TWI631211B - Method for producing xylene - Google Patents

Method for producing xylene Download PDF

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TWI631211B
TWI631211B TW104109714A TW104109714A TWI631211B TW I631211 B TWI631211 B TW I631211B TW 104109714 A TW104109714 A TW 104109714A TW 104109714 A TW104109714 A TW 104109714A TW I631211 B TWI631211 B TW I631211B
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reaction
aromatic hydrocarbon
hydrogenation
oil
transalkylation
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TW201542799A (en
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川田雄介
大鹽敦保
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科斯摩石油股份有限公司
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    • C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
    • C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
    • C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
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    • C07C2523/28—Molybdenum
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Abstract

本發明提供一種即使將芳香族烴之含有比例低，含有不飽和烴或硫分、氮分等之接觸分解汽油用於不均化反應或轉烷化反應等之轉化反應之原料，仍可簡便且依高產率製造二甲苯的方法。 The present invention provides a raw material which can be used for a conversion reaction of a heterogeneous reaction or a transalkylation reaction, such as an unsaturated hydrocarbon or a sulfur-containing or nitrogen-containing contact decomposition gasoline, even if the content ratio of the aromatic hydrocarbon is low. And a method of producing xylene in high yield.

本發明之二甲苯之製造方法，其特徵為包含：(a)對流動接觸分解汽油進行蒸餾處理，分餾出沸點範圍為145~205℃之餾分的分餾步驟；(b)使於上述(a)分餾步驟中所得之沸點範圍為145~205℃之餾分進行氫化去硫/去氮反應，而將硫含量調整為0~6質量ppm、氮含量調整為0~6質量ppm的氫化處理步驟；與(c)對含有於上述(b)氫化處理步驟中所得之芳香族烴的生成油，施行不均化反應或轉烷化反應的不均化/轉烷化步驟。 The method for producing xylene according to the present invention comprises: (a) a distillation step of distilling off the flow contact decomposed gasoline, and fractionating a fraction having a boiling point range of 145 to 205 ° C; (b) making the above (a) a hydrogenation treatment step in which a boiling point range of 145 to 205 ° C obtained in the fractionation step is subjected to hydrogenation desulfurization/denitrification reaction, and a sulfur content is adjusted to 0 to 6 mass ppm and a nitrogen content is adjusted to 0 to 6 mass ppm; (c) An unevenness/transalkylation step of performing a heterogeneous reaction or a transalkylation reaction on the produced oil of the aromatic hydrocarbon obtained in the above (b) hydrogenation treatment step.

Description

二甲苯之製造方法 Method for producing xylene

本發明係關於二甲苯之製造方法。 The present invention relates to a method for producing xylene.

二甲苯係作為製造成為聚酯原料之酞酸(對酞酸、異酞酸、鄰酞酸)等各種重要工業用化學藥品的出發原料，屬重要化合物。 Xylene is an important starting material for various important industrial chemicals such as citric acid (p-decanoic acid, isodecanoic acid, ortho-nic acid) which are used as polyester raw materials, and is an important compound.

作為製造二甲苯之方法，通常已知使石油腦於接觸改質裝置經改質處理後，進行萃取及分餾的方法；或對由石油腦之熱分解所副產的分解汽油進行萃取及分餾的方法。 As a method for producing xylene, a method of extracting and fractionating a petroleum brain in a contact reforming device after being subjected to a reforming treatment is generally known; or extracting and fractionating a decomposed gasoline which is produced by thermal decomposition of petroleum brain. method.

又，習知已嘗試以芳香族烴作為原料而生成碳數相異之其他芳香族烴的方法(例如參照專利文獻1(日本專利特開昭60-246330號公報))，作為製造二甲苯之方法，亦可考慮使芳香族烴彼此反應而轉化為碳數相異之芳香族烴，以轉烷化反應或芳香族烴之不均化反應所進行的製造方法。 In addition, a method of producing an aromatic hydrocarbon having a different carbon number as a raw material has been proposed (for example, see Patent Document 1 (Japanese Patent Laid-Open Publication No. SHO-60-246330)). Further, a production method in which an aromatic hydrocarbon is reacted with each other to be converted into an aromatic hydrocarbon having a different carbon number and a heteroalkylation reaction or an aromatic hydrocarbon heterogeneous reaction can be considered.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開昭60-246330號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. SHO 60-246330

轉烷化反應係使碳數相異之複數之芳香族烴反應而轉化為目標之芳香族烴的方法，又，芳香族烴之不均化反應係使2分子之相同之芳香族烴反應而轉化為目標之芳香族烴的方法。 The transalkylation reaction is a method in which a plurality of aromatic hydrocarbons having different carbon numbers are reacted to be converted into a target aromatic hydrocarbon, and the aromatic hydrocarbon heterogeneous reaction is carried out by reacting two molecules of the same aromatic hydrocarbon. A method of converting to a target aromatic hydrocarbon.

例如，作為利用芳香族烴之不均化反應的二甲苯之製造方法，可列舉藉由甲苯之不均化反應而製造苯與二甲苯的方法，進而可考慮加入碳數9以上之芳香族烴作為原料，亦發生轉烷化反應而提高二甲苯產率的方法。 For example, as a method for producing xylene using an aromatic hydrocarbon heterogeneous reaction, a method of producing benzene and xylene by a heterogeneous reaction of toluene may be mentioned, and further, an aromatic hydrocarbon having a carbon number of 9 or more may be added. As a raw material, a method of increasing the yield of xylene by a transalkylation reaction also occurs.

在利用轉烷化反應或不均化反應工業性製造二甲苯時，作為原料通常亦使用使對原油進行常壓蒸餾而獲得之重石油腦進一步於接觸改質裝置中進行接觸改質、藉此而獲得之芳香族成分豐富的重質接觸改質汽油。 When xylene is industrially produced by a transalkylation reaction or a heterogeneous reaction, as a raw material, a heavy petroleum brain obtained by subjecting crude oil to atmospheric distillation is further used for contact modification in a contact reforming apparatus. The heavy-weight modified gasoline with rich aromatic content is obtained.

另一方面，由於石油餾分屬於連產品，故對一定量原油進行精製而獲得之重石油腦量亦有其極限。 On the other hand, since the petroleum fraction is a continuous product, the amount of heavy petroleum brain obtained by refining a certain amount of crude oil also has its limit.

由於重石油腦亦可利用作為二甲苯以外之工業原料，故在工業性生產二甲苯時，要求有效活用重石油腦以外之石油餾分，使原料多樣化，達到減低製造成本。 Since the heavy petroleum brain can also be used as an industrial raw material other than xylene, in the industrial production of xylene, it is required to effectively utilize the petroleum fraction other than the heavy petroleum brain to diversify the raw materials and reduce the manufacturing cost.

作為含有芳香族成分之石油餾分，亦可列舉由流動接觸分解裝置所獲得的流動接觸分解汽油，相較於重質接觸改質汽油，流動接觸分解汽油除了芳香族烴之含有比例較低之外，反應性豐富之不飽和烴的含有比例亦較高，進而含有使觸媒劣化之硫分(硫化合物)、氮分(氮化合物)等，故並不適合作為二甲苯的工業原料。 As the petroleum fraction containing an aromatic component, a flow contact decomposed gasoline obtained by a flow contact decomposing device may be mentioned, and the flow contact decomposed gasoline has a lower content ratio of aromatic hydrocarbons than the heavy contact modified gasoline. The content of the unsaturated hydrocarbon rich in reactivity is also high, and further contains sulfur (sulfur compound) and nitrogen (nitrogen compound) which deteriorate the catalyst, and thus is not suitable as an industrial raw material for xylene.

於此種狀況下，本發明之目的在於，提供一種即使將芳香族烴之含有比例低，含有不飽和烴或硫分、氮分等之接觸分解 汽油用於不均化反應或轉烷化反應等之轉化反應之原料，仍可簡便且依高產率製造二甲苯的方法。 Under such circumstances, an object of the present invention is to provide a contact decomposition which contains an unsaturated hydrocarbon or a sulfur component, a nitrogen component, etc., even if the content ratio of the aromatic hydrocarbon is low. Gasoline is used as a raw material for a conversion reaction such as a heterogeneous reaction or a transalkylation reaction, and a method of producing xylene in a simple and high yield.

為了解決上述技術課題，本發明者等人經潛心研究，結果發現，藉由一種包含下述步驟之二甲苯之製造方法，可解決上述技術課題，根據此見解遂完成本發明：(a)對流動接觸分解汽油進行蒸餾處理，分餾出沸點範圍為145~205℃之餾分的分餾步驟；(b)使於上述(a)分餾步驟中所得之沸點範圍為145~205℃之餾分進行氫化去硫/去氮反應，而將硫含量調整為0~6質量ppm、氮含量調整為0~6質量ppm的氫化處理步驟；(c)對含有於上述(b)氫化處理步驟中所得之芳香族烴的生成油，施行不均化反應或轉烷化反應的不均化/轉烷化步驟。 In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that the above technical problem can be solved by a method for producing xylene containing the following steps, and the present invention is completed based on the following findings: (a) The flow contact decomposes the gasoline for distillation, and fractionates the fraction of the boiling point range of 145-205 ° C; (b) hydrogen disulfide the fraction having the boiling point range of 145-205 ° C obtained in the above (a) fractionation step / a dehydrogenation reaction, and a hydrogenation treatment step in which the sulfur content is adjusted to 0 to 6 mass ppm and the nitrogen content is adjusted to 0 to 6 mass ppm; (c) the aromatic hydrocarbons obtained in the above (b) hydrotreating step The resulting oil is subjected to an unevenness/transalkylation step of the heterogeneous reaction or the transalkylation reaction.

亦即，本發明提供： That is, the present invention provides:

(1)一種二甲苯之製造方法，其特徵為包含：(a)對流動接觸分解汽油進行蒸餾處理，分餾出沸點範圍為145~205℃之餾分的分餾步驟；(b)使於上述(a)分餾步驟中所得之沸點範圍為145~205℃之餾分進行氫化去硫/去氮反應，而將硫含量調整為0~6質量ppm、氮含量調整為0~6質量ppm的氫化處理步驟；與(c)對含有於上述(b)氫化處理步驟中所得之芳香族烴的生成油，施行不均化反應或轉烷化反應的不均化/轉烷化步驟。 (1) A method for producing xylene, comprising: (a) a step of distilling a flow contact decomposed gasoline, and fractionating a fraction having a boiling point range of 145 to 205 ° C; (b) making the above (a) a hydrogenation treatment step in which the fraction having a boiling point range of 145 to 205 ° C obtained in the fractionation step is subjected to hydrogenation desulfurization/denitrogenation reaction, and the sulfur content is adjusted to 0 to 6 mass ppm and the nitrogen content is adjusted to 0 to 6 mass ppm; And (c) performing an unevenness/transalkylation step of the heterogeneous reaction or the transalkylation reaction on the produced oil of the aromatic hydrocarbon obtained in the above (b) hydrogenation treatment step.

(2)如上述(1)記載之二甲苯之製造方法，其中，於上述(a)分餾步驟中所得之沸點範圍為145~205℃之餾分，係含有碳數9之芳香族烴25~45容量%、碳數10之芳香族烴15~25容量%。 (2) The method for producing xylene according to the above (1), wherein the fraction having a boiling point range of 145 to 205 ° C obtained in the fractionation step (a) is an aromatic hydrocarbon having a carbon number of 9 and 25 to 45 The aromatic hydrocarbon having a capacity of % and a carbon number of 10 is 15 to 25 % by volume.

