EP0792928A2 - Procédé de récupération d'aromates à partir d'essence de reforming et appareillage pour réaliser ce procédé - Google Patents

Procédé de récupération d'aromates à partir d'essence de reforming et appareillage pour réaliser ce procédé Download PDF

Info

Publication number
EP0792928A2
EP0792928A2 EP96120033A EP96120033A EP0792928A2 EP 0792928 A2 EP0792928 A2 EP 0792928A2 EP 96120033 A EP96120033 A EP 96120033A EP 96120033 A EP96120033 A EP 96120033A EP 0792928 A2 EP0792928 A2 EP 0792928A2
Authority
EP
European Patent Office
Prior art keywords
aromatics
hydrogenation
extraction
liquid
reformate
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.)
Granted
Application number
EP96120033A
Other languages
German (de)
English (en)
Other versions
EP0792928B1 (fr
EP0792928A3 (fr
Inventor
Gerd Emmrich
Hans-Christoph Schneider
Helmut Dr. Gehrke
Bernard Dr. Firnhaber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
Krupp Uhde GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Krupp Uhde GmbH filed Critical Krupp Uhde GmbH
Publication of EP0792928A2 publication Critical patent/EP0792928A2/fr
Publication of EP0792928A3 publication Critical patent/EP0792928A3/fr
Application granted granted Critical
Publication of EP0792928B1 publication Critical patent/EP0792928B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—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
    • C10G67/0409—Extraction of unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/08—Azeotropic or extractive distillation

