Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
  • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
  • C07C15/02—Monocyclic hydrocarbons
  • C07C15/067—C8H10 hydrocarbons
  • C07C15/08—Xylenes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
  • 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
  • C07C6/123—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 only one hydrocarbon
• • 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
  • 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
  • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
• • 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
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/20—Organic compounds not containing metal atoms
  • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
• • 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
  • 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
  • C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
• • 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
  • 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
  • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • C07C2523/24—Chromium, molybdenum or tungsten
  • C07C2523/28—Molybdenum
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• the present invention relates to a method for producing xylene.
• Xylene is an important compound as a starting material for producing various important industrial chemicals such as phthalic acid (terephthalic acid, isophthalic acid, orthophthalic acid), which is a raw material for polyester.
• phthalic acid terephthalic acid, isophthalic acid, orthophthalic acid
• the transalkylation reaction is a method in which a plurality of aromatic hydrocarbons having different carbon numbers are reacted to convert them into the target aromatic hydrocarbon, and the disproportionation reaction of aromatic hydrocarbons is the same for two molecules.
• This is a method in which an aromatic hydrocarbon reacts and is converted into a target aromatic hydrocarbon.
• a method for producing xylene using a disproportionation reaction of an aromatic hydrocarbon a method of producing benzene and xylene by a disproportionation reaction of toluene can be exemplified, and an aromatic having 9 or more carbon atoms is used as a raw material.
• a method of increasing the yield of xylene by adding a group hydrocarbon to cause a transalkylation reaction is also conceivable.
• the oil fraction is a co-product, there is a limit to the amount of heavy naphtha obtained by refining a certain amount of crude oil. Since heavy naphtha is also used as an industrial raw material other than xylene, in the industrial production of xylene, the oil fraction other than heavy naphtha is effectively utilized to diversify the raw material and reduce the production cost. Reduction is required.
• Examples of petroleum fractions containing aromatic components include fluid catalytic cracking gasoline obtained from fluid catalytic cracking equipment, but fluid catalytic cracking gasoline contains aromatic hydrocarbons compared to heavy catalytic reformed gasoline. It is not suitable as an industrial raw material for xylene because it contains a low proportion of unsaturated hydrocarbons that are highly reactive and contains sulfur (sulfur compounds), nitrogen (nitrogen compounds), etc. that degrade the catalyst. .
• the present invention has a low content ratio of aromatic hydrocarbons, and conversion of catalytic cracked gasoline containing unsaturated hydrocarbons, sulfur, nitrogen, etc., such as disproportionation reaction or transalkylation reaction, etc.
• An object of the present invention is to provide a method for producing xylene in a simple and high yield while being used as a raw material for the reaction.
• the present invention (1) A method for producing xylene, (A) a fractionation step in which fluid catalytic cracking gasoline is subjected to distillation treatment to fractionate a fraction having a boiling range of 145 to 205 ° C .; (B) A hydrodesulfurization / denitrification reaction is performed on the fraction having a boiling range of 145 to 205 ° C.
• the catalytic cracking gasoline containing a low content of aromatic hydrocarbons and containing unsaturated hydrocarbons, sulfur, nitrogen, etc. is used as a raw material for conversion reaction such as disproportionation reaction or transalkylation reaction. While being used, it is possible to provide a method for producing xylene in a simple and high yield.
• the method for producing xylene according to the present invention includes: (A) a fractionation step in which fluid catalytic cracking gasoline is subjected to distillation treatment to fractionate a fraction having a boiling range of 145 to 205 ° C .; (B) A hydrodesulfurization / denitrification reaction is performed on the fraction having a boiling range of 145 to 205 ° C.
• fluid catalytic cracking gasoline distilled from a fluid catalytic cracking device (FCC) is used as a raw material oil.
• the fluid catalytic cracking apparatus is for producing fluid catalytic cracking gasoline from heavy hydrocarbons by fluid catalytic cracking process (FCC process), where the fluid catalytic cracking process is a fluidized catalyst and hydrocarbon oil. Is a process for obtaining gasoline, middle distillate, etc.
• FCC process fluid catalytic cracking process
• Examples of fluid catalytic cracking processes include ABB Lummus Global Inc. on pages 107-110 of HYDRO CARBON PROCESSING / NOVEMBER 2000. ya, Kellogg Brown & Roots, Inc. And Shell Global Solutions International B. V. Also, Stone & Webster Inc. , A Shaw Group Co. / Institut Francais du Petrole. And UOP LLC. The process proposed by various process manufacturers can be listed.