(3)如上述(1)或(2)記載之二甲苯之製造方法，其中，上述(b)氫化處理步驟係於氫化去硫/去氮反應後進一步對非芳香族烴進行分離處理的步驟。 (3) The method for producing xylene according to the above (1) or (2), wherein the (b) hydrogenation treatment step is a step of further separating the non-aromatic hydrocarbon after the hydrogenation desulfurization/denitrogenation reaction .

根據本發明，可提供即使將芳香族烴之含有比例低，含有不飽和烴或硫分、氮分等之接觸分解汽油用於不均化反應或轉烷化反應等之轉化反應之原料，仍可簡便且依高產率製造二甲苯的方法。 According to the present invention, it is possible to provide a raw material which is used for a conversion reaction of a heterogeneous reaction or a transalkylation reaction, such as an unsaturated hydrocarbon or a sulfur-containing or nitrogen-containing contact decomposition gasoline, even if the content ratio of the aromatic hydrocarbon is low. A process for producing xylene in a simple and high yield.

本發明之二甲苯之製造方法的特徵在於包含：(a)對流動接觸分解汽油進行蒸餾處理，分餾出沸點範圍為145~205℃之餾分的分餾步驟；(b)使於上述(a)分餾步驟中所得之沸點範圍為145~205℃之餾分進行氫化去硫/去氮反應，而將硫含量調整為0~6質量ppm、氮含量調整為0~6質量ppm的氫化處理步驟；與(c)對含有於上述(b)氫化處理步驟中所得之芳香族烴的生成油，施行不均化反應或轉烷化反應的不均化/轉烷化步驟。 The method for producing xylene according to the present invention is characterized by comprising: (a) a distillation treatment for flowing contact decomposed gasoline, and a fractionation step of fractionating a fraction having a boiling point range of 145 to 205 ° C; (b) fractionating the above (a) The step of obtaining a boiling point in the range of 145 to 205 ° C for hydrogenation desulfurization / denitrification reaction, and adjusting the sulfur content to 0 to 6 mass ppm, and the nitrogen content is adjusted to 0 to 6 mass ppm of the hydrotreating step; c) An unevenness/transalkylation step of performing a heterogeneous reaction or a transalkylation reaction on the produced oil of the aromatic hydrocarbon obtained in the above (b) hydrogenation treatment step.

<(a)分餾步驟> <(a) Fractionation step>

本發明之二甲苯之製造方法中，係使用由流動接觸分解裝置(FCC(Fluid Catalytic Cracking)裝置)所餾出之流動接觸分解汽油(FCC汽油)作為原料油。 In the method for producing xylene of the present invention, a flow contact decomposed gasoline (FCC gasoline) distilled from a flow contact decomposing device (FCC (Fluid Catalytic Cracking)) is used as a raw material oil.

流動接觸分解裝置係藉由流動接觸分解製程(FCC製程)由重質之烴製造流動接觸分解汽油者；其中，所謂流動接觸分解製程，係指使流動之觸媒與烴油在高溫下接觸，而得到汽油或中間餾分等的製程。 The flow contact decomposition device is a flow contact decomposition process (FCC process) for manufacturing a fluid contact decomposition gasoline from a heavy hydrocarbon; wherein the so-called flow contact decomposition process means contacting the flow catalyst with the hydrocarbon oil at a high temperature, and A process for obtaining gasoline or a middle distillate or the like.

作為流動接觸分解製程，可列舉例如HYDROCARBON PROCESSING/NOVEMBER 2000第107~110頁中，ABB Lummus Global Inc,ya,Kellogg Brown&Roots,Inc.或Shell Global Solutions International B.V.或Stone&Webster Inc.,A Shaw Group Co./Institut Francais du Petorole.或UOP LLC.等各種製程製造商所提案的製程。 As a flow contact decomposition process, for example, HYDROCARBON PROCESSING/NOVEMBER 2000, pages 107 to 110, ABB Lummus Global Inc, ya, Kellogg Brown & Roots, Inc. or Shell Global Solutions International BV or Stone & Webster Inc., A Shaw Group Co./ Processes proposed by various process manufacturers such as Institut Francais du Petorole. or UOP LLC.

為了得到上述流動接觸分解汽油，若藉由流動接觸分解製程，將在汽油沸點以上進行沸騰之較重質之烴油(烴混合物)，在高溫下與沸石或矽鋁、氧化鋁等所謂顯示固體酸性之觸媒接觸即可。 In order to obtain the above-mentioned fluid contact decomposition gasoline, if a fluid contact decomposition process is used, a heavier hydrocarbon oil (hydrocarbon mixture) boiling above the boiling point of gasoline, at a high temperature, is said to be solid with zeolite or yttrium aluminum or alumina. The acidic catalyst can be contacted.

商業性規模之流動接觸分解製程通常可於包含垂直安裝之裂解反應器與觸媒再生器2種容器的流動接觸分解裝置中，藉由使具有固體酸性之流動接觸分解觸媒連續循環而進行。 The commercial scale flow contact decomposition process can generally be carried out by continuously circulating a flow contact decomposition catalyst having a solid acidity in a flow contact decomposition apparatus comprising two types of vertically installed pyrolysis reactors and catalyst regenerators.

亦即，在裂解反應器中供給於烴油(烴混合物)之處理後，結果將因表面析出之焦炭而失活之流動接觸分解觸媒，與分解生成物(各種生成油)予以分離、汽提後，移至觸媒再生器，將在觸媒再生器中所再生之熱再生觸媒，再度與應分解之烴油混合，於裂解反應器內引導至向上方向進行循環，藉此可連續進行反應，所得之分解生成物係被蒸餾分離為如乾氣、LPG、汽油餾分、LCO及HCO或漿油般之一種以上的餾分。又，亦可將上述分解生成物之一 部分或全部於裂解反應器內進行再循環而進一步進行分解反應。 That is, after the treatment of the hydrocarbon oil (hydrocarbon mixture) is supplied to the cleavage reactor, the flow-contact decomposition catalyst which is deactivated by the coke precipitated on the surface is separated from the decomposition product (various production oil) and vaporized. After being lifted, the catalyst is moved to the catalyst regenerator, and the heat regeneration catalyst regenerated in the catalyst regenerator is again mixed with the hydrocarbon oil to be decomposed, and guided in the cracking reactor to circulate upward, thereby being continuous. The reaction is carried out, and the resulting decomposition product is separated into one or more fractions such as dry gas, LPG, gasoline fraction, LCO, HCO or slurry oil. Also, one of the above decomposition products may be Part or all of the decomposition is carried out in the cleavage reactor to further carry out the decomposition reaction.

本發明之二甲苯之製造方法中，係由上述分解生成物所分離之餾分內，將汽油餾分使用作為流動接觸分解汽油。 In the method for producing xylene according to the present invention, the gasoline fraction is used as a fluid contact decomposition gasoline in the fraction separated by the decomposition product.

作為於流動接觸分解製程中供給於接觸分解反應的烴油(烴混合物)，可列舉於汽油沸點範圍以上進行沸騰的較重質之烴混合物，具體而言，有藉原油之常壓蒸餾或減壓蒸餾所得的輕油餾分或常壓蒸餾殘渣油及減壓蒸餾殘渣油等，亦可為焦化輕油、溶劑脫瀝青油、溶劑脫瀝青柏油、溚沙油、頁岩油、煤液化油等。 As the hydrocarbon oil (hydrocarbon mixture) supplied to the contact decomposition reaction in the flow contact decomposition process, a heavier hydrocarbon mixture boiling above the boiling point range of the gasoline may be mentioned, specifically, atmospheric distillation or reduction by crude oil. The light oil fraction obtained by pressure distillation or the atmospheric distillation residue oil and the vacuum distillation residue oil may be coking light oil, solvent deasphalted oil, solvent deasphalted asphalt, eucalyptus oil, shale oil, coal liquefied oil, and the like.

又，作為供給於流動接觸分解製程的烴油(烴混合物)，亦可列舉本領域業者所周知之氫化處理，亦即於Ni-Mo系觸媒、Co-Mo系觸媒、Ni-Co-Mo系觸媒、Ni-W系觸媒等之氫化處理觸媒的存在下，於高溫‧高壓下進行氫化去硫的氫化處理油。 Further, as the hydrocarbon oil (hydrocarbon mixture) supplied to the flow contact decomposition process, hydrogenation treatment well known in the art, that is, a Ni-Mo catalyst, a Co-Mo catalyst, and Ni-Co- may be mentioned. In the presence of a hydrogenation catalyst such as a Mo-based catalyst or a Ni-W-based catalyst, hydrogenated desulfurization-treated oil is subjected to high temperature and high pressure.

用於得到本發明所使用之流動接觸分解汽油的上述裂解反應器的運轉條件，係反應溫度較佳為400~600℃、更佳為450~550℃，反應壓力較佳為常壓~5kg/cm3、更佳為常壓~3kg/cm3，以「流動接觸分解觸媒/成為原料之烴油」所表示的質量比較佳為2~20、更佳為4~15。 The operating conditions of the above-mentioned cracking reactor for obtaining the flow contact decomposed gasoline used in the present invention are preferably 400 to 600 ° C, more preferably 450 to 550 ° C, and the reaction pressure is preferably normal pressure to 5 kg / cm 3, more preferably from normal pressure ~ 3kg / cm 3, with "fluid catalytic cracking catalyst / hydrocarbon oil as a raw material of" mass ratio is preferably represented by 2 to 20, more preferably 4 to 15.

藉由反應溫度為上述範圍內，可有效率地獲得含有既定量之芳香族烴的流動接觸分解汽油。在上述反應溫度未滿400℃時，烴油之分解反應進行變慢、分解生成物量降低，故難以進行經濟性運轉。又，在上述反應溫度超過600℃時，容易大量生成烯烴分，所得之流動接觸分解汽油中之芳香族烴的含有比例容易降低。 By the reaction temperature being within the above range, the flow contact decomposed gasoline containing a predetermined amount of aromatic hydrocarbon can be efficiently obtained. When the reaction temperature is less than 400 ° C, the decomposition reaction of the hydrocarbon oil is slowed down, and the amount of the decomposition product is lowered, so that economical operation is difficult. Further, when the reaction temperature exceeds 600 ° C, the olefin component is easily formed in a large amount, and the content ratio of the aromatic hydrocarbon in the obtained flow contact decomposed gasoline is likely to be lowered.

又，藉由反應壓力為上述範圍內，可使莫耳數增加之分解反應有效果地進行，在反應壓力超過5kg/cm3時，分解反應難以進行。 In addition, when the reaction pressure is within the above range, the decomposition reaction in which the number of moles is increased can be effectively carried out, and when the reaction pressure exceeds 5 kg/cm 3 , the decomposition reaction is difficult to proceed.

再者，藉由以「流動接觸分解觸媒/成為原料之烴油」所表示的質量比為上述範圍內，可有效率地獲得流動接觸分解汽油。在上述質量比未滿2時，裂解反應器內之觸媒濃度過低，成為原料之烴油的分解難以進行。又，在上述質量比超過20時，因觸媒濃度上升所造成的分解效果達到飽和，而變得不經濟。 In addition, the mass ratio indicated by the "flow contact decomposition catalyst/hydrocarbon oil as a raw material" is within the above range, and the flow contact decomposed gasoline can be efficiently obtained. When the mass ratio is less than 2, the concentration of the catalyst in the cracking reactor is too low, and decomposition of the hydrocarbon oil serving as a raw material is difficult to proceed. Further, when the mass ratio exceeds 20, the decomposition effect due to an increase in the concentration of the catalyst is saturated, which is uneconomical.

