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    • 专利摘要:
    METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS FROM HYDROCARBON OILS DERIVED FROM COAL OR WOOD, this patent application refers to a method for the production of olefins and aromatic compounds from oils derived from coal or wood , including saturation and partial cracking of oils derived from coal or wood, separating them depending on the number of carbons, recirculating heavy oils containing 11 or more carbons to the hydrogenation and reaction area, providing oils suitable for the production of BTX to a process of aromatic separation and a transalkylation process for the recovery of aromatic compounds, and providing hydrocarbon components containing 5 or less carbons for a light separation process, thus obtaining olefins.
    公开号:BR112013006211B1
    申请号:R112013006211-8
    申请日:2011-09-15
    公开日:2021-05-04
    发明作者:Hong Chan Kim；Yong Seung Kim；Sung Won Kim；Sang Hun Oh；Hyuck Jae Lee；Dae Hyun Choo；Cheol Joong Kim；Gyung Rok Kim；Myoung Han Noh；Jae Suk Koh；Hyun Chul Choi；Eun Kyoung Kim；Yoon Kyung Lee；Jong Hyung Lee；Sun Choi；Seung Hoon Oh；Jae Hyiun Koh；Sang Il Lee；Seung Woo Lee
    申请人:Sk Innovation Co., Ltd.；
    IPC主号:
    专利说明:

    Application field
    [001] The present patent application refers to a method for the production of olefins and aromatic compounds from hydrocarbon oils derived from coal or wood. State of the Art
    [002] The demand for aromatic compounds, eg benzene/toluene/xylene, has increased at an annual average of 4 ~ 6% worldwide, which is a drastic increasing trend that is twice the GDP and three times the demand for petroleum products in general. This increase is based on the dramatically growing demand for aromatic compounds in China.
    [003] Conventional aromatic compounds (benzene/toluene/xylene) have been produced by pyrolysis gasoline obtained together with key petroleum products, including ethylene, propylene, etc., in naphtha pyrolysis units using a supply of naphtha, or from reforming into a catalytic naphtha reformer.
    [004] However, due to the drastic increase in 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 cannot meet the growing demand for aromatic compounds because naphtha can only be obtained by atmospheric distillation of crude oil. Therefore, there is a need for an alternative supply for aromatic compounds that is usable as a substitute for naphtha, and furthermore, a need to increase the yield of olefins and aromatic compounds has received attention. Disclosure of Invention Technical Problem
    [005] In view of such circumstances, the present inventors found that aromatic components such as benzene, toluene or xylene, whose demand is increasing, can be prepared from oils derived from coal or wood, and also that it is possible to prepare valuable olefins containing having high applicability and, therefore, this patent application was conceived in a way to adapt to the need of the marked by the techniques mentioned above.
    [006] Consequently, an objective of the present patent application is to provide a new method for the production of olefins and aromatic compounds of high concentration using oils derived from coal or wood containing a large amount of components with high aromaticity, instead of use of a conventional naphtha supply. Solution to Problem
    [007] In order to achieve the above objective, the present patent application provides a method for the production of olefins and aromatic compounds from oils derived from coal or wood, comprising (a) the introduction of oils derived from coal or wood in a hydrogenation and reaction area, so that aromatic components containing aromatic rings are partially saturated and cracked; (b) separating the components obtained in (a) between hydrocarbon components containing 11 or more carbon atoms, hydrocarbon components containing 6-10 carbons, and hydrocarbon components containing 5 or less carbons; and (c) recirculating the hydrocarbon components containing 11 or more carbons separated in (b) back to (a), providing the hydrocarbon components containing 6-10 carbons to an aromatic separation unit and a transalkylation unit so that at least a part of the aromatic compounds is recovered, and supplying the hydrocarbonaceous components containing 5 or less carbons to a light separation unit, thus obtaining olefins. Advantageous Effects of the Invention
    [008] In a method of producing olefins and aromatic compounds according to the present patent application, aromatic compounds of high concentration such as benzene, toluene and xylene can be produced using oils that include coal tar or resulting light oil carbonation of coal or aromatic compounds resulting from pyrolysis, carbonation, destructive distillation, etc. of wood, instead of using the conventional supply of naphtha, and thus the method according to the present patent application can surpass the yield limits of aromatics.