Definitions

  • the invention relates to a method for obtaining pure aromatics from reformate gasoline.
  • the invention further relates to an apparatus for performing the method.
  • - Reformate gasoline is a gasoline rich in aromatics, which is produced by reforming, in particular catalytic reforming, crude oil fractions. When reforming, isomerizations, rearrangements, cyclizations, dehydrogenations and similar reactions take place on the alkanes and cycloalkanes contained in the petroleum or crude oil.
  • Aromatic-rich reformate gasoline produced in catalytic reforming is an important starting material for the production of aromatics.
  • Aromatics in particular benzene, toluene, xylenes and ethylbenzene, are important starting materials for the chemical industry, especially for the production of plastics and man-made fibers. Aromatics are also used as octane boosters in gasoline. Due to the increasing demand for aromatics in the chemical industry, the reaction conditions and the catalyst used in catalytic reforming of crude oil fractions are geared towards a high aromatics yield. However, this also results in a higher proportion of unsaturated non-aromatics, in particular olefins. However, the chemical industry primarily requires pure aromatics, ie aromatics that have as little contamination of unsaturated non-aromatics as possible.
  • the bromine index and the acid color number serve as a measure of the degree of purity of the aromatics, in particular also for pure benzene, and thus as a measure of the contamination with unsaturated non-aromatics.
  • the bromine index of pure benzene should not exceed the limit of 20 and the acid color number should not exceed the limit of 1.
  • the aromatics-containing mixtures are first subjected to an extractive distillation or a liquid-liquid extraction to remove the aromatics.
  • the aromatic fractions obtained during the extraction have to be post-treated in a complex manner.
  • chemical post-treatment is carried out either by washing with concentrated sulfuric acid or by treating the fraction with bleaching earth. Both chemical aftertreatment processes are complex and costly.
  • the acid sludge that arises during the sulfuric acid washing is difficult and expensive to dispose of.
  • the reaction with bleaching earth takes place at higher temperatures and leads to the formation of polymers which adhere to the bleaching earth.
  • oligomers are formed from unsaturated olefinic non-aromatics, which require a relatively high acid color number. Subsequent to Bleaching earth treatment therefore requires a complex separation of the pure aromatics from the non-aromatics by distillation, which causes high costs.
  • the invention is based on the technical problem of specifying a method of the type mentioned at the outset with which aromatics of high purity can be obtained, which meet all requirements with regard to the purity requirements required by the industry, in particular with regard to the bromine index and acid color number, and which method is suitable In addition to functional reliability, it is also characterized by simplicity and low cost.
  • the invention is also based on the technical problem of specifying a device for carrying out this method.
  • the invention teaches a process for obtaining pure aromatics from reformate gasoline, wherein the reformate gasoline is selectively hydrogenated in a first process step and the hydrogenation conditions are adjusted so that essentially non-aromatics, in particular olefins, diolefins and triolefins, are hydrogenated. and then in a second process stage the selectively hydrogenated and aromatics-containing products from the first process stage by extractive distillation and / or liquid-liquid extraction in aromatics and non-aromatics be separated.
  • reformate gasoline also means mixtures containing reformate gasoline or reformate cuts or distillation cuts from reformate gasoline.
  • the invention is based on the knowledge that by combining the selective hydrogenation of the unsaturated non-aromatics in reformate gasoline, in particular the olefins, diolefins and triolefins, on the one hand, and the extractive distillation and / or liquid-liquid extraction of the product from the hydrogenation, on the other hand, aromatics with very high degree of purity can be obtained.
  • the invention is further based on the knowledge that, in the extraction process for obtaining pure aromatics known from practice, which is described at the outset, the high acid color number of the extraction product is caused in particular by the olefins and a high acid color number is brought about even with a very low diolefin content.
  • these olefins in particular are selectively hydrogenated in a hydrogenation stage upstream of the extraction stage.
  • the combination of selective hydrogenation and downstream extractive distillation and / or liquid-liquid extraction gives aromatics in which the bromine index is below 20 and the Acid color number is below 1.
  • the pure aromatics obtained with the process according to the invention satisfy all requirements of the chemical industry with regard to the bromine uptake and the acid color number.
  • the process is both inexpensive and inexpensive. Therefore, considerable advantages are achieved compared to the methods known from practice.
  • a reformate cut is used as the reformate gasoline, which essentially contains benzene as the aromatic component.
  • the reformate gasoline is first subjected to a fractional distillation before the selective hydrogenation, so that the reformate cut obtained in this way contains essentially only aromatic benzene.
  • This embodiment of the method according to the invention is distinguished by the advantage that, on the one hand, the reformate gasoline is de-benzeneed and, on the other hand, pure benzene can be obtained, which is of considerable importance for the chemical industry.
  • a reformate cut with aromatics of a selected carbon number C x or with aromatics of several selected carbon numbers C x , C y ... is used as reformate gasoline .
  • Such a reformate cut or distillation cut is obtained by fractional distillation from reformate gasoline, aromatics of other carbon numbers being separated off essentially by distillation.
  • the reformate section contains only aromatics with a carbon number, for example C 6 or C 8 aromatics.
  • the reformate section contains aromatics with two or three carbon numbers, the boiling points of these aromatics preferably being in the boiling range of benzene, toluene or the xylenes.
