WO2009116561A1 - エチルベンゼンの転化方法及びパラキシレン製造方法 - Google Patents
エチルベンゼンの転化方法及びパラキシレン製造方法 Download PDFInfo
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- WO2009116561A1 WO2009116561A1 PCT/JP2009/055258 JP2009055258W WO2009116561A1 WO 2009116561 A1 WO2009116561 A1 WO 2009116561A1 JP 2009055258 W JP2009055258 W JP 2009055258W WO 2009116561 A1 WO2009116561 A1 WO 2009116561A1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
- C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
- C07C4/14—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene splitting taking place at an aromatic-aliphatic bond
- C07C4/18—Catalytic processes
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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 converting ethylbenzene and a method for producing paraxylene. More specifically, a method of converting ethylbenzene in a feedstock containing at least 1.0% by weight or more of an alicyclic hydrocarbon, ethylbenzene and xylene into benzene mainly, which reduces xylene loss and reduces catalyst activity.
- the present invention relates to a method which can be suppressed and can achieve a high conversion rate of paraxylene, and a method of distilling and purifying a C8 aromatic hydrocarbon mixture from the product obtained by such conversion and then separating paraxylene.
- paraxylene is the most industrially important raw material.
- Paraxylene is currently used as a raw material for polyester monomer, terephthalic acid, which is the main polymer along with nylon, and in recent years its demand is strong mainly in Asia, and the trend is expected to remain unchanged.
- orthoxylene and metaxylene which are xylene isomers other than paraxylene, have a significantly lower demand than paraxylene, it is industrially important to convert orthoxylene and metaxylene to paraxylene.
- the raw material of paraxylene is a C8 aromatic hydrocarbon mixture. Since the C8 aromatic hydrocarbon mixture generally contains a high-boiling component having 9 or more carbon atoms in addition to the xylene isomer and ethylbenzene, the high-boiling component having 9 or more carbon atoms is first removed by distillation.
- the purified C8 aromatic hydrocarbon mixture is supplied to a paraxylene separation step to separate paraxylene. Since the xylene isomer and ethylbenzene have close boiling points and it is difficult to separate para-xylene by distillation separation, a cryogenic separation method or an adsorption separation method is used.
- ethylbenzene is the component that most inhibits the separation of para-xylene among the C8 aromatic hydrocarbons. Therefore, reducing the concentration of ethylbenzene in the C8 aromatic hydrocarbon mixture supplied to the adsorption separation can reduce the load of the adsorption separation by reducing the amount of ethylbenzene that becomes an obstacle to the separation, and the C8 aroma supplied to the adsorption separation. Since the paraxylene concentration in the aromatic hydrocarbon mixture can be increased, the paraxylene production capacity in the same adsorption separation facility can be improved.
- the para-xylene-deficient C8 aromatic hydrocarbons that have exited the para-xylene separation process are then sent to the xylene isomerization process, where they are isomerized to a para-xylene concentration close to the thermodynamic equilibrium composition mainly by the zeolite catalyst and distilled.
- the product is recycled to a distillation column mixed with the new C8 aromatic hydrocarbon mixture to remove the high boiling point components.
- paraxylene is separated and recovered again in the paraxylene separation step. This series of circulating systems is hereinafter referred to as the “separation-isomerization cycle”.
- Fig. 4 shows the flow of the "separation-isomerization cycle" for general para-xylene production.
- the C8 aromatic hydrocarbon mixture which is the raw material of para-xylene is sent to the high boiling point component distillation separation step 1 from the supply line indicated by the stream 36.
- the low boiling point component distillation separation step 4 When it is desired to remove the low boiling point compound contained in the C8 aromatic hydrocarbon mixture raw material, it is supplied to the low boiling point component distillation separation step 4 from the supply line indicated by the stream 45, and the high boiling point component and the low boiling point component are removed. If not necessary, it may be provided directly to the paraxylene separation step 2 from the supply line indicated by stream 46.
- the C8 aromatic hydrocarbon mixture raw material is sent to the paraxylene separation step 2 together with the C8 aromatic hydrocarbon component isomerized to the paraxylene concentration close to the thermodynamic equilibrium composition in the xylene isomerization step 3.
- the high boiling point component is removed through a line indicated by a stream 38.
- the C8 aromatic hydrocarbon from which the high-boiling components have been removed is sent to the para-xylene separation step 2 through the line indicated by the stream 37, and para-xylene is separated and recovered from the line indicated by the stream 39.
- the C8 aromatic hydrocarbon having a low paraxylene concentration is sent to the xylene isomerization step 3 through the line indicated by the stream 40, and is isomerized to a paraxylene concentration close to a thermodynamic equilibrium composition.
- hydrogen or a gas containing hydrogen is also sent through the line indicated by the stream 41.
- the C8 aromatic hydrocarbon mixture containing by-products from the xylene isomerization step is sent to the low boiling point component distillation separation step 4 through the line indicated by the stream 42, and benzene and toluene by-produced in the xylene isomerization step.
- Such low-boiling components are separated and removed through a line indicated by a stream 43, and a recycled material containing a high-boiling component and having a high paraxylene concentration is sent to the high-boiling component distillation separation step 1 through a line indicated by a stream 44.
- the high-boiling component by-produced in the xylene isomerization step is removed from the recycled raw material having a high para-xylene concentration in the high-boiling component distillation separation step 1 and recycled to the para-xylene separation step 2 again.
- the C8 aromatic hydrocarbon mixture supplied to this “separation-isomerization cycle” contains ethylbenzene as described above.
- this ethylbenzene is not removed and thus accumulates in the circulation system.
- an amount corresponding to the removal rate circulates in the “separation-isomerization cycle”. If the amount of ethylbenzene circulated is reduced, the amount of circulation in the entire “separation-isomerization cycle” is also reduced, and the amount of utility usage is reduced.
- the most commonly used method is to convert ethylbenzene into a substance that can be easily separated from xylene or xylene during the isomerization reaction by imparting ethylbenzene conversion ability to the isomerization catalyst used in the xylene isomerization step.
- a reforming method in which xylene is isomerized in the xylene isomerization step and simultaneously isomerizing ethylbenzene into xylene for example, Patent Document 1
- hydrodealkylating ethylbenzene to convert it into benzene and ethane examples thereof include a dealkylation method in which benzene is separated by distillation (for example, Patent Document 2).
- the dealkylation method it is only necessary to give the catalyst a hydrogenation ability to hydrogenate ethylene produced by dealkylation from ethylbenzene, and it is possible to use a hydrogenation active metal cheaper than platinum, or platinum.
- the catalyst can be inexpensive because the content can be greatly reduced even when using the catalyst.
- the dealkylation reaction of ethylbenzene proceeds substantially as a non-equilibrium reaction, and a very high ethylbenzene conversion rate is obtained. Is possible.
- the para-xylene raw material that is usually used is a reformed C8 aromatic hydrocarbon mixture obtained by reforming naphtha and then fractional distillation.