    [009] In particular, among a variety of olefins/aromatic compounds, valuable aromatics, for example, benzene and xylene, and valuable olefins, such as propylene, 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 Drawings Fig. 1 is a schematic block flow diagram showing a process according to an embodiment of the present patent application; and Figure 2 is a schematic block flow diagram showing a process in accordance with another embodiment of the present patent application, including aromatic separation, transalkylation, xylene processing and then recirculation of unconverted oils. Mode of Invention
    [0010] Hereinafter, a detailed description of the present patent application will be presented.
    [0011] The present patent application refers to a method for the production of aromatic components including benzene, toluene or xylene and valuable olefins, from oils derived from coal or wood. According to the present patent application, oils derived from coal or wood, which are used as a supply, include, but are not limited to, oils containing aromatic compounds such as coal tar or light oil, wood tar, etc., and any oil containing aromatic components derivable from charcoal or wood may be used. For example, it is possible to use any materials selected from the group comprising liquid/solid products obtained by coal liquefaction or coal carbonation, such as coal tar, tar, light oil, phenolic oil or carbolic oil, naphthalene oil, oil washings, anthracene oil, light anthracene oil, heavy anthracene oil and pitch, wood carbonation products such as wood tar, hardwood tar, resin tar, and combinations thereof.
    [0012] The schematic block flow diagram for the method according to the present invention is shown in Figure 1. Referring to Figure 1, oils derived from coal and wood are introduced into a hydrogenation and reaction area. Oils derived from coal or wood are hydrocarbon compounds consisting of 40~99.9% aromatic components based on total hydrocarbon components and having a boiling point of 70~700°C. As the amount of aromatic components in the oils is increased, the production of valuable aromatic compounds can be favored.
    [0013] According to the present invention, aromatic components containing aromatic rings can be partially saturated and cracked in the area of hydrogenation and reaction. The hydrogenation and reaction area includes a hydroprocessing unit and a catalytic cracking unit. As such, hydroprocessing and catalytic cracking can be carried out in any sequence. Specifically, the supply can be introduced to the hydroprocessing unit and then to the catalytic cracking unit, or to the analytical cracking unit and then to the hydroprocessing unit.
    [0014] The hydroprocessing unit of the hydrogenation and reaction area is configured so that hydrogen is supplied from outside, in which oils derived from coal and wood are treated with hydrogen in the presence of a hydrotreating catalyst. By the hydroprocessing reaction, aromatic components containing two or more aromatic rings can be partially saturated. Upon such hydroprocessing, an aromatic component containing an aromatic ring must not be saturated. This is because the aromatic component containing an aromatic ring is either a valuable aromatic component or can be converted to a valuable aromatic component by transalkylation, which will be described later.
    [0015] In the hydroprocessing process, aromatic components containing two or more aromatic rings are saturated so that aromatic rings beyond just one aromatic ring are saturated. This is because it is not easy to crack the unnecessary aromatic rings in the later analytical cracking unit.
    [0016] To obtain the above results, the hydroprocessing unit can operate under conditions including a reaction pressure of 20~100kg/cm2, 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.
    [0017] In addition, a catalyst used in the hydroprocessing unit may comprise a carrier composed of one or more of those selected from the group consisting of alumina, silica, zirconium, titanium and activated carbon, and one or more metals selected from the composite group of metals from Groups 6, 8, 9, and 10. One or more metals selected from the composite group of cobalt, molybdenum, nickel, and tungsten are particularly useful.
    [0018] After hydroprocessing, not only the partial saturation of the aromatic rings, but also the denitrogenation, desulfurization and deoxygenation that are conducted to remove impurities such as sulfides or nitrogen compounds from the oils can be carried out. Therefore, the impurities present in the oils can be easily removed without the need for further impurity removal.
    [0019] After hydroprocessing, the partially saturated supply is supplied to the analytical cracking unit. A catalytic cracking catalyst used in the analytical cracking unit can include a solid-forming catalyst including one or more porous solid acids. The solid acid may include an amorphous solid acid such as silica, alumina or silica-alumina, or a crystalline zeolite molecular sieve having a Si/Al molar ratio of 300 or less and a pore size of 3~8Â (Angstrom) .
