• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:

    公开号:BR112013009805B1
    申请号:R112013009805-8
    申请日:2011-10-20
    公开日:2018-12-11
    发明作者:Hong Chan Kim；Yong Seung Kim；Sang Hun Oh；Hyuck Jae Lee；Jae Suk Koh；Gyung Rok Kim；Myoung Han Noh；Sang Il Lee；Seung Woo Lee；Do Woan Kim；Jae Hyun Koh；Jong Hyung Lee；Sun Choi；Seung Hoon Oh；Kyung Jong Oh
    申请人:Sk Innovation Co., Ltd.；
    IPC主号:
    专利说明:

    (54) Title: METHOD FOR THE PRODUCTION OF AROMATIC COMPOUNDS AND LIGHT Paraffins (73) Holder: SK INNOVATION CO., LTD., Korean Company. Address: 99, SEORIN-DONG, JONGRO-GU - SEOUL KOREA 110-110, REPUBLIC OF KOREA (KR) (72) Inventor: HONG CHAN KIM; YONG SEUNG KIM; SANG HUN OH; HYUCK JAE LEE; JAE SUK KOH; GYUNG ROK KIM; MYOUNG HAN NOH; SANG IL LEE; SEUNG WOO LEE; DO WOAN KIM; JAE HYUN KOH; JONG HYUNG LEE; SUN CHOI; SEUNG HOON OH; KYUNG JONG OH.
    Validity Period: 20 (twenty) years from 10/20/2011, subject to legal conditions
    Issued on: 12/11/2018
    Digitally signed by:
    Liane Elizabeth Caldeira Lage
    Director of Patents, Computer Programs and Topographies of Integrated Circuits
    1/39
    METHOD FOR THE PRODUCTION OF
    AROMATIC COMPOUNDS AND LIGHT SCREWS
    Application field
    The present patent application relates to aromatics and paraffins a method of producing compounds from hydrocarbonaceous oils derived from petroleum, coal or wood.
    Technical_State
    Demand for aromatic compounds, for example, benzene / toluene / xylene, has increased at an annual average of 4 ~ 6% worldwide, which is a drastic upward trend that is twice GDP and three times demand for petroleum products in general. This increase is based on the dramatically increasing demand for aromatic compounds in China.
    Conventional aromatics (benzene / toluene / xylene) have been produced by pyrolysis gasoline obtained along with key petroleum products, including ethylene, propylene, etc., in naphtha pyrolysis units using a naphtha supply, or from refurbishment in a naphtha catalytic reformer.
    However, due to the drastic increase in the demand for aromatic compounds mentioned above, a shortage of naphtha supply has been intensifying in the world market, including China since 2007, conventional techniques using naphtha are unable to meet the growing demand for aromatic compounds.
    2/39 because naphtha can only be obtained by atmospheric distillation of crude oil. Therefore, there is a need for an alternative supply for aromatic compounds, which can be used as a substitute for naphtha, and, in addition, a need to increase the yield of aromatic compounds and light paraffins has received attention.
    Invention Disclosure - Technical Problem
    ------- In the face of such circumstances, the present inventors have found that aromatic components such as benzene, toluene or xylene, whose demand is increasing, can be prepared from oils derived from petroleum, coal or wood, and therefore , the present invention patent application was designed in response to the need for the marked by the techniques mentioned above.
    Consequently, an objective of the present patent application is to provide a new method for the production of high concentration aromatic compounds using oils derived from petroleum, coal or wood containing a large amount of highly aromatic components, instead of using a supply of naphtha for conventional aromatic compounds.
    Solution to the Problem
    In order to achieve the above objective, the present application for a patent provides a method for the production of aromatic compounds and light paraffins from oils derived from petroleum, coal or wood, comprising (a) the introduction of derived oils
    3/39 oil, coal reaction, so that they are partially from the components or wood in a hydrogenation area and the saturated polycyclic aromatic components obtained from hydrocarbonaceous containing 11 hydrocarbonaceous and cracked components; (b) the separation between components or more containing hydrocarbon components containing 5 atoms
    6-10 carbon, carbons, and or less carbons; and or more carbons separated in (b) back to provide the hydrocarbon components containing
    6-10 carbons for a process of separation transalkylation process so that the aromatic compounds are recovered, hydrocarbonaceous components containing 5 or a light separation process, aromatics and paraffins.
    Advantageous effects aromatic compounds patent application aromatic compounds
    A paraffin aromatic invention minus one and one part and providing the least carbons thus obtaining compounds production method according to the present allows the production of high concentration such as benzene, toluene and xylene using oils that recycle obtained by fluidized cracking of petroleum , gasoline include light pyrolysis bed catalytic oil obtained by thermal cracking of naphtha, heavy aromatic compounds from a coal tar reformer or light oil resulting from carbon carbonation or aromatic compounds resulting from pyrolysis, carbonation, distillation
    Destructive 4/39, etc. of wood, in place of the use of the conventional supply of naphtha for aromatic compounds, and, thus, the method according to the present patent application can overcome the yield limits of aromatic compounds.
    In particular, among a variety of aromatic compounds / paraffins, valuable aromatic compounds, for example, benzene and xylene, and light paraffins, such as propane, butane or the like, can be selectively produced and by-products that are relatively worthless can be recovered and reprocessed in order to have their values increased, thus greatly increasing the value of the final products. Brief Description of the Figures
    Figure 1 is a schematic block flowchart showing a production process according to a configuration of the present invention application; and
    Figure 2 is a schematic block flow diagram showing a production process according to another configuration of the present patent application, including aromatic separation, transalkylation, xylene processing and then the recirculation of unconverted oils.
    Detailed Description
    Hereafter, a detailed description of the present invention patent application will be presented.
    5/39
    The present application for a patent relates to a method for the production of aromatic components including benzene, toluene or xylene from oils derived from petroleum, coal or wood.
    According to the present patent application, petroleum-derived oils can mainly include oils containing aromatic compounds, such as light oil), gas-O-1 i. pyrolysis, heavy aromatic compounds, and oils derived from coal or wood include, but are not limited to, oils containing aromatic compounds such as coal tar or light oil, wood tar, etc., and any oil containing petroleum-derived aromatic components , charcoal or wood can be used. For example, it is possible to use any materials selected from the group comprising petroleum-derived oils, such as crude pyrolysis gasoline (RPG raw pyrolysis gasoline), heavy crude pyrolysis gasoline (heavy RPG), treated pyrolysis gasoline (TPG treated pyrolysis reformed products, heavy aromatic compounds, kerosene, jet oil, atmospheric diesel, CCF gasoline (fluidized catalytic cracking), light cracked naphtha, heavy cracked naphtha, decanted oil from
    CCF, vacuum diesel, coke diesel, heavy and atmospheric coke naphtha vacuum, reduced crude petroleum oil, petroleum bottom residue, petroleum bottom residue, asphalt, bitumen, sand oil distillation
    6/39 bituminous, shale oil, liquid / solid products obtained by coal liquefaction or coal carbonation, such as coal tar, tar, light oil, phenolic or carbolic oil, naphthalene oil, washing oil, anthracene, light anthracene oil, heavy anthracene oil and tar, products derived from wood carbonation, such as wood tar, hard wood tar, tar resin, and combinations thereof.
    Schematic block flowchart for the method according to the present application is shown in FIG. 1. With reference to FIG. 1, oils are introduced into an area of hydrogenation and reaction. As the amount of aromatic components in oils is increased, the production of valuable aromatic compounds can be favored.
    According to the present patent application, polycyclic aromatic components can be partially saturated and cracked in the area of hydrogenation and reaction.
    The hydrogenation and reaction area includes a hydroprocessing unit and a hydrocracking unit.
    As such, hydroprocessing and hydrocracking can be performed in any sequence.
    Specifically, delivery can be introduced in the hydro-processing unit and then in the hydrocracking unit, or in the analytical cracking unit and then in the hydro-processing unit.
    7/39
    The hydroprocessing unit in the hydrogenation and reaction area is configured in such a way that hydrogen is supplied from the outside, in which the oils are treated with hydrogen in the presence of a hydrotreating catalyst. The hydroprocessing reaction obtains partial saturation of aromatic components, containing two or more aromatic rings. Such hydroprocessing should not saturate an aromatic component containing only one aromatic ring.
    This is because an aromatic component containing an aromatic ring is a valuable aromatic component or can be converted into a valuable aromatic component by transalkylation, which will be described later.
    In the hydroprocessing unit, aromatic components containing two or more aromatic rings are saturated so that the aromatic rings in addition to just one aromatic ring are saturated. This is because it is not easy to crack the unnecessary aromatic rings in the posterior hydrocracking unit.
    To obtain the above results, the hydroprocessing unit can operate under conditions including a reaction pressure of 20 ~ 100 kg / cm 2 , a reaction temperature of 150 ~ 450 ° C, and a liquid hourly space velocity (LHSV - liquid hourly space velocity) of 0.1 ~ 4.5 h 1 .