  • the embodiments of the process according to the invention according to patent claims 2 and 3 are distinguished by the advantage that particularly pure aromatics can be obtained with regard to the bromine index and acid color number.
  • An embodiment of the process according to the invention has proven particularly useful in which, in the first process step, hydrogenation is carried out using nickel or palladium on a support material as the hydrogenation catalyst. Nickel or palladium on an alumina support is preferably used as the hydrogenation catalyst.
  • hydrogenation catalysts of other compositions can also be used within the scope of the invention.
  • the hydrogenation conditions for the selective hydrogenation are adjusted depending on the desired hydrogenation reaction and the desired hydrogenation conversion. It is within the skill of a person skilled in the art to set these conditions, such as pressure, temperature, catalyst composition, hydrogen / hydrocarbon ratio and throughput and bed volume in the hydrogenation reactor accordingly.
  • the selective one Hydrogenation carried out so that in particular diolefins and triolefins are completely hydrogenated.
  • the hydrogenation conditions are set so that conjugated diolefins and triolefins are completely hydrogenated.
  • C 6 -dienes and C 6 -trienes and C 6 -triolefins whose boiling point is close to the boiling point of benzene and which are therefore difficult to separate from the benzene are preferably hydrogenated as completely as possible.
  • An embodiment of the process according to the invention in which the extractive distillation and / or liquid-liquid extraction is carried out using a selective solvent from the group N-formylmorpholine, N-methylpyrrolidone, sulfolane, ethylene glycol or ethylene glycol derivative has proven particularly useful.
  • an N-substituted morpholine having 1 to 8 carbon atoms in the substituent is as selective solvent used.
  • alkanediols having 2 to 5 carbon atoms and / or their mono- and / or dialkyl ethers are used as the selective solvent.
  • solvents mentioned as a selective solvent it is also within the scope of the invention to use mixtures of the solvents mentioned as a selective solvent.
  • other solvents can also be used which are suitable as selective solvents for the separation of aromatics in the context of the extractions.
  • Solvent / water mixtures can also be used.
  • mixtures of the selectively hydrogenated reformate gasoline and other hydrogenated aromatic-containing raw products and / or mixtures of distillation cuts of these raw products are used in the second process stage in which the extraction is carried out.
  • the pure aromatics are expediently separated from the selective solvent by distillation.
  • FIG. 1 shows the device for carrying out the process according to the invention with a hydrogenation reactor 1 and a downstream extraction device 2.
  • the hydrogenation reactor 1 has a first feed line 3 for feeding reformate gasoline.
  • a reformate cut obtained from fractional distillation from reformate gasoline is fed through the feed line 3 to the hydrogenation reactor 1.
  • the hydrogenation reactor 1 has a second feed line 4 for the feed of hydrogen.
  • the supply of hydrogen also includes the supply of a hydrogen-rich gas.
  • the hydrogenation reactor 1 further contains a fixed bed made of a hydrogenation catalyst.
  • Catalysts made of nickel or palladium on an alumina support are preferably used and in the exemplary embodiment.
  • the hydrogenation conditions for the selective hydrogenation such as temperature, pressure, hydrogen / hydrocarbon ratio and throughput and bed volume in the hydrogenation reactor 1, are set depending on the desired hydrogenation reaction and on the desired hydrogenation conversion.
  • Gaseous components leave the hydrogenation reactor 1 via the discharge pipeline 10.
  • the liquid, selectively hydrogenated and aromatic-containing products from the selective hydrogenation leave the hydrogenation reactor 1 together with still dissolved residual gases via the connecting line 5.
  • the extraction device 2 is connected to the hydrogenation reactor 1 via the connecting line 5 for the liquid selectively hydrogenated and aromatic-containing products from the selective hydrogenation.
  • the extraction device 2 is an extractive distillation column.
  • the product from the hydrogenation is fed via the connecting line 5 in the middle part of the extractive distillation column.
  • the aromatics are separated from the non-aromatics in the extractive distillation column.
  • the extraction device 2 has a feed device 6 for a selective solvent.
  • the selective solvent is fed in the upper part of the extractive distillation column through the feed device 6.
  • the selective solvent causes the distillative separation of non-aromatics and the aromatics (extract) dissolved in the selective solvent.
  • the extraction device 2 has a first discharge line 7 for the extract from selective solvent and aromatics.
  • the extraction device 2 also has a second discharge line 8 for the raffinate with the non-aromatics.
  • a distillation device 9 for the distillative separation of selective solvents and pure aromatics is connected to the first discharge line 7 for the extract.
  • the selective solvent removed by distillation in the distillation device 9 is fed back into the extractive distillation column via the feed device 6.
  • the pure automatic machines separated by distillation in the distillation device 9 are discharged via the pure aromatics line 11 or sent for further use.
  • the bromine index according to ASTM D-1492, the acid color number (Acid Wash Color, AWC) according to ASTM D-848 and the Hazen color number according to ASTM D-1209 are given throughout.
  • a benzene-rich reformate cut from a catalytic reforming was subjected to an extractive distillation in accordance with the prior art or the process known from practice.
  • This feed product for extractive distillation had a relatively high olefin content, which increased with the catalyst runtime of the reforming catalyst (see Table 1).
  • the benzene product had a non-aromatic content ⁇ 1000 ppm, a bromine index ⁇ 20 and an acid color number that was always greater than 1.
  • the high acid color number of the benzene product is already caused by traces of olefins, especially those of the group C 6 -cyclodienes (especially methyl-1,3-cyclopentadiene bp: 73 ° C and 1,3-cyclohexadiene bp: 81 , 5 ° C) or C 6 -diolefins and C 6 -triolefins (especially methyl-1,3-pentadienes bp: ⁇ 76 ° C or 1,3,5-hexatriene bp: 77.6 ° C or 2.6 -Hexadien Kp: 80 ° C).