    [0020] The crystalline zeolite molecular sieve can be a combination of a zeolite molecular sieve selected from FAU, MOR and BEA which are large zeolite molecular sieves having a pore size of 5.6 ~ 7.7 Â so that the components aromatics can react in pores and a zeolite selected from MFI, MEL and FER which are medium zeolite molecular sieves having a pore size of 5 ~ 6.5 Â. The weight ratio of large zeolite molecular sieve to medium zeolite molecular sieve is in the range of 5/95 ~ 95/5, and particularly 50/50 ~ 95/5.
    [0021] The catalytic cracking catalyst can be prepared by mixing 10-95% by weight of one or more zeolite molecular sieves selected from the group consisting of FAU, MOR, BEA, MFI, MEL and FER, and 5-90% by weight of an inorganic binder selected from the group consisting of alumina and clay, so that they are pulverized and dried to a particle size of 10 - 300 microns.
    [0022] Catalytic cracking plays a role in breaking the naphthenic ring or a long chain with two or more carbons attached to a 1-ring aromatic compound. 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 raw supplies for the production of aromatic components in the later units.
    [0023] To obtain the above results, the analytical cracking unit can operate under conditions that include a reaction pressure of 10 ~ 60 psig [ounds per square inch gauge], a reaction temperature of 400 ~ 600 °C, and a catalyst/oil ratio of 4 ~ 10.
    [0024] The products obtained from the hydrogenation and reaction area are separated between i) hydrocarbon components containing 11 or more carbons, ii) hydrocarbon components containing 6-10 carbons and iii) hydrocarbon components containing 5 or less carbons, by means of a separation column. The hydrocarbon components containing 11 or more carbons separated in this way are recirculated back to the hydrogenation and reaction area, and the hydrocarbon components containing 6-10 carbons are fed to an aromatics separation process and a transalkylation process, and the components hydrocarbons containing 5 or less carbons are continuously supplied to a lightweight separation unit.
    [0025] Heavy oils containing 11 or more carbons can be converted into valuable aromatic components or valuable olefinic components, and are thus recirculated back to the hydrogenation and reaction area, the recycled oils recovered by the separation column are about 30% of fresh supply oils, but after recirculation, the amount of oils that must be additionally recirculated is less than only 3% of the total.
    [0026] The hydrocarbon components containing 5 or less carbons that have been separated by the separation column are further separated into off-gases and olefinic components by a light separation process. Olefin components include 2 or more carbons such as ethylene, propylene, butylene, etc.
    [0027] The hydrocarbon components containing 6-10 carbons that have been separated by the separation column are provided for the aromatics separation process and for the transalkylation process. As such, among the hydrocarbon components containing 6 - 10 carbons, saturated hydrocarbons including cyclohexane are supplied to an additional reformer. A portion of the reformed oils in the reformer is fed to the aromatics separation process and to the transalkylation process, and the unconverted oils can be fed to the separation column or light separation unit. The reformer works to convert saturated hydrocarbons into aromatic components at around 400 ~ 600 °C using a Pt/Al2O3 or Pt-Re/Al2O3 catalyst in a hydrogen atmosphere. The products obtained by the reformer can include benzene, toluene and xylene, and such unsaturated hydrocarbons are supplied to the aromatics separation process and the transalkylation process.
    [0028] The hydrocarbon components containing 6-10 carbons separated by the separation column (and passed through the reformer) are transferred to the aromatics separation process and the transalkylation process. As such, aromatic separation and transalkylation can be carried out in any sequence. Specifically, (i) hydrocarbon components containing 6-10 carbons can be separated into benzene, toluene, xylene, and hydrocarbon components containing 9 or more carbons in the aromatics separation process, after which a portion of the separated oils is transferred 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 is additionally mixed with the rest of the oils that were not transferred to the transalkylation process, followed by supplying the resulting mixture to the aromatics separation process, thereby recovering the desired aromatic compounds, or (ii) the hydrocarbon components containing 6-10 carbons can be transferred directly to the transalkylation unit, thus obtaining a mixture composed of benzene, toluene, xylene, and hydrocarbon components containing 9 or more carbons, after which this mixture can be fed to the aromatics separation process, thereby recovering the desired aromatic compounds.
    [0029] After transalkylation, dealkylation of alkyl-aromatic compounds containing 9 and more carbons and transalkylation between benzene and aromatic compounds containing 9 and more carbons occur simultaneously together with dismutation of toluene in the presence of a catalyst and transalkylation between toluene and aromatic compounds containing 9 and more carbons.