• a relatively heavy hydrocarbon oil (hydrocarbon mixture) boiling above the boiling point of gasoline is converted to a so-called solid acid such as zeolite, silica alumina, and alumina by a fluid catalytic cracking process. What is necessary is just to make it contact with the catalyst shown at high temperature.
• a fluid catalytic cracking catalyst having a solid acidity is usually continuously added to a fluid catalytic cracking apparatus composed of two types of containers, a vertically installed cracking reactor and a catalyst regenerator. It can be done by circulating it.
• the fluid catalytic cracking catalyst deactivated by the coke deposited on the surface as a result of being subjected to the treatment of hydrocarbon oil (hydrocarbon mixture) in the cracking reactor is separated from the cracked products (various product oils), After stripping, transfer to the catalyst regenerator, mix the hot regenerated catalyst regenerated in the catalyst regenerator with the hydrocarbon oil to be cracked again, and circulate through the cracking reactor in the upward direction.
• the reaction can be carried out continuously and the resulting cracked product is distilled off into one or more fractions such as dry gas, LPG, gasoline fraction, LCO and HCO or slurry oil. Further, the decomposition reaction may be further advanced by recirculating part or all of the decomposition product into the cracking reactor.
• a gasoline fraction is used as fluid catalytic cracking gasoline among the fractions separated from the cracked product.
• the hydrocarbon oil (hydrocarbon mixture) used in the catalytic cracking reaction in the fluid catalytic cracking process is a relatively heavy hydrocarbon mixture that boils above the boiling range of gasoline, specifically, atmospheric distillation of crude oil.
• gas oil fraction obtained by vacuum distillation, atmospheric distillation residue oil and vacuum distillation residue oil, etc. can be mentioned, such as coker light oil, solvent desulfurization oil, solvent desulfurization asphalt, tar sand oil, shale oil oil, coal liquefaction Oil etc. may be sufficient.
• the hydrocarbon oil (hydrocarbon mixture) to be subjected to the fluid catalytic cracking process includes hydrotreatments known to those skilled in the art, that is, Ni—Mo based catalyst, Co—Mo based catalyst, Ni—Co—Mo based catalyst.
• hydrotreated oil obtained by hydrodesulfurization at high temperature and high pressure in the presence of a hydrotreating catalyst such as a Ni-W catalyst is also included.
• the operating conditions of the cracking reactor for obtaining the fluid catalytic cracking gasoline used in the present invention are preferably a reaction temperature of 400 to 600 ° C., more preferably 450 to 550 ° C., and a reaction pressure of preferably normal pressure to 5 kg / cm 3 , more preferably normal pressure to 3 kg / cm 3 , and the mass ratio represented by “fluid catalytic cracking catalyst / raw material hydrocarbon oil” is preferably 2 to 20, more preferably 4 to 15 It is.
• reaction temperature When the reaction temperature is within the above range, fluid catalytic cracking gasoline containing a predetermined amount of aromatic hydrocarbon can be efficiently obtained.
• the said reaction temperature is less than 400 degreeC, progress of the decomposition reaction of hydrocarbon oil becomes slow, and since the amount of decomposition products falls, it becomes difficult to perform economical driving
• the said reaction temperature is over 600 degreeC, it will become easy to produce
• the fluid catalytic cracking gasoline is not particularly limited as long as it contains a fraction having a boiling range of 145 to 205 ° C., and has a boiling range of 30 to 240 ° C.
• the temperature is 33 to 235 ° C., more preferably the boiling range is 35 to 220 ° C.
• fluid catalytic cracking gasoline is subjected to distillation treatment to fractionate a fraction having a boiling range of 145 to 205 ° C.
• the fraction to be fractionated in the fractionation step has a boiling range of 145 to 205 ° C., preferably 147 to 202 ° C., more preferably 150 to 200 ° C.
• the boiling range of the fraction obtained in the fractionation step is within the above range, thereby containing a predetermined amount of aromatic hydrocarbons as a raw material for xylene and hydrogen to be described later Degradation of the reaction catalyst due to coke formation can be suppressed during the chemical treatment reaction, the disproportionation reaction or the transalkylation reaction.
• the fraction having a boiling range of 145 to 205 ° C. obtained in the fractionation step preferably contains 25 to 45% by volume of aromatic hydrocarbon having 9 carbon atoms. 28 to 42% by volume is more preferable, and 30 to 40% by volume is more preferable.
