WO2013091337A1 - 甲醇和/或二甲醚与c4液化气相互转化制备对二甲苯的催化剂及其制备方法和应用 - Google Patents

甲醇和/或二甲醚与c4液化气相互转化制备对二甲苯的催化剂及其制备方法和应用 Download PDF

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WO2013091337A1
WO2013091337A1 PCT/CN2012/074709 CN2012074709W WO2013091337A1 WO 2013091337 A1 WO2013091337 A1 WO 2013091337A1 CN 2012074709 W CN2012074709 W CN 2012074709W WO 2013091337 A1 WO2013091337 A1 WO 2013091337A1
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catalyst
molecular sieve
liquefied gas
weight
dimethyl ether
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PCT/CN2012/074709
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English (en)
French (fr)
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许磊
刘中民
于政锡
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中国科学院大连化学物理研究所
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Priority to SG11201402787QA priority Critical patent/SG11201402787QA/en
Priority to EA201491154A priority patent/EA024296B1/ru
Priority to JP2014547674A priority patent/JP5873570B2/ja
Priority to EP12860423.8A priority patent/EP2803407B1/en
Priority to AU2012357512A priority patent/AU2012357512C1/en
Priority to US14/366,209 priority patent/US9968922B2/en
Priority to KR1020147016565A priority patent/KR101593467B1/ko
Publication of WO2013091337A1 publication Critical patent/WO2013091337A1/zh
Priority to ZA2014/05040A priority patent/ZA201405040B/en