本發明之二甲苯之製造方法中，作為流動接觸分解汽油，若為含有沸點範圍為145~205℃之餾分者則無特別限制，較佳係沸點範圍為30~240℃者、更佳係33~235℃者，再更佳係沸點範圍為35~220℃者。 In the method for producing xylene of the present invention, the fluid contact decomposition gasoline is not particularly limited as long as it has a boiling point range of 145 to 205 ° C, and preferably has a boiling point range of 30 to 240 ° C, and more preferably 33. For those who are ~235°C, it is better to have a boiling point range of 35~220°C.

本發明之二甲苯之製造方法，係於(a)分餾步驟中，對流動接觸分解汽油進行蒸餾處理，分餾出沸點範圍為145~205℃之餾分。 In the method for producing xylene according to the present invention, in the step (a), the flow contact decomposed gasoline is subjected to a distillation treatment, and a fraction having a boiling point range of 145 to 205 ° C is fractionated.

於(a)分餾步驟所分餾出之餾分，係沸點範圍為145~205℃者、較佳係147~202℃者、更佳係150~200℃者。 The fraction fractionated in the (a) fractionation step is those having a boiling point range of 145 to 205 ° C, preferably 147 to 202 ° C, and more preferably 150 to 200 ° C.

本發明之二甲苯之製造方法中，藉由使於(a)分餾步驟所得之餾分之沸點範圍為上述範圍內，可含有既定量之成為二甲苯原料的芳香族烴，同時在後述氫化反應或不均化反應或轉烷化反應時，可抑制因焦炭生成所造成之反應觸媒劣化。 In the method for producing xylene according to the present invention, the boiling point of the fraction obtained in the fractionating step (a) is within the above range, and the aromatic hydrocarbon which is a predetermined amount of the raw material of xylene may be contained, and the hydrogenation reaction or the hydrogenation reaction described later may be carried out. In the case of the heterogeneous reaction or the transalkylation reaction, deterioration of the reaction catalyst due to coke formation can be suppressed.

本發明之二甲苯之製造方法中，於(a)分餾步驟所得之沸點範圍為145~205℃之餾分，較佳係含有碳數9之芳香族烴25~45容量%者、更佳係含有28~42容量%者、再更佳係含有30~40容量%者。 In the method for producing xylene according to the present invention, the fraction having a boiling point range of 145 to 205 ° C obtained in the fractionation step (a) is preferably a fluorine-containing aromatic hydrocarbon of 25 to 45 % by volume, more preferably containing 28 to 42% by volume, and even better, 30 to 40% by volume.

再者，本發明之二甲苯之製造方法中，於(a)分餾步驟所得之沸點範圍為145~205℃之餾分，較佳係含有碳數10之芳香族烴15~25 容量%者、更佳係含有17~23容量%者、再更佳係19~21容量%者。 Further, in the method for producing xylene of the present invention, the fraction having a boiling point range of 145 to 205 ° C obtained in the fractional distillation step (a) preferably contains a hydrocarbon having a carbon number of 10 and 15 to 25 The capacity %, more preferably 17 to 23% by volume, and even more preferably 19 to 21% by volume.

本發明之二甲苯之製造方法中，藉由使於(a)分餾步驟所得之沸點範圍為145~205℃之餾分依上述比例含有碳數9之芳香族烴及碳數10之芳香族烴，可有效率地進行由後述不均化反應或轉烷化反應所進行的二甲苯製造。 In the method for producing xylene according to the present invention, the fraction having a boiling point range of 145 to 205 ° C obtained in the fractionating step (a) contains an aromatic hydrocarbon having 9 carbon atoms and an aromatic hydrocarbon having 10 carbon atoms in the above ratio. The xylene production by the heterogeneous reaction or the transalkylation reaction described later can be carried out efficiently.

本說明書中，作為碳數9之芳香族烴可列舉三甲苯或甲基乙基苯等，作為碳數10之芳香族烴可列舉二甲基乙基苯或四甲苯等。 In the present specification, examples of the aromatic hydrocarbon having a carbon number of 9 include trimethylbenzene or methylethylbenzene. Examples of the aromatic hydrocarbon having a carbon number of 10 include dimethylethylbenzene or tetramethylbenzene.

尚且，本說明書中，碳數9之芳香族烴的含有比例及碳數10之芳香族烴的含有比例係指根據JIS K 2536-2所測定之值。 In the present specification, the content ratio of the aromatic hydrocarbon having a carbon number of 9 and the content ratio of the aromatic hydrocarbon having a carbon number of 10 are values measured in accordance with JIS K 2536-2.

本發明之二甲苯之製造方法中，於(a)分餾步驟所得之沸點範圍為145~205℃之餾分，較佳係依總量計含有芳香族烴48~57容量%者、更佳係含有50~57容量%者、再更佳係含有52~57容量%者。 In the method for producing xylene according to the present invention, the fraction having a boiling point range of 145 to 205 ° C obtained in the fractional distillation step (a) preferably contains 48 to 57% by volume of aromatic hydrocarbons based on the total amount, and more preferably contains 50 to 57% by volume, and even better, 52 to 57% by volume.

尚且，本說明書中，芳香族烴之含有比例係指根據JIS K 2536-2所測定之值。 In the present specification, the content ratio of the aromatic hydrocarbon means a value measured in accordance with JIS K 2536-2.

本發明之二甲苯之製造方法中，於(a)分餾步驟所得之沸點範圍為145~205℃之餾分，較佳係為飽和烴之含有比例0~40容量%者、更佳係0~35容量%者、再更佳係0~30容量%者。 In the method for producing xylene of the present invention, the fraction having a boiling point range of 145 to 205 ° C obtained in the fractional distillation step (a) is preferably a saturated hydrocarbon content of 0 to 40% by volume, more preferably 0 to 35. The capacity is %, and the better is 0 to 30% by volume.

藉由使飽和烴之含有比例為上述範圍內，可容易地將成為二甲苯原料之芳香族烴的含有比例控制為既定範圍。 When the content ratio of the saturated hydrocarbon is within the above range, the content ratio of the aromatic hydrocarbon which is a raw material of xylene can be easily controlled to a predetermined range.

尚且，本說明書中，飽和烴之含有比例係指根據JIS K 2536-2所測定之值。 Further, in the present specification, the content ratio of the saturated hydrocarbon means a value measured in accordance with JIS K 2536-2.

本發明之二甲苯之製造方法中，於(a)分餾步驟所得之 沸點範圍為145~205℃之餾分，較佳係不飽和烴(烯烴)之含有比例為0~15容量%者、更佳係0~13容量%者、再更佳係0~11容量%者。 In the method for producing xylene of the present invention, obtained in (a) fractionation step a fraction having a boiling point range of 145 to 205 ° C, preferably a ratio of unsaturated hydrocarbons (olefins) of 0 to 15% by volume, more preferably 0 to 13% by volume, and even more preferably 0 to 11% by volume. .

藉由使不飽和烴之含有比例為上述範圍內，於後述之氫化去硫/去氮反應中，可降低反應效能，可抑制芳香族烴之過度氫化。 By setting the content ratio of the unsaturated hydrocarbon to the above range, in the hydrogenation desulfurization/denitrogenation reaction to be described later, the reaction efficiency can be lowered, and excessive hydrogenation of the aromatic hydrocarbon can be suppressed.

尚且，本說明書中，不飽和烴(烯烴)係指根據JIS K 2536-2所測定之值。 Further, in the present specification, the unsaturated hydrocarbon (olefin) means a value measured in accordance with JIS K 2536-2.

本發明之二甲苯之製造方法中，於(a)分餾步驟所得之沸點範圍為145~205℃之餾分，較佳係硫含量為30質量ppm以下者、更佳係20質量ppm以下者、再更佳係10質量ppm以下者。又，於(a)分餾步驟所得之沸點範圍為145~205℃之餾分中，硫含量通常為2質量ppm以上。 In the method for producing xylene according to the present invention, the fraction having a boiling point range of 145 to 205 ° C obtained in the fractional distillation step (a) is preferably a sulfur content of 30 ppm by mass or less, more preferably 20 ppm by mass or less, or more. More preferably, it is 10 mass ppm or less. Further, in the fraction having a boiling point range of 145 to 205 ° C obtained in the fractionation step (a), the sulfur content is usually 2 ppm by mass or more.

藉由使硫含量為上述數值以下，於後述之氫化去硫/去氮步驟中，可降低反應效能，可抑制芳香族烴之過度氫化。 By setting the sulfur content to be less than or equal to the above value, in the hydrogenation desulfurization/denitrification step described later, the reaction efficiency can be lowered, and excessive hydrogenation of the aromatic hydrocarbon can be suppressed.

尚且，本說明書中，硫含量係指根據JIS K 2541所測定之值。 Further, in the present specification, the sulfur content means a value measured in accordance with JIS K 2541.

本發明之二甲苯之製造方法中，於(a)分餾步驟所得之沸點範圍為145~205℃之餾分，較佳係氮含量為10質量ppm以下者、更佳係5質量ppm以下者、再更佳係3質量ppm以下者。又，於(a)分餾步驟所得之沸點範圍為145~205℃之餾分中，氮含量通常為2質量ppm以上。 In the method for producing xylene according to the present invention, the fraction having a boiling point range of 145 to 205 ° C obtained in the fractionating step (a) is preferably a nitrogen content of 10 ppm by mass or less, more preferably 5 ppm by mass or less, and further More preferably, it is 3 mass ppm or less. Further, in the fraction having a boiling point range of 145 to 205 ° C obtained in the fractional distillation step (a), the nitrogen content is usually 2 ppm by mass or more.

藉由使氮含量為上述數值以下，於後述之氫化去硫/去氮步驟中，可降低反應效能，可抑制芳香族烴之過度氫化。 By setting the nitrogen content to be less than or equal to the above value, in the hydrogenation desulfurization/denitrogenation step described later, the reaction efficiency can be lowered, and excessive hydrogenation of the aromatic hydrocarbon can be suppressed.

尚且，本說明書中，氮含量係指根據JIS K 2609所測定之值。 Further, in the present specification, the nitrogen content means a value measured in accordance with JIS K 2609.

本發明之二甲苯之製造方法中，作為(a)分餾步驟之實施形態，若為可得到沸點範圍為145~205℃之餾分的方法則無特別 限制，可藉由施行公知之分餾方法而進行。 In the method for producing xylene of the present invention, as an embodiment of the (a) fractionation step, there is no particular method for obtaining a fraction having a boiling point range of 145 to 205 °C. The restriction can be carried out by performing a known fractionation method.

<(b)氫化處理步驟> <(b) Hydrogenation treatment step>

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中，使於上述(a)分餾步驟所得之沸點範圍為145~205℃之餾分進行氫化去硫/去氮反應，藉此將硫含量調整為0~6質量ppm、氮含量調整為0~6質量ppm。 In the method for producing xylene according to the present invention, in the (b) hydrogenation treatment step, the fraction having a boiling point range of 145 to 205 ° C obtained in the fractionation step (a) is subjected to hydrogenation desulfurization/denitrogenation reaction, whereby The sulfur content is adjusted to 0 to 6 mass ppm, and the nitrogen content is adjusted to 0 to 6 mass ppm.

本發明之二甲苯之製造方法中，氫化去硫/去氮處理可使用公知技術進行，可列舉例如，使用一般用於石油精製之氫化去硫用觸媒，使於上述(a)分餾步驟所得之沸點範圍為145~205℃之餾分於高溫、高壓之反應條件下進行反應，而進行去硫、去氮處理的方法。 In the method for producing xylene of the present invention, the hydrogenation desulfurization/denitrification treatment can be carried out by a known technique, and for example, a catalyst for hydrogenation desulfurization generally used for petroleum purification can be used, and the fractionation step of the above (a) can be used. The method of desulfurization and denitrification is carried out by reacting a fraction having a boiling point range of 145 to 205 ° C under a reaction condition of high temperature and high pressure.