- the typical composition of this C8 aromatic hydrocarbon mixture is 18% by weight of ethylbenzene, 19% by weight of paraxylene, 42% by weight of metaxylene, and 21% by weight of orthoxylene.
- the demand for para-xylene increases, the supply of the reformed C8 aromatic hydrocarbon mixture is becoming insufficient.
- cracked gasoline a pyrolysis oil-based C8 aromatic hydrocarbon mixture
- ethylbenzene 60% by weight
- paraxylene 8% by weight
- metaxylene 19% by weight
- orthoxylene 10% by weight
- non-aromatic compound 3% by weight.
- “cracked gasoline” has a higher ethylbenzene concentration than the reformed C8 aromatic hydrocarbon mixture, ethylbenzene accumulates in the “separation-isomerization cycle” and circulates in the “separation-isomerization cycle”. As the amount of selenium increases, it imposes a burden on the para-xylene separation process, leading to a reduction in production of para-xylene, so far only a limited amount has been used.
- “cracked gasoline” contains not only ethylbenzene but also non-aromatic hydrocarbons. When using the dealkylation method, there are many non-aromatic hydrocarbons circulating in the “separation-isomerization cycle”. However, the xylene loss in the xylene isomerization process increases rapidly, and the deterioration rate of the catalyst increases.
- a high ethylbenzene conversion rate can be achieved.
- a feedstock containing non-aromatic hydrocarbons can be treated without increasing the catalyst degradation rate.
- a high paraxylene conversion can be achieved.
- the current situation is that the xylene loss rapidly increases in a raw material having a high ethylbenzene concentration such as “cracked gasoline” and containing a large amount of non-aromatic hydrocarbons.
- a method of treating by the above dealkylation method mainly converting to benzene, distilling and separating, and greatly reducing the concentration of ethylbenzene circulating in the “separation-isomerization cycle” (for example, Patent Document 5), raw material C8 aromatic hydrocarbon mixture Is supplied to a xylene isomerization step having hydrodealkylation ability and then supplied to a paraxylene separation step (for example, Patent Document 6).
- Japanese Patent Publication No.49-46606 Japanese Patent Laid-Open No. 57-300239 Japanese Examined Patent Publication No. 8-16074 US Pat. No. 4,899,001 (TABLE 1) Japanese Patent Publication No. 5-87054 Japanese Patent Laid-Open No. 5-24661
- the present invention is a method for converting ethylbenzene in a C8 aromatic hydrocarbon mixture containing a large amount of non-aromatic hydrocarbons mainly into benzene, which can reduce the loss of xylene, suppress the deterioration rate of catalytic activity, and have a high parameter. It is an object to provide a method capable of achieving xylene conversion.
- the present invention also provides a method for producing para-xylene, which can significantly reduce the ethylbenzene concentration in the C8 aromatic hydrocarbon mixture supplied to the para-xylene separation step. is there.
- non-aromatic hydrocarbons contained in the C8 aromatic hydrocarbon mixture As a result of detailed investigation of the influence of non-aromatic hydrocarbons contained in the C8 aromatic hydrocarbon mixture, the present inventors have found that, among non-aromatic hydrocarbons, alicyclic hydrocarbons are C8 aromatic hydrocarbon mixtures. It has been found that xylene loss is increased, catalyst deterioration rate is increased, and paraxylene conversion rate is decreased.
- the present invention has the following configuration. (1) Including conversion of ethylbenzene mainly in benzene by bringing a feedstock containing 1.0% by weight or more of an alicyclic hydrocarbon and ethylbenzene and xylene into contact with hydrogen in the presence of a catalyst.
- a C8 aromatic hydrocarbon mixture preferably a C8 aromatic hydrocarbon mixture mainly containing xylene, or a step of purifying xylene by distillation separation from the obtained reaction product, and then a purified C8 aromatic hydrocarbon mixture,
- a C8 aromatic hydrocarbon mixture mainly containing xylene, or a method for producing paraxylene comprising a step of supplying xylene to the paraxylene separation step.
- xylene loss can be reduced, the deterioration rate of the catalyst can be suppressed, and high paraxylene Conversion can be achieved.
- ethylbenzene in a C8 aromatic hydrocarbon mixture containing a large amount of alicyclic hydrocarbons is mainly converted to benzene, and the load of the paraxylene separation process, the amount of ethylbenzene recycled in the “separation-isomerization cycle”
- the amount of ethylbenzene recycled in the “separation-isomerization cycle” By reducing the amount, it is possible to increase the production of para-xylene, improve the basic unit of utility, and the basic unit of raw material.
- FIG. 6 is a graph showing the results of Examples 5 to 7, Comparative Example 4, and Reference Example 3.
- the method of the present invention is applied to a reaction in which ethylbenzene in the feedstock is mainly converted to benzene.
- “Mainly converted to benzene” refers to a state in which the ratio of the amount of benzene produced (hereinafter referred to as benzene selectivity) to the amount of substance of ethylbenzene converted is 80 mol% or more.
- the conversion reaction to other than benzene is, for example, a reaction in which benzene and diethylbenzene are produced by disproportionation of ethylbenzene, a reaction in which ethylmethylbenzene and toluene are produced by transalkylation of ethylbenzene and xylene, and a non-aromatic reaction by nuclear hydrogenation of ethylbenzene. Reaction to form a group hydrocarbon.
- a bimolecular reaction is preferentially caused.
- a catalyst containing a zeolite such as mordenite having an oxygen 12-membered ring structure having a relatively large pore diameter is generally used. Therefore, the effect of the present invention is small.
- platinum having hydrogenation / dehydrogenation ability is contained in the catalyst, so it is contained in the feedstock Therefore, an increase in xylene loss and an increase in catalyst deterioration rate are not confirmed.
- the present invention when applied to a feedstock containing at least 1.0% by weight or more of an alicyclic hydrocarbon, has the effect of reducing xylene loss, improving the paraxylene conversion rate, and suppressing catalyst deterioration.
- a feedstock rich in alicyclic hydrocarbons has a greater effect of reducing xylene loss, improving the conversion rate of paraxylene, and suppressing deterioration of the catalyst.
- a part of the alicyclic hydrocarbon contained in the feedstock is contained in the reaction product liquid unreacted, and, similarly to ethylbenzene, an amount corresponding to the removal rate circulates in the “separation-isomerization cycle”.
- the alicyclic hydrocarbon content in the feedstock is from 1.0% to 16% by weight, more preferably from 3.0% to 16% by weight, and from 10% to 16% by weight, the improvement according to the present invention. The effect is increased.
- the feedstock may contain a single type of alicyclic hydrocarbon or may contain a plurality of types of alicyclic hydrocarbons.
- Alicyclic hydrocarbons include cycloalkanes, which are saturated hydrocarbons, and cycloalkenes, which are unsaturated hydrocarbons that contain a double bond in the ring. Particularly when cycloalkanes are present, the effect of the present invention is great. Cycloalkanes include monocycloalkanes that are monocyclic saturated hydrocarbons, bicycloalkanes that are bicyclic saturated hydrocarbons, and the like. Especially when monocycloalkane is present, the effect of the present invention is the greatest. Among monocycloalkanes, when used as a raw material containing an alkyl monocycloalkane, the effect is remarkable.