  • MCPDEN methyl-1,3-cyclopentadiene
  • Table 1 shows the benzene and MCPDEN content with regard to the extractive distillation as a function of the catalyst runtime of the reforming catalyst. The weight ratio of selective solvent / hydrocarbon was 2.4 in the extractive distillation.
  • the input product means that the product added to the extractive distillation and the benzene product means the product after the extractive distillation.
  • the extractive distillation was preceded by a selective hydrogenation in accordance with the process according to the invention as claimed in claim 1 in order to selectively hydrogenate olefins and, if possible, not convert aromatics to saturated hydrocarbons.
  • a reformate cut with a maximum benzene content from a catalytic reforming was used, which had 65 ppm toluene, a bromine index of 3000 and an MCPDEN content of 120 ppm.
  • Table 2 test conditions and measurement results for Example 1a are listed, in which work was carried out without selective hydrogenation and only extractive distillation.
  • Examples 1b to 1d the Selective hydrogenation combined with extractive distillation.
  • nickel on aluminum oxide was used as the carrier material as the catalyst for the selective hydrogenation. The selective hydrogenation was carried out in 1b to 1d so that only 0.96% of the benzene used was hydrogenated to cyclohexane.
  • the extractive distillation (ED) was carried out in all examples 1a to 1d with N-formylmorpholine as solvent and with a theoretical number of plates in the ED column of 50.
  • the solvent / KW application ratio shown in the table under the conditions of the extractive distillation means the weight ratio of selective solvent for the hydrocarbon used in the extractive distillation column.
  • the heat requirement of the distillation column means the heat requirement of the distillation device or distillation column 9 connected downstream of the extractive distillation column for separating the pure benzene from the selective solvent. The heat requirement is given here and in the following tables 3 and 4 in kJ / kg of benzene produced.
  • Table 2 show that the bromine index of the reformate section was reduced to 330 in the selective hydrogenation.
  • selective hydrogenation removed C 6 diolefins to concentrations below their detection limit.
  • the table shows the MCPDEN content that was reduced to ⁇ 1 ppm.
  • the values for the benzene product from the extractive distillation show that in example 1a an unfavorably high bromine index and an unfavorably high acid color number are measured without selective hydrogenation, while in examples 1b to 1d with selective hydrogenation the bromine index remains ⁇ 10 and the acid color number is ⁇ 1 and so The pure benzene obtained meets all requirements.
  • a reformate cut corresponding to exemplary embodiment 1 was used.
  • Palladium on aluminum oxide was used as the carrier material here as the catalyst for the selective hydrogenation.
  • the selective hydrogenation was carried out milder than in Example 1, so that only about 0.29% of the benzene was hydrogenated to cyclohexane.
  • the hydrogenated feed product for Extractive distillation had a bromine index of 1,730 and an MCPDEN content of 4 ppm.
  • the extractive distillation was carried out in all examples 2a to 2d with N-formylmorpholine as the selective solvent and with a theoretical number of plates in the extractive distillation column of 50.
  • Example 2b to 2d in Table 3 shows that due to the lower or milder hydrogenation compared to Example 1 with a low solvent / KW application ratio of 2.0, no satisfactory values for the bromine index and the acid color number are obtained.
  • the dash-dotted The curve shows Examples 2b to 2d in Table 3, in which the selective hydrogenation was carried out in such a way that only about 0.29% of the benzene used was hydrogenated to cyclohexane.
  • the broken line in FIG. 2 represents the limit value 20 for the bromine index. From Fig. 2 it can be seen that by changing the hydrogenation conditions or the depth of hydrogenation and by changing the solvent / KW usage ratio, the process varies depending on the desired result, ie depending on the acceptable benzene loss on the one hand and depending on the desired bromine index on the other can be.
  • the benzene removal of reformate gasoline was carried out to obtain pure benzene, as claimed in claim 2.
  • a reformate gasoline with a distillation end point of 165 ° C. was first subjected to a fractional distillation.
  • the top product of the distillation contained 98% of the benzene used.
  • Table 4 shows Example 3a, in which the process was carried out without selective hydrogenation, and Examples 3b and 3c, in which hydrogenation was carried out selectively with a nickel catalyst on aluminum oxide. The selective hydrogenation was otherwise carried out so that the benzene loss was about 0.89%.
  • Example 3a shows that, without selective hydrogenation, unsatisfactory values of the bromine index and the acid color number were also achieved in the benzene product.
  • a comparison of Examples 3b and 3c shows that, under the hydrogenation conditions chosen here (loss of benzene 0.89%), even with a solvent / KW application ratio of 1.5, satisfactory values of the bromine index and the acid color number can be achieved.
  • this exemplary embodiment represents an example of the optimization of the method according to the invention mentioned with reference to FIG. 2.
  • example 3c with a very low solvent / KW application ratio and thus low energy consumption on the one hand and relatively low benzene loss on the other hand, a satisfactory result with regard to the bromine index and the acid color number reached.
  • Example 4a shows that without selective hydrogenation, the pure benzene has unfavorably high values of bromine index and acid color number. In contrast, optimum values can be achieved with selective hydrogenation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
EP96120033A 1996-02-03 1996-12-13 Procédé de récupération d'aromates à partir d'essence de reforming Expired - Lifetime EP0792928B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19603901A DE19603901A1 (de) 1996-02-03 1996-02-03 Verfahren zur Gewinnung von Reinaromaten aus Reformatbenzin und Vorrichtung zur Durchführung des Verfahrens
DE19603901 1996-02-03