    [0030] Such dealkylation is an important reaction that produces the toluene necessary for dismutation/transalkylation. In addition, transalkylation between benzene and aromatic compounds containing 9 and more carbons is considered important because it produces toluene and xylene.
    [0031] On the other hand, olefins including ethylene, propylene, etc., produced by dealkylation, need to be rapidly hydrogenated. If such olefins are not readily hydrogenated, they are realkylated to aromatic compounds, ultimately reducing the conversion rate of aromatic compounds containing 9 and more carbons. Furthermore, 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 may include, a catalyst disclosed in US Patent No. 6,867,340 by the present applicant.
    [0033] Specifically, transalkylation is carried out using 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 by weight of 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 are found in the above literature. The valuable aromatic components produced in this way, namely benzene and xylene, can be recovered and made into products.
    [0034] After transalkylation, aromatic components containing 11 or more carbons, which are not used as materials to make valuable aromatic components, are recovered, and then supplied to the hydrogenation reaction area. In addition, toluene, xylene and hydrocarbons containing 9 or more carbons produced by transalkylation can be supplied to a xylene processing which will be described later via 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 into para-xylene can be performed .
    [0035] Furthermore, the separation of para-xylene to separate only the para-xylene from the xylene components can be performed using a method known in the art, such as adsorption, crystallization, etc.
    [0036] Since para-xylene is much more valuable than ortho-xylene or meta-xylene, separation and recovery of only para-xylene is favorable.
    [0037] The xylene mixture including ortho-xylene and meta-xylene, except for para-xylene, can be transferred to the xylene isomerization process. Within the xylene mixture produced by separating aromatics, para-xylene, meta-xylene, and ortho-xylene are in an equilibrium state. Since only para-xylene is separated by the above separation, the xylene mixture that does not contain para-xylene is balanced using a catalyst, whereby para-xylene, which is economically valuable, can be further obtained.
    [0038] On the other hand, the method according to the present invention may include recovering at least a portion of the aromatic compounds, for example benzene and xylene components, from the transalkylation process and the xylene processing, and the recirculation of unconverted oils back to the aromatics separation unit. Specifically, a portion of benzene and toluene that are not recovered from the transalkylation process is recirculated back to the aromatics separation process and can thus be further supplied to the transalkylation process, and can also be recirculated back to the area of hydrogenation and reaction from the separation process of aromatics. After transalkylation, benzene and toluene can be converted to xylene. Furthermore, in the xylene isomerization unit, oils that are not isomerized to para-xylene can be recirculated back to the aromatics separation process, and thus can be supplied to the transalkylation process or xylene processing.
    [0039] 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 cracking process, thus obtaining para- additional xylene.
    [0040] 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 olefins and valuable aromatic compounds are possible no additional treatment and no waste of materials due to recirculation from the aromatics separation unit to the hydrogenation and reaction area.
    [0041] According to an embodiment of the present invention, coal tar is introduced into the area of hydrogenation and reaction that performs hydrotreating and hydrocracking. Coal tar cracked in the hydrogenation and reaction area is supplied to the separation column so that it is separated between (i) components containing 6~10 carbons, (ii) olefinic components, and (iii) hydrocarbon components containing 11 or more carbons.
    [0042] After being separated by the separation column, (iii) the oils containing 11 or more carbons are mixed with fresh coal tar and then recirculated back to the hydrogenation and reaction area.
    [0043] By such recirculation, aromatic components containing two or more rings can be cracked to a 1-ring aromatic component by hydroprocessing and catalytic cracking, and hydrocarbon groups containing two or more carbons or naphthenic rings can be cracked and converted to valuable aromatic components or materials to produce valuable aromatic components.
    [0044] 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 carried out. Furthermore, the amount of these that is converted into valuable aromatic compounds or materials to produce valuable aromatic compounds can be increased considerably. For example, in the case where recirculation is carried out, benzene, which is the valuable aromatic component, is increased by 15~25%, and xylene can be increased by 160~197%.
    [0045] Also, (i) components containing 6 ~ 10 carbons are supplied to the aromatics separation unit, thereby obtaining benzene, toluene, xylene and hydrocarbon components containing 9 or more carbons, which are then supplied to the process of transalkylation, after which the components including benzene, toluene and xylene produced by the transalkylation process are recirculated back to the aromatics separation unit, the transalkylation unit, the xylene treatment unit and the hydrogenation reaction area, by means of the aromatics separation unit, whereby the total yield of benzene and para-xylene is increased by about 75~85%.