• the fraction having a boiling range of 145 to 205 ° C. obtained in the fractionation step contains 15 to 25% by volume of C10 aromatic hydrocarbons. More preferably, the content is 17 to 23% by volume, and more preferably 19 to 21% by volume.
• the fraction having a boiling range of 145 to 205 ° C. obtained in the fractionation step contains the above-mentioned proportion of the aromatic hydrocarbon having 9 carbon atoms and the aromatic hydrocarbon having 10 carbon atoms.
• xylene can be efficiently produced by a disproportionation reaction or a transalkylation reaction described later.
• examples of the aromatic hydrocarbon having 9 carbon atoms include trimethylbenzene and methylethylbenzene, and examples of the aromatic hydrocarbon having 10 carbon atoms include dimethylethylbenzene and tetramethylbenzene. it can.
• the content ratio of aromatic hydrocarbons having 9 carbon atoms and the content ratio of aromatic hydrocarbons having 10 carbon atoms mean values measured according to JIS K 2536-2.
• the fraction having a boiling range of 145 to 205 ° C. obtained in the fractionation step preferably contains 48 to 57% by volume of aromatic hydrocarbons in total. More preferably, it contains 50 to 57% by volume, and even more preferably 52 to 57% by volume.
• the aromatic hydrocarbon content means a value measured according to JIS K 2536-2.
• the fraction having a boiling range of 145 to 205 ° C. obtained in the fractionation step (a) preferably has a saturated hydrocarbon content of 0 to 40% by volume. More preferably, it is ⁇ 35% by volume, and more preferably 0-30% by volume.
• the saturated hydrocarbon content means a value measured according to JIS K 2536-2.
• a fraction having a boiling range of 145 to 205 ° C. obtained in the fractionation step has an unsaturated hydrocarbon (olefin) content ratio of 0 to 15% by volume. It is preferably 0 to 13% by volume, more preferably 0 to 11% by volume.
• the reactivity of the unsaturated hydrocarbon is within the above range, so that the reactivity of the reaction can be lowered, and excessive hydrogenation of aromatic hydrocarbons can be suppressed. it can.
• the content ratio of unsaturated hydrocarbon (olefin) means a value measured according to JIS K 2536-2.
• the fraction having a boiling range of 145 to 205 ° C. obtained in the fractionation step preferably has a sulfur content of 30 ppm by mass or less, and 20 ppm by mass or less. Some are more preferable, and what is 10 mass ppm or less is still more preferable.
• the sulfur content is usually 2 ppm by mass or more.
• the fraction having a boiling range of 145 to 205 ° C. obtained in the fractionation step preferably has a nitrogen content of 10 mass ppm or less, and is 5 mass ppm or less. Some are more preferable, and what is 3 mass ppm or less is still more preferable.
• the nitrogen content is usually 2 mass ppm or more.
• the embodiment of the (a) fractionation step is not particularly limited as long as it is a method capable of obtaining a fraction having a boiling range of 145 to 205 ° C., and a known fractionation method. It can be performed by applying.
• the hydrodesulfurization / denitrification treatment can be performed using a known technique, for example, using the hydrodesulfurization catalyst generally used in petroleum refining, the above (a) Examples thereof include a method in which a fraction having a boiling point range of 145 to 205 ° C. obtained in the fractionation step is reacted under high temperature and high pressure reaction conditions to perform desulfurization and denitrogenation treatment.
• Examples of the hydrodesulfurization catalyst include a catalyst in which an active metal having a hydrogenation function is supported on an inorganic oxide support.
• Examples of the inorganic oxide carrier include one or more selected from various porous inorganic oxides such as alumina, silica, titania, magnesia, silica-alumina, and silica or silica-alumina is preferable.
• Examples of the active metal include one or more selected from Group VI metals such as molybdenum and tungsten, and Group VIII metals such as nickel and cobalt. For example, a combination of metals such as Ni—Mo or Co—Mo may be used. preferable.
• the hydrotreating conditions depend on the content of sulfur, nitrogen, and unsaturated hydrocarbon (olefin) contained in the fraction having a boiling range of 145 to 205 ° C. obtained in the above (a) fractionation step.
• the reaction temperature is usually 200 to 500 ° C.
• the hydrogen partial pressure is 0.5 to 10 MPa
• the liquid space velocity (LHSV) is 1.0 to 20 hr ⁇ 1
• the hydrogen oil ratio Is set within the range of 100 to 1000 NL / L.