Publications (3)

Publication Number Publication Date
EP0792928A2 true EP0792928A2 (fr) 1997-09-03
EP0792928A3 EP0792928A3 (fr) 1998-04-01
EP0792928B1 EP0792928B1 (fr) 2004-03-17

Family

ID=7784424

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96120033A Expired - Lifetime EP0792928B1 (fr) 1996-02-03 1996-12-13 Procédé de récupération d'aromates à partir d'essence de reforming

Country Status (10)

Country Link
US (1) US6124514A (fr)
EP (1) EP0792928B1 (fr)
JP (1) JP4514839B2 (fr)
KR (1) KR970061835A (fr)
AT (1) ATE262020T1 (fr)
CA (1) CA2196585A1 (fr)
CZ (1) CZ25097A3 (fr)
DE (2) DE19603901A1 (fr)
ES (1) ES2217298T3 (fr)
PL (1) PL318211A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7371908B2 (en) 2001-10-15 2008-05-13 Basf Aktiengesellschaft Process for catalytic hydrogenation
US9068125B2 (en) 2009-03-11 2015-06-30 Thyssenkrupp Uhde Gmbh Process for the recovery of pure aromatics from hydrocarbon fractions containing aromatics

Families Citing this family (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6469223B2 (en) * 2000-01-04 2002-10-22 Fina Technology, Inc. Selective hydrogenation of dienes
US6551502B1 (en) * 2000-02-11 2003-04-22 Gtc Technology Corporation Process of removing sulfur compounds from gasoline
US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US7158925B2 (en) * 2002-04-18 2007-01-02 International Business Machines Corporation Facilitating simulation of a model within a distributed environment
US20050171393A1 (en) 2003-07-15 2005-08-04 Lorkovic Ivan M. Hydrocarbon synthesis
US7018756B2 (en) 2003-09-05 2006-03-28 Xerox Corporation Dual charge transport layer and photoconductive imaging member including the same
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US20060100469A1 (en) 2004-04-16 2006-05-11 Waycuilis John J Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US20080275284A1 (en) 2004-04-16 2008-11-06 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
US7244867B2 (en) 2004-04-16 2007-07-17 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US7541123B2 (en) * 2005-06-20 2009-06-02 Xerox Corporation Imaging member
US7361440B2 (en) * 2005-08-09 2008-04-22 Xerox Corporation Anticurl backing layer for electrostatographic imaging members
US7422831B2 (en) * 2005-09-15 2008-09-09 Xerox Corporation Anticurl back coating layer electrophotographic imaging members
IN2008DN02156A (fr) * 2005-11-10 2010-04-16 Uop Llc
US7462434B2 (en) * 2005-12-21 2008-12-09 Xerox Corporation Imaging member with low surface energy polymer in anti-curl back coating layer
US7455941B2 (en) * 2005-12-21 2008-11-25 Xerox Corporation Imaging member with multilayer anti-curl back coating
US7517624B2 (en) * 2005-12-27 2009-04-14 Xerox Corporation Imaging member
US7754404B2 (en) * 2005-12-27 2010-07-13 Xerox Corporation Imaging member
AP2673A (en) 2006-02-03 2013-05-23 Grt Inc Continuous process for converting natural gas to liquid hydrocarbons
KR101335397B1 (ko) 2006-02-03 2013-12-02 지알티, 인코포레이티드 할로겐으로부터 가벼운 기체를 분리하는 방법
US7527906B2 (en) * 2006-06-20 2009-05-05 Xerox Corporation Imaging member having adjustable friction anticurl back coating
US7790943B2 (en) * 2006-06-27 2010-09-07 Amt International, Inc. Integrated process for removing benzene from gasoline and producing cyclohexane
US7767373B2 (en) * 2006-08-23 2010-08-03 Xerox Corporation Imaging member having high molecular weight binder
NZ581216A (en) 2007-05-24 2011-06-30 Grt Inc Zone reactor incorporating reversible hydrogen halide capture and release
EP2233550B1 (fr) * 2007-11-09 2014-04-30 Ranfeng Ding Système et procédé de recombinaison d'hydrocarbure catalytique pour produire une essence de haute qualité
KR100894400B1 (ko) * 2007-11-29 2009-04-20 주식회사 엘지화학 벤젠 회수 유닛 에너지 효율 개선 방법
US8007970B2 (en) * 2008-04-07 2011-08-30 Xerox Corporation Low friction electrostatographic imaging member
US8084173B2 (en) * 2008-04-07 2011-12-27 Xerox Corporation Low friction electrostatographic imaging member
US7998646B2 (en) * 2008-04-07 2011-08-16 Xerox Corporation Low friction electrostatographic imaging member
US8026028B2 (en) * 2008-04-07 2011-09-27 Xerox Corporation Low friction electrostatographic imaging member
US7943278B2 (en) * 2008-04-07 2011-05-17 Xerox Corporation Low friction electrostatographic imaging member