作為上述氫化去硫觸媒，可列舉於無機氧化物載體上載持了具氫化機能之活性金屬的觸媒。 The hydrogenation desulfurization catalyst is exemplified by a catalyst in which an inorganic oxide carrier carries an active metal having a hydrogenation function.

作為上述無機氧化物載體，可列舉選自氧化鋁、氧化矽、氧化鈦、氧化鎂、氧化矽-氧化鋁等各種多孔質無機氧化物的一種以上，較佳為氧化矽或氧化矽-氧化鋁。 The inorganic oxide carrier may be one or more kinds of various porous inorganic oxides selected from the group consisting of alumina, cerium oxide, titanium oxide, magnesium oxide, and cerium oxide-alumina, and preferably cerium oxide or cerium oxide-alumina. .

作為上述活性金屬，可列舉選自鉬或鎢等第VI族金屬、鎳或鈷等第VIII族金屬之一種以上，較佳為例如Ni-Mo或Co-Mo等之金屬組合。 The active metal may be one or more selected from Group VI metals such as molybdenum or tungsten, and Group VIII metals such as nickel or cobalt, and is preferably a metal combination such as Ni-Mo or Co-Mo.

氫化處理之條件係配合於上述(a)分餾步驟所得之沸點範圍為145~205℃之餾分所含的硫分、氮分、不飽和烴(烯烴分)之含有比例，適當選擇最適合條件即可，通常設定反應溫度為200~500℃，氫分壓為0.5~10MPa，液空間速度(LHSV)為 1.0~20hr-1，氫油比為100~1000NL/L之範圍內。 The conditions of the hydrotreating are the ratios of the sulfur, nitrogen, and unsaturated hydrocarbons (olefins) contained in the fraction having a boiling point range of 145 to 205 ° C obtained in the fractionation step (a), and the most suitable conditions are appropriately selected. Yes, the reaction temperature is usually set to 200 to 500 ° C, the partial pressure of hydrogen is 0.5 to 10 MPa, the liquid space velocity (LHSV) is 1.0 to 20 hr -1 , and the hydrogen to oil ratio is in the range of 100 to 1000 NL / L.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟之氫化去硫/去氮反應中，若使氫化反應條件嚴苛，雖然提升去硫效率或去氮效率，但由於芳香族烴亦被氫化而轉化為環狀飽和烴，故較佳係於較緩和之條件下進行氫化反應。 In the method for producing xylene of the present invention, in the hydrogenation desulfurization/denitrogenation reaction of the (b) hydrogenation treatment step, if the hydrogenation reaction conditions are severe, although the sulfur removal efficiency or the nitrogen removal efficiency is improved, the aromatic hydrocarbon is It is also converted to a cyclic saturated hydrocarbon by hydrogenation, so it is preferred to carry out the hydrogenation reaction under milder conditions.

本發明之二甲苯之製造方法中，藉由於(b)氫化處理步驟中進行氫化去硫/去氮反應，可使所得之氫化處理油中之硫之含有比例、氮分之含有比例減低；同時，可使二甲苯製造時所不需要的不飽和烴(烯烴)的含有比例減低。 In the method for producing xylene of the present invention, by the hydrogenation desulfurization/denitrogenation reaction in the (b) hydrogenation treatment step, the sulfur content ratio and the nitrogen content ratio in the obtained hydrotreated oil can be reduced; The content ratio of unsaturated hydrocarbons (olefins) which are not required for the production of xylene can be reduced.

本發明之二甲苯之製造方法，係藉由於(b)氫化處理步驟進行氫化去硫/去氮反應，將氫化處理油中之硫含量調整為0~6質量ppm、較佳係調整為0~4質量ppm、更佳係調整為0~2質量ppm。 The method for producing xylene according to the present invention is characterized in that the sulfur content in the hydrogenation treatment oil is adjusted to 0 to 6 mass ppm, preferably by 0 to 6 by the hydrodesulfurization/denitrogenation reaction in the (b) hydrogenation treatment step. 4 mass ppm, more preferably adjusted to 0 to 2 mass ppm.

又，本發明之二甲苯之製造方法中，藉由於(b)氫化處理步驟中進行氫化去硫/去氮反應，而將氫化處理油中之氮含量調整為0~6質量ppm、較佳係以成為0~4質量ppm的方式調整、更佳係以成為0~2質量ppm的方式調整。 Further, in the method for producing xylene of the present invention, the nitrogen content in the hydrogenated oil is adjusted to 0 to 6 ppm by mass, preferably by performing a hydrogenation desulfurization/denitrogenation reaction in the hydrogenation treatment step. It is adjusted so as to be 0 to 4 mass ppm, and more preferably adjusted to 0 to 2 mass ppm.

再者，本發明之二甲苯之製造方法中，藉由於(b)氫化處理步驟中進行氫化去硫/去氮反應，而將氫化處理油中之不飽和烴(烯烴)之含有比例較佳為以成為0~5容量%的方式調整、更佳係以成為0~3容量%的方式調整、更佳係以成為0~1容量%的方式調整。 Further, in the method for producing xylene of the present invention, the content of the unsaturated hydrocarbon (olefin) in the hydrogenated oil is preferably (b) by performing the hydrogenation desulfurization/denitrogenation reaction in the (b) hydrogenation treatment step. It is adjusted so as to be 0 to 5 % by volume, more preferably adjusted to 0 to 3 % by volume, and more preferably adjusted to 0 to 1 % by volume.

本發明之二甲苯之製造方法中，即使在於(a)分餾步驟所得之沸點範圍為145~205℃之餾分的硫含量或氮含量分別超過6質量ppm的情況，藉由(b)氫化處理步驟可使各含量減低為既定量，在於(a) 分餾步驟所得之沸點範圍為145~205℃之餾分中之硫含量分別為6質量ppm以下時，藉由(b)氫化處理步驟可使各含量更加減低。 In the method for producing xylene of the present invention, even if the sulfur content or the nitrogen content of the fraction having a boiling point range of 145 to 205 ° C obtained in the fractionation step (a) exceeds 6 ppm by mass, respectively, (b) the hydrotreatment step The content can be reduced to the same amount, in (a) When the sulfur content in the fraction having a boiling point range of 145 to 205 ° C obtained by the fractionation step is 6 mass ppm or less, respectively, the content can be further reduced by the (b) hydrogenation treatment step.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中，藉由氫化去硫/去氮反應而得之氫化處理油中之硫含量係指根據JIS K 2541所測定之值；藉由氫化去硫/去氮反應而得之氫化處理油中之氮含量係指根據JIS K 2609所測定之值；藉由氫化去硫/去氮反應而得之氫化處理油中之不飽和烴(烯烴)之含有比例係指根據JIS K 2536-2所測定之值。 In the method for producing xylene of the present invention, in the (b) hydrogenation treatment step, the sulfur content in the hydrotreated oil obtained by the hydrogenation desulfurization/denitrogenation reaction means a value measured according to JIS K 2541; The nitrogen content in the hydrotreated oil obtained by the hydrogenation desulfurization/denitrogenation reaction means a value measured according to JIS K 2609; an unsaturated hydrocarbon in a hydrogenated treatment oil obtained by hydrogenation desulfurization/denitrogenation reaction ( The content ratio of the olefin) means a value measured in accordance with JIS K 2536-2.

氫化處理油中之硫化合物或氮化合物，係在後述之不均化反應或轉烷化反應時有成為使構成反應觸媒之活性金屬之性能降低的中毒物質的情形，又，不飽和烴(烯烴)由於有進行聚合而析出焦炭的情形，故均於不均化反應或轉烷化反應時成為使反應觸媒之壽命降低的原因物質。 The sulfur compound or the nitrogen compound in the hydrotreated oil has a poisoning substance which is a property of reducing the performance of the active metal constituting the reaction catalyst in the case of the heterogeneous reaction or the transalkylation reaction described later, and is also an unsaturated hydrocarbon ( Since the olefin is precipitated by the polymerization, it is a cause of lowering the life of the reaction catalyst in the case of the heterogeneous reaction or the transalkylation reaction.

藉由使藉氫化去硫/去氮反應所得之氫化處理油中之硫含量、氮含量及不飽和烴(烯烴)的含有比例為上述範圍內，可於不均化反應或轉烷化反應時抑制反應觸媒之壽命降低，並有效率地製造二甲苯。 When the sulfur content, the nitrogen content, and the content ratio of the unsaturated hydrocarbon (olefin) in the hydrotreated oil obtained by the hydrogenation desulfurization/denitrogenation reaction are within the above range, the heterogeneous reaction or the transalkylation reaction may be carried out. The life of the reaction catalyst is suppressed to be lowered, and xylene is efficiently produced.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中，藉由氫化去硫/去氮反應所得之氫化處理油，係飽和烴的含有比例較佳為39~51容量%、更佳為41~49容量%、再更佳為43~47容量%。 In the method for producing xylene of the present invention, in the (b) hydrogenation treatment step, the hydrotreated oil obtained by the hydrogenation desulfurization/denitrogenation reaction preferably has a content of saturated hydrocarbon of 39 to 51% by volume, more preferably The ratio is 41 to 49% by volume, and more preferably 43 to 47% by volume.

藉由氫化去硫/去氮反應所得之氫化處理油，係藉由使飽和烴的含有比例為上述範圍內，而可於後述不均化反應或轉烷化反應中有效率地獲得二甲苯。 The hydrotreated oil obtained by the hydrogenation desulfurization/denitrification reaction can efficiently obtain xylene in the heterogeneous reaction or the transalkylation reaction described later by setting the content of the saturated hydrocarbon within the above range.

尚且，本說明書中，上述飽和烴之含有比例係指根據JIS K 2536-2所測定之值。 Further, in the present specification, the content ratio of the above saturated hydrocarbon means a value measured in accordance with JIS K 2536-2.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中，藉由氫化去硫/去氮反應所得之氫化處理油，較佳係芳香族烴依總量計含有45~60容量%者、更佳係含有48~58容量%者、再更佳係含有51~56容量%者。 In the method for producing xylene according to the present invention, in the (b) hydrogenation treatment step, the hydrotreated oil obtained by hydrogenation desulfurization/denitrogenation reaction, preferably aromatic hydrocarbons, contains 45 to 60% by volume based on the total amount. The better, the system contains 48 to 58% by volume, and the better is 51 to 56% by volume.

尚且，本說明書中，芳香族烴之含有比例係指根據JIS K 2536-2所測定之值。 In the present specification, the content ratio of the aromatic hydrocarbon means a value measured in accordance with JIS K 2536-2.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中，藉由氫化去硫/去氮反應所得之氫化處理油，係碳數9之芳香族烴的含有比例較佳為26~40容量%、更佳為28~39容量%、再更佳為30~38容量%。 In the method for producing xylene of the present invention, in the (b) hydrogenation treatment step, the hydrogenation treatment oil obtained by the hydrogenation desulfurization/denitrogenation reaction preferably has a content ratio of aromatic hydrocarbons having a carbon number of 9 to 26~ 40% by volume, more preferably 28 to 39% by volume, still more preferably 30 to 38% by volume.

