WO2012169651A1 - Procédé de fabrication d'un hydrocarbure aromatique et/ou d'une oléfine ayant au plus 4 atomes de carbone et appareil de fabrication d'un hydrocarbure aromatique et/ou d'une oléfine ayant au plus 4 atomes de carbone - Google Patents

Procédé de fabrication d'un hydrocarbure aromatique et/ou d'une oléfine ayant au plus 4 atomes de carbone et appareil de fabrication d'un hydrocarbure aromatique et/ou d'une oléfine ayant au plus 4 atomes de carbone Download PDF

Info

Publication number
WO2012169651A1
WO2012169651A1 PCT/JP2012/065054 JP2012065054W WO2012169651A1 WO 2012169651 A1 WO2012169651 A1 WO 2012169651A1 JP 2012065054 W JP2012065054 W JP 2012065054W WO 2012169651 A1 WO2012169651 A1 WO 2012169651A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
solid acid
acid catalyst
carbon atoms
zeolite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/065054
Other languages
English (en)
Inventor
Masayuki IKEGUCHI
Atsuyuki Miyaji
Satoshi Akiyama
Takashi Tatsumi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Tokyo Institute of Technology NUC
Original Assignee
Sumitomo Chemical Co Ltd
Tokyo Institute of Technology NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd, Tokyo Institute of Technology NUC filed Critical Sumitomo Chemical Co Ltd
Publication of WO2012169651A1 publication Critical patent/WO2012169651A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