    In addition, a catalyst used in the hydroprocessing unit can comprise
    8/39 a carrier composed of alumina or silica or both, and one or more metals selected from the group consisting of metals from Groups 6, 9, and 10. One or more metals selected from the group consisting of cobalt, molybdenum, nickel and tungsten are particularly useful.
    After hydroprocessing, not only partial saturation of the aromatic rings, but also denitrogenation, desulfurization and deoxygenation that are conducted to remove impurities such as sulfides or nitrogenous or oxygenated compounds from the oils can be performed. For this process of producing aromatic compounds, the removal of impurities is very important, and all impurities, such as sulfur, nitrogen and oxygen must be removed before being supplied to the transalkylation process. Generally, the oxygen level of oils derived from tar and wood is very high. Therefore, the impurities present in the oils can be easily removed without the need for additional impurity removal.
    After hydroprocessing, the partially saturated supply is supplied to the hydrocracking unit. A hydrocracking catalyst used in the hydrocracking unit can be composed of one or more types of zeolites having a pore size of 4 Â (Angstrom) or more, which can be optionally modified with a binder and one or more metals selected from metals of Groups 6, 9 and 10. The zeolite may include, without limitation, MOR, MEL, FAU, BEA,
    9/39 etc., and the binder can include silica, alumina, clay, etc., which can be used alone or in combinations thereof.
    hydrocracking plays a role in breaking the naphthenic ring or a long chain with two or more carbons attached to a 1 ring aromatic compound in the presence of added hydrogen. Thus, hydrocracking does not produce olefins, unlike catalytic cracking. According to the reaction mechanism, the cracked naphthenic ring is an unsaturated hydrocarbon (ie an olefin), which is unstable and therefore bonds easily with other hydrocarbons around it.
    This reaction hampers the production of a desired aromatic component or can cause polymerization to produce coke, thereby unwittingly deactivating the catalyst.
    In this way, hydrogen is added to the unsaturated hydrocarbon, which is thus converted into a saturated hydrocarbon that is stable.
    For this reason, hydrocracking requires a supply of hydrogen, unlike catalytic cracking.
    The purpose of hydroprocessing is, for aromatic components containing two or more aromatic rings, to partially saturate the aromatic rings in addition to an aromatic ring, so that the naphthenic ring can be broken, thus forming valuable aromatic components or materials that can be used to the production of aromatic components in later procedures.
    To obtain the above results, the hydrocracking unit can operate under conditions that
    10/39 include a reaction pressure of 400 ~ 4500 psig [ounds per square inch gauge - pounds per square inch
    gauge], a reaction temperature 200 ~ 500 ° C, and LHSV of 0.1 ~ 10.The products obtained at leave gives area hydrogenation and reaction are separated in between i)
    hydrocarbon components containing 11 or more carbons, ii) hydrocarbon components containing 6-1-0 carbons e_______ iii) hydrocarbon components containing 5 or less carbons, by means of a separation column. The hydrocarbonaceous components containing 11 or more carbons separated in this way are recirculated back to the hydrogenation and reaction area, and the hydrocarbonaceous components containing 6-10 carbons are supplied to an aromatic separation process and a transalkylation process, and the components hydrocarbons containing 5 or less carbons are supplied to a light separation process.
    Heavy oils containing 11 or more carbons can be converted into valuable aromatic components or valuable paraffinic components, and are thus recirculated back to the area of hydrogenation and reaction. Among the heavy oils obtained by the main separation column, the amount of oils passing through the hydroprocessing unit and the hydrocracking unit may vary depending on the supply, but it is about 40% of the total oils supplied, and after recirculation, the amount of oils that must be recirculated additionally is less than just 15% of the total.
    11/39
    The hydrocarbonaceous components containing 5 or less carbons that were separated by the main separation column are further separated into gaseous effluents and paraffinic components by a light separation process. The most carbons such as paraffinic components include 2 or ethane, propane, butane, etc.
    The hydrocarbonaceous components containing 6-10 carbons that were separated by the main-separation column are provided for the aromatics separation process for the transalkylation process.
    As among hydrocarbonaceous components containing 6 carbons, saturated hydrocarbons including additional reforming cyclohexane. A portion is supplied to one of the reformed oils to be unsaturated using the reformer is provided for the aromatic separation process and for the transalkylation process, and the unconverted oils can be supplied for the main separation column or the separation process Light. The reformer works to convert saturated hydrocarbons into aromatic components at about 400 ~ 600 ° C using a Pt / Al 2 O 3 , Pt-Re / Al 2 O 3 or Pt-Sn / Al 2 O 3 catalyst in a hydrogen atmosphere. The products obtained by the reformer can include benzene, toluene and xylene, and such unsaturated hydrocarbons are supplied for the aromatics separation process and the transalkylation process.
    Hydrocarbonaceous components containing 6-10 carbons separated by the separation column
    12/39 the transalkylation process.
    transalkylation
    Specifically, containing toluene, or more after mixing for the separation of aromatics and the process of
    As such, aromatic and a separation can be carried out in any sequence.
    hydrocarbon components
    6-10 carbons can be separated into benzene, xylene, carbons which a process and components in the hydrocarbonaceous process - separation of the portion of the separated oils is of transalkylation, obtaining benzene, toluene, xylene, hydrocarbons containing 9 or more carbons , this mixture is further mixed with oils that have not been transferred to the transalkylation, followed by the resulting supply to the aromatic containing process, thus transferring one component after which the remainder of the aromatic separation process, thereby recovering the compounds aromatic components, or (ii) hydrocarbon components containing 6-10 carbons can be transferred directly to the transalkylation process, thus obtaining a mixture composed of benzene, toluene, xylene, and hydrocarbon components containing 9 or more carbons, after which this mixture can be supplied for the aromatic separation process, recovering from that form the desired aromatic compounds.
    After transalkylation, dealalkylation of alkyl aromatic compounds containing 9 or more carbons and transalkylation between benzene and compounds
    13/39 aromatics containing 9 or more carbons occur simultaneously with the dismutation of toluene in the presence of a catalyst and the transalkylation between toluene and aromatic compounds containing 9 or more carbons.
    important that produces dismutation / transalkylation. between benzene ~ and compounds
    Such dealkylation is a reaction to the toluene required for. In addition, aromatic transalkylation containing 9 or more carbons is considered important because it produces toluene and xylene.
    On the other hand, olefins including ethylene, propylene, etc., produced by dealkylation, need to be quickly hydrogenated. If such olefins are not rapidly hydrogenated, they are re-alkylated to aromatic compounds, ultimately reducing the conversion rate of aromatic compounds containing 9 or more carbons. In addition, the olefins themselves can cause polymerization or the like, undesirably facilitating the production of coke, which inactivates the catalyst.
    The catalyst used for transalkylation is not limited to, but can include a catalyst disclosed in U.S. Patent No. 6,867,340 by the present applicant.
    Specifically, transalkylation is performed using a catalyst comprising a carrier composed of 10 ~ 95% by weight beta-zeolite or mordenite having a silica / alumina molar ratio adjusted to 20 ~ 200 based on alumina and 5% alumina.
    14/39 weight of one or more inorganic binders selected from the group consisting of gamma alumina, silica, silicaalumina, bentonite, kaolin, clinoptilolite and montmorillonite, and a hydrogenation metal composed of, based on 100 parts by weight of the carrier, 0.001 ~ 0.5 parts by weight of one or more metals selected from the group consisting of platinum, tin, indium and lead. The other properties of the catalyst can be found in the literature above.
    After transalkylation, aromatic components containing 11 or more carbons, which are not used as materials to make valuable aromatic components, are recovered, and can then be supplied to the reaction and hydrogenation area. toluene, xylene and hydrocarbons containing 9 or more carbons produced by transalkylation can be supplied for a xylene processing, which will be described later, through the aromatics separation process. In xylene processing, the separation of para-xylene from the xylene mixture (composed of ortho-xylene, meta-xylene and para-xylene) and the isomerization of the xylene mixture that does not contain para-xylene in para-xylene .
    In addition, the separation of para-xylene (p-X) to separate only the para-xylene from the xylene mixture can be performed using a method known in the art, such as adsorption, crystallization, etc.
    Since para-xylene is much more valuable than ortho-xylene or meta-xylene, the separation and recovery of only para-xylene is favorable.
    15/39
    The components of xylene including ortho-xylene and meta-xylene, except for paraxylene, can be transferred to the xylene isomerization process. Within the mixture of xylene produced by the separation of aromatics, para-xylene, metaxylene, and ortho-xylene are in a state of equilibrium. Since only para-xylene is separated by the above separation, the mixture of xylene that does not contain para-xylene is balanced using a catalyst, whereby para-xylene, which is economically valuable, can be obtained additionally.