又，本發明之二甲苯之製造方法中，於(b)氫化處理步驟中，藉由氫化去硫/去氮反應所得之氫化處理油，係碳數10之芳香族烴的含有比例較佳為15~26容量%、更佳為16~24容量%、再更佳為17~22容量%。 Further, in the method for producing xylene of the present invention, in the (b) hydrogenation treatment step, the hydrogenation treatment oil obtained by the hydrogenation desulfurization/denitrogenation reaction preferably has a content ratio of aromatic hydrocarbons having a carbon number of 10 15 to 26% by volume, more preferably 16 to 24% by volume, and even more preferably 17 to 22% by volume.

本發明之二甲苯之製造方法中，使藉由氫化去硫/去氮反應所得之氫化處理油中之碳數9之芳香族烴的含有比例及碳數10之芳香族烴的含有比例為上述範圍內，藉此可有效率地進行後述之不均化反應或轉烷化反應。 In the method for producing xylene according to the present invention, the content ratio of the aromatic hydrocarbons having a carbon number of 9 and the content of the aromatic hydrocarbons having a carbon number of 10 in the hydrotreated oil obtained by the hydrogenation desulfurization/denitrogenation reaction are as described above. Within the range, the heterogeneous reaction or the transalkylation reaction described later can be efficiently performed.

尚且，本說明書中，上述碳數9之芳香族烴的含有比例及碳數10之芳香族烴的含有比例係指根據JIS K 2536-2所測定之值。 In the present specification, the content ratio of the aromatic hydrocarbon having a carbon number of 9 and the content ratio of the aromatic hydrocarbon having a carbon number of 10 are values measured in accordance with JIS K 2536-2.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中，藉由氫化去硫/去氮反應所得之氫化處理油，係屬於碳數9之芳 香族烴之正丙苯的含有比例較佳為0~5容量%、更佳為0~4容量%、再更佳為0~3容量%。 In the method for producing xylene of the present invention, in the (b) hydrogenation treatment step, the hydrogenation treatment oil obtained by hydrogenation desulfurization/denitrogenation reaction belongs to the carbon number 9 The content of n-propylbenzene in the aromatic hydrocarbon is preferably from 0 to 5% by volume, more preferably from 0 to 4% by volume, still more preferably from 0 to 3% by volume.

又，本發明之二甲苯之製造方法中，於(b)氫化處理步驟中，藉由氫化去硫/去氮反應所得之氫化處理油，係屬於碳數9之芳香族烴之三甲苯的含有比例較佳為12~20容量%、更佳為13~19容量%、再更佳為14~18容量%。 Further, in the method for producing xylene of the present invention, in the step (b), the hydrogenation treatment oil obtained by the hydrogenation desulfurization/denitrogenation reaction is a content of trimethylbenzene which is an aromatic hydrocarbon having a carbon number of 9 The ratio is preferably 12 to 20% by volume, more preferably 13 to 19% by volume, still more preferably 14 to 18% by volume.

於藉由氫化去硫/去氮反應所得之氫化處理油中，藉由使屬於碳數9之芳香族烴的正丙苯之含有比例為上述範圍內，可抑制因去烷反應所造成之飽和烴生成。 In the hydrotreated oil obtained by the hydrogenation desulfurization/denitrogenation reaction, the content of n-propylbenzene belonging to the aromatic hydrocarbon having a carbon number of 9 is within the above range, and the saturation due to the dealkylation reaction can be suppressed. Hydrocarbon formation.

又，於藉由氫化去硫/去氮反應所得之氫化處理油中，藉由使屬於碳數9之芳香族烴的三甲苯之含有比例為上述範圍內，可於後述不均化反應或轉烷化反應中有效率地獲得二甲苯。 Further, in the hydrotreated oil obtained by the hydrogenation desulfurization/denitrogenation reaction, the content ratio of trimethylbenzene belonging to the aromatic hydrocarbon having a carbon number of 9 is within the above range, and the heterogeneous reaction or the conversion described later can be carried out. Xylene is efficiently obtained in the alkylation reaction.

尚且，本說明書中，上述正丙苯及三甲苯的含有比例係指根據JIS K 2536-2所測定之值。 Further, in the present specification, the content ratio of n-propylbenzene and trimethylbenzene refers to a value measured in accordance with JIS K 2536-2.

本發明之二甲苯之製造方法中，在施行上述(a)分餾步驟前，亦可進一步進行去硫/去氮反應作為另外之前處理。 In the method for producing xylene of the present invention, the desulfurization/denitrogenation reaction may be further carried out as an additional pretreatment before the step (a) of fractionation.

此時，可列舉對由流動接觸分解裝置所餾出之流動接觸分解汽油全餾分直接進行去硫/去氮反應處理後，進行(a)蒸餾處理而分餾出沸點範圍為145~205℃之餾分的態樣。 In this case, the desulfurization/denitrogenation reaction is directly performed on the whole fraction of the flow contact decomposed gasoline distilled by the flow contact decomposition apparatus, and then (a) the distillation treatment is performed to fractionate the fraction having a boiling point range of 145 to 205 ° C. The way.

本發明之二甲苯之製造方法中，可將於(b)氫化處理步驟藉由氫化去硫/去氮反應所得之氫化處理油，直接作為含芳香族烴之生成油而供給於(c)不均化/轉烷化步驟。 In the method for producing xylene of the present invention, the hydrotreated oil obtained by the hydrogenation desulfurization/denitrogenation reaction in (b) the hydrotreating step can be directly supplied as the aromatic hydrocarbon-containing oil (c). Homogenization / transalkylation step.

本發明之二甲苯之製造方法中，上述(b)氫化處理步驟亦可於氫化去硫/去氮反應後進一步對非芳香族烴(芳香族烴以外之 烴類)進行分離處理。 In the method for producing xylene according to the present invention, the (b) hydrogenation treatment step may further be a non-aromatic hydrocarbon (other than an aromatic hydrocarbon) after the hydrogenation desulfurization/denitrogenation reaction. The hydrocarbons are subjected to separation treatment.

非芳香族烴之分離處理，較佳係藉由對上述藉氫化去硫/去氮反應所得之氫化處理油進行蒸餾或萃取而進行。 The separation treatment of the non-aromatic hydrocarbon is preferably carried out by subjecting the above-mentioned hydrotreated oil obtained by the hydrodesulfurization/denitrogenation reaction to distillation or extraction.

作為由上述氫化處理油分離芳香族烴的方法，具體而言，可列舉液-液萃取法及萃取蒸餾法。作為於液-液萃取法所使用之選擇溶媒，可列舉選自甘油或環丁碸衍生物等之一種以上。 Specific examples of the method for separating the aromatic hydrocarbon from the hydrotreated oil include a liquid-liquid extraction method and an extractive distillation method. The solvent to be selected for the liquid-liquid extraction method may be one or more selected from the group consisting of glycerin and a cyclobutane derivative.

上述液-液萃取法，係例如美國專利第4,058,454號說明書所記載般，已知為用於由含有極性烴與非極性烴之烴混合物將極性烴分離及回收的方法(溶劑萃取方法)；本發明之二甲苯之製造方法中，可利用上述藉由氫化去硫/去氮反應所得之氫化處理油中含有的所有芳香族烴為極性的特性而實施。 The liquid-liquid extraction method is known, for example, as described in the specification of U.S. Patent No. 4,058,454, which is a method for separating and recovering a polar hydrocarbon from a hydrocarbon mixture containing a polar hydrocarbon and a non-polar hydrocarbon (solvent extraction method); In the method for producing xylene of the invention, all of the aromatic hydrocarbons contained in the hydrotreated oil obtained by the hydrogenation desulfurization/denitrogenation reaction described above can be used as a polar property.

亦即，如環丁碸(sulfolane)般，在將可溶解極性物質之溶劑添加至上述藉由氫化去硫/去氮反應所得之氫化處理油中時，由於極性之芳香族烴選擇性地被溶解，因而可分離非極性之非芳香族烴，故由上述藉由氫化去硫/去氮反應所得之氫化處理油將非芳香族烴分離去除，可得到含有高純度芳香族烴的生成油。 That is, as in the case of sulfolane, when a solvent capable of dissolving a polar substance is added to the above-mentioned hydrotreated oil obtained by a hydrogenation desulfurization/denitrogenation reaction, the aromatic hydrocarbon due to polarity is selectively Since it is dissolved and thus the non-polar non-aromatic hydrocarbon can be separated, the hydrogenated oil obtained by the hydrogenation desulfurization/denitrogenation reaction described above separates and removes the non-aromatic hydrocarbon to obtain a produced oil containing a high-purity aromatic hydrocarbon.

本發明之二甲苯之製造方法中，在(b)氫化處理步驟中分離非芳香族烴時，所得之含有芳香族烴之生成油，較佳係硫含量為0~6質量ppm者、更佳係0~4質量ppm者、再更佳係0~2質量ppm者。 In the method for producing xylene of the present invention, when the non-aromatic hydrocarbon is separated in the (b) hydrogenation treatment step, the resulting oil containing an aromatic hydrocarbon is preferably a sulfur content of 0 to 6 ppm by mass, more preferably It is 0~4 mass ppm, and more preferably 0~2 mass ppm.

又，本發明之二甲苯之製造方法中，在(b)氫化處理步驟中分離非芳香族烴時，所得之含有芳香族烴之生成油，較佳係氮含量為0~6質量ppm者、更佳係0~4質量ppm者、再更佳係0~2質量ppm者。 Further, in the method for producing xylene according to the present invention, when the non-aromatic hydrocarbon is separated in the (b) hydrogenation treatment step, the resulting aromatic hydrocarbon-containing oil is preferably 0 to 6 ppm by mass. More preferably 0 to 4 mass ppm, and even better 0 to 2 mass ppm.

尚且，本說明書中，上述硫含量係指根據JIS K 2541所測定之 值；氮含量係指根據JIS K 2609所測定之值。 Further, in the present specification, the above sulfur content means measured according to JIS K 2541. Value; nitrogen content means a value measured in accordance with JIS K 2609.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中分離非芳香族烴時，所得之含有芳香族烴之生成油，較佳係芳香族烴依總量計為含有90~100容量%者、更佳係含有92~100容量%者、再更佳係含有94~100容量%者。 In the method for producing xylene according to the present invention, when the non-aromatic hydrocarbon is separated in the (b) hydrogenation treatment step, the resulting aromatic hydrocarbon-containing oil is preferably contained in an aromatic hydrocarbon content of 90 to 100 in total. The capacity %, more preferably 92 to 100% by volume, and even more preferably 94 to 100% by volume.

尚且，本說明書中，芳香族烴之含有比例係指根據JIS K 2536-2所測定之值。 In the present specification, the content ratio of the aromatic hydrocarbon means a value measured in accordance with JIS K 2536-2.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中分離非芳香族烴時，所得之含有芳香族烴之生成油，較佳係碳數9之芳香族烴的含有比例為50~70容量%者、更佳係55~67容量%者、再更佳係60~65容量%者。 In the method for producing xylene of the present invention, when the non-aromatic hydrocarbon is separated in the (b) hydrogenation treatment step, the resulting aromatic hydrocarbon-containing oil is preferably contained in an aromatic hydrocarbon content of 50. ~70% by volume, more preferably 55 to 67% by volume, and even more preferably 60 to 655% by volume.

又，本發明之二甲苯之製造方法中，於(b)氫化處理步驟中分離非芳香族烴時，所得之生成油，較佳係碳數10之芳香族烴的含有比例為30~42容量%者、更佳係32~40容量%者、再更佳係35~38容量%者。 Further, in the method for producing xylene of the present invention, when the non-aromatic hydrocarbon is separated in the (b) hydrogenation treatment step, the resulting oil is produced, and the content of the aromatic hydrocarbon having a carbon number of 10 is preferably 30 to 42. %, better 32 to 40% by volume, and even better 35 to 38% by volume.