US8021812B2 (en) * 2008-04-07 2011-09-20 Xerox Corporation Low friction electrostatographic imaging member
US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US8415517B2 (en) 2008-07-18 2013-04-09 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8168356B2 (en) 2009-05-01 2012-05-01 Xerox Corporation Structurally simplified flexible imaging members
US8173341B2 (en) * 2009-05-01 2012-05-08 Xerox Corporation Flexible imaging members without anticurl layer
US8124305B2 (en) * 2009-05-01 2012-02-28 Xerox Corporation Flexible imaging members without anticurl layer
US20100297544A1 (en) 2009-05-22 2010-11-25 Xerox Corporation Flexible imaging members having a plasticized imaging layer
US8241825B2 (en) 2009-08-31 2012-08-14 Xerox Corporation Flexible imaging member belts
US8003285B2 (en) 2009-08-31 2011-08-23 Xerox Corporation Flexible imaging member belts
WO2011082993A1 (fr) 2009-12-15 2011-07-14 Basf Se Procédé d'hydrogénation en phase gazeuse d'un courant d'hydrocarbures qui contient des composants polymérisables dans des conditions réactionnelles de l'hydrogénation en phase gazeuse
US8198495B2 (en) 2010-03-02 2012-06-12 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8367884B2 (en) 2010-03-02 2013-02-05 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8232030B2 (en) 2010-03-17 2012-07-31 Xerox Corporation Curl-free imaging members with a slippery surface
US8343700B2 (en) 2010-04-16 2013-01-01 Xerox Corporation Imaging members having stress/strain free layers
US8470505B2 (en) 2010-06-10 2013-06-25 Xerox Corporation Imaging members having improved imaging layers
US8394560B2 (en) 2010-06-25 2013-03-12 Xerox Corporation Imaging members having an enhanced charge blocking layer
US8475983B2 (en) 2010-06-30 2013-07-02 Xerox Corporation Imaging members having a chemical resistive overcoat layer
DE102010051396A1 (de) 2010-11-16 2012-05-16 Thyssenkrupp Uhde Gmbh Verfahren zur Entfernung schwersiedender Kohlenwasserstoffe aus Lösungsmittelströmen
US8263298B1 (en) 2011-02-24 2012-09-11 Xerox Corporation Electrically tunable and stable imaging members
US8465892B2 (en) 2011-03-18 2013-06-18 Xerox Corporation Chemically resistive and lubricated overcoat
US8815050B2 (en) 2011-03-22 2014-08-26 Marathon Gtf Technology, Ltd. Processes and systems for drying liquid bromine
US8436220B2 (en) 2011-06-10 2013-05-07 Marathon Gtf Technology, Ltd. Processes and systems for demethanization of brominated hydrocarbons
US8829256B2 (en) 2011-06-30 2014-09-09 Gtc Technology Us, Llc Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons
US8877413B2 (en) 2011-08-23 2014-11-04 Xerox Corporation Flexible imaging members comprising improved ground strip
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
ES2664626T3 (es) * 2012-08-09 2018-04-20 Council Of Scientific & Industrial Research Un proceso para la producción de gasolina pobre en benceno mediante la recuperación de benceno de alta pureza a partir de la fracción de gasolina craqueada sin procesar que contiene peróxidos orgánicos
CN103160310A (zh) * 2013-03-15 2013-06-19 西南石油大学 一种萃取分离芳烃所用的复合溶剂及其萃取方法
US9091949B2 (en) 2013-08-16 2015-07-28 Xerox Corporation Imaging members having electrically and mechanically tuned imaging layers
US9046798B2 (en) 2013-08-16 2015-06-02 Xerox Corporation Imaging members having electrically and mechanically tuned imaging layers
US9017908B2 (en) 2013-08-20 2015-04-28 Xerox Corporation Photoelectrical stable imaging members
US9075327B2 (en) 2013-09-20 2015-07-07 Xerox Corporation Imaging members and methods for making the same
KR102300823B1 (ko) * 2017-12-29 2021-09-09 한화솔루션 주식회사 수소화 반응용 촉매 및 이의 제조방법
US11802248B2 (en) * 2020-09-07 2023-10-31 Sk Innovation Co., Ltd. Process for reducing unsaturated hydrocarbons in aromatic fraction through selective hydrogenation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3316318A (en) * 1961-03-22 1967-04-25 Shell Oil Co Process for recovery of aromatics from cracked gasoline fractions
DE1470553A1 (de) * 1960-07-07 1968-12-05 Bayer Ag Verfahren zur Gewinnung von Aromaten aus Krackbenzinen
US3869377A (en) * 1971-12-14 1975-03-04 Metallgesellschaft Ag Production of extrapure aromatics