- alicyclic hydrocarbons examples include cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, dimethylcyclopentane, ethylcyclopentane, dimethylcyclohexane, ethylcyclohexane, propylcyclopentane, ethylmethylcyclopentane, trimethylcyclohexane, propyl Monocycloalkanes such as cyclohexane, ethylmethylcyclohexane, diethylcyclopentane, methylpropylcyclopentane, bicyclo [2.1.1] hexane, bicyclo [2.2.0] hexane, bicyclo [3.1.0] hexane, bicyclo [2.2.1] Heptane, bicyclo [3.1.1] heptane, bicyclo [3.2.0] heptane, bicyclo [4.1.0] heptane
- octane bicyclo [5.1.0] octane and other bicycloalkanes, cyclopentene, cyclohexene, methylcyclopentene, methylcyclohexene, dimethylcyclopentene, ethylcyclopentene, dimethylcyclohexene, ethylcyclohexene, propylcyclopentene, ethylmethylcyclopentene, trimethylcyclohexene, propyl And cycloalkene such as cyclohexene, ethylmethylcyclohexene, diethylcyclopentene, and methylpropylcyclopentene.
- Cycloaliphatic hydrocarbons are methylcyclopentane, methylcyclohexane, dimethylcyclopentane, ethylcyclopentane, dimethylcyclohexane, ethylcyclohexane, propylcyclopentane, ethylmethylcyclopentane, trimethylcyclohexane, propylcyclohexane, ethylmethylcyclohexane, diethylcyclohexane.
- alkyl monocycloalkane such as pentane and methylpropylcyclopentane
- a platinum component which is a typical component, has an extremely high hydrogenation activity for benzene nuclei and hydrogenation activity for olefin components. Therefore, the catalyst supporting the platinum component has a feature that when the reaction pressure is increased and the hydrogen partial pressure is increased, the hydrogenation reaction of the benzene nucleus proceeds preferentially and the loss of the aromatic component is remarkably increased. ing.
- the rhenium component is characterized in that the hydrogenation activity of the benzene nucleus is low, and the hydrogenation activity of the olefin component is not as high as that of the platinum component.
- the deterioration rate of the catalyst due to the presence of the alicyclic hydrocarbon is smaller for the platinum component and larger for the rhenium component.
- the rhenium component has a characteristic that the loss of the aromatic component is extremely low because the hydrogenation activity to the benzene nucleus is extremely low.
- the MFI-type zeolite has pores formed of oxygen 10-membered rings.
- the pore size is small and close to the minimum molecular diameter of an aromatic hydrocarbon compound such as xylene.
- the pore size of the MFI-type zeolite becomes smaller, and benzene, toluene, and xylene (particularly paraxylene), which tend to enter the pores, are translocated within the pores. It is considered that an alkylation reaction is caused and it is easy to produce toluene having a small molecular diameter.
- the feedstock used in the present invention contains ethylbenzene.
- the content of ethylbenzene is not particularly specified, but in order to keep the ethylbenzene concentration after the reaction low, it is necessary to increase the ethylbenzene conversion rate as the feedstock containing more ethylbenzene increases the reaction temperature and the load on the catalyst. The loss is great. That is, the feedstock containing more ethylbenzene increases the effect of improving xylene loss by the ethylbenzene conversion method of the present invention.
- the present invention is effective when the feedstock used contains 8 wt% or more of ethylbenzene, more preferably the feedstock contains 45 wt% or more of ethylbenzene.
- the feedstock used contains 8 wt% or more of ethylbenzene, more preferably the feedstock contains 45 wt% or more of ethylbenzene.
- the ethylbenzene concentration in the feedstock becomes too high, the amount of xylene contained in the feedstock becomes relatively small, so that the amount of xylene that can be recovered decreases and the economic efficiency deteriorates.
- the present invention is effective when the feedstock used contains 80 wt% or less of ethylbenzene.
- ⁇ Used in the present invention is a feedstock further containing xylene.
- the content of xylene is not particularly limited, but is usually about 15% to 91% by weight.
- xylene is subjected to an isomerization step, so that each isomer is produced at a predetermined ratio. Therefore, the ratio of each isomer of xylene in the raw material is not limited at all.
- the proportion of paraxylene in each isomer is about 0 to 24% by weight, the proportion of metaxylene is about 50 to 75% by weight, and the proportion of orthoxylene is about 25 to 35% by weight.
- the proportion of paraxylene in each isomer of xylene is 23% by weight, the proportion of metaxylene is 53% by weight, and the proportion of orthoxylene is about 26% by weight.
- the proportion of para-xylene in each isomer of xylene is about 0.5% by weight, the proportion of meta-xylene is about 73.5% by weight, ortho-xylene The ratio is about 26% by weight.
- the feedstock used in the present invention may contain aliphatic hydrocarbons and / or C9 aromatic hydrocarbons in addition to alicyclic hydrocarbons, ethylbenzene and xylene.
- aliphatic hydrocarbon examples include n-octane, methyl heptane, dimethylhexane, n-nonane, methyl octane, ethyl heptane and the like.
- C9 aromatic hydrocarbons examples include n-propylbenzene, iso-propylbenzene, ortho-ethylmethylbenzene, meta-ethylmethylbenzene, para-ethylmethylbenzene, 1,2,3-trimethylbenzene, 1,2 , 4-trimethylbenzene, 1,3,5-trimethylbenzene, indane, indene and the like.
- the total content of these components other than the alicyclic hydrocarbon, ethylbenzene and xylene is not particularly limited, but is usually 30% by weight or less based on the entire raw material.
- the ethylbenzene conversion reaction of the present invention is carried out at a reaction pressure of 1.0 MPa-G or more.
- reaction pressure When the reaction pressure is excessively increased, disproportionation, transalkylation reaction, and aromatic hydrocarbon hydrogenation reaction take place preferentially, and preferably 1.3 MPa-G to 5.0 MPa-G.
- the pressure is preferably 1.7 MPa-G to 3.0 MPa-G. “-G” means gauge pressure.
- the ethylbenzene conversion reaction of the present invention is carried out in the presence of hydrogen.
- Hydrogen is essential for irreversibly proceeding the conversion reaction of ethylbenzene by hydrogenating ethylene produced as a by-product in the conversion of ethylbenzene into benzene.
- the larger the amount of hydrogen added the better from the viewpoint of suppressing the deterioration of the catalyst, but the smaller the amount of hydrogen added is preferable from the viewpoint of economy.
- the molar ratio of hydrogen to the feedstock (hereinafter referred to as H 2 / HC) is 3 mol / mol to 15 mol / mol.
- a preferable range of H 2 / HC is 4 mol / mol to 12 mol / mol, and more preferably 5 mol / mol to 10 mol / mol.