本發明之二甲苯之製造方法中，藉由使於分離去除非芳香族烴而得之含有芳香族烴之生成油中，碳數9之芳香族烴的含有比例及碳數10之芳香族烴的含有比例為上述範圍內，可有效率地進行不均化反應或轉烷化反應。 In the method for producing xylene of the present invention, the aromatic hydrocarbon-containing product having a carbon number of 9 and the aromatic hydrocarbon having a carbon number of 10 are produced in the aromatic hydrocarbon-containing product oil obtained by separating and removing the non-aromatic hydrocarbon. The content ratio is within the above range, and the heterogeneous reaction or the transalkylation reaction can be carried out efficiently.

尚且，本說明書中，上述碳數9之芳香族烴的含有比例及碳數10之芳香族烴的含有比例係指根據JIS K 2536-2所測定之值。 In the present specification, the content ratio of the aromatic hydrocarbon having a carbon number of 9 and the content ratio of the aromatic hydrocarbon having a carbon number of 10 are values measured in accordance with JIS K 2536-2.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中分離非芳香族烴時，所得之含有芳香族烴之生成油，係屬於碳數9之芳香族烴的正丙苯之含有比例較佳為0~9容量%、更佳為0~7容 量%、再更佳為0~5容量%。 In the method for producing xylene of the present invention, when the non-aromatic hydrocarbon is separated in the (b) hydrogenation treatment step, the resulting aromatic hydrocarbon-containing oil is contained in the n-propylbenzene of the aromatic hydrocarbon having 9 carbon atoms. The ratio is preferably 0 to 9% by volume, more preferably 0 to 7%. The amount %, more preferably 0 to 5 % by volume.

又，本發明之二甲苯之製造方法中，於(b)氫化處理步驟中分離非芳香族烴時，所得之含有芳香族烴之生成油，係屬於碳數9之芳香族烴的三甲苯之含有比例較佳為25~36容量%、更佳為26~34容量%、再更佳為27~32容量%。 Further, in the method for producing xylene according to the present invention, when the non-aromatic hydrocarbon is separated in the (b) hydrogenation treatment step, the resulting oil containing an aromatic hydrocarbon is a toluene which is an aromatic hydrocarbon having 9 carbon atoms. The content ratio is preferably 25 to 36% by volume, more preferably 26 to 34% by volume, still more preferably 27 to 32% by volume.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中對非芳香族烴進行分離處理而得之含有芳香族烴之生成油，係使正丙苯之含有比例為上述範圍內，藉此可抑制因去烷反應所造成的飽和烴生成。 In the method for producing xylene according to the present invention, the aromatic hydrocarbon-containing product obtained by subjecting the non-aromatic hydrocarbon to separation treatment in the (b) hydrogenation treatment step is such that the content ratio of n-propylbenzene is within the above range. Thereby, the formation of saturated hydrocarbons due to the dealkylation reaction can be suppressed.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中對非芳香族烴進行分離處理而得之生成油，係使三甲苯之含有比例為上述範圍內，藉此可於後述不均化反應或轉烷化反應中有效率地得到二甲苯。 In the method for producing xylene according to the present invention, in the step (b), the non-aromatic hydrocarbon is subjected to a separation treatment to obtain an oil, and the content of the toluene is within the above range, which can be described later. Xylene is efficiently obtained in the homogenization reaction or the transalkylation reaction.

尚且，本說明書中，上述正丙苯及三甲苯的含有比例係指根據JIS K 2536-2所測定之值。 Further, in the present specification, the content ratio of n-propylbenzene and trimethylbenzene refers to a value measured in accordance with JIS K 2536-2.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中對非芳香族烴進行分離處理而得之含有芳香族烴之生成油，較佳係飽和烴的含有比例為0~7容量%者、更佳係0~5容量%者、再更佳係0~4容量%者。 In the method for producing xylene according to the present invention, in the step (b), the non-aromatic hydrocarbon is subjected to separation treatment to obtain an aromatic hydrocarbon-containing oil, preferably a saturated hydrocarbon content of 0 to 7 %, better 0 to 5 capacity%, and even better 0 to 4%.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中對非芳香族烴進行分離處理而得之生成油，係使飽和烴之含有比例為上述範圍內，藉此可於後述不均化反應或轉烷化反應中有效率地得到二甲苯。 In the method for producing xylene according to the present invention, in the step (b), the non-aromatic hydrocarbon is subjected to a separation treatment to obtain an oil, and the content of the saturated hydrocarbon is within the above range, which can be described later. Xylene is efficiently obtained in the homogenization reaction or the transalkylation reaction.

尚且，本說明書中，上述飽和烴的含有比例係指根據JIS K 2536-2所測定之值。 Further, in the present specification, the content ratio of the above saturated hydrocarbons is based on JIS K. The value determined by 2536-2.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中對非芳香族烴進行分離處理而得之含有芳香族烴之生成油，較佳係不飽和烴的含有比例為0~2容量%者、更佳係0~1容量%者、再更佳係0~0.5容量%者。 In the method for producing xylene according to the present invention, the aromatic hydrocarbon-containing oil is obtained by subjecting the non-aromatic hydrocarbon to a separation treatment in the (b) hydrogenation treatment step, and preferably the unsaturated hydrocarbon is contained in a ratio of 0 to 2. % of capacity, more preferably 0 to 1% by volume, and even more preferably 0 to 0.5% by volume.

本發明之二甲苯之製造方法中，於(b)氫化處理步驟中對非芳香族烴進行分離處理而得之生成油，係使不飽和烴(烯烴)之含有比例為上述範圍內，藉此可抑制氫消耗量，於後述不均化反應或轉烷化反應中有效率地得到二甲苯。 In the method for producing xylene according to the present invention, in the step (b), the non-aromatic hydrocarbon is subjected to separation treatment to obtain an oil, and the content ratio of the unsaturated hydrocarbon (olefin) is within the above range. The amount of hydrogen consumption can be suppressed, and xylene can be efficiently obtained in the heterogeneous reaction or the transalkylation reaction described later.

尚且，本說明書中，上述不飽和烴的含有比例係指根據JIS K 2536-2所測定之值。 Further, in the present specification, the content ratio of the above unsaturated hydrocarbon means a value measured in accordance with JIS K 2536-2.

本發明之二甲苯之製造方法，係於上述(b)氫化處理步驟中，藉由於氫化去硫/去氮反應後進一步對非芳香族烴進行分離處理，可有效率地施行(c)不均化/轉烷化步驟。 The method for producing xylene according to the present invention is characterized in that (b) the hydrogenation treatment step is carried out by further separating the non-aromatic hydrocarbons after the hydrogenation desulfurization/denitrogenation reaction, thereby efficiently performing (c) unevenness Conversion/transalkylation step.

<不均化/轉烷化步驟> <Unevenness / transalkylation step>

本發明之二甲苯之製造方法中，係於(c)不均化/轉烷化步驟中，對含有藉上述(b)氫化處理步驟所得之芳香族烴的生成油，施行不均化反應或轉烷化反應。 In the method for producing xylene according to the present invention, in the step (c) of the heterogeneization/transalkylation, the formation oil containing the aromatic hydrocarbon obtained by the (b) hydrogenation treatment step is subjected to an uneven reaction or Transalkylation reaction.

上述不均化反應或轉烷化反應的反應條件，若為可獲得二甲苯者，則無特別限定。 The reaction conditions of the above heterogeneous reaction or transalkylation reaction are not particularly limited as long as xylene is available.

上述不均化反應或轉烷化反應，較理想係藉由將含有藉(b)氫化處理步驟所得之芳香族烴的生成油，依液空間速度(LHSV)較佳為0.01h-1以上、更佳為0.1h-1以上，且較佳為10h-1以下、更佳為5h-1 以下進行供給，與觸媒接觸而進行。 Preferably, the above-mentioned heterogeneous reaction or transalkylation reaction is carried out by using a product of the aromatic hydrocarbon obtained by the (b) hydrotreating step, and the liquid space velocity (LHSV) is preferably 0.01 h -1 or more. more preferably 0.1h -1 or more, and preferably 10h -1 or less, more preferably supplied to 5h -1 or less, and the contact with the catalyst.

上述不均化反應或轉烷化反應，係反應溫度較佳為200℃以上、更佳為230℃以上、再更佳為260℃以上，且較佳為550℃以下、更佳為530℃以下、特佳為510℃以下。 The above-mentioned unevenness reaction or transalkylation reaction is preferably 200 ° C or higher, more preferably 230 ° C or higher, still more preferably 260 ° C or higher, and is preferably 550 ° C or lower, more preferably 530 ° C or lower. It is particularly good at 510 ° C or less.

若反應溫度未滿200℃，則芳香族烴之活性化不足，且因藉反應所生成之水使活性點中毒，故芳香族烴的轉化率容易變低。另一方面，若反應溫度超過550℃，除了消耗較多能量之外，觸媒壽命亦容易變短。 When the reaction temperature is less than 200 ° C, the activation of the aromatic hydrocarbon is insufficient, and the active point is poisoned by the water formed by the reaction, so that the conversion ratio of the aromatic hydrocarbon tends to be low. On the other hand, if the reaction temperature exceeds 550 ° C, the catalyst life is likely to be shortened in addition to consuming a large amount of energy.

上述不均化反應或轉烷化反應，係反應壓力較佳為大氣壓以上、更佳為0.1MPaG以上、再更佳為0.5MPaG以上，且較佳為10MPaG以下、更佳為5MPaG以下。 The above-mentioned unevenness reaction or transalkylation reaction is preferably atmospheric pressure or higher, more preferably 0.1 MPaG or more, still more preferably 0.5 MPaG or more, and is preferably 10 MPaG or less, more preferably 5 MPaG or less.

又，在施行上述不均化反應或轉烷化反應時，亦可於反應系統中流通如氮氣或氦氣般之惰性氣體或用於抑制焦化之氫氣，或者進行加壓。 Further, when the above heterogeneous reaction or transalkylation reaction is carried out, an inert gas such as nitrogen gas or helium gas or hydrogen gas for suppressing coking may be circulated in the reaction system or may be pressurized.

作為使用於上述不均化反應或轉烷化反應的反應觸媒，若為芳香族之轉化用觸媒、產生不均化反應或轉烷化反應者，則無特別限制。 The reaction catalyst used in the above heterogeneous reaction or transalkylation reaction is not particularly limited as long as it is an aromatic conversion catalyst and generates an unevenness reaction or a transalkylation reaction.

作為上述反應觸媒，較佳係於保持甲基之下，使乙基、丙基選擇性地去烷化，同時具有轉烷化能力者。 As the above reaction catalyst, it is preferred to carry out the selective dealkylation of the ethyl group and the propyl group while maintaining the methyl group, and the transalkylation ability.

具體而言，較佳為形狀選擇性金屬矽酸鹽觸媒，更佳為矽酸鋁，再更佳為沸石。 Specifically, a shape selective metal ruthenate catalyst is preferred, and aluminum ruthenate is more preferred, and more preferably zeolite.

作為沸石，可使用選自絲光沸石、Y型沸石、X型沸石、β型沸石、ZSM-5等之任一種沸石，較佳為絲光沸石。 As the zeolite, any one selected from the group consisting of mordenite, Y-type zeolite, X-type zeolite, β-type zeolite, and ZSM-5 can be used, and preferably mordenite.