    [0046] In this way, when the above recirculation step is added, the accumulation of unnecessary components after transalkylation and xylene treatment is avoided, and components that are not used as materials to produce valuable aromatic components can be converted into components valuable aromatics, thus increasing the yield of valuable aromatic compounds. The effects of recirculation are described in detail in the example below.
    [0047] In order to further explain the principle of the present invention, the example is described below, but the present example is not intended to limit the scope of the present invention as envisioned by the present inventors. Example
    [0048] Production of Valuable Olefins and Aromatics from Coal Tar using Hydrogenation Reaction, Aromatics Separation, and Transalkylation
    [0049] The properties and compositions of the coal-derived oils 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 1 below was prepared as an oil derived from coal. Table 1

    [0050] Coal tar containing the above composition was supplied to a hydroprocessing process. The hydrotreatment was carried out in a fixed bed reactor in the presence of a catalyst composed of an alumina/silica carrier and nickel/molybdenum metals. The conditions of the hydrotreating reaction are shown in Table 2 below. Table 2

    [0051] After hydroprocessing, the composition was changed as shown in Table 3 below. Table 3

    [0052] As is apparent from Table 3, prior to hydroprocessing, the amount of aromatic components containing two or more aromatic rings was considerable but was drastically reduced after hydroprocessing. Furthermore, the amount of aromatic components of 1 aromatic ring increased by about 8 times or more, and in particular, the amount of components with 1 aromatic ring containing the naphthenic ring increased from about 3.4 to about 74.7, that is, at least 21 times, based on a value of 100 for the delivery. The 1 aromatic ring 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 naphthenic ring
    [0053] in the posterior catalytic cracking process.
    [0054] The products obtained from the hydroprocessing process were supplied to a fluidized bed catalytic cracking reactor that allows the continuous regeneration of a catalyst, so that the catalytic cracking was performed. The catalyst used in this example was a readily commercially available silica/alumina FAU zeolite catalyst (49% alumina, 33% silica, 2% rare earth metal and the other inorganic binder). In addition, the catalytic cracking operating conditions were a reaction temperature of 549 °C, a reaction pressure of 25.3 psig, and a catalyst/oil ratio of 8.
    [0055] After catalytic cracking, the composition was changed as shown in Table 4 below. Table 4

    [0056] As is apparent from Table 4, compared to the supply before catalytic cracking, namely, the supply after hydroprocessing, the amount of benzene and xylene, which are valuable aromatic components, was increased by 262%. Furthermore, the amount of toluene/C9/C10, which are the materials to produce benzene/xylene by subsequent transalkylation, was increased by about 410%.
    [0057] The products obtained by catalytic cracking included light olefins composed of 0.43% by weight of ethylene, 0.92% by weight of propylene and 1.58% by weight of butylene, which were absent in the original composition.
    [0058] Among the components produced by catalytic cracking, the light olefins were recovered, and only components containing 6 ~ 10 carbons were provided for the transalkylation process. 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 gamma 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 5 below. Table 5


    [0059] As is apparent from Table 5, compared to the supply before transalkylation, the supply after transalkylation had benzene as the valuable aromatic component, the amount of which was increased by 134%, and xylene, which further increased in amount by 41%. In addition, the total of benzene and xylene was increased by about 88%. Since transalkylation was not a cracking procedure, there was no further increase in the amount of olefins.
    [0060] Production of Valuable Olefins and Aromatic Compounds from Coal Tar by Recirculation of Hydrocarbons Containing 11 or More Carbons
    [0061] In the process of producing olefins and valuable aromatic compounds, the same supply and reaction conditions were applied, with the exception that hydrocarbon components containing 11 or more carbons resulting from hydroprocessing and catalytic cracking were recirculated back to the area of hydrogenation and reaction.
    [0062] The supply of Coal tar (A0), the product (A1) 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 the Table 6 below. Table 6

    [0063] As is apparent from Table 6, recirculation was carried out further, whereby aromatic components containing two or more rings were excluded and, as a valuable aromatic component, benzene was increased by 21% and xylene was further increased by 187%. The total of benzene and xylene was increased by about 82%. In addition, the total of light olefins including ethylene, propylene and butylene has been increased by about 5 times. Therefore, valuable olefins and aromatics could be obtained in higher yields because of recirculation.