- the range of H 2 / HC is from 5 mol / mol to 9 mol / mol, the most preferable effect is obtained.
- Hydrogen is supplied to the reaction system in the form of hydrogen gas or hydrogen-containing gas.
- the hydrogen-containing gas include a hydrogen-containing gas obtained by high-pressure separation of a gas obtained by naphtha reforming treatment, a hydrogen-containing gas obtained by high-pressure separation of a gas obtained by naphtha pyrolysis, and steam reforming. Examples thereof include a hydrogen-containing gas obtained by separating carbon dioxide from a gas obtained by a quality method, and a hydrogen-containing gas obtained by purifying the hydrogen-containing gas by adsorption separation or the like.
- the reaction temperature in the ethylbenzene conversion method of the present invention is usually 200 ° C. to 550 ° C., preferably 250 ° C. to 500 ° C.
- the weight hourly space velocity representing a contact time of the reaction (WHSV) is 50 hr -1 from 0.1 hr -1, preferably from 0.5 hr -1 20 hr -1.
- the reaction method of the ethylbenzene conversion reaction of the present invention may be any of a fixed bed, moving bed, and fluidized bed method, but the fixed bed reaction method is preferred from the viewpoint of ease of operation.
- the zeolite used for the catalyst used in the present invention is MFI type zeolite.
- MFI-type zeolite can be synthesized, for example, by the method of Example 1 on page 4-5 of JP-B-60-35284 and Example 1 on page 7 of JP-B-46-10064.
- Such MFI-type zeolite itself and the production method thereof are well known, and one example of the synthesis method is also specifically described in the following examples.
- the catalyst performance varies depending on the composition, particularly the silica / alumina molar ratio (hereinafter referred to as SiO 2 / Al 2 O 3 molar ratio) or the size of the zeolite crystallites.
- SiO 2 / Al 2 O 3 molar ratio silica / alumina molar ratio
- the preferable range of the SiO 2 / Al 2 O 3 molar ratio in the MFI type zeolite is 20 to 60, more preferably 25 to 55.
- the SiO 2 / Al 2 O 3 molar ratio can be achieved by controlling the raw material composition ratio during zeolite synthesis.
- the SiO 2 / Al 2 O 3 molar ratio of the zeolite is increased by removing the aluminum constituting the zeolite structure with an acid aqueous solution such as hydrochloric acid or an aluminum chelating agent such as ethylenediaminetetraacetic acid (EDTA). It can be made.
- an aqueous solution containing aluminum ions such as an aqueous aluminum nitrate solution or an aqueous sodium aluminate solution, aluminum is introduced into the zeolite structure to reduce the SiO 2 / Al 2 O 3 molar ratio of the zeolite. It is also possible to obtain a preferable SiO 2 / Al 2 O 3 molar ratio.
- the measurement of the SiO 2 / Al 2 O 3 molar ratio can be easily known by atomic absorption method, fluorescent X-ray diffraction method, ICP (inductively coupled plasma) emission spectroscopy or the like.
- Such zeolite is appropriately selected and used for forming a catalyst. Since synthetic zeolite is generally a powder, it is preferably molded when used. Examples of the molding method include a compression molding method, a rolling method, and an extrusion method, and the extrusion method is more preferable. In the extrusion method, binders such as alumina sol, alumina gel, bentonite, and kaolin and surfactants such as sodium dodecylbenzenesulfonate, span (trade name), and twin (trade name) are added to the synthetic zeolite powder as needed. It is added as an agent and kneaded. If necessary, a machine such as a kneader is used. The addition amount of the binder is not particularly limited, but is usually about 0 to 30 parts by weight, preferably about 10 to 20 parts by weight with respect to 100 parts by weight of zeolite and inorganic oxide.
- an inorganic oxide such as alumina or titania is added during zeolite molding in order to increase the amount of metal supported on the catalyst and improve dispersibility.
- alumina is particularly preferable.
- Known aluminas include boehmite, boehmite gel, dipsite, vialite, norstrandite, diaspore, amorphous alumina gel, and the like. Any alumina can be preferably used.
- the amount of inorganic oxide added is not particularly limited, but is usually about 10 to 700 parts by weight, preferably about 100 to 400 parts by weight, per 100 parts by weight of zeolite.
- the kneaded kneaded material is extruded from the screen.
- an extruder is used.
- the kneaded product extruded from the screen becomes a noodle-like product.
- the size of the molded body is determined by the screen diameter to be used.
- the screen diameter is preferably 0.2 mm to 2 mm.
- the noodle-like molded body extruded from the screen is preferably treated with a Malmerizer (trademark) in order to round the corners.
- the molded body thus molded is dried at 50 ° C. to 250 ° C. After drying, in order to improve the molding strength, baking is performed at 250 to 600 ° C, preferably 350 to 600 ° C.
- the molded body thus prepared is subjected to an ion exchange treatment for imparting solid acidity.
- ion exchange treatment is performed with a compound containing ammonium ions (for example, NH 4 Cl, NH 4 NO 3 , (NH 4 ) 2 SO 4, etc.), and NH 4 ions are added to the ion exchange site of the zeolite. After that, it is converted into hydrogen ions by drying and calcination, or directly with an acid-containing compound (for example, HCl, HNO 3 , H 3 PO 4, etc.) at the ion exchange site of the zeolite.
- an acid-containing compound for example, HCl, HNO 3 , H 3 PO 4, etc.
- the ion exchange treatment is preferably performed with the former, that is, a compound containing ammonium ions.
- Solid acidity can also be imparted to the zeolite by introducing divalent and trivalent metal ions into the zeolite ion exchange site.
- divalent metal ions include alkaline earth metal ions Mg 2+ , Ca 2+ , Sr 2+ , and Ba 2+ .
- trivalent metal ions include rare earth metal ions such as Ce 3+ and La 3+ .
- ion exchange treatment is usually carried out by treating the catalyst material mainly composed of the zeolite and the inorganic oxide with an aqueous solution, and is carried out by a batch method or a distribution method.
- the concentrations of ammonium ions and Ca 2+ in the aqueous solution are not particularly limited, but are usually about 0.5 mol / L to 2.0 mol / L and about 0.08 mol / L to 0.40 mol / L, respectively.
- the treatment temperature is usually from room temperature to 100 ° C.
- rhenium as a hydrogenation active metal is supported.
- the role of the hydrogenation active metal is to quickly dehydrogenate ethyl group dealkylated from ethylbenzene in the raw material or decomposed non-aromatic hydrocarbons in the presence of hydrogen to dealkylate and decompose them. And may further suppress the formation of oligomers that poison the catalyst.
- the amount of the hydrogenation active metal is increased, the aromatic hydrocarbon is hydrogenated, which is not preferable.
- the amount of the hydrogenation active metal supported is too small, the hydrogenation ability becomes insufficient during the deethylation reaction or the non-aromatic hydrocarbon decomposition reaction, leading to a decrease in the catalyst activity.
- a catalyst supporting rhenium is used as the hydrogenation active metal.