本發明之二甲苯之製造方法，係於(c)不均化/轉烷化 步驟中，藉由不均化反應，轉化同一芳香族烴2分子，可得到更低分子量之芳香族烴1分子、與更高分子量之芳香族烴(二甲苯)1分子；具體而言，轉化甲苯2分子可得到苯1分子與二甲苯1分子。 The method for producing xylene of the present invention is based on (c) unevenness/transalkylation In the step, by converting the same aromatic hydrocarbon 2 molecules by the heterogeneous reaction, one molecule of a lower molecular weight aromatic hydrocarbon and one molecule of a higher molecular weight aromatic hydrocarbon (xylene) can be obtained; specifically, conversion Toluene 2 molecules can give benzene 1 molecule and 1 molecule of xylene.

又，本發明之二甲苯之製造方法，係於(c)不均化/轉烷化步驟中，藉由轉烷化反應，轉化碳數相異之芳香族烴2分子而可得到二甲苯2分子；具體而言，轉化甲苯1分子與三甲苯1分子可得到二甲苯2分子。 Further, in the method for producing xylene according to the present invention, in the step (c) of the heterogeneization/transalkylation, two molecules of aromatic hydrocarbons having different carbon numbers are converted by a transalkylation reaction to obtain xylene 2 Molecules; specifically, conversion of 1 molecule of toluene with 1 molecule of toluene can give 2 molecules of xylene.

本發明之二甲苯之製造方法，係於(c)不均化/轉烷化步驟中，藉由施行芳香族烴彼此之不均化反應或轉烷化反應，可選擇性製造二甲苯。 In the method for producing xylene according to the present invention, in the step (c), the heterogeneization/transalkylation step, xylene can be selectively produced by performing an uneven reaction or a transalkylation reaction of aromatic hydrocarbons.

本發明之二甲苯之製造方法中，於(c)不均化/轉烷化步驟所得的生成油，較佳係二甲苯之含有比例為28~32容量%、更佳29~32容量%者、再更佳係30~32容量%者。 In the method for producing xylene of the present invention, the product obtained by the (c) unevenness/transalkylation step preferably has a xylene content of 28 to 32% by volume, more preferably 29 to 32% by volume. More preferably, the system is 30 to 32% by volume.

尚且，本說明書中，二甲苯的含有比例係指根據JIS K 2536-2所測定之值。 Further, in the present specification, the content ratio of xylene means a value measured in accordance with JIS K 2536-2.

根據本發明，可提供即使將芳香族烴之含有比例低，含有不飽和烴或硫分、氮分等之接觸分解汽油用於不均化反應或轉烷化反應等之轉化反應之原料，仍可簡便且依高產率製造二甲苯的方法。 According to the present invention, it is possible to provide a raw material which is used for a conversion reaction of a heterogeneous reaction or a transalkylation reaction, such as an unsaturated hydrocarbon or a sulfur-containing or nitrogen-containing contact decomposition gasoline, even if the content ratio of the aromatic hydrocarbon is low. A process for producing xylene in a simple and high yield.

[實施例] [Examples]

以下藉由實施例說明本發明，但此等僅為例示，本發明並不為此等實施例所限制。 The invention is illustrated by the following examples, but these are merely illustrative, and the invention is not limited thereto.

(實施例1) (Example 1) (a)分餾步驟 (a) Fractionation step

將具有表1所示之組成及蒸餾特性之流動接觸分解汽油1於沸點範圍150~200℃下進行分餾，得到原料分解汽油1。將所得之原料分解汽油1之組成及蒸餾特性示於表2。 The flow contact decomposed gasoline 1 having the composition and distillation characteristics shown in Table 1 was fractionated at a boiling point range of 150 to 200 ° C to obtain a raw material decomposed gasoline 1. The composition and distillation characteristics of the obtained raw material decomposed gasoline 1 are shown in Table 2.

(b)氫化處理步驟 (b) Hydrogenation step

將所得之原料分解汽油1，使用Co-Mo系觸媒，依反應溫度300℃、反應壓力3.0MPa、液空間速度(LHSV)2.0h-1、氫油比300NL/L、反應時間2.0小時之條件，進行去硫、去氮處理，藉此得到硫含量為1質量ppm、氮含量為1質量ppm、芳香族烴含量為53.6容量%、不飽和烴(烯烴)含量為0.5容量%的去硫/去氮流動接觸分解汽油1。將所得之去硫/去氮流動接觸分解汽油1之組成示於表3。 The obtained raw material is decomposed into gasoline 1, and a Co-Mo catalyst is used, and the reaction temperature is 300 ° C, the reaction pressure is 3.0 MPa, the liquid space velocity (LHSV) is 2.0 h -1 , the hydrogen oil ratio is 300 NL / L, and the reaction time is 2.0 hours. Under conditions, desulfurization and denitrification treatment were carried out, thereby obtaining desulfurization having a sulfur content of 1 mass ppm, a nitrogen content of 1 mass ppm, an aromatic hydrocarbon content of 53.6 vol%, and an unsaturated hydrocarbon (olefin) content of 0.5 vol%. /Denitrification flow contact decomposes gasoline 1 . The composition of the resulting desulfurized/denitrogenated flow contact decomposed gasoline 1 is shown in Table 3.

進而，對此去硫/去氮流動接觸分解汽油1進行環丁碸處理而萃取芳香族烴，藉此得到含有碳數9之芳香族烴58.5容量%、碳數10之芳香族烴36.4容量%的不均化/轉烷化原料油1。將所得之不均化/轉烷化原料油1之組成示於表4。 Further, this desulfurization/denitrogenation flow contact decomposed gasoline 1 is subjected to cyclobutane treatment to extract aromatic hydrocarbons, thereby obtaining 58.5% by volume of aromatic hydrocarbons having a carbon number of 9 and 36.4% by volume of aromatic hydrocarbons having 10 carbon atoms. Uneven/transalkylated feedstock 1 . The composition of the obtained heterogeneous/transalkylated feedstock 1 is shown in Table 4.

(c)不均化/轉烷化步驟 (c) Non-uniformization/transalkylation step

將上述不均化/轉烷化原料油1，使用Mo觸媒作為反應觸媒，依反應溫度345℃、液空間速度3h-1、反應壓力2.0MPa、反應時間1.0小時之條件進行不均化/轉烷化反應，藉此得到含有二甲苯30.9容量%的目標之生成油1。將所得之生成油1之組成示於表4。 The above heterogeneous/transalkylated feedstock 1 was subjected to non-uniformization using a Mo catalyst as a reaction catalyst according to a reaction temperature of 345 ° C, a liquid space velocity of 3 h -1 , a reaction pressure of 2.0 MPa, and a reaction time of 1.0 hour. /Transalkylation reaction, whereby a target produced oil 1 containing 30.9% by volume of xylene was obtained. The composition of the resulting produced oil 1 is shown in Table 4.

(實施例2) (Example 2) (a)分餾步驟 (a) Fractionation step

將具有表1所示之組成及蒸餾特性之流動接觸分解汽油2於沸點範圍150~200℃下進行分餾，得到原料分解汽油2。將所得之原料分解汽油2之組成及蒸餾特性示於表2。 The flow contact decomposed gasoline 2 having the composition and distillation characteristics shown in Table 1 was fractionated at a boiling point range of 150 to 200 ° C to obtain a raw material decomposed gasoline 2 . The composition and distillation characteristics of the obtained raw material decomposed gasoline 2 are shown in Table 2.

(b)氫化處理步驟 (b) Hydrogenation step

將所得之原料分解汽油2，使用Co-Mo系觸媒，依反應溫度300℃、反應壓力3.0MPa、液空間速度(LHSV)2.0h-1、氫油比300NL/L、反應時間2.0小時之條件，進行去硫、去氮處理，藉此得到硫含量為1質量ppm、氮含量為1質量ppm、芳香族烴含量為52.7容量%、不飽和烴(烯烴)含量為0.6容量%的去硫/去氮流動接觸分解汽油2。 The obtained raw material is decomposed into gasoline 2, and a Co-Mo catalyst is used, and the reaction temperature is 300 ° C, the reaction pressure is 3.0 MPa, the liquid space velocity (LHSV) is 2.0 h -1 , the hydrogen oil ratio is 300 NL / L, and the reaction time is 2.0 hours. Under conditions, desulfurization and denitrification treatment were carried out, thereby obtaining desulfurization having a sulfur content of 1 mass ppm, a nitrogen content of 1 mass ppm, an aromatic hydrocarbon content of 52.7 vol%, and an unsaturated hydrocarbon (olefin) content of 0.6 vol%. /Denitrification flow contact decomposes gasoline 2 .

將所得之去硫/去氮流動接觸分解汽油2之組成示於表3。進而，對此去硫/去氮流動接觸分解汽油2進行環丁碸處理而萃取芳香族烴，藉此得到含有碳數9之芳香族烴58.1容量%、碳數10之芳香族烴36.9容量%的不均化/轉烷化原料油2。 The composition of the resulting desulfurized/denitrogenated flow contact decomposed gasoline 2 is shown in Table 3. Further, this desulfurization/denitrogenation flow contact decomposed gasoline 2 is subjected to cyclobutane treatment to extract aromatic hydrocarbons, thereby obtaining 58.1% by volume of aromatic hydrocarbons having a carbon number of 9 and 36.9% by volume of aromatic hydrocarbons having 10 carbon atoms. Uneven/transalkylated feedstock oil 2.

(c)不均化/轉烷化步驟 (c) Non-uniformization/transalkylation step

將上述不均化/轉烷化原料油2，使用Mo觸媒作為反應觸媒，依反應溫度345℃、液空間速度3h-1、反應壓力2.0MPa、反應時間1.0小時之條件進行不均化/轉烷化反應，藉此得到含有二甲苯31.0容量%的目標之生成油2。將所得之生成油2之組成示於表4。 The above heterogeneous/transalkylated feedstock 2 was subjected to non-uniformization using a Mo catalyst as a reaction catalyst according to a reaction temperature of 345 ° C, a liquid space velocity of 3 h -1 , a reaction pressure of 2.0 MPa, and a reaction time of 1.0 hour. /Transalkylation reaction, whereby a target produced oil 2 containing 31.0% by volume of xylene was obtained. The composition of the resulting produced oil 2 is shown in Table 4.

(實施例3) (Example 3) (a)分餾步驟 (a) Fractionation step

將具有表1所示之組成及蒸餾特性之流動接觸分解汽油3於沸點範圍150~200℃下進行分餾，得到原料分解汽油3。將所得之原 料分解汽油3之組成及蒸餾特性示於表2。 The flow contact decomposed gasoline 3 having the composition and distillation characteristics shown in Table 1 was subjected to fractional distillation at a boiling point range of 150 to 200 ° C to obtain a raw material decomposed gasoline 3. The original The composition and distillation characteristics of the decomposition gasoline 3 are shown in Table 2.