    On the other hand, the method according to the present patent application may include the recovery of at least a portion of the aromatic compounds, for example, benzene and xylene mixture, among aromatic compounds resulting from the transalkylation process and the processing of xylene, and the recirculation of unconverted oils. Specifically, a portion of benzene and toluene among the aromatic compounds resulting from the transalkylation can be recirculated back to the aromatic separation process and can thus be additionally supplied for the transalkylation process, and can also be recirculated back to the area of hydrogenation and reaction from the aromatics separation process. In addition, in the xylene isomerization process, oils that are not isomerized in para-xylene can be recirculated back to the aromatics separation process, and thus can be supplied
    16/39 for the transalkylation process or the xylene processing.
    Consequently, all oils obtained from the xylene isomerization process can be recirculated back to the transalkylation process and the para-xylene separation process through the aromatics separation process, thereby obtaining additional para-xylene.
    Specifically, the recirculation procedure from the transalkylation process and the xylene isomerization process to the aromatics separation process can increase the yield of para-xylene, and improvements in the yield of valuable paraffins and aromatics are possible without further treatment and no waste of materials due to the recirculation from the aromatics separation process to the hydrogenation and reaction area.
    According to configurations of the present patent application, as a supply, the LCO derived from petroleum or the coal tar derived from coal is introduced in the area of hydrogenation and reaction that performs hydrotreating and hydrocracking. The cracked oils in the hydrogenation and reaction area are supplied to the main separation column so that they are separated between (i) components containing 6 ~ 10 carbons, (ii) light paraffinic components, and (iii) hydrocarbonaceous components containing 11 or more carbons.
    After being separated by the main separation column, (iii) oils containing 11 or
    17/39 more carbons are mixed with the above supply and then recirculated back to the hydrogenation and reaction area.
    Through such recirculation, aromatic components containing two or more rings can be cracked to a 1-ring aromatic component using hydroprocessing and hydrocracking catalysts, and hydrocarbon groups containing two or more carbons- or — naphthenic rings can also— cracked and converted into valuable aromatic components or materials to produce valuable aromatic components.
    When recirculation is carried out in this way, the amount of aromatic components containing two or more rings can be drastically reduced, compared to when recirculation is not
    fulfilled. Besides that, the amount of these which is converted in aromatic compounds valuable or materials to produce aromatic compounds valuable Can be increased considerably. Also, once that
    composition of (i) components containing 6 ~ 10 carbons varies depending on the supply used in the examples, the aromatic separation process, the transalkylation process and the xylene processing can be configured in different ways to suit the properties of the components, and unconverted oils are recirculated to the hydrogenation and reaction area.
    When the configuration of these processes is changed and recirculation is used
    18/39 in addition as mentioned above, unnecessary components are prevented from accumulating at the end of the trans-alkylation and processing of xylene, the components that are not used as materials to produce aromatic components converted in this way, - valuable. Valuables can be valuable aromatic components, increasing the yield of components and detail effects in Examples 1 and 2 in addition to the aromatic recirculation principle are described — in the following.
    In order to explain the present patent application, the examples are described below, but the present examples are not intended to limit the scope of the present patent application of the present inventors.
    EXAMPLE
    Example 1 Production of
    Light Paraffins from
    Valuable Aromatics using Reaction and Transalkylation was composed of catalytic oils in bed compositions and can vary invention as imagined by
    Aromatic Compounds
    Valuable and LCO
    Production
    Paraffins
    Hydrogenation,
    The LCO of
    Compounds
    Light from LCO
    Aromatic Separation, used in this example cracked resulting from fluidized cracking (FCC). The properties, yields of oils resulting from,
    FCC depending on supply and operating conditions in a
    FCC. In the present example, the
    LCO
    19/39 having a boiling point of 170 ~ 360 ° C among the resulting FCC oils was prepared as shown in Table 1 below.
    Table 1
    Composition Supply quantity Paraffin 4.68 Ethane 0.00 Propane 0.00 Butane 0.00 Naphthene 0.50 Total Aromatic Compounds 84.12 Total 1 ring aromatics 39.02 1 ring aromatics without naphthenic ring 26.95 B 0.02 T 0.34 X 1.72 C9 7.61 C10 11.55 1-ring aromatics with a naphthenic ring 12.07 1-ring aromatics with two naphthenic rings 0.00 Total 2-ring Aromatics 40.98 2-ring aromatics without naphthenic ring 38.40 2-ring aromatics with a naphthenic ring 2.58 2-ring aromatics with two naphthenic rings 0.00 Total 3-ring Aromatics 4.12 Others 10.70
    The above supply was introduced in a hydro-processing unit. The hydroprocessing was carried out in a fixed bed reactor in the presence of a combined nickel-molybdenum catalyst. The conditions of the hydroprocessing reaction are shown in Table 2 below.
    Table 2
    20/39
    Catalyst NÍMO / AI2O3 Operation conditions Reaction pressure, kg / [sic] 60 LHSV, hr- 1 1.5 Reaction Temperature, ° C 300
    After hydroprocessing, the composition was changed as shown in Table 3 below.
    Table 3
    Composition Supply-Quantity After 0 Hydroprocessing— Paraffin 4.68 5.38 Ethane 0.00 0.01 Propane 0.00 0.01 Butane 0.00 0.01 Naphthene 0.50 1.74 Total Aromatics 84.12 80.02 Total 1 ring aromatics 39.02 71.33 1 ring aromatics without naphthenic ring 26.95 27.28 B 0.02 0.00 T 0.34 0.10 X 1.72 0.84 C9 7.61 5.08 C10 11.55 10.39 1-ring aromatics with a naphthenic ring 12.07 39.89 1-ring aromatics with two naphthenic rings 0.00 4.16 Total 2-ring Aromatics 40.98 8.03 2-ring aromatics without naphthenic ring 38.40 4.29 2-ring aromatics with a naphthenic ring 2.58 3.60 2-ring aromatics with two naphthenic rings 0.00 0.13 Total 3-ring Aromatics 4.12 0.66 Others 10.70 13.63
    How is it apparent from gives Table 3, before the hydroprocessing, the amount in components containing two or more aromatic rings it was
    21/39 considerable, but was drastically reduced after hydroprocessing. In addition, the amount of aromatic components of 1 aromatic ring increased by about 80%, and, in particular, the amount of components with 1 aromatic ring containing the naphthenic ring increased from about 12.07 to about 39.89, ie at least 230% based on a supply value of 100. The aromatic component of 1 ring containing the naphthenic ring can be transformed into a valuable aromatic component or a direct material to produce the valuable aromatic component by breaking the naphthenic ring in the hydrocracking unit.
    The products obtained from the hydroprocessing unit were supplied to a hydrocracking reactor, so that hydrocracking was carried out. The catalyst used in this example was a combination of cobalt and beta-zeolite, the reaction temperature was 380 ° C, and the reaction pressure was 1200 psig.
    After hydrocracking, the composition was changed as shown in Table 4 below.
    Table 4
    Composition Supply quantity After Hydroprocessing After Hydrocracking Paraffin 4.68 5.38 40.85 Ethane 0.00 0.01 0.41 Propane 0.00 0.01 8.20 Butane 0.00 0.01 19.25 Naphthene 0.50 1.74 1.51 Total Aromatics 84.12 80.02 59.98 Total 1 ring aromatics 39.02 71.33 55.52 1 ring aromatics without naphthenic ring 26.95 27.28 52.72 B 0.02 0.00 1.79
    22/39
    Continuation of Table 4 T 0.34 0.10 9.04 X 1.72 0.84 16.44 C9 7.61 5.08 15.14 C10 11.55 10.39 8.34 1-ring aromatics with a naphthenic ring 12.07 39.89 2.50 1-ring aromatics with two naphthenic rings 0.00 4.16 0.30 Total 2-ring Aromatics 40.98 8.03 4.41 2-ring aromatics without naphthenic ring 38.40 4.29 2.57 2-ring aromatics with a naphthenic ring 2.58 3.60 1.84 2-ring aromatics with two naphthenic rings 0.00 0.13 0.00 Total 3-ring Aromatics 4.12 0.66 0.06 Others 10.70 13.63 1.99
    As is apparent to leave gives Table 4, compared as supply before of hydrocracking, the to know, O supply after O hydroprocessing, the amount in benzene and x ileno, what
    are valuable aromatic components, has been increased by 2000% or more. In addition, the amount of toluene / C9 / C10, which is the material to produce benzene / xylene by subsequent transalkylation, has been increased by about
    109%. After hydrocracking, only paraffin, produced.
    Among the olefins, there were components produced by the recovered, and supplied for hydrocracking, the light paraffins were components containing 6 carbons were the process of transalkylation.
    The catalyst used in the transalkylation process was composed of a carrier composed of 50% by weight of mordenite having a silica / alumina molar ratio of 90 and 50% by weight of alumina gamma binder and
    23/39
    0.05 parts by weight of platinum and 0.5 parts by weight of tin supported on it.
    composition of the products obtained by trans-alkylation shown in Table 5 below.