- the supported amount of rhenium is 0.05 to 2% by weight, more preferably 0.1 to 1% by weight.
- rhenium is supported by a method in which a catalyst is immersed in an aqueous solution of a rhenium compound.
- aqueous solution for example, a perrhenic acid aqueous solution, a perrhenium ammonium aqueous solution, or the like can be used.
- the catalyst thus prepared is preferably dried at 50 ° C. to 250 ° C. for 30 minutes or longer, and is preferably calcined at 350 ° C. to 600 ° C. for 30 minutes or longer prior to use.
- the catalyst used in the present invention is mainly composed of MFI-type zeolite and an inorganic oxide and supports rhenium.
- the content in a range that does not inhibit the effect of the present invention that is, the effect of the present invention.
- the content of the obtained range may contain other types of zeolite other than MFI type, hydrogenation active metals other than rhenium, and the like.
- “consisting mainly of MFI-type zeolite and inorganic oxide” means that the content of MFI-type zeolite and inorganic oxide exceeds 50% by weight, preferably 80%.
- the catalyst portion other than rhenium consists essentially of MFI-type zeolite and an inorganic oxide.
- FIG. 1 shows an example of a preferred paraxylene production flow in the case of producing paraxylene using only a C8 aromatic hydrocarbon mixture containing a large amount of ethylbenzene and alicyclic hydrocarbons.
- the stream 11 After being supplied to Step 1 and mainly separating aromatic hydrocarbons of C9 or higher through a line indicated by a stream 12, the stream 11 is sent to a paraxylene separation step 2, where the product paraxylene is separated by a stream 13.
- the feedstock containing alicyclic hydrocarbons, ethylbenzene and xylene suppresses an increase in xylene loss, while reducing the xylene isomerization step.
- the paraxylene is supplied to the paraxylene separation step.
- the paraxylene concentration contained in the C8 aromatic hydrocarbon mixture supplied to the paraxylene separation step is increased, and the ethylbenzene concentration is decreased.
- the load on the separation process can be reduced, leading to an increase in production of para-xylene.
- Figure 2 shows the production of para-xylene using both a C8 aromatic hydrocarbon mixture rich in ethylbenzene and alicyclic hydrocarbons and a C8 aromatic hydrocarbon mixture low in ethylbenzene and alicyclic hydrocarbons.
- An example of a preferred para-xylene production flow is shown.
- the C8 aromatic hydrocarbon mixture rich in ethylbenzene joins with the paraxylene-poor C8 aromatic hydrocarbon from the paraxylene separation step 2 indicated by stream 14 as stream 15 and contains a hydrodealkylation catalyst.
- Sent to xylene isomerization step 3 where it is isomerized to a paraxylene concentration close to the thermodynamic equilibrium composition and at the same time paraxylene separation step 2 as shown by ethylbenzene in stream C8 aromatic hydrocarbon and stream 15
- the ethylbenzene in the liquid coming out of the product is deethylated and converted mainly to benzene.
- hydrogen or a gas containing hydrogen is also sent to the xylene isomerization step 3 through a line indicated by a stream 16.
- the reaction product is supplied to the low-boiling component distillation separation step 4 via the stream 17, and C7 or lower hydrocarbons such as benzene are separated through the line indicated by the stream 18, and then the high-boiling component distillation separation is performed via the stream 19.
- Supply to step 1 the C8 aromatic hydrocarbon mixture having a low content of ethylbenzene and alicyclic hydrocarbons is supplied to the high boiling point component distillation separation step 1 by the stream 20, and the C8 aromatic hydrocarbon mixture shown by the stream 19 and the stream 20 is supplied.
- the xylene isomerization is suppressed while suppressing an increase in xylene loss in the feedstock containing alicyclic hydrocarbons, ethylbenzene and xylene. Since ethylbenzene is reduced in the process and then supplied to the paraxylene separation process, the paraxylene concentration contained in the C8 aromatic hydrocarbon mixture supplied to the paraxylene separation process is increased and the ethylbenzene concentration is decreased. By reducing the load of the separation process, the production of para-xylene is increased.
- FIG. 3 shows a preferred para-xylene production flow when most of the ethylbenzene contained in the C8 aromatic hydrocarbon mixture rich in ethylbenzene and alicyclic hydrocarbons is converted and then fed to the “separation-isomerization cycle”.
- the raw material C8 aromatic hydrocarbon mixture is supplied to the ethylbenzene dealkylation step 24 from the supply line shown by the stream 25, and the ethylbenzene contained in the C8 aromatic hydrocarbon mixture is deethylated to be mainly converted into benzene. .
- hydrogen or a gas containing hydrogen is also sent to the ethylbenzene dealkylation step 24 through a line indicated by a stream 26.
- the resulting reaction product is passed through the line indicated by stream 27 and the low boiling component distillation separation step together with the C8 aromatic hydrocarbon mixture containing by-products from the xylene isomerization step through the line indicated by stream 28. Sent to 4. C 7 or lower hydrocarbons such as benzene are separated from stream 29.
- the C8 aromatic hydrocarbon mixture from which the low-boiling components have been separated is sent from the stream 30 to the high-boiling component distillation separation step 1, and the high-boiling components are removed through the line indicated by the stream 32.
- the C8 aromatic hydrocarbon from which the high-boiling components have been removed is sent to the para-xylene separation step 2 through the line indicated by the stream 31, and the para-xylene is separated and recovered from the line indicated by the stream 33. Then, the C8 aromatic hydrocarbon having a low paraxylene concentration is sent to the xylene isomerization step 3 through the line indicated by the stream 34, and is isomerized to a paraxylene concentration close to a thermodynamic equilibrium composition. In the xylene isomerization step, hydrogen or a gas containing hydrogen is also sent through the line indicated by the stream 35.
- the C8 aromatic hydrocarbon mixture containing by-products from the xylene isomerization step is sent to the low boiling point component distillation separation step 4 through the line indicated by the stream 28, and benzene and toluene by-produced in the xylene isomerization step.
- Such low-boiling components are separated and removed through a line indicated by a stream 29, and a recycle raw material containing a high-boiling component and having a high paraxylene concentration is sent to the high-boiling component distillation separation step 1 through a line indicated by a stream 30.
- the content of the alicyclic hydrocarbon in the feedstock is the same as the content in the feedstock supplied to the xylene isomerization step 3 and ethylbenzene dealkylation step 24 in FIGS. Say.
- the alicyclic hydrocarbon and the feedstock containing ethylbenzene and xylene can suppress the increase in loss of xylene while suppressing the increase in loss of ethylbenzene.
- the “separation-isomerization cycle” is fed. This increases the paraxylene concentration contained in the C8 aromatic hydrocarbon mixture supplied to the paraxylene separation process and lowers the ethylbenzene concentration, thereby reducing the load of the paraxylene separation process and increasing the production of paraxylene. Connected.
- the raw material unit of para-xylene can be improved.