• the hydrodesulfurization / denitrification reaction in the hydrotreating step reduces the sulfur content and the nitrogen content in the resulting hydrotreated oil. At the same time, the content of unsaturated hydrocarbons (olefins) unnecessary for xylene production can be reduced.
• the method for producing xylene of the present invention adjusts the sulfur content in hydrotreated oil to 0-6 mass ppm by hydrodesulfurization / denitrification reaction in (b) hydrotreating step. Yes, it is preferably adjusted to 0 to 4 ppm by mass, more preferably 0 to 2 ppm by mass.
• the nitrogen content in the hydrotreated oil is adjusted to 0 to 6 mass ppm by hydrodesulfurization / denitrification reaction in (b) hydrotreating step. It is preferable to adjust the content to 0 to 4 ppm by mass, and it is more preferable to adjust to 0 to 2 ppm by mass.
• the content ratio of unsaturated hydrocarbon (olefin) in the hydrotreated oil is determined by hydrodesulfurization / denitrification reaction in (b) hydrotreating step. It is preferably adjusted to be 0 to 5% by volume, preferably adjusted to be 0 to 3% by volume, and more preferably adjusted to be 0 to 1% by volume.
• (a) the sulfur content and the nitrogen content of the fraction having a boiling point range of 145 to 205 ° C. obtained in the fractionation step are each greater than 6 ppm by mass.
• each content can be reduced to a predetermined amount by the hydrotreating step, and (a) the sulfur content in the fraction having a boiling point range of 145 to 205 ° C. obtained in the fractionation step is In the case of 6 mass ppm or less, each content can be further reduced by the (b) hydrotreatment process.
• the sulfur content in the hydrotreated oil obtained by hydrodesulfurization / denitrification reaction in (b) hydrotreating step is a value measured according to JIS K2541.
• the nitrogen content in the hydrotreated oil obtained by hydrodesulfurization / denitrification reaction means a value measured according to JIS K 2609, and is obtained by hydrodesulfurization / denitrification reaction.
• the content ratio of the unsaturated hydrocarbon (olefin) in the hydrotreated oil is a value measured according to JIS K 2536-2.
• Sulfur compounds and nitrogen compounds in hydrotreated oils may become poisonous substances that degrade the performance of the active metal that constitutes the reaction catalyst during the disproportionation reaction or transalkylation reaction described below, and are also unsaturated. Since hydrocarbons (olefins) may be polymerized to precipitate coke, any of them becomes a causative substance that reduces the life of the reaction catalyst during the disproportionation reaction or transalkylation reaction.
• sulfur content, nitrogen content, and unsaturated hydrocarbon (olefin) content in the hydrotreated oil obtained by hydrodesulfurization / denitrification reaction are within the above ranges, disproportionation reaction or transalkyl Xylene can be efficiently produced while suppressing a decrease in the lifetime of the reaction catalyst during the conversion reaction.
• the hydrotreated oil obtained by hydrodesulfurization / denitrification reaction in the hydrotreating step (b) has a saturated hydrocarbon content of 39 to 51% by volume. It is preferably 41 to 49% by volume, more preferably 43 to 47% by volume.
• the hydrotreated oil obtained by the hydrodesulfurization / denitrification reaction has a saturated hydrocarbon content in the above range, so that xylene can be efficiently used in the disproportionation reaction or transalkylation reaction described later. Obtainable.
• the content ratio of the saturated hydrocarbon means a value measured according to JIS K 2536-2.
• the hydrotreated oil obtained by the hydrodesulfurization / denitrification reaction in the hydrotreating step (b) is a total of 45 to 60% by volume of aromatic hydrocarbons. Preferably, it contains 48 to 58% by volume, more preferably 51 to 56% by volume.
• the aromatic hydrocarbon content means a value measured according to JIS K 2536-2.
• the hydrotreated oil obtained by hydrodesulfurization / denitrification reaction in the hydrotreating step (b) has a content ratio of 9-carbon aromatic hydrocarbons. It is preferably 26 to 40% by volume, more preferably 28 to 39% by volume, and further preferably 30 to 38% by volume.
• the hydrotreated oil obtained by the hydrodesulfurization / denitrification reaction in the (b) hydrotreating step is a content ratio of C10 aromatic hydrocarbons. Is preferably 15 to 26% by volume, more preferably 16 to 24% by volume, and still more preferably 17 to 22% by volume.