    Table 5
    Composition Quantity ofSupply after theHydroprocessing after theHydrocracking AfterTransalkylation Paraffin 4.68 5.38 40.85 49.18 Ethane 0.00 0.01 0.41 5.08 Propane 0.00 0.01 8.20 10.95 Butane 0.00 0.01 19.25 20.18 Naphthene 0.50 1.74 1.51 0.02 Total Aromatics 84.12 80.02 59.98 53.76 Total 1 ring aromatics 39.02 71.33 55.52 49.30 1 ring aromatics without naphthenic ring 26.95 27.28 52.72 47.26 B 0.02 0.00 1.79 7.95 T 0.34 0.10 9.04 0.00 X 1.72 0.84 16.44 34.89 C9 7.61 5.08 15.14 0.00 C10 11.55 10.39 8.34 2.83 1-ring aromatics with a naphthenic ring 12.07 39.89 2.50 1.74 1-ring aromatics with two naphthenic rings 0.00 4.16 0.30 0.30 Total 2-ring Aromatics 40.98 8.03 4.41 4.41 2-ring aromatics without naphthenic ring 38.40 4.29 2.57 2.57 2-ring aromatics with a naphthenic ring 2.58 3.60 1.84 1.84 2-ring aromatics with two naphthenic rings 0.00 0.13 0.00 0.00 Total 3-ring Aromatics 4.12 0.66 0.06 0.06 Others 10.70 13.63 1.99 1.99
    As it is apparent starting gives Table 5, compared as supply before gives
    transalkylation, the supply after transalkylation had benzene as the valuable aromatic component, the amount of which was increased by 345%, and xylene, which additionally increased in quantity by
    112%.
    Once the
    24/39 transalkylation was not a cracking procedure, there was an additional increase in the amount of paraffins, not olefins.
    Component Production
    Valuable Aromatics and Light Paraffins from LCO by Hydrocarbon Recirculation containing 11 or more Carbons
    In the process of producing valuable aromatic compounds, the me-sma-s - supply and reaction conditions were applied, with the exception that 10 hydrocarbonaceous components containing 11 or more carbons resulting from hydroprocessing and hydrocracking were recirculated back to the area hydrogenation and reaction.
    The supply of LCO (AO), the product (Al) obtained without the recirculation of hydrocarbons containing 11 or more carbons, and the product (A2) obtained by the recirculation of hydrocarbons containing 11 or more carbons are shown in Table 6 below.
    Table 6
    Composition TO TO 1 A2 Paraffin 4.68 49.18 55.98 Ethane 0.00 5.08 5.78 Propane 0.00 10.95 12.47 Butane 0.00 20.18 22.97 Naphthene 0.50 0.02 0.02 Total Aromatics 84.12 53.76 49.69 Total 1 ring aromatics 39.02 49.30 49.69 1 ring aromatics without naphthenic ring 26.95 47.26 49.69 B 0.02 7.95 9.05 T 0.34 0.00 0.00
    25/39
    Continuation of table 6 X 1.72 34.89 39.72 C9 7.61 0.00 0.00 C10 11.55 2.83 0.91 1-ring aromatics with a naphthenic ring 12.07 1.74 0.00 1-ring aromatics with two naphthenic rings 0.00 0.30 0.00 Total 2-ring Aromatics 40.98 4.41 0.00 2-ring aromatics without naphthenic ring 38.40 2.57 0.00 2-ring aromatics with a naphthenic ring 2.58 1.84 0.00 2-ring aromatics with two naphthenic rings 0.00 0.00 0.00 Total 3-ring Aromatics 4.12 0.06 0.00 Others 10.70 1.99 0.00
    As is apparent from the
    Table 6, recirculation was performed additionally, by which aromatic components containing two or more rings were excluded and, as a valuable aromatic component, benzene was increased by 14% and xylene was additionally increased by 14%. The total of light paraffins was increased by about 14%. Therefore, the valuable aromatic compounds and light paraffins could be obtained in higher yields because of the recirculation.
    Compound Production
    Valuable Aromatics and Light Paraffins from LCO by Recirculating Unconverted Oils after Transalkylation ---------- In the process of producing valuable aromatic compounds by recirculating the hydrocarbonaceous components containing 11 or more carbons to the hydroprocessing, the same supply and reaction conditions were applied, with the exception that, among the valuable aromatic components resulting from transalkylation, a portion of benzene, toluene and xylene was
    26/39 recovered through the aromatics separation process, and the rest of them were repeatedly recirculated back to the transalkylation process and the hydrogenation and reaction area.
    The supply of LCO (AO), the product (Al) obtained without the recirculation of hydrocarbons containing 11 or more carbons, the product (A2) obtained by the recirculation of hydrocarbons containing 11 or — more carbons, and the product (A3) obtained by recirculation of unconverted heavy oils after transalkylation are shown in Table 7 below.
    Table 7
    Composition TO Al A2 A3 Paraffin 4.68 49.18 55.98 56.50 Ethane 0.00 5.08 5.78 5.83 Propane 0.00 10.95 12.47 12.51 Butane 0.00 20.18 22.97 23.02 Naphthene 0.50 0.02 0.02 0.02 Total Aromatics 84.12 53.76 49.69 49.17 Total 1 ring aromatics 39.02 49.30 49.69 49.17 1 ring aromatics without naphthenic ring 26.95 47.26 49.69 49.17 B 0.02 7.95 9.05 9.14 T 0.34 0.00 0.00 0.00 X 1.72 34.89 39.72 40.02 C9 7.61 0.00 0.00 0.00 C10 11.55 2.83 0.91 0.00 1-ring aromatics with a naphthenic ring 12.07 1.74 0.00 0.00 . 1-ring aromatics with two naphthenic rings 0.00 0.30 0.00 0.00 Total 2-ring Aromatics 40.98 4.41 0.00 0.00 2-ring aromatics without naphthenic ring 38.40 2.57 0.00 0.00 2-ring aromatics with a naphthenic ring 2.58 1.84 0.00 0.00 2-ring aromatics with two naphthenic rings 0.00 0.00 0.00 0.00 Total 3-ring Aromatics 4.12 0.06 0.00 0.00 Others 10.70 1.99 0.00 0.00
    27/39
    As is apparent from the
    Table 7, the recirculation was performed twice, whereby the amount of benzene and xylene, which are valuable aromatic components, was increased by 0.4 weight, and the amount of light paraffins such as ethane, propane and butane was increased by 0.14% by weight, compared to when the recirculation was performed once.
    ..Therefore, the valuable aromatics could be obtained in higher yields by performing two recirculations.
    Production of
    Components
    Valuable Aromatics and Light Paraffins from LCO by
    Processing of Xylene after Transalkylation.
    In the recirculation of unconverted oils after transalkylation, the same conditions of supply and reaction were applied, with the exception that the xylene mixture obtained with xylene processing by transalkylation was treated comprising paraxylene separation and xylene isomerization.
    The supply of LCO (AO), the product (Al) obtained without the recirculation of hydrocarbons containing 11 or more carbons, the product (A2) obtained by the recirculation of hydrocarbons containing 11 or more carbons, the product (A3) obtained by the recirculation of heavy oils not converted after transalkylation, and the product (A4) obtained by the isomerization and separation of xylene are shown in Table 8 below.
    Table 8
    28/39
    Composition TO TO 1 A2 A3 A4 Paraffin 4.68 49.18 55.98 56.50 57.02 Ethane 0.00 5.08 5.78 5.83 6.10 Propane 0.00 10.95 12.47 12.51 12.63 Butane 0.00 20.18 22.97 23.02 23.02 Naphthene 0.50 0.02 0.02 0.02 0.02 Total Aromatics 84.12 53.76 49.69 49.17 48.66 Total 1 ring aromatics 39.02 49.30 49.69 49.17 48.66 1 ring aromatics without naphthenic ring 26.95 47.26 49.69 49.17 48.66 B 0.02 7.95 9.05 9.14 9.86 T 0.34 0.00 0.00 0.00 0.00 X Mixed 1.45 34.07 39.72 39.04 38.80 (*) EB 0.27 0.82 0.94 0.98 0.00 C9 7.61 0.00 0.00 0.00 0.00 C10 11.55 2.83 0.91 0.00 0.00 1-ring aromatics with a naphthenic ring 12.07 1.74. 0.00- - 0.00 0.00 - Lanei aromatics with two naphthenic rings 0.00 0.30 0.00 0.00 0.00 Total 2-ring Aromatics 40.98 4.41 0.00 0.00 0.00 2-ring aromatics without naphthenic ring 38.40 2.57 0.00 0.00 0.00 2-ring aromatics with a naphthenic ring 2.58 1.84 0.00 0.00 0.00 2-ring aromatics with two naphthenic rings 0.00 0.00 0.00 0.00 0.00 Total 3-ring Aromatics 4.12 0.06 0.00 0.00 0.00 Others 10.70 1.99 0.00 0.00 0.00
    (*) Whole para-Xylene
    As a mixture of is apparent from xylene it could be converted to para-xylene, which is a valuable product, by separating para-xylene and xylene isomerization, and what is an impurity in the xylene component, has been completely removed and converted in benzene. Therefore, the yield and purity of the valuable aromatic compound, Paraxylene, could be increased by performing additional xylene processing.