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2084471A (en) * 1933-10-18 1937-06-22 Standard Oil Dev Co Process of treating lubricating oils with selective solvents
US2960548A (en) * 1958-09-19 1960-11-15 Pure Oil Co Extraction of aromatics from hydrocarbon fractions
US3044950A (en) * 1958-12-15 1962-07-17 Gulf Research Development Co Process for upgrading catalytically cracked gasoline
US3221078A (en) * 1961-07-06 1965-11-30 Engelhard Ind Inc Selective hydrogenation of olefins in dripolene
US3514395A (en) * 1968-05-29 1970-05-26 Sun Oil Co Process for producing a high aromatic,low color,uv stable process oil
GB1400884A (en) * 1972-03-13 1975-07-16 Ici Ltd Treatment of the feedstock for a aromatic hydrocarbon extraction process
FR2213335B1 (fr) * 1973-01-10 1976-04-23 Inst Francais Du Petrole
US3865716A (en) * 1973-09-13 1975-02-11 Exxon Research Engineering Co Process for the selective hydrogenation of olefins
US4503267A (en) * 1983-10-24 1985-03-05 Union Camp Corporation Extraction of phenolics from hydrocarbons
US4781820A (en) * 1985-07-05 1988-11-01 Union Carbide Corporation Aromatic extraction process using mixed polyalkylene glycols/glycol ether solvents
US5202520A (en) * 1989-03-09 1993-04-13 Uop Method for aromatic hydrocarbon recovery
US5139651A (en) * 1989-09-18 1992-08-18 Uop Aromatic extraction process using mixed polyalkylene glycol/glycol ether solvents
DE3942950A1 (de) * 1989-12-23 1991-06-27 Krupp Koppers Gmbh Verfahren zur gleichzeitigen gewinnung von reinem benzol und reinem tuluol
US5225072A (en) * 1990-08-03 1993-07-06 Uop Processes for the separation of aromatic hydrocarbons from a hydrocarbon mixture
DE4101848A1 (de) * 1991-01-23 1992-07-30 Krupp Koppers Gmbh Verfahren zur abtrennung von aromaten aus kohlenwasserstoffgemischen beliebigen aromatengehaltes
US5336840A (en) * 1991-02-20 1994-08-09 Uop Process for the separation of aromatic hydrocarbons with energy redistribution
US5191152A (en) * 1991-02-20 1993-03-02 Uop Process for the separation of aromatic hydrocarbons with energy redistribution
US5310480A (en) * 1991-10-31 1994-05-10 Uop Processes for the separation of aromatic hydrocarbons from a hydrocarbon mixture
US5399244A (en) * 1993-12-06 1995-03-21 Glitsch, Inc. Process to recover benzene from mixed hydrocarbons by extractive distillation
US5685972A (en) * 1995-07-14 1997-11-11 Timken; Hye Kyung C. Production of benzene, toluene, and xylene (BTX) from FCC naphtha
FR2743080B1 (fr) * 1995-12-27 1998-02-06 Inst Francais Du Petrole Procede de reduction selective de la teneur en benzene et en composes insatures legers d'une coupe d'hydrocarbures

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1470553A1 (de) * 1960-07-07 1968-12-05 Bayer Ag Verfahren zur Gewinnung von Aromaten aus Krackbenzinen
US3316318A (en) * 1961-03-22 1967-04-25 Shell Oil Co Process for recovery of aromatics from cracked gasoline fractions
US3869377A (en) * 1971-12-14 1975-03-04 Metallgesellschaft Ag Production of extrapure aromatics

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7371908B2 (en) 2001-10-15 2008-05-13 Basf Aktiengesellschaft Process for catalytic hydrogenation
US9068125B2 (en) 2009-03-11 2015-06-30 Thyssenkrupp Uhde Gmbh Process for the recovery of pure aromatics from hydrocarbon fractions containing aromatics

Also Published As

Publication number Publication date
JP4514839B2 (ja) 2010-07-28
EP0792928B1 (fr) 2004-03-17
ES2217298T3 (es) 2004-11-01
CZ25097A3 (en) 1997-08-13
EP0792928A3 (fr) 1998-04-01
DE59610939D1 (de) 2004-04-22
US6124514A (en) 2000-09-26
CA2196585A1 (fr) 1997-08-04
JPH09309846A (ja) 1997-12-02
ATE262020T1 (de) 2004-04-15
PL318211A1 (en) 1997-08-04
DE19603901A1 (de) 1997-08-07
KR970061835A (ko) 1997-09-12