• the content ratio of the aromatic hydrocarbon having 9 carbon atoms and the content ratio of the aromatic hydrocarbon having 10 carbon atoms in the hydrotreated oil obtained by hydrodesulfurization / denitrification reaction Is within the above range, the disproportionation reaction or transalkylation reaction described later can be carried out efficiently.
• the content ratio of the aromatic hydrocarbon having 9 carbon atoms and the content ratio of the aromatic hydrocarbon having 10 carbon atoms mean values measured according to JIS K 2536-2.
• the hydrotreated oil obtained by the hydrodesulfurization / denitrification reaction in the (b) hydrotreating step is a normal propylbenzene, which is an aromatic hydrocarbon having 9 carbon atoms.
• the content is preferably 0 to 5% by volume, more preferably 0 to 4% by volume, and still more preferably 0 to 3% by volume.
• the hydrotreated oil obtained by hydrodesulfurization / denitrification reaction in the hydrotreating step (b) is trimethylbenzene, which is an aromatic hydrocarbon having 9 carbon atoms. Is preferably 12 to 20% by volume, more preferably 13 to 19% by volume, and still more preferably 14 to 18% by volume.
• the content ratio of normal propylbenzene which is an aromatic hydrocarbon having 9 carbon atoms
• saturated hydrocarbons by dealkylation reaction are obtained. Generation can be suppressed.
• the content ratio of trimethylbenzene which is an aromatic hydrocarbon having 9 carbon atoms
• Xylene can be efficiently obtained in the reaction or transalkylation reaction.
• the content ratios of normal propylbenzene and trimethylbenzene mean values measured according to JIS K 2536-2.
• a desulfurization / denitrification reaction may be further performed as a separate pretreatment before the (a) fractionation step.
• all the fluid catalytic cracking gasoline fraction distilled from the fluid catalytic cracking device is directly desulfurized / denitrified and then (a) distilled to fractionate the fraction having a boiling range of 145 to 205 ° C.
• Embodiments can be mentioned.
• the hydrotreated oil obtained by hydrodesulfurization / denitrification reaction in the hydrotreating step is directly used as a product oil containing aromatic hydrocarbons. It can be subjected to a conversion / transalkylation step.
• the above-mentioned (b) hydrotreating step further separates non-aromatic hydrocarbons (hydrocarbons other than aromatic hydrocarbons) after hydrodesulfurization / denitrification reaction. It may be.
• the separation treatment of the non-aromatic hydrocarbon is preferably performed by distilling or extracting the hydrotreated oil obtained by the hydrodesulfurization / denitrification reaction.
• 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.
• Examples of the selective solvent used in the liquid-liquid extraction method include one or more selected from glycerol and sulfolane derivatives.
• the liquid-liquid extraction method separates and recovers polar hydrocarbons from a hydrocarbon mixture containing polar and nonpolar hydrocarbons as described, for example, in US Pat. No. 4,058,454.
• all aromatic hydrocarbons contained in the hydrotreated oil obtained by the hydrodesulfurization / denitrification reaction are known.
• non-polar non-aromatic hydrocarbons can be separated, non-aromatic hydrocarbons are separated and removed from the hydrotreated oil obtained by the above hydrodesulfurization / denitrification reaction, and high-purity aromatic hydrocarbons are obtained.
• a product oil containing can be obtained.
• the resulting oil containing the aromatic hydrocarbon has a sulfur content of 0 to Those having 6 ppm by mass are preferred, those having 0-4 ppm by mass are more preferred, and those having 0-2 ppm by mass are more preferred.
• the resulting oil containing the aromatic hydrocarbon has a nitrogen content of 0-6.
• the mass is preferably ppm, more preferably 0 to 4 ppm by mass, and still more preferably 0 to 2 ppm by mass.
• the said sulfur content means the value measured according to JISK2541
• the nitrogen content means the value measured according to JISK2609.
• the resulting oil containing aromatic hydrocarbons contains 90 to 90 aromatic hydrocarbons in total.
• the content is preferably 100% by volume, more preferably 92-100% by volume, and still more preferably 94-100% by volume.
• the aromatic hydrocarbon content means a value measured according to JIS K 2536-2.
• the resulting oil containing the aromatic hydrocarbon is a content ratio of the aromatic hydrocarbon having 9 carbon atoms. However, it is preferably 50 to 70% by volume, more preferably 55 to 67% by volume, and still more preferably 60 to 65% by volume.
• the resulting product oil has a C 10 aromatic hydrocarbon content ratio of 30 to 42. Those having a volume% are preferred, those having 32 to 40% by volume are more preferred, and those having 35 to 38% by volume are even more preferred.