    [0064] Production of Valuable Olefins and Aromatic Compounds from Coal Tar by Recirculation of Unconverted Oils after Transalkylation
    [0065] In the process of producing olefins and valuable aromatic compounds by recirculating hydrocarbon components containing 11 or more carbons to the hydroprocessing process, the same supply and reaction conditions were applied, with the exception that a portion of benzene, toluene , xylene and components containing 9 or more carbons resulting from the transalkylation were repetitively recirculated back to the transalkylation process and the hydrogenation and reaction area via the aromatics separation unit.
    [0066] The supply of coal tar (A0), the product (A1) 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


    [0067] As is apparent from Table 7, the recirculation was performed twice, whereby the amount of benzene and xylene, which are valuable aromatic components, was increased by 1.2% by weight, and the amount of light olefins such as ethylene, propylene and butylene was increased by 0.46% in weight compared to when recirculation was performed once. Therefore, valuable olefins and aromatic compounds could be obtained in higher yields by carrying out the recirculation twice.
    [0068] Production of Valuable Olefins and Aromatic Components from Coal Tar by Xylene Processing After Transalkylation
    [0069] In the recirculation of unconverted oils after transalkylation, the same supply and reaction conditions were applied, with the exception that the xylene components obtained by transalkylation were treated with xylene processing comprising para-xylene separation and isomerization of para-xylene.
    [0070] The supply of coal tar (A0), the product (A1) 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 isomerization and separation of xylene are shown in Table 8 below. Table 8


    [0071] As is apparent from Table 8, almost the entire xylene mixture could be converted to para-xylene, which is a valuable product, by separation of para-xylene and isomerization of para-xylene, and ethylbenzene (EB ), which is an impurity in the xylene component, was completely removed and converted to benzene. Therefore, the yield of valuable aromatic compounds could be increased by carrying out additional xylene treatment.
    [0072] Although the configurations of the present invention have been presented for illustrative purposes, those skilled in the art will appreciate that a variety of different modifications, additions and substitutions are possible without departing from the scope and spirit of the invention presented in the appended claims. Thus, such modifications, additions and substitutions are to be understood as part of the scope of the present invention. Legend of figures 1 and 2 T1) Supply T2) Reaction Area T3) Separation Column T4) Light Separation T5) Heavy Aromatics (11+ C) T6) Aromatic Separation and Transalkylation T7) Aromatics T8) Gas Outlet T9) Propylene T10) Renovation T11) Aromatic Separation T12) Xylene T13) PX Separation T14) Xylene Isomerization
    权利要求:
    Claims (14)
    [0001]
    1. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", characterized by comprising: a) introduction of oils derived from coal or wood in a hydrogenation reaction area, so that the aromatic components containing aromatic rings are partially saturated and cracked ; b) separation of the components obtained in (a) into hydrocarbon components containing 11 or more carbons, hydrocarbon components containing 6-10 carbons and hydrocarbon components containing 5 or less carbons; and c) recirculating the hydrocarbon components containing 11 or more carbons separated in (b) to (a) supplying the hydrocarbon components containing 6-10 carbons to an aromatic separation unit and a transalkylation unit, so that at least one part of the aromatic compounds is recovered and supplying the hydrocarbon components containing 5 or less carbons to a light separation unit, thus obtaining olefins.
    [0002]
    2. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", according to claim 1, characterized in that the hydrocarbon components containing 6-10 carbons separated in (b) are transferred to an aromatic separation unit, so that they are separated between benzene, toluene, xylene and hydrocarbon components containing 9 or more carbons, and a part of the hydrocarbon components is then supplied to the transalkylation unit to thereby obtain a mixture comprising benzene, toluene, xylene and hydrocarbon components containing 9 or more carbons, which is then mixed with the remainder of the hydrocarbon components that have not been transferred to the transalkylation unit, so that at least a portion of the aromatic compounds is recovered; or the hydrocarbon components containing 6-10 carbons separated in (b) are transferred to the transalkylation unit, thereby obtaining a mixture comprising benzene, toluene, xylene and hydrocarbon components containing 9 or more carbons which is then supplied to aromatic separation unit.