    Example 2 - Production of Valuable Aromatic Compounds and
    Light Paraffins from Coal Tar
    Compound Production
    Valuable Aromatics and Light Paraffins from Coal Tar 15 using Hydroprocessing and Hydrocracking Reaction, Aroma Separation and Transalkylation
    29/39
    The properties and compositions of the oils derived from coal used in this example may differ depending on the type of supply and operating conditions. In the present example, coal tar having a boiling point of 78 ~ 350 ° C and having the composition shown in Table 9 below was prepared as oil 5 derived from coal carbonation.
    Table 9 - - -
    Composition Supply Quantity Paraffin 0.77 Ethane 0.00 Propane 0.77 Butane 0.00 Naphthene 0.00 Total Aromatics 99.23 Total 1 ring aromatics 9.73 1 ring aromatics without naphthenic ring 6.30 B 2.05 T 0.70 X 1.59 C9 1.65 C10 0.30 1-ring aromatics with a naphthenic ring 3.43 1-ring aromatics with two naphthenic rings 0.00 Total 2-ring Aromatics 89.50 2-ring aromatics without naphthenic ring 66.92 2-ring aromatics with a naphthenic ring 22.58 2-ring aromatics with two naphthenic rings 0.00 Total 3-ring Aromatics 0.00 Others 0.00
    The coal tar containing the above composition was supplied to a hydro-processing unit. The hydroprocessing wa was carried out in a fixed bed reactor using a combined nickel-molybdenum catalyst.
    The conditions of the hydroprocessing reaction are shown in Table 10 below.
    Table 10
    30/39
    Catalyst NÍMO / AI2O3 Operation conditions Reaction pressure, kg / [sic] 60 LHSV, hr 1 1.5 Reaction Temperature, ° C 300
    After hydroprocessing, the composition was changed as shown in Table 11 below.
    Table 11
    Composition Supply Quantity After 0 Hydroprocessing _ .. Paraffin · - · - * ~ 0.77 0.81 Ethane 0.00 0.00 Propane 0.77 0.81 Butane 0.00 0.00 Naphthene 0.00 0.00 Total Aromatics 99.23 104.47 Total 1 ring aromatics 9.73 83.73 1 ring aromatics without naphthenic ring 6.30 6.63 B 2.05 2.16 T 0.70 0.74 X 1.59 1.68 C9 1.65 1.73 C10 0.30 0.32 1-ring aromatics with a naphthenic ring 3.43 61.59 1-ring aromatics with two naphthenic rings 0.00 15.51 Total 2-ring Aromatics 89.50 20.74 2-ring aromatics without naphthenic ring 66.92 12.48 2-ring aromatics with a naphthenic ring 22.58 8.26 2-ring aromatics with two naphthenic rings 0.00 0.00 Total 3-ring Aromatics 0.00 0.00 Others 0.00 0.00
    As is apparent from the
    Table 11, before hydroprocessing, the number of components containing two or more aromatic rings was considerable but was drastically reduced after hydroprocessing. In addition, the amount of aromatic components of 1 ring increased by 7.6 times or more, and
    31/39 in particular, the amount of components with 1 aromatic ring containing the naphthenic ring increased from about 3.43 to about 61.59, that is, 17 times, based on a value of 100 for the supply. The 5 1 ring aromatic component containing the naphthenic ring can be transformed into a valuable aromatic component or a direct material to produce the valuable aromatic component by breaking the ring. naphthenic in the hydrocracking unit.
    The products obtained from the hydroprocessing unit were supplied to a hydrocracking reactor, so that hydrocracking was carried out. The catalyst used in this example was a combination of cobalt and beta-zeolite, the reaction temperature was 370 ° C, and the reaction pressure was 1100 psig.
    After cracking, the composition was changed as shown in Table 12 below.
    Table 12
    Composition Quantity ofSupply After Hydroprocessing After theHydrocracking Paraffin 0.77 0.81 35.63 Ethane 0.00 0.00 0.30 Propane 0.77 0.81 9.80 Butane 0.00 0.00 14.51 Naphthene 0.00 0.00 0.90 Total Aromatics 99.23 104.47 70.70 Total 1 ring aromatics 9.73 83.73 50.39 . 1 ring aromatics without naphthenic ring 6.30 6.63 47.72 B 2.05 2.16 19.95 T 0.70 0.74 9.36 X 1.59 1.68 9.58 C9 1.65 1.73 5.51 C10 0.30 0.32 2.99 1-ring aromatics with a naphthenic ring 3.43 61.59 2.67 1-ring aromatics with two naphthenic rings 0.00 15.51 0.00 Total 2-ring Aromatics 89.50 20.74 20.29
    32/39
    Continuation of table 12 2-ring aromatics without naphthenic ring 66.92 12.48 20.27 2-ring aromatics with a naphthenic ring 22.58 8.26 0.02 2-ring aromatics with two naphthenic rings 0.00 0.00 0.00 Total 3-ring Aromatics 0.00 0.00 0.02 Others 0.00 0.00 0.56
    As it is apparent to leave gives Table 12, compared to supply - before - 'of cracking, The know the supply after O hydroprocessing, the amount benzene and xylene, what
    are valuable aromatic components, has been increased by about 670% or more. In addition, the amount of toluene / C9 / C10, which is the materials used to produce benzene / xylene by subsequent transalkylation, has been increased by about 540%. In the hydrocracking unit, only paraffins, not olefins, were produced.
    Among the components produced by hydrocracking, light paraffins were recovered, and components containing 6 ~ 10 carbons were supplied for the aromatics separation process, so that benzene was separated and the remaining components were supplied for the transalkylation process. In Example 1, since the amount of the benzene component is not large, even when the components containing 6 ~ 10 carbons are supplied directly to the transalkylation process without the separation of benzene, the charge in the transalkylation process is small and the process is simplified. However, in the present example, since the benzene component is large, when the components containing
    33/39 carbons are supplied for the transalkylation process without the separation of benzene, which is a burden on the large transalkylation process, increasing the investment cost undesirable comparatively while decreasing the yield of valuable aromatic compounds.
    The catalyst used in the trans-quijation process was composed of a carrier-compound of 50% by weight of mordenite having a 10 molar ratio of silica / alumina of 90 and 50% by weight of alumina binder and 0, 05 parts by weight of platinum and 0.5 parts by weight of tin supported on it. The composition of the products obtained by transalkylation is shown in Table 13 below.
    Table 13
    Composition Quantity ofSupply after theHydroprocessing after theHydrocracking AfterTransalkylation Paraffin 0.77 0.81 35.63 40.82 Ethane 0.00 0.00 0.30 3.07 Propane 0.77 0.81 9.80 11.43 Butane 0.00 0.00 14.51 15.06 Naphthene 0.00 0.00 0.90 0.01 Total Aromatics 99.23 104.47 70.70 66.77 Total 1 ring aromatics 9.73 83.73 50.39 46.46 1 ring aromatics without naphthenic ring 6.30 6.63 47.72 44.82 B 2.05 2.16 19.95 28.20 T 0.70 0.74 9.36 0.00 X 1.59 1.68 9.58 15.01 C9 1.65 1.73 5.51 0.00 C10 0.30 0.32 2.99 1.33 1-ring aromatics with a naphthenic ring 3.43 61.59 2.67 1.64 1-ring aromatics with two naphthenic rings 0.00 15.51 0.00 0.00 Total 2-ring Aromatics 89.50 20.74 20.29 20.29 2-ring aromatics without naphthenic ring 66.92 12.48 20.27 20.27 2-ring aromatics with a naphthenic ring 22.58 8.26 0.02 0.02 2-ring aromatics with two naphthenic rings 0.00 0.00 0.00 0.00 Total 3-ring Aromatics 0.00 0.00 0.02 0.02 Others 0.00 0.00 0.56 0.56
    Table 13
    As is apparent from compared to the supply before the
    34/39 transalkylation, the supply after transalkylation had benzene as the valuable aromatic component, the amount of which was increased by 41%, and and xylene, which additionally increased in quantity by 57%. Since transalkylation was not a cracking procedure, there was an additional increase in the amount of light paraffins, not olefins.
    - - · - Production of - Valuable Aromatic Compounds and Light Paraffins from Coal Tar by Recirculating Hydrocarbons containing 11 or more Carbons
    In the process of producing valuable aromatic compounds, the same supply and reaction conditions were applied, with the exception that the hydrocarbonaceous components containing 11 or more carbons resulting from hydroprocessing and hydrocracking were recirculated back to the area of hydrogenation and reaction.
    The supply of coal tar (AO), the product (Al) obtained without the recirculation of hydrocarbons containing 11 or more carbons, and the product (A2) obtained by the recirculation of hydrocarbons containing 11 or more carbons are shown in Table 14 below.