• the content ratio of aromatic hydrocarbons having 9 carbon atoms and aromatic carbonization having 10 carbon atoms mean values measured according to JIS K 2536-2.
• the resulting oil containing the aromatic hydrocarbon is normal, which is an aromatic hydrocarbon having 9 carbon atoms.
• the content of propylbenzene is preferably 0 to 9% by volume, more preferably 0 to 7% by volume, and further preferably 0 to 5% by volume.
• the resulting oil containing the aromatic hydrocarbon is an aromatic hydrocarbon having 9 carbon atoms.
• the content ratio of a certain trimethylbenzene is preferably 25 to 36% by volume, more preferably 26 to 34% by volume, and further preferably 27 to 32% by volume.
• the product oil containing aromatic hydrocarbons obtained by separating non-aromatic hydrocarbons in the hydrotreating step has a normal propylbenzene content ratio within the above range.
• generation of the saturated hydrocarbon by a dealkylation reaction can be suppressed.
• the product oil obtained by separating the non-aromatic hydrocarbons in the hydrotreating step will be described later because the content ratio of trimethylbenzene is within the above range.
• Xylene can be efficiently obtained in the disproportionation reaction or transalkylation reaction.
• the content ratios of normal propylbenzene and trimethylbenzene mean values measured according to JIS K 2536-2.
• the product oil containing aromatic hydrocarbons obtained by separating non-aromatic hydrocarbons in the hydrotreating step has a saturated hydrocarbon content of 0 to 7 volumes. %, Preferably 0 to 5% by volume, more preferably 0 to 4% by volume.
• the product oil obtained by separating the non-aromatic hydrocarbon in the hydrotreating step will be described later because the content ratio of the saturated hydrocarbon is within the above range.
• Xylene can be efficiently obtained in the disproportionation reaction or transalkylation reaction.
• the content ratio of the saturated hydrocarbon means a value measured according to JIS K 2536-2.
• the product oil containing aromatic hydrocarbons obtained by separating non-aromatic hydrocarbons in the hydrotreating step has an unsaturated hydrocarbon content ratio of 0-2. Those having a volume% are preferred, those having 0 to 1 volume% are more preferred, and those having 0 to 0.5 volume% are more preferred.
• the product oil obtained by separating non-aromatic hydrocarbons in the hydrotreating step has an unsaturated hydrocarbon (olefin) content in the above range.
• the content ratio of the unsaturated hydrocarbon means a value measured according to JIS K 2536-2.
• the method for producing xylene of the present invention comprises (c) disproportionation / transalkylation by further separating non-aromatic hydrocarbons after hydrodesulfurization / denitrification reaction in the (b) hydrotreating step.
• the process can be performed efficiently.
• the reaction conditions for the disproportionation reaction or alkylation reaction are not particularly limited as long as xylene can be obtained.
• the product oil containing the aromatic hydrocarbon obtained in the hydrotreating step has a liquid space velocity (LHSV) of preferably 0.01 h ⁇ 1 or more, more preferably 0.1 h -1 or more, preferably 10h -1 or less, more preferably supplied in 5h -1 or less, it is preferable to carried out by contacting the catalyst.
• LHSV liquid space velocity
• the reaction temperature is preferably 200 ° C. or higher, more preferably 230 ° C. or higher, further preferably 260 ° C. or higher, preferably 550 ° C. or lower, more preferably 530 ° C. or lower. Particularly preferably, it is 510 ° C. or lower. If the reaction temperature is less than 200 ° C., the activation of aromatic hydrocarbons is insufficient, and the active sites are poisoned by the water produced by the reaction, so the conversion rate of aromatic hydrocarbons is low. It is easy to become. On the other hand, when the reaction temperature exceeds 550 ° C., in addition to consuming a lot of energy, the catalyst life tends to be shortened.
• the reaction pressure is preferably at least atmospheric pressure, more preferably at least 0.1 MPaG, even more preferably at least 0.5 MPaG, preferably at most 10 MPaG, more preferably at most 5 MPaG. .
• an inert gas such as nitrogen gas or helium gas or hydrogen gas for suppressing coking may be circulated or pressurized in the reaction system.
• the reaction catalyst used in the above disproportionation reaction or transalkylation reaction is not particularly limited as long as it is an aromatic conversion catalyst and causes disproportionation reaction or transalkylation.
• the reaction catalyst is preferably one that selectively dealkylates an ethyl group or a propyl group while retaining a methyl group and simultaneously has a transalkylation ability.