Similar Documents

Publication Publication Date Title
EP0792928B1 (fr) Procédé de récupération d'aromates à partir d'essence de reforming
EP2406349B1 (fr) Procédé de préparation de composés aromatiques purs a partir de fractions d'hydrocarbure renfermant des composés aromatiques
EP0940381B1 (fr) Procédé de récupération de cyclopentane et/ou de cyclopentène
EP0141316B1 (fr) Procédé pour la récupération d'isoprène d'un mélange d'hydrocarbures en C 5
DE2051447A1 (de) Verfahren zur Herstellung von Benzin hoher Oktanzahl
DE10217863A1 (de) Verfahren und Vorrichtung zur Olefinherstellung
DE1568940A1 (de) Verfahren zur Abtrennung von Aromaten aus Kohlenwasserstoffgemischen beliebigen Aromatengehaltes
DE102010011014A1 (de) Verfahren und Vorrichtung zur destillativen Gewinnung von Rein-1,3-Butadien aus Roh-1,3-Butadien
EP0708072B1 (fr) Procédé pour l'obtention de benzène pur et de toluène pur
DE10217866A1 (de) Verfahren und Vorrichtung zur Olefinherstellung
EP0241638B1 (fr) Procédé de préparation d'un concentré aromatique utilisable comme produit de mélange d'un combustible pour moteurs à carburateur
DE2444232C3 (de) Verfahren zur Gewinnung eines azeotropsiedenden Gemisches aus Isopren und n-Pentan aus einem Kohlenwasserstoffstrom
EP0329958A2 (fr) Procédé de préparation d'un concentré aromatique utilisable comme produit de mélange d'un combustible pour moteurs à carburateur
DE2059568A1 (de) Verfahren zur Trennung des Ausflusses aus einer Reaktionszone zur katalytischen hydrierenden Verarbeitung von Kohlenwasserstoffen
EP0904336B1 (fr) Procede de preparation de composes aliphatiques a faible teneur en soufre
DE1468566C3 (de) Verfahren zur Isolierung von aromatischen Kohlenwasserstoffen aus Gemischen, die Alkene und stärker ungesättigte Verbindungen enthalten
WO2000031007A1 (fr) Procede de decoloration de styrene obtenu a partir d'essence de pyrolyse et contamine par des chromophores
WO2015032804A1 (fr) Procédé de production de produits à base d'hydrocarbures
DE2026693C3 (de) Verfahren zur Gewinnung von Rein benzol durch Extraktivdestillation
EP0024299B1 (fr) Procédé pour l'obtention de composés aromatiques à partir de benzine pyrolisée
DE1518240C (de) Verfahren zur Reinigung von aroma tischen Kohlenwasserstoffen durch Destil lation
DE1959869B2 (de) Verfahren zur Herstellung einer Schmierölfraktion mit erhöhtem Viskositätsindex
DE2046976C3 (de) Verfahren zur Gewinnung von Benzol, Toluol und C tief 8 -Aromaten aus aromatenreichen Kohlenwasserstoffgemischen
AT303702B (de) Verfahren zur Abtrennung von Aromaten aus Kohlenwasserstoffgemischen beliebigen Aromatengehaltes
DE1593486C3 (de) Verfahren zur Gewinnung von Benzol von Nitnerquahtat aus einem benzol haltigen Gemisch flussiger Kohlenwasser stoffe durch Gegenstrom Extraktion

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FI FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FI FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19980219

17Q First examination report despatched

Effective date: 19991229

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF AKTIENGESELLSCHAFT

RTI1 Title (correction)

Free format text: PROCESS FOR THE RECOVERY OF PURE AROMATICS FROM REFORMING GASOLINE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FI FR GB IT LI NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040317

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59610939

Country of ref document: DE

Date of ref document: 20040422

Kind code of ref document: P

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20040510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040617

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040617

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2217298

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041231

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20041220

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20141230

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20141223

Year of fee payment: 19

Ref country code: NL

Payment date: 20141219

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20141218

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20150227

Year of fee payment: 19

Ref country code: ES

Payment date: 20150127

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20141230

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20141230

Year of fee payment: 19

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151231

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 59610939

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 262020

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151213

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20151213

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20160101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151213

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160701

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151213

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151213

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151214

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20180507