Definitions

  • Light olefins such as ethylene, propylene and butene, and aromatic hydrocarbons such as BTX (benzene, toluene and xylene) are important chemical materials serving as raw materials for polymers and various chemical materials.
  • One production method therefor includes a thermal cracking process of naphtha, but this process requires so high temperature as 800°C or higher and consumes a great deal of energy because of conducting thermal cracking which is an endothermic reaction.
  • the ethylene selectivity is high in such thermal cracking and it is difficult to respond to an increase in production of propylene.
  • catalytic cracking of naphtha by using a catalyst.
  • Such catalytic cracking enables a reaction at low temperatures of about 600 to 700°C, thereby enabling energy saving, and generally exerting a higher selectivity to propylene than the thermal cracking.
  • it is expected to control the selectivity of each product depending on the demand and supply balance and to enhance the selectivity of all valuable components, by controlling the catalyst.
  • Patent Literature 1 Japanese Patent Application Laid-Open No. 2010-42344
  • Patent Literature 1 describes that with respect to the catalytic cracking by using zeolite which supports an alkali earth metal, a rare earth element and phosphorus, a reduction in activity is suppressed by using a catalyst prepared by supporting on the zeolite phosphorus and components other than phosphorus in separate steps than the case of using a catalyst prepared by supporting them at the same time.
  • Patent Literature 2 Japanese Patent Application Laid-Open No. 2010-104878 describes that with respect to the catalytic cracking by using zeolite which supports an alkali earth metal, a rare earth element and phosphorus, a reduction in activity is suppressed by using a catalyst prepared by sequentially supporting on the zeolite an alkali earth metal, phosphorus and a rare earth element in this order or an alkali earth metal, phosphorus, rare earth and phosphorus in this order, than the case of using a catalyst prepared by supporting them at the same time or in a different order from the above orders.
  • Patent Literature 3 describes that with respect to the catalytic cracking by using zeolite which supports an alkali earth metal and phosphorus, a reduction in activity is suppressed by supporting on the zeolite by using a water-soluble salt containing the alkali earth metal and the phosphorus.
  • Patent Literature 4 describes that with respect to the catalytic cracking of paraffins by using MCM-68, a reduction in activity is suppressed by dealuminizing MCM-68 having a low Si/Al ratio by a nitric acid treatment to make the Si/Al ratio higher, as compared with MCM-68 without being dealuminated.
  • Patent Literature 5 As the reaction using a plurality of catalysts, for example, US Patent Application Publication No. 2010/0213101 A 1 (Patent Literature 5) describes that a catalyst, in which a group VIII metal is supported on beta-zeolite having a small acid amount, is placed on the front stage, and a catalyst, in which a group VIII metal is supported on ZSM-5 having high Si, is placed on the rear stage. These catalysts are selected for the purpose of enhancing the selectivity for naphtha reforming at about 800 to about 1100°F (about 427 to about 593°C) to increase the octane number of an oil fraction to be generated.
  • Patent Literature 1 Japanese Patent Application Laid-Open No. 2010-42344
  • Patent Literature 2 Japanese Patent Application Laid-Open No. 2010-104878
  • Patent Literature 3 Japanese Patent Application Laid-Open No.
  • Patent Literature 4 Japanese Patent Application Laid-Open No. 2010-202613
  • Patent Literature 5 US Patent Application Publication No. 2010/0213101 Al
  • Patent Literature 5 does not suppose to suppress the deactivation of the catalyst due to coking in the catalytic cracking.
  • the present invention has been made under such circumstances, and an object thereof is to provide a method for producing an aromatic hydrocarbon and/or a light olefin that can suppress the deactivation of the catalyst due to coking.
  • a certain aspect of the present invention is a method for producing an aromatic hydrocarbon and/or an olefin having 4 or less carbon atoms.
  • This method includes passing a hydrocarbon through a first catalyst portion containing a solid acid catalyst (A) having an acid amount of 0.001 to 1 mmol/g, and then further through a second catalyst portion containing a solid acid catalyst (B) having an acid amount of 90% or less of the acid amount of the solid acid catalyst (A), and catalytically-cracking the hydrocarbon in the first catalyst portion and in the second catalyst portion at a reaction temperature of 600°C or higher.
  • Another aspect of the present invention is an apparatus for producing an aromatic hydrocarbon and/or an olefin having 4 or less carbon atoms.