• a shape-selective metallosilicate catalyst is preferable, crystalline aluminosilicate is more preferable, and zeolite is more preferable.
• the zeolite any zeolite selected from mordenite, Y-type zeolite, X-type zeolite, beta-type zeolite, ZSM-5 and the like can be used, but mordenite is preferable.
• (c) in the disproportionation / transalkylation step two molecules of the same aromatic hydrocarbon are converted by a disproportionation reaction, and the aromatic hydrocarbon 1 having a lower molecular weight is converted. Molecule and one higher molecular weight aromatic hydrocarbon (xylene) molecule can be obtained. Specifically, two molecules of toluene can be converted to obtain one molecule of benzene and one molecule of xylene.
• (x) in the disproportionation / transalkylation step two aromatic hydrocarbons having different carbon numbers are converted to obtain two xylene molecules by transalkylation reaction. Specifically, one molecule of toluene and one molecule of trimethylbenzene can be converted to obtain two molecules of xylene.
• the xylene is selectively produced by performing a disproportionation reaction or a transalkylation reaction between aromatic hydrocarbons in the (c) disproportionation / transalkylation step. Can do.
• the product oil obtained in the (c) disproportionation / transalkylation step preferably has a xylene content of 28 to 32% by volume, More preferably, it is 32% by volume, and even more preferably 30-32% by volume.
• the xylene content means a value measured according to JIS K 2536-2.
• the catalytic cracking gasoline containing a low content of aromatic hydrocarbons and containing unsaturated hydrocarbons, sulfur, nitrogen, etc. is used as a raw material for conversion reaction such as disproportionation reaction or transalkylation reaction. While being used, it is possible to provide a method for producing xylene in a simple and high yield.
• Example 1 (A) Fractionation process A fluid catalytic cracking gasoline 1 having the composition and distillation characteristics shown in Table 1 was fractionated at a boiling range of 150 to 200 ° C. to obtain a raw material cracked gasoline 1. Table 2 shows the composition and distillation properties of the obtained raw material cracked gasoline 1. (B) Hydrotreating process The obtained raw material cracked gasoline 1 was subjected to a reaction temperature of 300 ° C., a reaction pressure of 3.0 MPa, a liquid space velocity (LHSV) of 2.0 h ⁇ 1 , hydrogen oil using a Co—Mo catalyst.
• LHSV liquid space velocity
• a desulfurization / denitrification fluid catalytic cracking gasoline 1 having a volume% and an unsaturated hydrocarbon (olefin) content of 0.5 volume% was obtained.
• the composition of the obtained desulfurization / denitrification fluid catalytic cracking gasoline 1 is shown in Table 3.
• this desulfurization / denitrification fluid catalytic cracking gasoline 1 is subjected to sulfolane treatment to extract aromatic hydrocarbons, so that 58.5% by volume of C9 aromatic hydrocarbons and C10 aromatic hydrocarbons are obtained.
• the composition of the resulting disproportionated / transalkylated feedstock 1 is shown in Table 4.
• Example 2 (A) Fractionation process Fluidized cracked 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 raw material cracked gasoline 2. Table 2 shows the composition and distillation properties of the obtained raw material cracked gasoline 2. (B) Hydrotreating process The obtained raw material cracked gasoline 2 was subjected to a reaction temperature of 300 ° C., a reaction pressure of 3.0 MPa, a liquid space velocity (LHSV) of 2.0 h ⁇ 1 using a Co—Mo catalyst, and a hydrogen oil ratio.
• LHSV liquid space velocity
• Desulfurization / denitrification fluid catalytic cracking gasoline 2 having an unsaturated hydrocarbon (olefin) content of 0.6% by volume was obtained.
• the composition of the obtained desulfurization / denitrification fluid catalytic cracking gasoline 2 is shown in Table 3.
• the desulfurization / denitrification fluid catalytic cracking gasoline 2 is subjected to sulfolane treatment to extract aromatic hydrocarbons, whereby 58.1% by volume of C9 aromatic hydrocarbons and C10 aromatic hydrocarbons are obtained. Was obtained as a disproportionated / transalkylated feedstock 2 containing 36.9% by volume.