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    • 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
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    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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    • 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
    • B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/08—Xylenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/865—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an ether
    • 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
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/005—General concepts, e.g. reviews, relating to methods of using catalyst systems, the concept being defined by a common method or theory, e.g. microwave heating or multiple stereoselectivity
    • 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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    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • 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
    • 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
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    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a technique for aromatization of methanol and/or dimethyl ether with C 4 liquefied gas to produce aromatic hydrocarbons, in particular to a high selectivity preparation of methanol and/or dimethyl ether and C 4 liquefied gas.
  • Para-xylene is the basic raw material for synthetic polyester. At present, paraxylene production is mainly carried out by using toluene, C 9 aromatic hydrocarbons and mixed xylene obtained by catalytic reforming of naphtha as raw materials, and is obtained by disproportionation, isomerization, adsorption separation or cryogenic separation. Since p-xylene content in its product is thermodynamically controlled, p-xylene is present. 8 mixed aromatics only accounted for
  • Aromatic hydrocarbons are directly aromatized by methanol or dimethyl ether on a metal-molecular sieve composite catalyst.
  • Chinese patent CN 101244969 discloses a stream of dC 2 hydrocarbons or methanol aromatization and catalyst regeneration
  • the chemical bed device can adjust the coking state of the catalyst in the aromatization reactor at any time by using the device and the catalyst, thereby achieving the purpose of continuously and efficiently converting dC 2 hydrocarbons or methanol and highly selective aromatic hydrocarbons.
  • Chinese patent CN 1880288 discloses a process for converting methanol to aromatics.
  • methanol is catalytically converted into an aromatic hydrocarbon-based product, which has the advantages of high total selectivity of aromatic hydrocarbons and flexible process operation.
  • U.S. Patent No. 4,615,995 discloses a ZSM-5 molecular sieve catalyst supported on Zn and Mn for methanol conversion to produce olefins and aromatic hydrocarbons, and the low olefin/aromatic compound in the product can be modified by modulating the content of Zn and Mn in the catalyst. The ratio.
  • Aromatization of liquefied petroleum gas by-products from petroleum refineries is also an effective way to increase the source of aromatics.
  • liquefied gas aromatization can produce high-quality gasoline.
  • liquefied gas aromatization can directly obtain benzene and toluene.
  • xylene (BTX) products U.S. Patent 4,642,402 discloses the development of a process for the conversion of light hydrocarbons to aromatics by UOP, using a Ga-modified ZSM-5 molecular sieve catalyst to aromatize carbon tris and carbon tetrahydrocarbons into BTX aromatics with an aromatics yield of about 60. %.
  • Chinese patent CN 1023633C discloses a gallium, zinc and platinum modified HZSM-5 catalyst for low carbon chain hydrocarbon aromatization, suitable for C5-C8 alkane, especially suitable for olefin aromatization reaction to prepare benzene, toluene and xylene mixture.
  • the aromatic hydrocarbons have a total aromatic yield of about 50% by weight.
  • Chinese patent CN 1660724A discloses a fluidized bed process for aromatization of liquefied gas to produce benzene, toluene and xylene.
  • the DLC-2 catalyst is used, and the mixed triphenyl yield is about 65 wt%.
  • An object of the present invention is to provide a catalyst for preparing aromatic hydrocarbons by high-yield mutual conversion of methanol and/or dimethyl ether and C 4 liquefied gas, and a preparation method and application thereof, that is, a method for preparing aromatic hydrocarbons in high yield.
  • the method organically combines methanol from coal resources with liquefied gas resources from by-products of petroleum refineries on raw materials to maximize the availability of aromatic products.
  • the aromatization of methanol and the aromatization process of liquefied gas are organically combined, which can effectively increase the yield of aromatic hydrocarbons.
  • Another object of the present invention is to provide a process for preparing para-xylene by high-selective conversion of methanol and/or dimethyl ether with C 4 liquefied gas.
  • the molecular sieve catalyst with shape-selective function prepared by the combined modification of bimetal and silicon can convert alkaneization and shape-selective alkylation of methanol and/or dimethyl ether with C 4 liquefied gas into para-xylene products.
  • the present invention provides a catalyst for the interconversion of methanol and/or dimethyl ether with a C 4 liquefied gas to produce p-xylene using a bimetallic and siloxane-based compound.
  • siloxane-based compound is represented by Formula I:
  • R, R 2 , R 3 and are independently selected from the group consisting of d-doalkyl.
  • the siloxane-based compound is tetraethyl silicate.
  • the combined modification of the bimetallic modification and the siloxane-based compound comprises the following steps: (1) impregnating the molecular sieve with a soluble salt solution of one of zinc and gallium, Filtration, drying and calcination to obtain a metal modified molecular sieve; (2) impregnating the metal modified molecular sieve obtained in the step (1) with another soluble salt solution of zinc and gallium, filtering, drying and Calcination to obtain a bimetallic modified molecular sieve; and (3) impregnating the above bimetallic modified molecular sieve with a siloxane-based compound, filtering, drying and calcining to obtain a molecular sieve modified by a combination of a bimetallic and a siloxane-based compound .
  • the molecules in the aromatized molecular sieve catalyst having a shape-selective function are screened for one or both of the group consisting of HZSM-5 molecular sieves and HZSM-11 molecular sieves.
  • the supported amount of zinc and gallium is 0.5-8 wt% of the total mass of the catalyst, respectively, and the supported amount of the siloxane based compound in terms of silica is the total weight of the catalyst. 0.5-10% by weight.
  • the present invention provides a method of preparing the catalyst described above, the method comprising the steps of:
  • the present invention provides a mutual conversion of methanol and/or dimethyl ether with C 4 liquefied gas to prepare a dimethylene
  • a method of benzene comprising the steps of: passing a mixed gas containing methanol and/or dimethyl ether and a C 4 liquefied gas through a reactor equipped with the above catalyst at a reaction temperature of 350 to 550 ° C and a reaction pressure of The aromatization reaction occurs at a pressure of -5 MPa and a raw material feed weight space velocity of 0. l ⁇ Oh- 1 to form p-xylene.
  • the aromatic yield is more than 70% by weight, wherein the selectivity of para-xylene in the aromatic component is more than 80% by weight,
  • the p-xylene is more than 99% by weight selective in the xylene isomer.
  • the process is carried out in a fixed bed or a fluidized bed.
  • the present invention provides a catalyst for the mutual conversion of methanol and/or dimethyl ether and C 4 liquefied gas to produce p-xylene, which is prepared by the combined modification of a bimetallic and a siloxane-based compound.
  • the bimetallic and silanated combined modified molecular sieve catalysts used in the present invention are prepared according to the method comprising the following steps:
  • the zeolite molecular sieve raw powder is prepared into an acidic zeolite molecular sieve by H 4 + ion exchange and calcination;
  • the metal modified zeolite molecular sieve obtained in the step 2 is again subjected to immersion modification using another metal soluble salt solution to obtain a bimetallic modified zeolite molecular sieve;