  • This apparatus is provided with a reaction portion having at least a first catalyst portion and a second catalyst portion.
  • the first catalyst portion contains a solid acid catalyst (A) having an acid amount of 0.001 to 1 mmol/g
  • the second catalyst portion is placed on the downstream side from the first catalyst portion and contains a solid acid catalyst (B) having an acid amount of 90% or less of the acid amount of the solid acid catalyst (A).
  • the reaction portion is configured so as to be capable of catalytically-cracking the hydrocarbon supplied at a reaction temperature of 600°C or higher.
  • the first catalyst portion (solid acid catalyst (A)) is placed on the upstream side from the second catalyst portion (solid acid catalyst (B)).
  • the second catalyst portion is placed on the downstream side from the first catalyst portion.
  • examples of the hydrocarbon suitable for raw materials include alkanes having 2 to 20 carbon atoms, olefins having 2 to 20 carbon atoms, aromatic hydrocarbons having 6 to 20 carbon atoms and naphthenes having 5 to 20 carbon atoms.
  • the hydrocarbon is preferably hydrocarbons having 5 to 12 carbon atoms, and more preferably saturated hydrocarbons having 5 to 9 carbon atoms and/or aromatic hydrocarbons having 6 to 9 carbon atoms.
  • Examples of the saturated hydrocarbon having 5 to 9 carbon atoms include pentane, hexane and heptane
  • examples of the aromatic hydrocarbon having 6 to 9 carbon atoms include benzene, toluene and xylene.
  • the hydrocarbon is preferably hydrocarbons containing a hydrocarbon having 5 to 12 carbon atoms at 80% by weight or more, and more preferably hydrocarbons containing a saturated hydrocarbon having 5 to 9 carbon atoms and/or a aromatic hydrocarbons having 6 to 9 carbon atoms at 80% by weight or more.
  • the examples of the hydrocarbon include heavy oils, light oils and naphtha, and the hydrocarbon is preferably naphtha. While naphtha is classified into light naphtha, heavy naphtha and full range naphtha depending on its boiling point, raw material naphtha may be any of them and is preferably light naphtha.
  • light naphtha refers to one having a relatively low boiling point among naphtha
  • heavy naphtha refers to one having a relatively high boiling point among naphtha.
  • raw materials may be mixed an unreacted raw materials and a part of products in the catalytic cracking, which are recycled, or may be mixed hydrocarbons generated in other process.
  • These raw materials may be diluted with an inert gas such as nitrogen when being introduced into a reactor, but it is preferable not to use such an inert gas in light of the cost of supplying an inert gas.
  • an inert gas such as nitrogen when being introduced into a reactor, but it is preferable not to use such an inert gas in light of the cost of supplying an inert gas.
  • To a reactor may also be supplied hydrogen, but it is preferable not to supply hydrogen because a higher hydrogen concentration causes products to be hydrogenated to thereby lower the yield of an aromatic hydrocarbon and/or a light olefin.
  • To these raw materials may also be entrained steam for the purposes of heat supply and coking suppression.
  • the reaction temperature of catalytic cracking of the hydrocarbon is 600°C or higher, preferably 600 to 900°C, more preferably 610 to 750°C, and still preferably 630 to 700°C. If the temperature is too low, the reaction does not progress sufficiently and the equilibrium between paraffins and olefins as products is shifted to the side of paraffins, and thus the yield of an aromatic hydrocarbon and/or a light olefin is lowered. On the other hand, if the temperature is too high, thermal cracking progresses to thereby lower the yield of an aromatic hydrocarbon and/or a light olefin, and also coking is increased to thereby speed up the deactivation of the catalyst.
  • the solid acid catalysts include zeolite, silica alumina, sulfated zirconia and tungstated zirconia, it is preferable that at least one of the solid acid catalysts to be used in the catalyst layers be zeolite having an 8, 10 or 12-membered ring pore structure, and it is more preferable that at least two of the solid acid catalysts to be used in the catalyst layers be zeolites having an 8, 10 or 12-membered ring pore structure. Still preferably, at least two of the solid acid catalysts are zeolites having an 8 or 10-membered ring pore structure. It is to be noted that each of the above catalyst layers functions as the catalyst portion.
  • a catalyst layer as a form of the catalyst portion will be described as an example, but the catalyst portion can take any of various forms.