    Table 14
    Composition TO TO 1 A2 Paraffin 0.77 40.82 53.21 Ethane 0.00 3.07 4.03 Propane 0.77 11.43 14.74 Butane 0.00 15.06 19.76 Naphthene 0.00 0.01 0.01 Total Aromatics 99.23 66.77 57.48 Total 1 ring aromatics 9.73 46.46 57.48 1 ring aromatics without naphthenic ring 6.30 44.82 57.48
    35/39
    Continuation of table 14 B 2.05 28.20 36.99 T 0.70 0.00 0.00 X 1.59 15.01 19.69 C9 1.65 0.00 0.00 C10 0.30 1.33 0.79 1-ring aromatics with a naphthenic ring 3.43 1.64 0.00 1-ring aromatics with two naphthenic rings 0.00 0.00 0.00 Total 2-ring Aromatics 89.50 20.29 0.00 2-ring aromatics without naphthenic ring 66.92 20.27 0.00 2-ring aromatics with a naphthenic ring 22.58 0.02 0.00 2-ring aromatics with two naphthenic rings 0.00 0.00 0.00 Total 3-ring Aromatics 0.00 ~~ 0.02 0.00 ' Others 0.00 0.56 0.00
    As is apparent from the
    Table 14, recirculation was performed additionally, by which aromatic components containing two or more rings were excluded and, as a valuable aromatic component, benzene was increased by 31% and xylene was additionally increased by 31%. In addition, the total of light paraffins has been increased by about 30%. Therefore, the valuable aromatic compounds and light paraffins could be obtained in higher yields because of the recirculation.
    Production of Valuable Aromatics and Light Paraffins from Coal Tar by Recirculating Unconverted Oils after Transalkylation
    In the process of producing valuable aromatic compounds by recirculating the 15 hydrocarbonaceous components containing 11 or more carbons to the hydroprocessing unit, the same supply and reaction conditions were applied, with the exception that, among the valuable aromatic components resulting from transalkylation, a portion of benzene, toluene and xylene was
    36/39 recovered through the aromatics separation process, and the rest of them were repeatedly recirculated back to the transalkylation process and to the hydrogenation and reaction area.
    0 supply of coal tar (AO), the product (Al) obtained without the recirculation of hydrocarbons containing 11 or more carbons, the product (A2) ------ obtained by the recirculation of hydrocarbons containing 11 or more carbons, and the product (A3) obtained by recirculating unconverted heavy oils after transalkylation is shown in Table 15 below.
    Table 15
    Composition TO Al A2 A3 Paraffin 0.77 40.82 53.21 53.66 Ethane 0.00 3.07 4.03 4.07 Propane 0.77 11.43 14.74 14.78 Butane 0.00 15.06 19.76 19.80 Naphthene 0.00 0.01 0.01 0.01 Total Aromatics 99.23 66.77 57.48 57.02 Total 1 ring aromatics 9.73 46.46 57.48 57.02 1 ring aromatics without naphthenic ring 6.30 44.82 57.48 57.02 B 2.05 28.20 36.99 37.07 T 0.70 0.00 0.00 0.00 X 1.59 15.01 19.69 19.96 C9 1.65 0.00 0.00 0.00 C10 0.30 1.33 0.79 0.00 1-ring aromatics with a naphthenic ring 3.43 1.64 0.00 0.00 1-ring aromatics with two naphthenic rings 0.00 0.00 0.00 0.00 Total 2-ring Aromatics 89.50 20.29 0.00 0.00 2-ring aromatics without naphthenic ring 66.92 20.27 0.00 0.00 2-ring aromatics with a naphthenic ring 22.58 0.02 0.00 0.00 2-ring aromatics with two naphthenic rings 0.00 0.00 0.00 0.00 Total 3-ring Aromatics 0.00 0.02 0.00 0.00 Others 0.00 0.56 0.00 0.00
    As is apparent from the
    Table 15, recirculation was performed twice, by which the amount of benzene and xylene, which are components
    37/39 valuable aromatics, was increased by 0.3 wt% by weight, and the amount of light paraffins such as ethane, propane and butane was increased by 0.12% by weight, compared to the product (A2) when recirculation was performed once. Therefore, higher yields of valuable aromatic compounds could be obtained by performing two recirculations.
    -. ---- ----- Production ---- of - Valuable Aromatic Compounds and Light Paraffins from Coal Tar by Xylene Processing after Transalkylation
    In the recirculation of unconverted oils after transalkylation, the same conditions of supply and reaction were applied, with the exception that the xylene mixture obtained by transalkylation was treated with xylene processing comprising paraxylene separation and xylene isomerization.
    The supply of coal tar (AO), the product (Al) obtained without the recirculation of hydrocarbons containing 11 or more carbons, the product (A2) obtained by the recirculation of hydrocarbons containing 11 or more carbons, the product (A3) obtained by recirculation of unconverted heavy oils after transalkylation, and the product (A4) obtained by the xylene isomerization and separation are shown in Table 16 below.
    Table 16
    Composition TO Al A2 A3 A4 Paraffin 0.77 40.82 53.21 53.66 54.30 Ethane 0.00 3.07 4.03 4.07 4.59 Propane 0.77 11.43 14.74 14.78 14.84 Butane 0.00 15.06 19.76 19.80 19.80 Naphthene 0.00 0.01 0.01 0.01 0.01
    38/39
    Continuation of table 16 Total Aromatics 99.23 66.77 57.48 57.02 56.42 Total 1 ring aromatics 9.73 46.46 57.48 57.02 56.42 1 ring aromatics without naphthenic ring 6.30 44.82 57.48 57.02 56.42 B 2.05 28.20 36.99 37.07 38.42 T 0.70 0.00 0.00 0.00 0.00 X Mixed 0.97 13.64 19.69 18.11 18.00 (*) EB 0.63 1.38 1.81 1.85 0.00 C9 1.65 0.00 0.00 0.00 0.00 C10 0.30 1.33 0.79 0.00 0.00 1-ring aromatics with a naphthenic ring 3.43 1.64 0.00 0.00 0.00 1-ring aromatics with two naphthenic rings 0.00 0.00 0.00 0.00 0.00 Total 2-ring Aromatics 89.50  20.29 0.00 0.00 0.00 2-ring aromatics without naphthenic ring 66.92 20.27 0.00 0.00 0.00 2-ring aromatics with a naphthenic ring 22.58 0.02 0.00 0.00 0.00 2-ring aromatics with two naphthenic rings 0.00 0.00 0.00 0.00 0.00 Total 3-ring Aromatics 0.00 0.02 0.00 0.00 0.00 Others 0.00 0.56 0.00 0.00 0.00
    (*) Para-Xylene
    As is apparent from Table 16, almost the entire xylene mixture could be converted into para-xylene, which is a valuable product, by separating para-xylene and isomerization of xylene, and ethylbenzene (EB), which is a impurity in the xylene component, was completely removed and converted to benzene. Therefore, the yield and purity of valuable aromatic compounds could be increased by performing additional processing of 10 xylene.
    Although the configurations of the present invention patent application have been presented for illustrative purposes, those of skill in the art will appreciate that a variety of different modifications and substitutions are possible, without deviating from the scope and spirit of the present filed patent application. in the attached claims. So, such
    39/39 modifications and replacements should also be understood
    as part of the scope of this patent application for
    invention.
    Figures Legend
    Figure 1
    Tl) Supply T2) Hydrogenation and reaction area T 3) Main Separation ----- - · - - T4) Light Separation T5) Gaseous Effluents T6) Heavy Aromatics (C11 +) T7) Aromatic Separation and Transalkylation T8) Aromatic Compounds
    Figure 2
    Tl) Supply T2) Hydrogenation and reaction area T3 Main Separation T4) Light Separation T5) Gaseous Effluents T6) Heavy Aromatics (C11 +) T8) Aromatic Compounds T9) Cycle C6 UNCLE) Remodeling Tll) Aromatics Separation T12) PX separation T13) Xylene isomerization T14) Xylene T15) Transalkylation
    1/6
    权利要求:
    Claims (6)
    [1]
    1. METHOD FOR THE PRODUCTION OF AROMATIC COMPOUNDS AND LIGHT Paraffins, characterized by comprising: a) introduction of oils derived from petroleum, coal or wood in an area of hydrogenation and reaction, so that the polycyclic aromatic components are partially saturated and cracked; b) separation of the components ~ obtained ~ in ~ (a) ~ between hydrocarbon-containing components
    11 or more carbons, hydrocarbon components containing
    6-10 carbons, and hydrocarbon components containing
    5 or less carbons; and c) recirculation of the hydrocarbon components containing 11 or more separate carbons in supply of the hydrocarbon components containing 6-10 carbons for an aromatic separation process and a transalkylation process, so that at least a part of the aromatic compounds is recovered, and supply of the hydrocarbonaceous components containing 5 or less carbons for a light separation process, thus obtaining paraffins.