  • the bismuth-modified zeolite molecular sieve obtained in the step 3 is subjected to immersion modification using a siloxane-based reagent to modulate the acidity and pore structure of the outer surface of the catalyst to obtain a bimetal and silanization combined modification catalyst;
  • the bimetals are zinc and gallium.
  • siloxane-based compound modification is also referred to as silylation modification.
  • step 1 can be omitted.
  • the silylation modification can also be carried out prior to the bimetallic modification.
  • R 2 , R 3 and both are selected from the group consisting of d-doalkyl.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, decyl group and fluorenyl group.
  • various isomerized groups are included. For example, propyl includes n-propyl and isopropyl, and butyl includes n-butyl, isopropyl and t-butyl.
  • the siloxane-based compound is preferably a liquid at room temperature. In the case where the siloxane-based compound is solid at room temperature, it is heated to a liquid and then used for impregnation.
  • the supported amount of the metal is 0.5 to 8% by weight based on the total mass of the catalyst, and the amount of the siloxane-based compound supported on the silica is 0.5 to 10% by weight based on the total weight of the catalyst.
  • the molecular sieve may specifically be a ZSM-5 molecular sieve or a ZSM-11 molecular sieve, preferably a ZSM-5 molecular sieve;
  • the siloxane-based compound may specifically be ethyl silicate (Ri, R 2 , R 3 and both are ethyl; ).
  • the invention uses methanol and / or dimethyl ether and C 4 liquefied gas mixture as raw materials, wherein methanol can be aqueous methanol, methanol concentration is 50-100%; wherein methanol and / or dimethyl ether and C 4 liquefied gas mixture
  • the feed can be used in any ratio, that is, a single feed reaction of methanol, a single feed reaction of dimethyl ether, a single feed reaction of C 4 liquefied gas, and a mixed feed of methanol, dimethyl ether and C 4 liquefied gas in any ratio.
  • the preferred ratio of methanol and/or dimethyl ether to C 4 liquefied gas feed is (10-90): (90-10), preferably (30-70): (70- 30) (weight ratio).
  • the reaction mode of the methanol and/or dimethyl ether of the present invention and the C 4 liquefied gas conversion reaction is either a fixed bed or a fluidized bed.
  • the reaction temperature is 350-550 ° C, preferably 400-500 ° C;
  • the reaction pressure is atmospheric pressure - 5 MPa, preferably atmospheric pressure - 2 MPa;
  • raw material feed weight space velocity is O. l ⁇ Oh - 1 , preferably l - 10h -
  • step 2) Take 20 g of each of the HZSM-5 zeolite molecular sieves prepared in step 1), and immerse them in a 5% mass concentration of zinc nitrate [Zn(N0 3 ) 2 ] solution at room temperature for 4 hours, pour out the upper liquid and then dry at 120 ° C, then The mixture was calcined in air at 550 ° C for 6 hours to obtain a zinc-modified HZSM-5 zeolite molecular sieve.
  • the zinc-modified HZSM-5 zeolite molecular sieve prepared in the step 2) is immersed in a 8% mass concentration of gallium nitrate [Ga(N0 3 ) 3 ] solution at room temperature for 4 hours, and the upper liquid is decanted and dried at 120 ° C. Then, it was calcined in air at 550 ° C for 6 hours to obtain a zinc and gallium bimetallic modified HZSM-5 zeolite molecular sieve.
  • the zinc and gallium bimetallic modified HZSM-5 zeolite molecular sieve obtained in step 3) is immersed at room temperature for 24 hours, and the upper liquid is decanted and dried at 120 ° C and air at 550 ° C. After calcination for 6 hours, a HZSM-5 catalyst modified by zinc gallium bimetal and silanization was obtained.
  • the elemental analysis catalyst had a zinc content of 2.8 wt%, a gallium content of 3.6% by weight, and a silanization supported by silica.
  • the catalyst was named CPX-01 at 7.9% by weight of the total mass of the catalyst.
  • Example 2 Preparation of fixed bed catalyst
  • the gallium-modified HZSM-5 zeolite molecular sieve prepared in the step 1) is immersed in a 8% mass concentration zinc nitrate [Zn(N0 3 ) 2 ] solution at room temperature for 4 hours, and the upper liquid is decanted and dried at 120 ° C. It was then calcined in air at 550 ° C for 6 hours to obtain a gallium and zinc bimetallic modified HZSM-5 zeolite molecular sieve.
  • step 2 Using tetraethyl orthosilicate (TEOS), the gallium and zinc bimetallic modified HZSM-5 zeolite molecular sieve obtained in step 2) is immersed at room temperature for 24 hours, and the upper liquid is decanted and dried at 120 ° C and air at 550 ° C. After calcination for 6 hours, a HZSM-5 catalyst modified by zinc gallium bimetal and silanization was obtained.
  • the elemental analysis catalyst had a zinc content of 3.7 wt%, a gallium content of 5.2 wt%, and a silanization supported by silica.
  • the catalyst was named CPX-02, which was 6.7% by weight of the total mass of the catalyst.
  • Example 3 Preparation of Fluidized Bed Catalyst
  • Example 1 200 g of HZSM-5 zeolite molecular sieve prepared in Example 1 was immersed in a 10% mass concentration zinc nitrate [Zn(N0 3 ) 2 ] solution at room temperature for 4 hours, and the upper liquid was decanted and dried at 120 ° C, then 550 The mixture was calcined in air at °C for 6 hours to obtain a zinc-modified HZSM-5 zeolite molecular sieve.
  • the zinc-modified HZSM-5 zeolite molecular sieve prepared in the step 1) is immersed in a 15% mass concentration of gallium nitrate [Ga(N0 3 ) 3 ] solution at room temperature for 4 hours, and the upper liquid is decanted and dried at 120 ° C. Then, it was calcined in air at 550 ° C for 6 hours to obtain a zinc and gallium bimetallic modified HZSM-5 zeolite molecular sieve.
  • step 3 Using zinc orthosilicate (TEOS), the zinc and gallium bimetallic modified HZSM-5 zeolite molecular sieve obtained in step 3) is immersed at room temperature for 24 hours, and the upper liquid is decanted and dried at 120 ° C and air at 550 ° C. After calcination for 6 hours, a HZSM-5 zeolite molecular sieve modified by zinc gallium bimetal and silanization was obtained.
  • TEOS zinc orthosilicate
  • step 4) Mixing the zinc gallium bimetal obtained in step 3) with the silanized modified HZSM-5 zeolite molecular sieve with kaolin, silica sol, aluminum sol and deionized water to form a slurry, molecular sieve with kaolin, silica sol, aluminum sol
  • the dry basis mass ratio is 30:32:26:12, and the slurry has a solid content of about 35% by weight.
  • the slurry was aged at room temperature for 5 hours and spray-molded by a colloidal film to obtain a microsphere catalyst having a particle diameter of 20 to 100 ⁇ m.
  • the elemental analysis catalyst had a zinc content of 2.3% by weight and a gallium content of 3.1% by weight.
  • the amount of silanization supported on the silica was 5.3 % by weight based on the total mass of the catalyst, and the catalyst was named CPX-03.
  • Example 4 fixed bed reaction evaluation
  • the aromatics yield in the non-aqueous product was 71.31% by weight and 73.03% by weight, respectively, and the para-xylene content in the aromatic hydrocarbon product was 87.17% by weight and 86.67% by weight, respectively.
  • the selectivity of toluene in the xylene isomer was 99.41% by weight and 99.32% by weight, respectively. Table 1, raw material and product distribution
  • the aromatics yield in the non-aqueous product was 75.21% by weight and 79.01% by weight, respectively, and the para-xylene content in the aromatic product was 85.88% by weight and 85.74, respectively.
  • the weight %, p-xylene selectivity in the xylene isomers were 99.21% by weight and 99.19% by weight, respectively.
  • Example 3 Using the CPX-03 catalyst prepared in Example 3 as a reaction catalyst, 10 g of the catalyst was placed in a fixed fluidized bed reactor, treated in an air atmosphere at 550 ° C for 1 hour, and cooled in a nitrogen atmosphere to a reaction temperature of 450 ° C. 0.1 MPa. The dimethyl ether and the C 4 liquefied gas were pumped into the preheater at a temperature of 280 ° C by a feed pump, and then entered into a fixed fluidized bed reactor to be contacted with the catalyst. The weight ratio of raw material methanol to C 4 liquefied gas feed was 50:50 and 30:70, respectively, and the total feed space velocity was 21 ⁇ .
  • the reaction raw material composition and non-aqueous product distribution are shown in Table 3, non-aqueous products.
  • the yield of aromatic hydrocarbons was 70.12% by weight and 72.87% by weight respectively
  • the para-xylene content in the aromatic hydrocarbon product was 84.47% by weight and 85.21% by weight, respectively
  • the selectivity of p-xylene in the xylene isomer was 99.04% by weight and 99.08, respectively. weight%.