  • the zeolite having an 8, 10 or 12-membered ring pore structure be at least one selected from MFI-type, MEL-type, MWW-type, TON-type, BEA-type, MSE-type, MOR-type, MTW-type and FAU-type zeolites, it is more preferable to be at least one selected from MFI-type, MSE-type and FAU-type zeolites, and most preferable is, in particular, MFI-type zeolite among them, which has high catalytic cracking activity and stability.
  • ZSM-5 is one MFI-type zeolite.
  • One or more catalysts among the solid acid catalysts to be used may be modified by one or more components selected from alkali metals, alkali earth metals, rare earth metals, phosphorus, and transition metals such as group 4A, group 5A, group 6A, group 7A, group 8, group IB and group 2B metals.
  • the acid amount of the catalyst is also referred to as "acidity" in the art, and is defined by a molar number of an acid per gram of the catalyst.
  • the solid acid catalysts may be used in any form of a powder and a molded object.
  • the catalyst in the form of a molded object is designated as a molded catalyst.
  • the molded catalyst may contain, as a binder and the like, one or more of clay minerals such as kaolin and bentonite and/or inorganic oxides such as silica, alumina and zirconia, in addition to the solid acid catalyst components.
  • the acid amount of the solid acid catalyst (A) is 0.001 to 1 mmol/g, preferably 0.01 to 0.8 mmol/g, and more preferably 0.1 to 0.5 mmol/g. If the acid amount of the solid acid catalyst (A) is too large, the activity thereof is high, but the catalyst is easily deactivated due to coking, and on the other hand, if the acid amount is too small, a sufficient activity is not obtained.
  • two or more catalyst layers may be formed by packing the solid acid catalysts which are different in terms of the acid amount into the respective separate reactors, and placing the two or more reactors each thus packed with the catalyst in series.
  • one reactor packed with the catalyst constitutes one catalyst layer.
  • the type of each of the reactors may be any of a fixed bed, a moving bed and a fluidized bed, or may be a combination of different types of the reactors.
  • the "fixed-bed” flow type reactor so-called “fixed bed reactor” is, for example, a type of a reactor which holds a granular catalyst by any member, which can be realized at low costs.
  • the member that holds a granular catalyst for example, a combination of quartz wool and quartz sand, a network bed, or the like is used.
  • the "fluidized bed” type reactor so-called “fixed bed reactor” is a reactor configured so that gas explodes like bubbles in a powdery catalyst.
  • the stages of the solid acid catalysts which are different in terms of the acid amount may be directly in contact with each other, or may be apart from each other via an inert layer or a layer of a catalyst other than the solid acid catalysts which are different in terms of the acid amount, interposed therebetween.
  • the mutual positions of at least two thereof may be so that the solid acid catalyst having a larger acid amount is present at the upstream and the solid acid catalyst having a smaller acid amount is present at the downstream, and the position(s) of the remaining catalyst(s) is(are) not particularly limited.
  • the solid acid catalyst having a larger acid amount be separated into a plurality of stages depending on its type sequentially from the upstream side and packed into the reactor.
  • the reactor according to the present embodiment is packed with the solid acid catalyst having a relatively large acid amount at the upstream side, and packed with the solid acid catalyst having a relatively low acid amount at the downstream side.
  • the weight of the solid acid catalyst (B) be 1/100 to 100 times the weight of the solid acid catalyst (A), and it is more preferable to be 1/10 to 10 times the weight of the solid acid catalyst (A).
  • the weight of any one solid acid catalyst corresponding to the solid acid catalyst (B) may be within the above range relative to the weight of any one solid acid catalyst corresponding to the solid acid catalyst (A).
  • the catalyst layers to be used two or more catalyst layers may be used, but it is preferable to use 2 to 5 catalyst layers, and it is most preferable to use 2 to 3 catalyst layers, in light of the effects on cost of catalyst production and time and effort of packing.
  • the solid acid catalysts having different systems such as zeolite and silica alumina may be combined, and a combination of the same systems which are different in terms of the acid amount, such as a combination of zeolites which are different in the acid amount is more preferable from the operability.
  • zeolites which are different in terms of the structure such as MFI and FAU may be combined, but at least two of the solid acid catalysts are preferably MFI-type zeolites which are the same in terms of the crystal structure, and it is more preferable that all the solid acid catalysts be MFI-type zeolite.