- Hydrous silicic acid (SiO 2 content 90.4% by weight, NaOH content 0.22% by weight, Al 2 O 3 content 0.26% by weight, H 2 O content 9.12% by weight, nip seal VN-3, Nippon Silica Co., Ltd.) 95.2 grams was gradually added with stirring to prepare a uniform slurry aqueous reaction mixture.
- the composition ratio (molar ratio) of this reaction mixture was as follows. SiO 2 / Al 2 O 3: 55 OH ⁇ / SiO 2 : 0.26 A / Al 2 O 3 : 4.0 (A: tartrate) H 2 O / SiO 2 : 22
- the reaction mixture was sealed in a 1000 ml autoclave and then reacted at 160 ° C. for 72 hours while stirring at 800 rpm. After completion of the reaction, washing with distilled water 5 times and filtration were repeated, followed by drying at about 120 ° C. overnight to obtain MFI type zeolite.
- the average crystallite size was 1.8 microns for the major axis and 1.3 microns for the minor axis.
- the SiO 2 / Al 2 O 3 molar ratio of this zeolite was 43 as a result of fluorescent X-ray diffraction analysis.
- Catalyst A As a result of measuring the calcium content and sodium content in the catalyst by atomic absorption spectrometry, it was 0.17% by weight as Ca and 0.3% by weight as Na. The amount of rhenium supported in the catalyst was measured by ICP emission spectroscopy and found to be 0.5% by weight as Re metal.
- Catalyst B was produced in the same manner as Catalyst A, except that the perrhenic acid aqueous solution (Rare Metal Co., Ltd.) containing 80 milligrams of Re was used.
- the perrhenic acid aqueous solution containing 80 milligrams of Re was used.
- the calcium content and sodium content in the catalyst was 0.17% by weight as Ca and 0.3% by weight as Na.
- the amount of rhenium supported in the catalyst was measured by ICP emission spectroscopy and found to be 0.3% by weight as Re metal.
- Example 1 The catalyst A was filled in a reaction tube to conduct a reaction test.
- the composition of the feedstock used, reaction conditions, and test results are shown in Table 1 below.
- the composition analysis of the feedstock and the reaction product used three gas chromatographs with a hydrogen flame detector.
- the separation column is as follows.
- Liquid component having a lower boiling point than benzene from methane dissolved in liquid to n-butane and liquid component 2-methyl-butane to benzene component: Filler 25% polyethylene glycol 20M / carrier "Simalite" 60-80 mesh, Column: Stainless steel, 12m long, 3mm inner diameter N 2 : 2.25 kg / cm2-G Temperature: It carried out from 68 degreeC to 180 degreeC with the temperature increase rate of 2 degree-C / min.
- Liquid components having a boiling point higher than benzene from benzene to heavy-end components: Spellco wax fused silica capillary; length 60m, inner diameter 0.32mm ⁇ , film thickness 0.5 ⁇ m He linear velocity: 23 cm / sec Temperature: From 67 ° C. to 80 ° C., the heating rate was 1 ° C./min, and from 80 ° C. to 2 ° C./min.
- Example 1 and Comparative Example 1 raw materials containing 15.8% by weight of cyclohexane, which is an alicyclic hydrocarbon, were set to reaction pressures of 1.8 MPa-G and 0.9 MPa-G, respectively, and the ethylbenzene conversion was approximately It is the result of making it react on the same conditions except adjusting to the reaction temperature used as equivalent. From these results, by increasing the reaction pressure from 0.9 MPa-G to 1.8 MPa-G, the xylene loss was reduced by about 20 wt%, the benzene selectivity was 3.3 mol%, and the para-xylene conversion rate was 0.00. It turns out that it improves by 1 weight%.
- Comparative Examples 2 and 3 were reacted under the same reaction conditions as Comparative Example 1 except that alicyclic hydrocarbons added to the feedstock were dimethylcyclohexane and ethylcyclohexane, respectively.
- alicyclic hydrocarbons added to the feedstock were dimethylcyclohexane and ethylcyclohexane, respectively.
- the reaction pressure is 0.9 MPa-G
- the xylene loss and the benzene selectivity are greatly deteriorated.
- the increase in xylene loss is significant.
- Examples 2 and 3 a raw material containing about 4% by weight of alicyclic hydrocarbon dimethylcyclohexane was set to have a reaction pressure of 1.3 MPa-G and 1.7 MPa-G, respectively, and the ethylbenzene conversion was the same. The results are obtained under the same conditions except that the reaction temperature is adjusted. From these comparisons, it can be seen that the higher the reaction pressure, the better the xylene loss, benzene selectivity, and paraxylene conversion.
- Example 4 the H 2 / HC and 3.1 mol / mol, except that ethylbenzene conversion rate was adjusted to reaction temperature as the same is a result of the reaction under the same conditions as in Example 3. From the comparison between Examples 3 and 4, it can be seen that if the reaction pressure is kept at 1.0 MPa-G or more, even if H 2 / HC is lowered, the influence on xylene loss and benzene selectivity is small.
- Example 5 The reaction was continued under the conditions of Example 4, and the relationship between the reaction time and the ethylbenzene conversion rate was examined. The results are shown in FIG. The rate of decrease in the conversion of ethylbenzene was 0.25% by weight per day.
- Example 6 The reaction was continued under the conditions of Example 2, and the relationship between the reaction time and the ethylbenzene conversion rate was examined. The results are shown in FIG. The rate of decrease in ethylbenzene conversion was 0.03% by weight per day.
- Example 7 The reaction was continued under the conditions of Example 3, and the relationship between the reaction time and the ethylbenzene conversion rate was examined. The results are shown in FIG. The rate of decrease in the conversion of ethylbenzene was 0.07% by weight per day.
- Comparative Example 4 The reaction was continued under the conditions of Comparative Example 3, and the relationship between the reaction time and the ethylbenzene conversion rate was examined. The results are shown in FIG. The rate of decrease in ethylbenzene conversion was 4.0% by weight per day.
- Reference example 3 The reaction was continued under the same conditions as in Reference Example 1 except that the reaction temperature was 403 ° C., and the relationship between the reaction time and the ethylbenzene conversion rate was examined. The results are shown in FIG. The rate of decrease in ethylbenzene conversion was 0.01% by weight per day.
- Example 5 the reaction pressure was 1.3 MPa-G, and in Examples 6 and 7, the reaction pressure was 1.7 MPa-G.
- Comparative Example 4 the reaction pressure was 0.9 MPa-G. It is the result of having reacted with G.
- Reference Example 3 is a result of performing the reaction with a feedstock that does not contain alicyclic hydrocarbons and a reaction pressure of 0.9 MPa-G. From the results of Examples 5 and 6 and Comparative Example 4, it can be seen that when the reaction pressure is 1.0 MPa-G or more, the deterioration rate of the ethylbenzene conversion rate can be reduced.
- Example 8 Comparative Example 5, Reference Examples 4, 5
- the reaction was carried out in the same manner as in Example 1 except that the feedstock composition and reaction conditions were changed as shown in Table 2 and catalyst B was used. The test results are shown in Table 2.
