40:1.
本発明に従って使用することができる共溶媒には、個々
の溶媒、例えばれ−ベンクンらしくはｎ−ヘプタン、（
ＣＳ〜Ｃ，）パラフィン類又は（Ｃ，〜Ｃ，）ナフテン
類と（Ｃ６〜Ｃ，）芳香族類との混合物がある。芳香族
類はベンゼン及びトルエンである。Co-solvents that can be used according to the invention include individual solvents such as n-heptane,
There are mixtures of CS-C,) paraffins or (C,-C,) naphthenes and (C6-C,) aromatics. Aromatics are benzene and toluene.
ｎ−ヘプタンでの脱歴の利点を示すため、未処理の未転
換真空釜残の試料及びその未転換真空釜残試料からの種
々の脱歴された油状物を、連続撹拌槽反応容器（ＣＳＴ
Ｒ）中、０．１３ ｂｂｌ／ｌｂ／日の触媒空間速度及
び７９５．８０５そして８１５７へと連続する温度にて
、市販のＮｉＭｏ／Ａβ３０．の定常活性に類似するＭ
Ｏ／ Ａ Ａ ＊ Ｏ＊触媒上で処理した。Ｃ５ＴＲ
の圧力を水素で２．２５０ ｐｓｉｇに維持し、）Ｉｓ
処理速度を７．０ＯＯＳＣＦ／ｂｂｌとした。未処理か
つ未転換の真空釜残及び、トルエン、シクロヘキサン及
びｎ−ヘプタンで個々に脱歴されたその未転換真空釜残
の試料を処理すると、以下の結果が得られた。To demonstrate the benefits of deasphalting with n-heptane, a sample of untreated unconverted vacuum bottoms and various deasphalted oils from the unconverted vacuum bottoms sample were placed in a continuous stirred tank reactor (CST).
R) at catalyst space velocity of 0.13 bbl/lb/day and temperatures ranging from 795.805 to 8157. M similar to the steady-state activity of
O/AA* Treated over O* catalyst. C5TR
The pressure of )Is is maintained at 2.250 psig with hydrogen,
The processing speed was set to 7.0 OOSCF/bbl. The following results were obtained when processing a sample of the untreated and unconverted vacuum bottoms and that unconverted vacuum bottoms that had been individually deasphalted with toluene, cyclohexane, and n-heptane.
上記の結果は、ｎ−ヘプタンで脱歴された真空釜′ｇｉ
（ｆ）ＡＶＢ）試料が、沸点１０００″Ｆ以上の成分を
改質することを意図した残留物水素化分解法について再
１１１流の大幅な改善をちたらすということを示す、一
定の温度で可能である転換率が増大されるだけでなく、
実質的に沈降物の形成が存在しない、後者は、触媒の被
毒を減少させ、反応域の下流にある流量制御弁、熱交換
器及び分離容器中の沈降物の形成及び沈着が原因である
詰まり問題を解消することから、非常に重要である。さ
らに、真空釜残再循環流をｎ−ヘプタンで脱歴すると、
他の溶媒で脱歴した場合に対比して、反応容器の温度を
少なくとｔｌｏｌ上下させることができ、追加的な沈降
物を形成することなく、水素化分解での転換をさらに改
善する。The above results were obtained using a vacuum kettle deasphalted with n-heptane.
(f) AVB) Samples show that the sample yields a significant improvement in re-111 flow for residue hydrocracking processes intended to reform components with boiling points above 1000"F, possible at a given temperature. Not only is the conversion rate increased, but
Virtually no sediment formation, the latter reducing poisoning of the catalyst and due to sediment formation and deposition in flow control valves, heat exchangers and separation vessels downstream of the reaction zone This is very important because it solves the clogging problem. Furthermore, when the vacuum kettle recycle stream is deasphalted with n-heptane,
Compared to deasphalting with other solvents, the temperature of the reaction vessel can be raised or lowered by less than a troll, further improving the conversion in hydrocracking without forming additional precipitates.