  • the acid amount can be controlled by various factors such as raw materials, compositions, preparation methods, preparation conditions, post-treatments and metal supporting, and a method for obtaining the solid acid catalysts which are different in terms of the acid amount is not particularly limited.
  • the acid amount can be easily controlled by methods such as a method of changing a Si/Al 2 molar ratio, a method of conducting a water vapor treatment, a method of conducting an acid treatment, a method of conducting an alkali treatment and a method of changing an ion exchange rate.
  • the change in Si/Al 2 molar ratio is preferable in terms of no need for a post-treatment of zeolite.
  • zeolites which are different in terms of the acid amount can be prepared from one zeolite, and thus there is an advantage that zeolites differing in acid amount are less expensively available than the case of purchasing a plurality of zeolites.
  • a water vapor treatment is preferable because a waste liquid is only water unlike the cases of an acid treatment and an alkali treatment and such a treatment is thus easier and does not involve a reduction in catalyst amount.
  • Both of the solid acid catalyst (A) and the solid acid catalyst (B) may contain zeolite represented by the formula xM 2 OyAl 2 0 3 zSi0 2 -nH 2 O.
  • the molar ratio z/y of Si to Al 2 in the zeolite (Al) contained in the solid acid catalyst (A) may be different from the molar ratio z/y of Si to Al 2 in the zeolite (Bl) contained in the solid acid catalyst (B).
  • the Si/Al 2 molar ratio of zeolite in this way, it is possible to control the acid amount.
  • the Si/Al 2 molar ratio can be modulated by changing the composition of the raw materials, and zeolites which are different in terms of the Si/Al 2 molar ratio can be easily purchased.
  • the water vapor treatment means a method for treating zeolite with water vapor or water vapor diluted with an inert gas such as nitrogen at a temperature of usually 400 to 900°C, preferably 500 to 700°C, in the gas phase, this method making it possible to partially remove aluminum in the zeolite framework to thereby make the acid amount smaller.
  • At least one of the zeolite (Al) of the solid acid catalyst (A) and the zeolite (Bl) of the solid acid catalyst (B) may be one which has an acid amount modulated by having been treated with water vapor.
  • the acid treatment means a method for treating zeolite with an acid such as hydrochloric acid, nitric acid or sulfuric acid at 30 to 100°C, this method making it possible to partially remove aluminum in the zeolite framework to thereby make the acid amount smaller.
  • the above-described method is performed in a reaction appratus including the first catalyst portion and the second catalyst portion, and the selectivity defined as the ratio of the total number of carbon atoms contained in olefins having 4 or less carbon atoms, benzene, toluene and xylene discharged from the reaction apparatus in a unit time to the total number of carbon atoms contained in the hydrocarbon supplied to the reaction apparatus in the unit time is 55% or more.
  • the first catalyst portion and the second catalyst portion may be located either within the same reactor or within different reactors.
  • the alkali treatment means a method for treating zeolite with an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, this method making it possible to elute silicon in the zeolite framework to thereby make the acid amount larger.
  • an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution
  • An acid amount of each catalyst was measured by the ammonia TPD method. Measurement was conducted by using BELCAT manufactured by BEL Japan, Inc. A powder sample was packed into a quartz cell, and the temperature thereof was raised to 500°C under a He flow and held for 1 hour, and the sample was cooled to 100°C. Subsequently, 5% by volume of NH 3 /He was supplied thereto at 100°C for 30 minutes to allow ammonia to be adsorbed, and thereafter He purge was conducted for 15 minutes. Thereafter, the temperature was raised to 700°C at a rate of 10°C/min and held for 20 minutes to quantitatively measure ammonia desorbed.
  • peaks at low temperatures of 200 to 300°C and peaks at high temperature of not less than 300°C are apparent, and the peaks at high temperatures are derived from acids and thus peak separation was conducted between 200°C and 300°C to thereby calculate the acid amount.
  • Zeolite was set in a water vapor treatment apparatus, the temperature thereof was raised to 600°C at a rate of 5°C/min in a nitrogen stream, and thereafter 20% by volume of water vapor/nitrogen was supplied thereto to conduct a water vapor treatment. After a treatment for a predetermined period, stream was switched to nitrogen to cool the zeolite.
  • catalytic cracking was conducted.