- Reference Examples 4 and 5 are the results of reacting the feedstock to which no alicyclic hydrocarbon was added with reaction pressures of 1.0 MPa-G and 0.65 MPa-G, respectively, at the same temperature. From these comparisons, it can be seen that the feedstock to which no alicyclic hydrocarbons are added reduces the xylene loss and improves the benzene selectivity when the reaction pressure is lowered.
- Example 8 and Comparative Example 5 the feedstock added with 1.0% by weight of ethylcyclohexane, an alicyclic hydrocarbon, was reacted at the same temperature with reaction pressures of 1.0 MPa-G and 0.65 MPa-G, respectively. This is the result. Surprisingly for feeds containing alicyclic hydrocarbons, contrary to feeds without alicyclic hydrocarbons, increasing the reaction pressure can improve benzene selectivity and reduce xylene loss. be able to.
- the present invention is a method for producing para-xylene from a C8 aromatic hydrocarbon mixture, in which the loss of xylene is small, the deterioration rate of catalytic activity can be suppressed, and a high para-xylene conversion rate can be achieved. This method is useful in the field of para-xylene production.
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Abstract
Description
(2)非芳香族炭化水素を含む供給原料を触媒の劣化速度を速めることなく処理できる。
(3)エチルベンゼン転化率を高くしても、キシレン損失を低くすることができる。
(4)高いパラキシレン転化率を達成できる。
(1)1.0重量%以上の脂環式炭化水素と、エチルベンゼン及びキシレンを含む供給原料を、触媒の存在下、水素と接触させて供給原料中のエチルベンゼンを主としてベンゼンに転化することを含むエチルベンゼンの転化方法であって、前記触媒が、MFI型ゼオライトと無機酸化物から主として構成され、レニウムを担持する触媒であり、前記転化を、1.0MPa-G以上の反応圧力下で行う、エチルベンゼンの転化方法。
2 パラキシレン分離工程
3 キシレン異性化工程
4 低沸点成分蒸留分離工程
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24 エチルベンゼンの脱アルキル化工程
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脂環式炭化水素は、ゼオライトの固体酸点上で分解する時、オレフィン成分とパラフィン成分が生成する。特に、脂環式炭化水素はパラフィン系炭化水素より炭素原子数当たりの水素原子数が少ないため、パラフィン系炭化水素が分解する時に較べてより多くのオレフィン成分が生成する。オレフィン成分は、直ちに水素化してパラフィン成分に変換できないと、ゼオライトの固体酸点上で重合反応を起こし、固体酸点を被覆するため、触媒の劣化速度を促進させると考えられる。
オレフィン成分が、固体酸点上で重合し、固体酸点を被毒することにより、同じ固体酸点で起きるキシレンの異性化反応が抑制されると考えられる。
オレフィンの重合により、固体酸点が被覆され、有効な固体酸点が減少すると、触媒活性が低下する。この為、反応温度を上昇させる必要がある。しかし、キシレンの異性化反応の活性化エネルギーに較べ、生成ベンゼンとキシレンとのトランスアルキル化反応、或いは、キシレン分子同士の不均化反応の活性化エネルギーは高いので、反応温度が高くなると、異性化反応よりも、トランスアルキルや不均化反応が起こりやすくなり、キシレン損失の増大を引き起こす。
苛性ソーダ水溶液(NaOH含量48.6重量%、H2O含量51.4重量%、三若純薬研究所)40.9グラム、酒石酸(酒石酸含量99.7重量%、H2O含量0.3重量%、株式会社カーク)15.7グラムを水529グラムに溶解した。この溶液にアルミン酸ソーダ溶液(Al2O3含量18.9重量%、NaOH含量25.4重量%、H2O含量55.7重量%、ダイソー株式会社)12.83グラムを加え、均一な溶液とした。この溶液に含水ケイ酸(SiO2含量90.4重量%、NaOH含量0.22重量%、Al2O3含量0.26重量%、H2O含量9.12重量%、ニップシールVN-3、日本シリカ株式会社)95.2グラムを攪拌しながら徐々に加え、均一なスラリー性水性反応混合物を調製した。この反応混合物の組成比(モル比)は次のとおりであった。
SiO2/Al2O3:55
OH-/SiO2:0.26
A/Al2O3:4.0 (A:酒石酸塩)
H2O/SiO2:22
このゼオライトのSiO2/Al2O3モル比は、蛍光X線回折分析の結果、43であった。
上記のようにして合成されたMFI型ゼオライトを絶対乾燥基準(500℃、20分間焼成した時の灼熱減量から計算)で11グラム、擬ベーマイト構造を有する含水アルミナ(住友化学工業株式会社製)を絶対乾燥基準で29グラム、アルミナゾル(Al2O3含量10重量%、日産化学工業株式会社製)を60グラム加え、充分混合した。その後、120℃の乾燥器に入れ、粘土状になるまで、乾燥した。その混練り物を1.6mmφの穴を有するスクリーンを通して押出した。押出し成型物を、120℃で一晩乾燥し、次いで、350℃から徐々に500℃に昇温し、500℃で2時間焼成した。焼成した成型体20グラムを取り、蒸留水60グラムに塩化アンモニウム(シグマアルドリッチ株式会社)2.2グラム、塩化カルシウム・2水和物(株式会社カーク)1.3グラムを溶解した水溶液に入れ、80℃で1時間、時々攪拌しながら処理した。処理後、水溶液を除去し、蒸留水で5回水洗、濾過を繰り返した。Reとして120ミリグラム含む過レニウム酸水溶液(希産金属株式会社)30ml中に室温で浸し、2時間放置した。30分毎に攪拌した。その後、液を切り、120℃で一晩乾燥した。乾燥後、280℃、2時間、17mmolの硫化水素気流中で処理した。その後、空気中で、540℃、2時間焼成した。この触媒を以下”触媒A”と略する。触媒中のカルシウム含量及びナトリウム含量は原子吸光法で測定した結果、Caとして0.17重量%、Naとして0.3重量%であった。触媒中のレニウム担持量はICP発光分光法で測定した結果、Re金属として0.5重量%であった。
Reとして80ミリグラム含む過レニウム酸水溶液(稀産金属株式会社)とした以外、触媒Aと同様に触媒Bを製造した。触媒中のカルシウム含量及びナトリウム含量は原子吸光法で測定した結果、Caとして0.17重量%、Naとして0.3重量%であった。触媒中のレニウム担持量はICP発光分光法で測定した結果、Re金属として0.3重量%であった。
上記触媒Aを反応管に充填して反応テストを行った。使用した供給原料の組成、反応条件、テスト結果を下記表1に示す。尚、供給原料及び反応生成物の組成分析は水素炎検出器付きガスクロマトグラフィー3台を用いた。分離カラムは次の通りである。
充填剤:“ユニパックS”(“Unipak S” (商標))100~150メッシュ、
カラム:ステンレス製 長さ4m 内径3mmφ
N2:1.65kg/cm2-G
温度:80℃
充填剤 25%ポリエチレングリコール20M/担体“シマライト” 60~80メッシュ、
カラム:ステンレス製 長さ12m 内径3mmφ
N2:2.25kg/cm2-G
温度:68℃から2℃/分の昇温速度で180℃まで実施した。
スペルコ ワックス フューズド シリカキャピラリィー; 長さ60m 内径0.32mmφ、膜厚0.5μm