    [2]
    2. METHOD FOR THE PRODUCTION OF
    AROMATIC COMPOUNDS AND LIGHT PARAFFINS, according to claim 1, characterized in that the hydrocarbonaceous components containing 6-10 carbons separated in (b) are transferred to the aromatic separation process, so that they are separated between benzene, toluene, xylene , and hydrocarbonaceous components containing 9 or more carbons, and a portion of the hydrocarbonaceous components is then supplied to the transalkylation process to thereby obtain a
    2/6 mixture containing benzene, toluene, xylene and hydrocarbon components containing
    9 or more carbons, which is then mixed with the rest of the hydrocarbon components that have not been transferred to the transalkylation process, so that at least part of the aromatic compounds is recovered, or the hydrocarbon components containing 6-10 carbons separated into (b ) are obtaining a mixture comprising benzene, toluene, xylene and
    hydrocarbon components containing 9 or more carbons, which is then supplied to the process in separation in aromatic. 3. METHOD FOR THE PRODUCTION IN AROMATIC COMPOUNDS AND LIGHT SCREWS , in a deal with The
    claim 1, characterized in that it further comprises (d) supplying the xylene mixture separated in the aromatics separation process to a xylene processing to recover at least part of the aromatic compounds, and recirculating oils that are not treated in the xylene processing to the aromatic separation process.
    4. METHOD FOR THE PRODUCTION OF AROMATIC COMPOUNDS AND LIGHT Paraffins, according to claim 3, characterized in that in the xylene processing, the separation of para-xylene from the xylene mixture and the isomerization in para-xylene of the mixture of xylene not containing para-xylene.
    5. METHOD FOR THE PRODUCTION OF AROMATIC COMPOUNDS AND LIGHT WAXES, according to the
    [3]
    3/6 claims 1, or 2, or 3, or 4, characterized in that the area of hydrogenation and reaction in (a) includes a hydroprocessing unit and a hydrocracking unit.
    6. METHOD FOR THE PRODUCTION OF AROMATIC COMPOUNDS AND LIGHT Paraffins, according to claim 5, characterized in that a catalyst used in the hydroprocessing unit is a catalyst comprising an alumina carrier and one or more metals
    selected from among the metals Groups 6, 9 and 10 supported in him.7. METHOD FOR THE PRODUCTION IN COMPOUNDS AROMATIC AND PARAFFINS LEVES, from a deal with The
    claim 5, characterized in that a catalyst used in the hydrocracking unit is a modified zeolite catalyst containing one or more metals selected from Group 6 (Mo, W), Group 9 (Co), and Group 10 (Ni) supported on it.
    8. METHOD FOR THE PRODUCTION OF AROMATIC COMPOUNDS AND LIGHT Paraffins, according to claim 7, characterized in that the modified zeolite catalyst used in the hydrocracking unit is a catalyst comprising one or more types of zeolite having a pore size of 4 Â or more, which can be modified with a binder.
    9. METHOD FOR THE PRODUCTION OF AROMATIC COMPOUNDS AND LIGHT Paraffins, according to claim 8, characterized in that the modified zeolite catalyst used in the hydrocracking unit
    [4]
    4/6 comprises one or more of those selected from MOR, MEL, FAU, and BEA.
    10. METHOD FOR THE PRODUCTION OF
    AROMATIC COMPOUNDS AND LIGHT Paraffins, according to claims 1, or 2, or 3, or 4, characterized in that petroleum-based oils contain 15 ~ 99% by weight of aromatic components based on a total of hydrocarbon components, and have a boiling point of 70 ~ 700 ° C.
    11. METHOD FOR THE PRODUCTION OF AROMATIC COMPOUNDS AND LIGHT Paraffins, according to claim 1, or 2, or 3, or 4, characterized in that oils derived from coal or wood contain 40 ~ 99.9% by weight of components aromatic based on a total of hydrocarbonaceous components, and have a boiling point of 70 ~ 700 ° C.
    12. METHOD FOR THE PRODUCTION OF AROMATIC COMPOUNDS AND LIGHT Paraffins, according to claims 1, or 2, or 3, or 4, characterized in that oils derived from petroleum, coal or wood are selected from oils derived from petroleum, including crude pyrolysis gasoline (RPG), heavy crude pyrolysis gasoline (heavy RPG), treated pyrolysis gasoline (TPG), reformed compounds, heavy aromatic compounds, kerosene, jet oil, atmospheric diesel, CCF (catalytic bed cracking) gasoline fluidized), light cracked naphtha, heavy cracked naphtha, CCF decanted oil, vacuum diesel, coke diesel, coke diesel, coke naphtha, heavy and reduced crude oil,
    [5]
    5/6 atmospheric petroleum distillation bottom residue, heavy and reduced crude petroleum bottom, atmospheric petroleum distillation bottom residue, vacuum petroleum distillation bottom residue, asphalt, bitumen, bituminous sand oil, shale oil , oils derived from coal or wood including coal tar, tar, light oil, phenolic oil or carbolic oil, naphthalene oil, washing oil, —anthracene oil, light anthracene oil, heavy anthracene oil, tar , wood tar, hard wood tar, tar resin or mixtures thereof.
    13. METHOD FOR PRODUCTION IN AROMATIC COMPOUNDS AND SCREWS LIGHT, in a deal with at claims 1, or2, or 3, or 4, featured per further understand (e) The oil recirculation containing 11 or more carbons obtained in the process separation of aromatics to the). 14. METHOD FOR THE PRODUCTION IN AROMATIC COMPOUNDS AND SCREWS LIGHT, in a deal with at
    claims 1, or 2, or 3, or 4, characterized in that it further comprises (c *) providing saturated hydrocarbons, including cyclohexane, between the hydrocarbonaceous components containing 6-10 carbons separated in (b) to a reformer for them to be reformed and then supplied for the aromatics separation process and the transalkylation process.
    15. METHOD FOR THE PRODUCTION OF AROMATIC COMPOUNDS AND LIGHT WAXES, according to
    [6]
    6/6
    claim 14, characterized on what O reformer is operated on a temperature of 400 ~ 600 ° C in an atmosphere hydrogen using a catalyst in Pt / Al 2 O 3 , Pt— Re / Al 2 O 3 or Pt- • Sn / Al 2 O 3 . 16. METHOD FOR THE PRODUCTION OF AROMATIC COMPOUNDS AND PARAFFINS LIGHT, in according to claim 1, characterized on what the compounds
    aromatics in (c) comprise benzene, toluene, xylene or mixtures thereof.
    17. METHOD FOR THE PRODUCTION OF AROMATIC COMPOUNDS AND LIGHT Paraffins, according to claim 1, characterized in that a catalyst used in the process of transalkylation is a catalyst comprising a carrier composed of 10 ~ 95% by weight of beta-zeolite or mordenite having a silica / alumina molar ratio adjusted to 20 ~ 200 based on alumina and
    5-90% by weight of one or more inorganic binders selected from the group consisting of gamma alumina, silica, silica-alumina, bentonite, kaolin, clinoptilolite and montmorillonite, and a hydrogenation metal composed of, based on 100 parts per carrier weight, 0.001 - 0.5 parts by weight of one or more metals selected from the group consisting of platinum, tin, indium and lead.