  • the catalyst one whose particle size was regulated to a particle size of 250 to 500 ⁇ was used.
  • a granular catalyst was held by using quartz wool and quartz sand.
  • the catalyst was packed into an Inconel reaction tube so that the total amount was 0.36 g.
  • the upper and the lower of a catalyst layer were held by quartz wool, and the more upper and the more lower thereof was packed with quartz sand in order to make the retention time of gas in the reaction tube shorter.
  • thermocouple was set so as to be located at the center of the catalyst layer to measure the temperature of the catalyst layer.
  • Gas was supplied from the upper portion of the reaction tube and extracted from the lower portion thereof.
  • the temperature of the reaction tube was raised to a predetermined temperature at a rate of 5°C/min under atmospheric pressure in a nitrogen stream. Thereafter, the supply of nitrogen was stopped, and n-hexane was supplied at a rate of 7.2 g/h. In addition to n-hexane, neither diluted gas nor water vapor was supplied during the reaction.
  • the temperature of an electric furnace was modulated so that the temperature of the catalyst layer was a predetermined temperature. After a reaction for a predetermined period, the supply of n-hexane was stopped, followed by cooling in a nitrogen stream. Analysis was conducted by gas chromatography to calculate the conversion (%) from the result. The selectivity of ethylene, propylene, butenes and BTX was calculated.
  • the present embodiment relates to an effect of simultaneously satisfying a high activity and suppression of a reduction in activity in the method for producing an aromatic hydrocarbon and/or a light olefin, and such an effect is higher in the method that exhibits a high total selectivity of ethylene, propylene, butenes and BTX, a high initial conversion, and a high conversion also after the lapse of a predetermined period from the start of reaction.
  • the upper stage of the catalyst layer was packed with 0.18 g of H-ZSM-5 (catalyst A) having a Si/Al 2 molar ratio of 80 and an acid amount of 0.424 mmol/g
  • the lower stage of the catalyst layer was packed with 0.18 g of H-ZSM-5 (catalyst B) having a Si/Al 2 molar ratio of 500 and an acid amount of 0.091 mmol/g.
  • the ratio of the acid amount of the catalyst at the lower stage to the acid amount of the catalyst at the upper stage (catalyst B/catalyst A) was 21%. With respect to this, the reaction test was conducted at 650°C. The reaction results are shown in Table 1.
  • the upper stage of the catalyst layer was packed with 0.18 g of the catalyst B, and the lower stage of the catalyst layer was packed with 0.18 g of the catalyst A.
  • the ratio of the acid amount of the catalyst at the lower stage to the acid amount of the catalyst at the upper stage was 466%. With respect to this, the reaction test was conducted at 650°C. The reaction results are shown in Table 1.
  • the catalyst layer was packed with 0.36 g of a catalyst in which the catalyst A and the catalyst B whose particle sizes were regulated were mixed in a weight ratio of 1 : 1. With respect to this, the reaction test was conducted at 650°C. The reaction results are shown in Table 1.
  • the catalyst layer was packed with 0.36 g of only the catalyst B. With respect to this, the reaction test was conducted at 650°C. The reaction results are shown in Table 1.
  • Example 2 The same operation as in Example 1 was conducted except that the reaction temperature was 550°C. The reaction results are shown in
  • Example 1 The same operation as in Example 1 was conducted except that the reaction temperature was 500°C. The reaction results are shown in Table 1.
  • the catalyst A was treated with water vapor for 6 hours to obtain H-ZSM-5 (catalyst C) having an acid amount of 0.087 mmol/g.
  • the upper stage of the catalyst layer was packed with 0.18 g of H-ZSM-5 (catalyst D) having a Si/Al 2 molar ratio of 150 and an acid amount of
  • the catalyst layer was packed with 0.36 g of a catalyst in which the catalyst C and the catalyst D whose particle sizes were regulated were mixed in a weight ratio of 1 : 1. With respect to this, the reaction test was conducted at 650°C. The reaction results are shown in Table 2.
  • H-ZSM-5 (catalyst E) different from the catalyst A, having a Si/Al 2 molar ratio of 80 and an acid amount of 0.175 mmol/g, was treated with water vapor for 1 hour to obtain H-ZSM-5 (catalyst F) having a Si/Al 2 molar ratio of 80 and an acid amount of 0.110 mmol/g.
  • the catalyst E was treated with water vapor for 4 hours to obtain H-ZSM-5 (catalyst G) having a Si/Al 2 molar ratio of 80 and an acid amount of 0.064 mmol/g.
  • the upper stage of the catalyst layer was packed with 0.18 g of the catalyst F, and the lower stage of the catalyst layer was packed with 0.18 g of the catalyst G.