He線速:23cm/秒
温度:67℃から80℃までは1℃/分の昇温速度、80℃から2℃/分の昇温速度で200℃まで実施した。
供給原料組成、反応条件を表1の通り変更した以外は、実施例1と同様に反応させた。テスト結果を上記表1に示す。
実施例4の条件のまま、反応を継続し、反応時間とエチルベンゼン転化率の関係を調べた。結果を図5に示す。エチルベンゼンの転化率の低下速度は一日あたり0.25重量%であった。
実施例2の条件のまま、反応を継続し、反応時間とエチルベンゼン転化率の関係を調べた。結果を図5に示す。エチルベンゼンの転化率の低下速度は一日あたり0.03重量%であった。
実施例3の条件のまま、反応を継続し、反応時間とエチルベンゼン転化率の関係を調べた。結果を図5に示す。エチルベンゼンの転化率の低下速度は一日あたり0.07重量%であった。
比較例3の条件のまま、反応を継続し、反応時間とエチルベンゼン転化率の関係を調べた。結果を図5に示す。エチルベンゼンの転化率の低下速度は一日あたり4.0重量%であった。
反応温度を403℃とした以外は、参考例1と同じ条件で反応を継続し、反応時間とエチルベンゼン転化率の関係を調べた。結果を図5に示す。エチルベンゼンの転化率の低下速度は一日あたり0.01重量%であった。
供給原料組成、反応条件を表2の通り変更し、触媒Bを使用した以外は、実施例1と同様に反応させた。テスト結果を表2に示す。
Claims (12)
- 1.0重量%以上の脂環式炭化水素と、エチルベンゼン及びキシレンを含む供給原料を、触媒の存在下、水素と接触させて供給原料中のエチルベンゼンを主としてベンゼンに転化することを含むエチルベンゼンの転化方法であって、前記触媒が、MFI型ゼオライトと無機酸化物から主として構成され、レニウムを担持する触媒であり、前記転化を、1.0MPa-G以上の反応圧力下で行う、エチルベンゼンの転化方法。
- 前記水素の前記供給原料に対する比率が、前記供給原料1mol当たり3mol以上である、請求項1記載の方法。
- 前記水素の前記供給原料に対する比率が、前記供給原料1mol当たり15mol以下である、請求項2記載の方法。
- 前記供給原料中の前記脂環式炭化水素の含量が3.0重量%以上である、請求項1ないし3のいずれか1項に記載の方法。
- 前記供給原料中の前記脂環式炭化水素の含量が16重量%以下である請求項1ないし4のいずれか1項に記載の方法。
- 前記反応圧力が1.3MPa-Gから5.0MPa-Gである請求項1ないし5のいずれか1項に記載の方法。
- 前記反応圧力が1.7MPa-Gから3.0MPa-Gである請求項6記載の方法。
- 前記脂環式炭化水素が、シクロアルカン類である、請求項1ないし7のいずれか1項に記載の方法。
- 前記シクロアルカン類が、アルキルシクロアルカンである請求項8記載の方法。
- 前記レニウムの担持量が、触媒全体に対し0.05重量%から2重量%である請求項1ないし9のいずれか1項に記載の方法。
- 前記無機酸化物が、アルミナ及び/又はチタニアである請求項1ないし10のいずれか1項に記載の方法。
- 1.0重量%以上の脂環式炭化水素と、エチルベンゼン及びキシレンを含む供給原料を、請求項1ないし11のいずれか1項に記載の方法に付して前記供給原料中のエチルベンゼンを主としてベンゼンに転化する工程と、
得られた反応生成物から蒸留分離でC8芳香族炭化水素混合物を精製する工程と、
次いで精製されたC8芳香族炭化水素混合物をパラキシレン分離工程に供給する工程を含む、パラキシレンの製造方法。
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EP09721291A EP2253607B1 (en) | 2008-03-19 | 2009-03-18 | Method of converting ethylbenzene and process for producing p-xylene |
US12/933,118 US8071832B2 (en) | 2008-03-19 | 2009-03-18 | Method of converting ethylbenzene and process for producing p-xylene |
ES09721291T ES2389046T3 (es) | 2008-03-19 | 2009-03-18 | Procedimiento de conversión de etilbenceno y procedimiento para producir p-xileno |
KR1020107020627A KR101124005B1 (ko) | 2008-03-19 | 2009-03-18 | 에틸벤젠의 전화 방법 및 파라크실렌 제조 방법 |
CN2009801080975A CN101965323B (zh) | 2008-03-19 | 2009-03-18 | 乙苯的转化方法和对二甲苯制造方法 |
JP2010503898A JP4735774B2 (ja) | 2008-03-19 | 2009-03-18 | エチルベンゼンの転化方法及びパラキシレン製造方法 |
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KR20210035844A (ko) * | 2018-07-20 | 2021-04-01 | 에스씨지 케미컬스 컴퍼니, 리미티드. | 파라-자일렌 생산을 위한 통합 공정 |
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FR3104579B1 (fr) * | 2019-12-17 | 2021-12-31 | Ifp Energies Now | Dispositif et procédé de conversion de composés aromatiques par alkylation de benzène par de l’éthylène |
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ITMI20040077A1 (it) * | 2004-01-22 | 2004-04-22 | Polimeri Europa Spa | Procedimento per la idrodealchilazione catalitica di idrocarburi alchilaromatici |
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- 2009-03-18 WO PCT/JP2009/055258 patent/WO2009116561A1/ja active Application Filing
- 2009-03-18 EP EP09721291A patent/EP2253607B1/en not_active Not-in-force
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JPS4946606B1 (ja) | 1970-12-12 | 1974-12-11 | ||
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JPS57200319A (en) | 1981-06-03 | 1982-12-08 | Toray Ind Inc | Conversion of xylenes containing ethylbenzene |
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TWI439447B (zh) | 2014-06-01 |
CN101965323A (zh) | 2011-02-02 |
ES2389046T3 (es) | 2012-10-22 |
CN101965323B (zh) | 2013-06-12 |
JP4735774B2 (ja) | 2011-07-27 |
EP2253607A1 (en) | 2010-11-24 |
US20110021854A1 (en) | 2011-01-27 |
EP2253607B1 (en) | 2012-06-20 |
JPWO2009116561A1 (ja) | 2011-07-21 |
KR101124005B1 (ko) | 2012-03-23 |
US8071832B2 (en) | 2011-12-06 |
TW200946490A (en) | 2009-11-16 |
KR20100124294A (ko) | 2010-11-26 |
EP2253607A4 (en) | 2011-06-15 |
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