(b)氫化處理步驟 (b) Hydrogenation step

將所得之原料分解汽油3，使用Co-Mo系觸媒，依反應溫度300℃、反應壓力3.0MPa、液空間速度(LHSV)2.0h-1、氫油比300NL/L、反應時間2.0小時之條件，進行去硫、去氮處理，藉此得到硫含量為1質量ppm、氮含量為1質量ppm、芳香族烴含量為55.1容量%、不飽和烴(烯烴)含量為0.6容量%的去硫/去氮流動接觸分解汽油3。將所得之去硫/去氮流動接觸分解汽油3之組成示於表3。進而，對此去硫/去氮流動接觸分解汽油3進行環丁碸處理而萃取芳香族烴，藉此得到含有碳數9之芳香族烴62.9容量%、碳數10之芳香族烴32.2容量%的不均化/轉烷化原料油3。將所得之不均化/轉烷化原料油3之組成示於表4。 The obtained raw material is decomposed into gasoline 3, and a Co-Mo catalyst is used, and the reaction temperature is 300 ° C, the reaction pressure is 3.0 MPa, the liquid space velocity (LHSV) is 2.0 h -1 , the hydrogen oil ratio is 300 NL / L, and the reaction time is 2.0 hours. Under conditions, desulfurization and denitrification treatment were carried out, thereby obtaining desulfurization having a sulfur content of 1 mass ppm, a nitrogen content of 1 mass ppm, an aromatic hydrocarbon content of 55.1% by volume, and an unsaturated hydrocarbon (olefin) content of 0.6% by volume. /Denitrification flow contact decomposes gasoline 3. The composition of the resulting desulfurized/denitrogenated flow contact decomposed gasoline 3 is shown in Table 3. Further, this desulfurization/denitrogenation flow contact decomposition gasoline 3 is subjected to cyclobutane treatment to extract aromatic hydrocarbons, thereby obtaining 62.9% by volume of aromatic hydrocarbons having a carbon number of 9 and 32.2% by volume of aromatic hydrocarbons having 10 carbon atoms. Uneven/transalkylated feedstock 3 . The composition of the obtained uneven/transalkylated feedstock 3 is shown in Table 4.

(c)不均化/轉烷化步驟 (c) Non-uniformization/transalkylation step

將上述不均化/轉烷化原料油3，使用Mo觸媒作為反應觸媒，依反應溫度345℃、液空間速度3h-1、反應壓力2.0MPa、反應時間1.0小時之條件進行不均化/轉烷化反應，藉此得到含有二甲苯31.2容量%的目標之生成油3。將所得之生成油3之組成示於表4。 The above-mentioned heterogeneous/transalkylated feedstock 3 was subjected to non-uniformization using a Mo catalyst as a reaction catalyst according to a reaction temperature of 345 ° C, a liquid space velocity of 3 h -1 , a reaction pressure of 2.0 MPa, and a reaction time of 1.0 hour. /Transalkylation reaction, whereby a target produced oil 3 containing 31.2% by volume of xylene was obtained. The composition of the resulting produced oil 3 is shown in Table 4.

(比較例1) (Comparative Example 1)

對流動接觸分解汽油1不進行(a)分餾步驟，得到生成油。 The flow contact decomposition gasoline 1 is not subjected to the (a) fractionation step to obtain a produced oil.

亦即，將具有表1所示之組成及蒸餾特性之流動接觸分解汽油1，使用Co-Mo系觸媒，依反應溫度300℃、反應壓力3.0MPa、液空間速度(LHSV)2.0h-1、氫油比300NL/L、反應時間2.0小時之條件，進行去硫、去氮處理，得到硫含量為1質量ppm、氮含量為1 質量ppm、芳香族烴含量為23.4容量%、不飽和烴(烯烴)含量為0.6容量%的去硫/去氮流動接觸分解汽油4。將所得之去硫/去氮流動接觸分解汽油4之組成示於表3。 That is, the flow contact decomposition gasoline 1 having the composition and distillation characteristics shown in Table 1 was used, and a Co-Mo catalyst was used, and the reaction temperature was 300 ° C, the reaction pressure was 3.0 MPa, and the liquid space velocity (LHSV) was 2.0 h -1 . The hydrogen-oil ratio is 300 NL/L and the reaction time is 2.0 hours. Desulfurization and denitrification are carried out to obtain a sulfur content of 1 mass ppm, a nitrogen content of 1 mass ppm, an aromatic hydrocarbon content of 23.4% by volume, and an unsaturated hydrocarbon. The desulfurized/denitrogenated flow contact (degradation of gasoline) having a (olefin) content of 0.6% by volume. The composition of the resulting desulfurized/denitrogenated flow contact decomposed gasoline 4 is shown in Table 3.

進而，對此去硫/去氮流動接觸分解汽油4進行環丁碸處理而萃取芳香族烴，藉此得到含有碳數9之芳香族烴25.8容量%、碳數10之芳香族烴21.4容量%的不均化/轉烷化原料油4。將所得之不均化/轉烷化原料油4之組成示於表5。 Further, this desulfurization/denitrogenation flow contact decomposition gasoline 4 is subjected to cyclobutane treatment to extract aromatic hydrocarbons, thereby obtaining 25.8% by volume of aromatic hydrocarbons having a carbon number of 9 and 21.4% by volume of aromatic hydrocarbons having 10 carbon atoms. Uneven/transalkylated feedstock 4 . The composition of the obtained uneven/transalkylated feedstock 4 is shown in Table 5.

將上述不均化/轉烷化原料油4，使用Mo觸媒作為反應觸媒，依反應溫度345℃、液空間速度3h-1、反應壓力2.0MPa、反應時間1.0小時之條件進行不均化/轉烷化反應，藉此得到目標之生成油4。將所得之生成油4之組成示於表5。 The heterogeneous/transalkylated feedstock 4 was subjected to non-uniformization using a Mo catalyst as a reaction catalyst according to a reaction temperature of 345 ° C, a liquid space velocity of 3 h -1 , a reaction pressure of 2.0 MPa, and a reaction time of 1.0 hour. /Transalkylation reaction, whereby the target produced oil 4 is obtained. The composition of the resulting produced oil 4 is shown in Table 5.

(比較例2) (Comparative Example 2)

對流動接觸分解汽油1不施行(b)氫化處理步驟之氫化去硫/去氮反應，得到生成油。 The hydrodesulfurization/denitrogenation reaction of the (b) hydrogenation treatment step is not carried out on the flow contact decomposed gasoline 1 to obtain a produced oil.

亦即，將具有表1所示之組成及蒸餾特性之流動接觸分解汽油1，於沸點範圍150~200℃下進行分餾，得到原料分解汽油1。將所得之原料分解汽油1之組成及蒸餾特性示於表2。 That is, the flow-contact decomposition gasoline 1 having the composition and distillation characteristics shown in Table 1 was subjected to fractional distillation at a boiling point range of 150 to 200 ° C to obtain a raw material decomposed gasoline 1. The composition and distillation characteristics of the obtained raw material decomposed gasoline 1 are shown in Table 2.

將所得之原料分解汽油1進行環丁碸處理而萃取芳香族烴，藉此得到含有碳數9之芳香族烴58.1容量%、碳數10之芳香族烴36.1容量%的不均化/轉烷化原料油5。將所得之不均化/轉烷化原料油5之組成示於表5。 The obtained raw material is decomposed into gasoline 1 and subjected to cyclobutyl hydrazine treatment to extract aromatic hydrocarbons, thereby obtaining heterogeneous/transalkylane having 58.1% by volume of aromatic hydrocarbons having a carbon number of 9 and 36.1% by volume of aromatic hydrocarbons having 10 carbon atoms. Raw material oil 5. The composition of the obtained unevenness/transalkylation feedstock 5 is shown in Table 5.

將此不均化/轉烷化原料油5，使用Mo觸媒作為反應觸媒，依反應溫度345℃、液空間速度3h-1、反應壓力2.0MPa、反應時間1.0 小時之條件嘗試進行不均化/轉烷化反應，但在反應途中觸媒失活。 The heterogeneous/transalkylated feedstock 5 was used, and Mo catalyst was used as a reaction catalyst, and unevenness was attempted according to the reaction temperature of 345 ° C, liquid space velocity of 3 h -1 , reaction pressure of 2.0 MPa, and reaction time of 1.0 hour. Conversion/transalkylation reaction, but the catalyst is deactivated during the reaction.

由表1~表4可知，實施例1~實施例3中，由於依序施行(a)分餾步驟、(b)氫化處理步驟及(c)不均化/轉烷化步驟所進行之處理，故即使將芳香族烴之含有比例低，含有不飽和烴或硫分、氮分等之接觸分解汽油用於不均化反應或轉烷化反應等之轉化反應之原料，仍可簡便且依高產率製造二甲苯。 As can be seen from Tables 1 to 4, in Examples 1 to 3, the treatments performed by (a) fractionation step, (b) hydrotreatment step, and (c) unevenness/transalkylation step were sequentially performed. Therefore, even if the content ratio of the aromatic hydrocarbon is low, the contact decomposed gasoline containing an unsaturated hydrocarbon or a sulfur component or a nitrogen component can be used as a raw material for a conversion reaction such as a heterogeneous reaction or a transalkylation reaction, and can be easily and highly produced. The rate of manufacture of xylene.

另一方面，由表1~表3及表5可知，比較例1中，由於未施行(a)分餾步驟，故二甲苯之產率低；比較例2中，由於未施行(b)氫化處理步驟之氫化去硫/去氮反應，故於反應途中反應觸媒失活，無法供於實用。 On the other hand, as is clear from Tables 1 to 3 and Table 5, in Comparative Example 1, since the (a) fractionation step was not carried out, the yield of xylene was low; in Comparative Example 2, since (b) hydrogenation treatment was not carried out The step of hydrogenation desulfurization / denitrification reaction, so the reaction catalyst is inactivated during the reaction, can not be used for practical purposes.

(產業上之可利用性) (industrial availability)

根據本發明，可提供即使將芳香族烴之含有比例低，含有不飽和烴或硫分、氮分等之接觸分解汽油用於不均化反應或轉烷化反應等之轉化反應之原料，仍可簡便且依高產率製造二甲苯的方法。 According to the present invention, it is possible to provide a raw material which is used for a conversion reaction of a heterogeneous reaction or a transalkylation reaction, such as an unsaturated hydrocarbon or a sulfur-containing or nitrogen-containing contact decomposition gasoline, even if the content ratio of the aromatic hydrocarbon is low. A process for producing xylene in a simple and high yield.

Claims (2)

一種二甲苯之製造方法，其特徵為包含：(a)對流動接觸分解汽油進行蒸餾處理，分餾出含有碳數9之芳香族烴25~45容量%、碳數10之芳香族烴15~25容量%之沸點範圍為145~205℃之餾分的分餾步驟；(b)使於上述(a)分餾步驟中所得之沸點範圍為145~205℃之餾分進行氫化去硫/去氮反應，而將硫含量調整為0~6質量ppm、氮含量調整為0~6質量ppm的氫化處理步驟；與(c)對含有於上述(b)氫化處理步驟中所得之芳香族烴的生成油，施行不均化反應或轉烷化反應的不均化/轉烷化步驟。 A method for producing xylene, comprising: (a) subjecting a flow contact decomposed gasoline to a distillation treatment, and fractionating an aromatic hydrocarbon having a carbon number of 9 and an aromatic hydrocarbon of 15 to 25 % by volume and having a carbon number of 10 a fractional distillation step of a fraction having a boiling point range of 145 to 205 ° C; (b) subjecting a fraction having a boiling point range of 145 to 205 ° C obtained in the fractionation step (a) to a hydrogenation desulfurization/denitrogenation reaction, a hydrogenation treatment step in which the sulfur content is adjusted to 0 to 6 mass ppm and the nitrogen content is adjusted to 0 to 6 mass ppm; and (c) the production oil of the aromatic hydrocarbon obtained in the above (b) hydrotreatment step is not carried out A homogenization/transalkylation step of the homogenization reaction or the transalkylation reaction. 如申請專利範圍第1項之二甲苯之製造方法，其中，上述(b)氫化處理步驟係於氫化去硫/去氮反應後進一步對非芳香族烴進行分離處理的步驟。 The method for producing a xylene according to the first aspect of the invention, wherein the (b) hydrogenation treatment step is a step of further subjecting the non-aromatic hydrocarbon to a separation treatment after the hydrogenation desulfurization/denitrogenation reaction.
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