  • the catalyst layer was packed with 0.36 g of only the catalyst F. With respect to this, the reaction test was conducted at 650°C. The reaction results are shown in Table 3.
  • the catalyst layer was packed with 0.36 g of only the catalyst G. With respect to this, the reaction test was conducted at 650°C. The reaction results are shown in Table 3.
  • Example 1 Comparisons of Example 1 with Comparative Examples 1 to 4, Example 2 with Comparative Examples 7 and 8, and Example 3 with Comparative Examples 9 to 11 revealed that the catalyst having a larger acid amount was placed upstream and the catalyst having a smaller acid amount than the former catalyst was placed downstream to thereby allow a high activity to be maintained for a longer period than the case of a placement different from the above placements or the use of any catalyst singly.
  • the configuration in Comparative Example 1 in which the catalyst A having a larger acid amount was placed downstream and the catalyst B having a smaller acid amount than the former catalyst was placed on the upstream, is compared with the configuration in Example 1 to thereby find out that the conversion is low from the earlier phase.
  • the configuration in Comparative Example 2 in which the catalyst A having a larger acid amount and the catalyst B having a smaller acid amount were mixed, is compared with the configuration in Example 1 to thereby find out that while the conversion at the earlier phase (reaction time: 1 hour) is high, the conversion at a reaction time of 13 hours is rapidly lowered.
  • Example 1 is compared with Comparative Examples 5 and 6 to thereby find out that when the reaction temperature is lower than 600°C, a reduction in activity is suppressed, but the conversion is low from the earlier phase and the total selectivity of ethylene, propylene, butenes and BTX is remarkably lower than the case where the reaction temperature is 600°C or higher.
  • the production method according to Examples is configured so that a selectivity defined as a ratio of a total number (molar number) of carbon atoms of olefins having 4 or less carbon atoms, benzene, toluene and xylene generated in a unit time to a total number of carbon atoms in the hydrocarbon supplied n the unit time is 55% or more. It may be preferably configured so that the selectivity is 60% or more.
  • the production method may also be configured so that a selectivity defined as a ratio of a total number (molar number) of carbon atoms of olefins having 4 or less to the total number of carbon atoms in the hydrocarbon supplied is 30% or more.
  • Another production method according to Examples can also be considered as a method for producing an aromatic hydrocarbon and/or a light olefin, including passing a hydrocarbon through a first catalyst portion containing a first zeolite having an acid amount of 0.001 to 1 mmol/g and a 10-membered ring pore structure, and then further through a second catalyst portion containing a second zeolite having an acid amount of 90% or less of the acid amount of the first zeolite and a 10-membered ring pore structure, and catalytically-cracking the hydrocarbon.
  • an apparatus for producing an aromatic hydrocarbon and/or a light olefin according to the present embodiment is provided with a reactor having at least a first catalyst portion and a second catalyst portion.
  • the first catalyst portion contains a solid acid catalyst (A) having an acid amount of 0.001 to 1 mmol/g
  • the second catalyst portion is placed on the downstream side from the first catalyst portion and contains a solid acid catalyst (B) having an acid amount of 90% or less of the acid amount of the solid acid catalyst (A).
  • the reaction portion is configured so as to be capable of catalytically-cracking the hydrocarbon supplied at a reaction temperature of 600°C or higher.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Un procédé de fabrication d'un hydrocarbure aromatique et/ou d'une oléfine ayant au plus 4 atomes de carbone consiste à : (1) faire passer un hydrocarbure à travers une première partie de catalyseur contenant un catalyseur acide solide (A) ayant une quantité d'acide de 0,001 à 1 mmol/g, puis à travers une seconde partie de catalyseur contenant un catalyseur acide solide (B) ayant une quantité d'acide de 90 % ou moins de la quantité d'acide du catalyseur acide solide (A) ; et (2) craquer catalytiquement l'hydrocarbure dans la première partie du catalyseur et dans la seconde partie de catalyseur à une température de réaction de 600°C ou plus.
PCT/JP2012/065054 2011-06-10 2012-06-06 Procédé de fabrication d'un hydrocarbure aromatique et/ou d'une oléfine ayant au plus 4 atomes de carbone et appareil de fabrication d'un hydrocarbure aromatique et/ou d'une oléfine ayant au plus 4 atomes de carbone Ceased WO2012169651A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-130306 2011-06-10
JP2011130306 2011-06-10