トルエンでの真空釜残の脱歴は、未処理の真空釜残と比
較して、沸点１０００゜Ｆ以上の成分全体の転換率にお
いて無視しつるほどの改善しか示さず、トルエンでのソ
ックスレー抽出によって測定されるように、沈降物形成
の減少において実質的に改善を示さない、一方、シクロ
ヘキサンで脱歴された真空釜残は、未処理の、あるいは
、トルエンで脱歴された真空釜残と比較して転換率が相
当に改善されているが、１０００″Ｆを超える沸点を有
する成分全体の転換率を向上させるために反応容器の温
度を上昇させるにつれ、反応容器からの流出液中に沈降
物が形成しはじめるという点で、中間の重要な再循環流
を与える。Deasphalting of vacuum bottoms with toluene showed negligible improvement in overall conversion of components boiling above 1000°F compared to untreated vacuum bottoms, and Soxhlet extraction with toluene As measured, vacuum bottoms deasphalted with cyclohexane show no substantial improvement in reducing sediment formation compared to untreated or toluene deasphalted bottoms. However, as the temperature of the reactor is increased to improve the overall conversion of components with boiling points above 1000"F, sedimentation occurs in the effluent from the reactor. begins to form, providing an important intermediate recirculation flow.
三種の基本的炭化水素類のそれぞれから選択される溶媒
を用い、周囲条件下、２０：１の溶媒／真空釜残（ＶＢ
）試料の用量比で特定のＶＢ試料から除去された沈降物
の相対量に注目することは興味深い。20:1 solvent/vacuum bottoms (VB) under ambient conditions using a solvent selected from each of the three basic hydrocarbons.
) It is interesting to note the relative amount of sediment removed from a particular VB sample with sample dose ratio.
火隆艷二盈盈旦上
トルエンでの脱歴 ＜０．５シクロヘキサン
での脱歴 ６〜７
ｎ−ヘプタノでの脱歴 １５〜１６脱歴に使用さ
れるｎ−パラフィンがより軽質になるにつれ、より多量
の沈降物（アスファルト、他の炭素系物質及び微量金属
からなる）が真空又は大気圧での残留物から除去される
ということは、当接術においては周知である０例えば、
この同一の真空釜残試料をｎ−ペンクンで脱歴すると、
２０〜２２．！！量％の沈降物が除去された。この目的
は、可能な限り少量の沈降物を除去しながらも、なお、
それ以上の沈降物を形成することなく、沸点１０００″
Ｆ以上の物質全体の転換率を改善することである。As the n-paraffins used for deasphalting become lighter, It is well known in abutment technology that larger amounts of sediment (consisting of asphalt, other carbon-based materials and trace metals) are removed from the residue in vacuum or at atmospheric pressure.
When this same vacuum pot residue sample is deasphalted with n-penkun,
20-22. ! ! % of sediment was removed. The aim is to remove as little sediment as possible while still
Boiling point 100″ without forming further sediment
The objective is to improve the overall conversion rate of F or higher substances.
確かに、ｎ−ヘプタンで脱歴された真空釜残がさらなる
沈降物をもたらすことなく転換率を改善するならば、ｎ
−ペンタンで脱歴された真空釜残もまた同程度の効果を
示すであろうが、除去されるべき追加量のアスファルト
が存在するであろう、したがって、ｎ−ヘプタンでの脱
歴は、パラフィン類、ナフテン類及び芳香族類からなる
混合溶媒を使用する場合、一定の真空釜残流につき、ど
れほどのアスファルト相を除去すべきかを測定するため
の基準を提供する。Indeed, if vacuum bottoms deasphalted with n-heptane improve conversion without introducing further sediment, then n
- Vacuum bottoms deasphalted with pentane would also be as effective, but there would be an additional amount of asphalt to be removed, so deasphalting with n-heptane When using a mixed solvent consisting of esters, naphthenes, and aromatics, it provides a basis for determining how much asphalt phase should be removed for a given vacuum kettle bottom stream.
必要以上の沈降物を除去しないことのもう一つの理由は
、縮合芳香族類の数がより少ないために、比較的高比率
の水素及び比較的少量の炭素を含有する軽質のアスファ
ルトを除去してしまうことを回避するためである。この
軽質のアスファルトはより容易に分解し、したがって、
沸点１０００゜Ｆ以上の成分全体の転換率を改善するよ
う作用する。脱歴された真空釜残（ＶＢ）試料の主要な
分析上の指標のいくつかを表ＩＩにまとめた。Another reason for not removing more sediment than necessary is that lighter asphalts, which contain a relatively high proportion of hydrogen and a relatively small amount of carbon, may be removed due to the lower number of condensed aromatics. This is to avoid putting it away. This lighter asphalt breaks down more easily and therefore
It acts to improve the overall conversion of components with boiling points above 1000°F. Some of the key analytical indicators of deasphalted vacuum bottoms (VB) samples are summarized in Table II.