    1/1
    ΓΤ5Ι
    03.04
    05+
    Η2
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112013009805B1|2018-12-11|method for the production of aromatic compounds and light paraffins
    BR112013006211B1|2021-05-04|method for the production of olefins and aromatics
    US8975462B2|2015-03-10|Method for producing high-added-value aromatic products and olefinic products from an aromatic-compound-containing oil fraction
    JP2017524664A|2017-08-31|Process for producing benzene from C5 to C12 hydrocarbon mixtures
    EP3110915B1|2018-11-14|Process for producing btx from a c5-c12 hydrocarbon mixture
    CN110139915A|2019-08-16|Waste plastics is by being pyrolyzed the conversion to the high value products of such as benzene and dimethylbenzene
    US9376353B2|2016-06-28|Method of producing aromatic hydrocarbons and olefin from hydrocarbonaceous oils comprising large amounts of polycyclic aromatic compounds
    KR101173345B1|2012-08-10|The method for producing valuable aromatics and olefin from hydrocarbonaceous oils comprising aromatic compounds
    JP6914261B2|2021-08-04|Process for producing C2 and C3 hydrocarbons
    US11066609B2|2021-07-20|Integrated methods and systems of hydrodearylation and hydrodealkylation of heavy aromatics to produce benzene, toluene, and xylenes
    BR112013012925B1|2018-08-21|METHOD OF PRODUCTION OF AROMATIC PRODUCTS AND OIL PRODUCTS FROM AN OIL FRACTION CONTAINING AROMATIC COMPOUND
    同族专利:
    公开号 | 公开日
    WO2012053848A2|2012-04-26|
    CN103249699B|2015-04-01|
    KR101800463B1|2017-12-21|
    BR112013009805A2|2016-07-26|
    JP2014500859A|2014-01-16|
    KR20120042687A|2012-05-03|
    SG189484A1|2013-05-31|
    EP2630106A4|2015-08-26|
    JP5917532B2|2016-05-18|
    ES2654404T3|2018-02-13|
    CN103249699A|2013-08-14|
    EP2630106A2|2013-08-28|
    WO2012053848A3|2012-06-21|
    EP2630106B1|2017-09-27|
    US20130267744A1|2013-10-10|
    US8962900B2|2015-02-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4341914A|1980-12-22|1982-07-27|Uop Inc.|Transalkylation process with recycle of C10 hydrocarbons|
    US4585545A|1984-12-07|1986-04-29|Ashland Oil, Inc.|Process for the production of aromatic fuel|
    JPH07278571A|1991-03-30|1995-10-24|Agency Of Ind Science & Technol|Hydrogenating dealkylation of polycyclic aromatic oil|
    US6867340B2|1998-12-24|2005-03-15|Sk Corporation|Disproportionation/transalkylation of aromatic hydrocarbons|
    US6900365B2|1999-11-15|2005-05-31|Chevron Phillips Chemical Company Lp|Process for converting heavy hydrocarbon feeds to high octane gasoline, BTX and other valuable aromatics|
    US6565739B2|2000-04-17|2003-05-20|Exxonmobil Research And Engineering Company|Two stage FCC process incorporating interstage hydroprocessing|
    KR100557558B1|2000-11-30|2006-03-03|에스케이 주식회사|Process for Producing Aromatic Hydrocarbons and Liquefied Petroleum Gas from Hydrocarbon Mixture|
    CN100487080C|2004-03-08|2009-05-13|中国石油化工股份有限公司|Chemical oil-refining method for preparing low carbon olefin and arene|
    KR100710542B1|2005-06-21|2007-04-24|에스케이 주식회사|The method of production increase of light olefins from hydrocarbon feedstock|
    KR100645659B1|2005-06-21|2006-11-14|에스케이 주식회사|The method of production increase of benzene from hydrocarbon feedstock|
    CA2541051C|2005-09-20|2013-04-02|Nova Chemicals Corporation|Aromatic saturation and ring opening process|
    KR101234448B1|2005-11-14|2013-02-18|에스케이이노베이션 주식회사|Process for The Preparation of Aromatic Hydrocarbons and Liquefied Petroleum Gas from Hydrocarbon Mixture|
    US20080146859A1|2006-12-18|2008-06-19|Rekoske James E|Selective Aromatics Isomerization Process|
    JP5462789B2|2007-07-06|2014-04-02|ユーオーピーエルエルシー|Multi-zone process for the production of diesel fuel and aromatic compounds|
    CN101348405B|2007-07-18|2011-01-19|中国石油化工股份有限公司|Method for preparing light arene and light alkane from hydrocarbon raw material|
    US7663010B2|2007-10-31|2010-02-16|Exxonmobil Chemical Patents Inc.|Heavy aromatics processing catalyst and process of using the same|
    CN102015969B|2008-03-04|2015-05-27|马萨诸塞大学|Catalytic pyrolysis of solid biomass and related biofuels, aromatic, and olefin compounds|
    JP2009235248A|2008-03-27|2009-10-15|Toray Ind Inc|Method for producing aromatic hydrocarbon having six to eight carbon atoms|
    KR101503069B1|2008-10-17|2015-03-17|에스케이이노베이션 주식회사|Production of valuable aromatics and olefins from FCC light cycle oil|
    CN101734986A|2008-11-21|2010-06-16|中国石油化工股份有限公司|Method for hydrogenation pyrolysis of prolific benzene and xylene by using pyrolysis gasoline|
    US20100160699A1|2008-12-23|2010-06-24|Frey Stanley Joseph|Method for efficient use of hydrogen in aromatics production from heavy aromatics|US6204906B1|1999-03-22|2001-03-20|Lawrence E. Tannas, Jr.|Methods of customizing the physical size and shape of commercial off-the-shelfelectronic displays|
    KR101735108B1|2010-09-16|2017-05-15|에스케이이노베이션 주식회사|The method for producing valuable aromatics and olefins from hydrocarbonaceous oils derived from coal or wood|
    AU2012245199A1|2011-04-22|2013-11-07|University Of North Dakota|Production of aromatics from noncatalytically cracked fatty acid based oils|
    CN103160331B|2013-03-29|2014-12-10|陕西煤业化工技术研究院有限责任公司|System and process for preparing PTA/PETbased on pyrolysis and gasification devices|
    US9061953B2|2013-11-19|2015-06-23|Uop Llc|Process for converting polycyclic aromatic compounds to monocyclic aromatic compounds|
    US9061955B2|2013-11-19|2015-06-23|Uop Llc|Method of converting a coal to chemicals|
    US9073811B2|2013-11-19|2015-07-07|Uop Llc|Process for providing aromatics from coal tar|
    US9073805B2|2013-11-19|2015-07-07|Uop Llc|Hydrocracking process for a hydrocarbon stream|
    US9162955B2|2013-11-19|2015-10-20|Uop Llc|Process for pyrolysis of a coal feed|
    US9067853B2|2013-11-19|2015-06-30|Uop Llc|Process for selectively dealkylating aromatic compounds|
    US9079816B2|2013-11-19|2015-07-14|Uop Llc|Process for producing alkylated aromatic compounds|
    RU2687104C2|2014-02-13|2019-05-07|Бипи Корпорейшен Норт Америка Инк.|Energy-saving method of fractionation for separation of outpream flow reactor of realactylation processes tol/c9+|
    ES2681801T3|2014-02-25|2018-09-17|Saudi Basic Industries Corporation|Process to produce BTX from a mixed hydrocarbon source through the use of catalytic cracking|
    CN106103663B|2014-02-25|2018-09-11|沙特基础工业公司|Method for oil plant heavy hydrocarbon to be modified to petroleum chemicals|
    US9434894B2|2014-06-19|2016-09-06|Uop Llc|Process for converting FCC naphtha into aromatics|
    CN106660025B|2014-07-07|2020-05-19|国际壳牌研究有限公司|Isomerization catalyst|
    CN104370677A|2014-11-11|2015-02-25|中国海洋石油总公司|C10<+> heavy aromatic hydrocarbon lightening combination process method|
    CN107207968A|2014-11-20|2017-09-26|安耐罗技术股份有限公司|Improved catalysis fast pyrolysis process|
    EP3237582B1|2014-12-22|2020-09-16|SABIC Global Technologies B.V.|Process for producing lpg and btx|
    WO2016102250A1|2014-12-22|2016-06-30|Sabic Global Technologies B.V.|Process for producing lpg and btx|
    WO2016107823A1|2014-12-29|2016-07-07|Shell Internationale Research Maatschappij B.V.|Process for production of aromatics via pyrolysis of lignin-comprising material|
    US10053403B2|2015-02-04|2018-08-21|Exxonmobil Chemical Patents Inc.|Catalyst compositions and their use in transalkylation of heavy aromatics to xylenes|
    US10118165B2|2015-02-04|2018-11-06|Exxonmobil Chemical Patents Inc.|Catalyst compositions and use in heavy aromatics conversion processes|
    CN108025296A|2015-09-30|2018-05-11|沙特基础工业全球技术有限公司|By the method for heavy hydrocarbon charge production LPG|
    US10738246B2|2015-09-30|2020-08-11|Sabic Global Technologies B.V.|Process for producing aromatics from a heavy hydrocarbon feed|
    CN108025294A|2015-09-30|2018-05-11|沙特基础工业全球技术有限公司|For the method by heavy hydrocarbon feedstocks production aromatic hydrocarbons|
    WO2017055095A1|2015-09-30|2017-04-06|Sabic Global Technologies B.V.|Process for producing lpg from a heavy hydrocarbon feed|
    EP3374338A1|2015-11-12|2018-09-19|SABIC Global Technologies B.V.|Methods for producing aromatics and olefins|
    WO2017102645A1|2015-12-16|2017-06-22|Sabic Global Technologies B.V.|Process for producing monoaromatics|
    US11001765B2|2016-02-25|2021-05-11|Sabic Global Technologies B.V.|Process for combined hydrodesulfurization and hydrocracking of heavy hydrocarbons|
    US11001772B2|2016-02-29|2021-05-11|Sabic Global Technologies B.V.|Process for producing olefins using aromatic saturation|
    EP3423548B1|2016-03-01|2020-11-25|SABIC Global Technologies B.V.|Process for producing monoaromatic hydrocarbons from a hydrocarbon feed comprising polyaromatics|
    US10590349B2|2016-06-14|2020-03-17|Fluor Technologies Corporation|Processing of gasification tars to high yields of BTX|
    JP2020514297A|2017-01-05|2020-05-21|サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ|Conversion of waste plastics into high-value products such as benzene and xylenes by pyrolysis|
    US10035742B1|2017-05-26|2018-07-31|Saudi Arabian Oil Company|Process for maximizing xylenes production from heavy aromatics for use therein|
    KR102295333B1|2018-11-13|2021-08-27|한화토탈 주식회사|Method for Benzene, Toluene and Xylene from pyrolysis fuel oil|
    法律状态:
    2018-10-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2018-12-11| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/10/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    KR20100103629|2010-10-22|
    KR10-2010-0103629|2010-10-22|
    PCT/KR2011/007852|WO2012053848A2|2010-10-22|2011-10-20|The method for producing valuable aromatics and light paraffins from hydrocarbonaceous oils derived from oil, coal or wood|
    [返回顶部]