Publications (1)

Publication Number Publication Date
WO2012169651A1 true WO2012169651A1 (fr) 2012-12-13

Family

ID=46420490

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/065054 Ceased WO2012169651A1 (fr) 2011-06-10 2012-06-06 Procédé de fabrication d'un hydrocarbure aromatique et/ou d'une oléfine ayant au plus 4 atomes de carbone et appareil de fabrication d'un hydrocarbure aromatique et/ou d'une oléfine ayant au plus 4 atomes de carbone

Country Status (3)

Country Link
JP (1) JP2013014760A (fr)
TW (1) TW201313890A (fr)
WO (1) WO2012169651A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9862897B2 (en) 2013-02-21 2018-01-09 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbon
US10087376B2 (en) 2010-01-20 2018-10-02 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbons

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111120955A (zh) * 2020-01-17 2020-05-08 梁清晖 一种室外灯

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3847793A (en) * 1972-12-19 1974-11-12 Mobil Oil Conversion of hydrocarbons with a dual cracking component catalyst comprising zsm-5 type material
US4591425A (en) * 1984-12-14 1986-05-27 Ashland Oil, Inc. Cascading of fluid cracking catalysts
US6258257B1 (en) * 1998-05-05 2001-07-10 Exxonmobil Research And Engineering Company Process for producing polypropylene from C3 olefins selectively produced by a two stage fluid catalytic cracking process
US20010042700A1 (en) * 2000-04-17 2001-11-22 Swan, George A. Naphtha and cycle oil conversion process
JP2010042344A (ja) 2008-08-12 2010-02-25 National Institute Of Advanced Industrial & Technology 低級オレフィン製造用触媒、その製造方法及びこれを用いた低級オレフィンの製造方法
JP2010104878A (ja) 2008-10-29 2010-05-13 National Institute Of Advanced Industrial Science & Technology 低級オレフィン製造用触媒、その製造方法及びこれを用いた低級オレフィンの製造方法
JP2010104909A (ja) 2008-10-30 2010-05-13 National Institute Of Advanced Industrial Science & Technology 低級オレフィン製造用触媒
US20100213101A1 (en) 2009-02-26 2010-08-26 Chevron U.S.A., Inc. Reforming process at low pressure
JP2010202613A (ja) 2009-03-05 2010-09-16 Yokohama National Univ パラフィンの接触分解法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3847793A (en) * 1972-12-19 1974-11-12 Mobil Oil Conversion of hydrocarbons with a dual cracking component catalyst comprising zsm-5 type material
US4591425A (en) * 1984-12-14 1986-05-27 Ashland Oil, Inc. Cascading of fluid cracking catalysts
US6258257B1 (en) * 1998-05-05 2001-07-10 Exxonmobil Research And Engineering Company Process for producing polypropylene from C3 olefins selectively produced by a two stage fluid catalytic cracking process
US20010042700A1 (en) * 2000-04-17 2001-11-22 Swan, George A. Naphtha and cycle oil conversion process
JP2010042344A (ja) 2008-08-12 2010-02-25 National Institute Of Advanced Industrial & Technology 低級オレフィン製造用触媒、その製造方法及びこれを用いた低級オレフィンの製造方法
JP2010104878A (ja) 2008-10-29 2010-05-13 National Institute Of Advanced Industrial Science & Technology 低級オレフィン製造用触媒、その製造方法及びこれを用いた低級オレフィンの製造方法
JP2010104909A (ja) 2008-10-30 2010-05-13 National Institute Of Advanced Industrial Science & Technology 低級オレフィン製造用触媒
US20100213101A1 (en) 2009-02-26 2010-08-26 Chevron U.S.A., Inc. Reforming process at low pressure
JP2010202613A (ja) 2009-03-05 2010-09-16 Yokohama National Univ パラフィンの接触分解法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10087376B2 (en) 2010-01-20 2018-10-02 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbons
US9862897B2 (en) 2013-02-21 2018-01-09 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbon

Also Published As

Publication number Publication date
TW201313890A (zh) 2013-04-01
JP2013014760A (ja) 2013-01-24

Similar Documents

Publication Publication Date Title
JP4953817B2 (ja) エチレン及びプロピレンの製造法
JP5051924B2 (ja) メタン転換製造プロセス
CN101460432B (zh) 由甲烷制备芳烃
TWI385140B (zh) A method for producing olefins and a manufacturing apparatus thereof
CN101652182B (zh) 由甲烷生产芳烃
JP4976424B2 (ja) 移動床技術および熱水安定化二重機能触媒系を使用したオキシゲネートのプロピレンへの選択的変換
WO1996010548A1 (fr) Procede de production d'hydrocarbure aromatique
WO2007123977A2 (fr) Production d'agents aromatiques à partir de méthane
EP3755767A1 (fr) Conversion sélective de naphta paraffinique en propylène en présence d'hydrogène
CN103119131A (zh) 循环脱氢方法与fcc的联合用于炼油厂链烷烃脱氢
US20230357654A1 (en) Process for converting naphtha to light olefins with separation
RU2417249C1 (ru) Способ получения высокооктанового бензина или ароматических углеводородов
US12247005B2 (en) Process for catalytically converting naphtha to light olefins
EP3768656B1 (fr) Procédés et systèmes de conversion d'hydrocarbures
WO2012169651A1 (fr) Procédé de fabrication d'un hydrocarbure aromatique et/ou d'une oléfine ayant au plus 4 atomes de carbone et appareil de fabrication d'un hydrocarbure aromatique et/ou d'une oléfine ayant au plus 4 atomes de carbone
CA3059556C (fr) Procedes et systemes pour la conversion d'hydrocarbures acycliques
WO2017052859A1 (fr) Déshydrocyclisation d'hydrocarbures
WO2006000449A1 (fr) Catalyseurs zeolite
CN104870089A (zh) 脱氢芳构化催化剂及其制备方法和用途
WO2007032447A1 (fr) Procede pour produire de l'ethylene et du propylene
KR101591578B1 (ko) 벤젠 알킬화 방법
US11845705B2 (en) Processes integrating hydrocarbon cracking with metathesis for producing propene
WO2018204025A1 (fr) Procédés de réjuvénation de catalyseurs
JP2013006965A (ja) 芳香族炭化水素及び／又は炭素数４以下のオレフィンの製造方法、並びに、芳香族炭化水素及び／又は炭素数４以下のオレフィンの製造装置
WO2025144902A1 (fr) Catalyseurs et procédé de conversion catalytique de naphta en oléfines légères

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12731188

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12731188

Country of ref document: EP

Kind code of ref document: A1