• Example 3 (A) Fractionation process Fluidized cracked gasoline 3 having the composition and distillation characteristics shown in Table 1 was fractionated at a boiling point range of 150 to 200 ° C. to obtain raw material cracked gasoline 3. Table 2 shows the composition and distillation properties of the obtained raw material cracked gasoline 3. (B) Hydrotreating process The obtained raw material cracked gasoline 3 was subjected to a reaction temperature of 300 ° C., a reaction pressure of 3.0 MPa, a liquid space velocity (LHSV) of 2.0 h ⁇ 1 , hydrogen oil using a Co—Mo catalyst.
• LHSV liquid space velocity
• the sulfur content is 1 mass ppm
• the nitrogen content is 1 mass ppm
• the aromatic hydrocarbon content is 55.
• a desulfurization / denitrification fluid catalytic cracking gasoline 3 having 1% by volume and an unsaturated hydrocarbon (olefin) content of 0.6% by volume was obtained.
• the composition of the obtained desulfurization / denitrification fluid catalytic cracking gasoline 3 is shown in Table 3.
• the desulfurization / denitrification fluid catalytic cracking gasoline 3 is subjected to sulfolane treatment to extract aromatic hydrocarbons, whereby 62.9% by volume of aromatic hydrocarbons having 9 carbon atoms and 10 hydrocarbon atoms are obtained.
• sulfolane treatment to extract aromatic hydrocarbons, whereby 62.9% by volume of aromatic hydrocarbons having 9 carbon atoms and 10 hydrocarbon atoms are obtained.
• the composition of the resulting disproportionated / transalkylated feedstock 3 is shown in Table 4.
• (C) Disproportionation / transalkylation step Using the above disproportionation / transalkylation feedstock 3 as a reaction catalyst, a Mo catalyst, a reaction temperature of 345 ° C., a liquid space velocity of 3 h ⁇ 1 , a reaction pressure of 2.0 MPa, By subjecting the disproportionation / transalkylation reaction to a reaction time of 1.0 hour, the desired product oil 3 containing 31.2% by volume of xylene was obtained. The composition of the resulting product oil 3 is shown in Table 4.
• a product oil was obtained without subjecting the fluid catalytic cracking gasoline 1 to (a) fractionation step. That is, a fluid catalytic cracking gasoline 1 having the composition and distillation characteristics shown in Table 1 was prepared using a Co—Mo-based catalyst at a reaction temperature of 300 ° C., a reaction pressure of 3.0 MPa, a liquid space velocity (LHSV) of 2.0 h ⁇ 1 , By performing desulfurization and denitrification treatment under the conditions of a hydrogen oil ratio of 300 NL / L and a reaction time of 2.0 hours, the sulfur content is 1 mass ppm, the nitrogen content is 1 mass ppm, and the aromatic hydrocarbon content is A desulfurization / denitrification fluid catalytic cracking gasoline 4 having 23.4% by volume and an unsaturated hydrocarbon (olefin) content of 0.6% by volume was obtained.
• a fluid catalytic cracking gasoline 1 having the composition and distillation characteristics shown in Table 1 was prepared using a Co—Mo-based catalyst at a reaction temperature
• the composition of the obtained desulfurization / denitrification fluid catalytic cracking gasoline 4 is shown in Table 3. Further, this desulfurized fluid catalytic cracking gasoline 4 is treated with sulfolane to extract an aromatic fraction, whereby 25.8% by volume of C9 aromatic hydrocarbons and 21C of C10 aromatic hydrocarbons are extracted. A disproportionated / transalkylated feedstock 4 containing 4% by volume was obtained. The composition of the resulting disproportionated / transalkylated feedstock 4 is shown in Table 5.
• the above disproportionated / transalkylated feedstock 4 was disproportionated under the conditions of using a Mo catalyst as a reaction catalyst, 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.
• a Mo catalyst as a reaction catalyst
• a reaction temperature 345 ° C.
• a liquid space velocity 3 h ⁇ 1
• a reaction pressure of 2.0 MPa a reaction time of 1.0 hour.
• the composition of the resulting product oil 4 is shown in Table 5.
• the composition of the resulting disproportionated / transalkylated feedstock 5 is shown in Table 5.
• This disproportionated / transalkylated feedstock 5 was disproportionated under the conditions of using a Mo catalyst as a reaction catalyst, 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. An attempt was made to carry out the conversion / transalkylation, but the catalyst was deactivated during the reaction.
• the catalytic cracking gasoline containing a low content of aromatic hydrocarbons and containing unsaturated hydrocarbons, sulfur, nitrogen, etc. is used as a raw material for conversion reaction such as disproportionation reaction or transalkylation reaction. While being used, it is possible to provide a method for producing xylene in a simple and high yield.

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