    [0003]
    3. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", according to claim 1, further comprising: (d) the supply of the xylene components separated in the aromatic separation unit to a xylene treatment unit to recover at least a part of the aromatic compounds and recirculation of the untreated oils in the xylene treatment unit to the aromatic separation unit.
    [0004]
    4. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", according to claim 3, characterized in that the separation of para-xylene from xylene components and the isomerization of xylene components in the xylene treatment unit which are not para-xylene into para-xylene.
    [0005]
    5. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", according to any one of claims 1 to 4, characterized in that the hydrogenation reaction area in (a) includes a hydrotreating unit and a catalytic cracking unit.
    [0006]
    6. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", according to claim 5, characterized in that a catalyst used in the hydrotreatment unit comprises a carrier composed of one or more of the items selected from the group consisting of alumina, silica, zirconium , titanium and active carbon and one or more metal(s) selected from the group consisting of the metals of Groups 6, 8, 9 and 10.
    [0007]
    7. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", according to claim 5, characterized in that a catalyst used in the catalytic cracking unit is obtained by mixing a zeolite selected from the group consisting of FAU, MOR, BEA, MFI , HONEY and FER or combinations thereof and an inorganic binder selected from the group consisting of alumina and clay.
    [0008]
    8. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", according to any one of claims 1 to 4, characterized in that the oils derived from coal or wood contain 40~99.9% by weight of aromatic components based on in a total of hydrocarbonaceous components and have a boiling point of 70~700°C.
    [0009]
    9. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", according to any one of claims 1 to 4, characterized in that oils derived from coal or wood are coal tar, tar, light oil, phenolic oil or carbolic oil , naphthalene oil, washing oil, anthracene oil, light anthracene oil, heavy anthracene oil, pitch, wood tar, hardwood tar, tar resin or mixtures thereof.
    [0010]
    10. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", according to any one of claims 1 to 4, characterized in that it further comprises: (e) the recirculation of oils containing 11 or more carbons obtained in the aromatic separation unit for (The).
    [0011]
    11. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", according to any one of claims 1 to 4, characterized in that it further comprises: (c) the supply of saturated hydrocarbons, including cyclohexane, among the hydrocarbonaceous components containing 6- 10 carbons separated in (b) to a reformer, so that they are reformed to be unsaturated, and then supplied to the aromatic separation unit and the transalkylation unit.
    [0012]
    12. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", according to claim 11, characterized in that the reformer is operated at a temperature of 400~600°C in a hydrogen atmosphere using a Pt/Al2O3 or Pt catalyst -Re/Al2O3.
    [0013]
    13. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", according to claim 1, characterized in that the aromatic compounds in (c) comprise benzene, toluene, xylene or mixtures thereof.
    [0014]
    14. "METHOD FOR THE PRODUCTION OF OLEFINS AND AROMATIC COMPOUNDS", according to claim 1, characterized in that a catalyst used in the transalkylation unit comprises a carrier composed of 10~95% by weight of beta-zeolite or modernite, having a silica/alumina molar ratio adjusted to 20~200 based on alumina and 5-90% by weight of one or more inorganic binder(s) 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 by weight of the carrier, 0.001-0.5 parts by weight of one or more metal(s) selected from the group consisting of platinum, tin, indium and lead.
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    同族专利:
    公开号 | 公开日
    BR112013006211A2|2020-08-25|
    JP2013537223A|2013-09-30|
    US20130178673A1|2013-07-11|
    EP2616415A2|2013-07-24|
    WO2012036484A2|2012-03-22|
    CN103108849A|2013-05-15|
    SG188984A1|2013-06-28|
    KR101735108B1|2017-05-15|
    EP2616415A4|2015-03-04|
    CN103108849B|2016-04-06|
    JP5890836B2|2016-03-22|
    EP2616415B1|2016-08-31|
    KR20120029143A|2012-03-26|
    WO2012036484A3|2012-05-18|
    US8962901B2|2015-02-24|
    ES2597702T3|2017-01-20|
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    法律状态:
    2020-09-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-09-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/09/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    KR1020100091052A|KR101735108B1|2010-09-16|2010-09-16|The method for producing valuable aromatics and olefins from hydrocarbonaceous oils derived from coal or wood|
    KR10-2010-0091052|2010-09-16|
    PCT/KR2011/006813|WO2012036484A2|2010-09-16|2011-09-15|Method of producing valuable aromatics and olefins from hydrocarbonaceous oils derived from coal or wood|
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