未処理’Ｖ Ｂ
トルエンＤＡＶＢ
シクロヘキサンＤＡＶＢ
ｎ−ヘプタンＤＡＶＢ
ｎ−ペンタンＤＡＶＢ
２２．５
２２．３
１８．１
１２．３
１０．４
水素／炭素
−ｍ
ｏ、１１４０
０．１１５６
０．１２１１
０．１３４１
８
９
３
く５
く５
下記の表ｎｌでは、商業上の用途をより近似に模倣する
ため、最初の例で説明したように、未処理の試料及びｎ
−ヘプタンで脱歴された真空釜残の試料を、未処理の真
空残原料と混合させ、Ｃ５ＴＲ中で処理した。この混合
物は、未処理のＶＢ（又はｎ−ヘプタンＤＡＶＢ）１重
量部及び未処理の真空類２重量部からなっていた。結果
は、温度を８１５７に上昇させるこヒによって水素化分
解容器の過酷さが増大するにつれ、ｎ−ヘプタンＤＡＶ
Ｂは、さらなる沈降物を生じさせることなく、沸点１０
００７以上の物質の転換率を増大させることができたと
いうことを示す、そのうえ、この同一の真空釜残試料な
ｎ−ヘプタンで脱歴することにより１反応容器の温度を
少なくともさらに１０″Ｆ上昇させ、さらなる沈降物を
形成させることなく、転換率の増大を達成することがで
きた。Untreated 'V B Toluene DAVB Cyclohexane DAVB n-heptane DAVB n-pentane DAVB 22.5 22.3 18.1 12.3 10.4 Hydrogen/carbon-mo, 1140 0.1156 0.1211 0.1341 8 9 3 ku5 ku5 In the table nl below, to more closely mimic commercial applications, the untreated sample and
- A sample of heptane deasphalted vacuum bottoms was mixed with untreated vacuum bottoms feed and processed in a C5TR. This mixture consisted of 1 part by weight of untreated VB (or n-heptane DAVB) and 2 parts by weight of untreated vacuum. The results show that as the severity of the hydrocracking vessel increases by increasing the temperature to 8157, the n-heptane DAV
B has a boiling point of 10 without producing further sediment.
Furthermore, the temperature of one reaction vessel was increased by at least an additional 10"F by deasphalting this same vacuum bottoms sample with n-heptane. It was possible to achieve an increase in conversion without the formation of further precipitates.
■ １、ｌ ζ 未使用真空類を含む 未処理の Ｂ 未使用真空類を含む ｎ−ヘプタン脱歴の ＶＢ再循環物 温」ＬユニＥ１ １点１０００″Ｆ以上の物質 つ計算された全転換量 ％ ９５ ０５ １５ ９５ ０５ １５ ２５ 汰ＪＪＬ辺」Ｌ△■ 1, l ζ Including unused vacuum equipment untreated B Including unused vacuum equipment n-heptane withdrawal VB recycle material On” L Uni E1 Substances with a temperature of 1000″F or more per item total conversion amount calculated % 95 05 15 95 05 15 25 TAJJL side”L△
Claims (1)
分解域から留出物を回収及び分離し、未転換の真空釜残
の液流を水素化分解域へと再循環させることからなる、
水素化分解法における真空残原料の転換を増大する方法
であって、再循環流中の未転換の真空釜残を、抽出域に
おいて共溶媒を用いて、周囲温度又は高温で、共溶媒を
液状に維持するのに充分な圧力下で処理することによっ
て脱歴し、大部分の望ましくない沈降物を該未転換真空
残液から選択的に除去して該真空残原料の転換を増大す
ることを特徴とする方法。 ２ 該共溶媒がｎ−ヘプタンである請求項１記載の方法
。 ３ ｎ−ヘプタンと未転換の真空釜残との容量比が１：
１〜４０：１である請求項２記載の方法。 ４ 共溶媒が、（Ｃ＿５〜Ｃ＿７）パラフィン類、（Ｃ
＿５〜Ｃ＿６）ナフテン類及び（Ｃ＿６〜Ｃ＿７）芳香
族類から選択される炭化水素類の混合物である請求項１
記載の方法。 ５ パラフィン類がｎ−ペンタン、ｎ−ヘキサン及びｎ
−ヘプタンであり、芳香族類がトルエン及びベンゼンで
ある請求項４記載の方法。 ６ 未転換の真空釜残を、周囲温度〜７００゜Ｆ（３７
１℃）の温度下、共溶媒で処理する請求項１〜５のいず
れか一項に記載の方法。 ７ 温度が１５０〜６５０゜Ｆ（６５．５〜３４３℃）
である請求項６記載の方法。 ８ 圧力が１〜６０気圧（０．１０〜６．０８ＭＰａ）
である請求項１〜７のいずれか一項に記載の方法。 ９ 圧力が１〜４０気圧（０．１０〜４．０５ＭＰａ）
である請求項８記載の方法。 １０ 選択的に除去される、大部分の望ましくない水素
欠乏のアスファルトの量が１０〜２０％である請求項１
〜９のいずれか一項に記載の方法。[Claims] 1. Hydrocracking the vacuum residue feedstock in a hydrocracking zone, recovering and separating the distillate from the hydrocracking zone, and sending a liquid stream of unconverted vacuum pot residue to the hydrocracking zone. consisting of recirculating and
A method of increasing the conversion of vacuum bottoms in a hydrocracking process, comprising: converting unconverted vacuum bottoms in a recycle stream into a liquid state using a co-solvent in an extraction zone at ambient or elevated temperature; deasphalting by processing under a pressure sufficient to maintain the temperature of the vacuum retentate to selectively remove most undesired sediment from the unconverted vacuum retentate to increase the conversion of the vacuum retentate. How to characterize it. 2. The method of claim 1, wherein the co-solvent is n-heptane. 3 The volume ratio of n-heptane and unconverted vacuum pot residue is 1:
3. The method of claim 2, wherein the ratio is 1 to 40:1. 4 The co-solvent is (C_5-C_7) paraffins, (C
Claim 1 which is a mixture of hydrocarbons selected from __5-C_6) naphthenes and (C_6-C_7) aromatics.
Method described. 5 Paraffins include n-pentane, n-hexane and n-
-heptane and the aromatics are toluene and benzene. 6. Place unconverted vacuum pot residue at ambient temperature to 700°F (37°F).
6. The method according to claim 1, wherein the treatment is carried out with a co-solvent at a temperature of 1[deg.] C.). 7 Temperature is 150-650°F (65.5-343°C)
The method according to claim 6. 8 Pressure is 1 to 60 atmospheres (0.10 to 6.08 MPa)
The method according to any one of claims 1 to 7. 9 Pressure is 1 to 40 atmospheres (0.10 to 4.05 MPa)
The method according to claim 8. 10. Claim 1, wherein the amount of predominantly undesirable hydrogen-deficient asphalt selectively removed is 10-20%.
10. The method according to any one of 1 to 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US36429789A | 1989-06-12 | 1989-06-12 | |
| US364297 | 1989-06-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0374491A true JPH0374491A (en) | 1991-03-29 |
Family
ID=23433885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15175690A Pending JPH0374491A (en) | 1989-06-12 | 1990-06-12 | Method for increasing the degree of conversion of vacuum residue |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0403087A1 (en) |
| JP (1) | JPH0374491A (en) |
| CA (1) | CA2010774A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2906813A1 (en) * | 2006-10-06 | 2008-04-11 | Inst Francais Du Petrole | Heavy petroleum feed e.g. vacuum residue, hydroconverting method for producing petrol, involves de-asphalting vacuum residue to obtain de-asphalted oil, and recycling totality of oil by hydroconversion |
| US8287720B2 (en) | 2009-06-23 | 2012-10-16 | Lummus Technology Inc. | Multistage resid hydrocracking |
| US9777226B2 (en) | 2014-09-08 | 2017-10-03 | Uop Llc | Methods and systems for slurry hydrocracking with reduced feed bypass |
| US10479947B2 (en) | 2014-10-07 | 2019-11-19 | Shell Oil Company | Hydrocracking process integrated with solvent deasphalting to reduce heavy polycyclic aromatic buildup in heavy oil hydrocracker recycle stream |
| CN107966347B (en) * | 2016-10-20 | 2020-07-24 | 中国石油化工股份有限公司 | Extract liquid for soluble matters of waterproof coiled material and application thereof |
| US11180701B2 (en) | 2019-08-02 | 2021-11-23 | Saudi Arabian Oil Company | Hydrocracking process and system including separation of heavy poly nuclear aromatics from recycle by extraction |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3905892A (en) * | 1972-03-01 | 1975-09-16 | Cities Service Res & Dev Co | Process for reduction of high sulfur residue |
| CA1222471A (en) * | 1985-06-28 | 1987-06-02 | H. John Woods | Process for improving the yield of distillables in hydrogen donor diluent cracking |
-
1990
- 1990-02-23 CA CA 2010774 patent/CA2010774A1/en not_active Abandoned
- 1990-05-18 EP EP90305447A patent/EP0403087A1/en not_active Withdrawn
- 1990-06-12 JP JP15175690A patent/JPH0374491A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CA2010774A1 (en) | 1990-12-12 |
| EP0403087A1 (en) | 1990-12-19 |
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