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Abstract

本申请提供甲醇和/或二甲醚与C4液化气相互转化制备对二甲苯的催化剂及其制备方法及应用。所述催化剂是采用双金属和硅氧烷基化合物联合改性制备的具有择形功能的芳构化催化剂。甲醇和/或二甲醚与C4液化气共同进料在改性的择形分子筛催化剂上发生芳构化反应，可以有效提高芳烃产物收率，在芳烃产物中主要为对二甲苯产品。甲醇和/或二甲醚与C4液化气转化得到的产物中芳烃收率大于70重量％，其中芳烃组分中对二甲苯选择性大于80重量％，对二甲苯在二甲苯异构体中选择性大于99重量％。

Description

甲醇和 /或二甲醚与 C4液化气相互转化制备对二甲苯的催化剂
及其制备方法和应用 技术领域
本发明涉及一种甲醇和 /或二甲醚与 C4液化气芳构化制备芳烃的技术， 具体地涉 及一种由甲醇和 /或二甲醚与 C4液化气相互转化高选择性制备对二甲苯的催化剂及其 制备方法和应用。 背景技术
对二甲苯是合成聚酯的基本原料。 目前， 对二甲苯生产主要采用石脑油催化重整 得到的甲苯、 C9芳烃及混合二甲苯为原料， 通过歧化、 异构化、 吸附分离或深冷分离 而制取。 由于其产物中的对二甲苯含量受热力学控制， 对二甲苯在。8混合芳烃中只占
20%左右， 工艺过程中物料循环处理量大， 设备庞大， 操作费用高。 特别是二甲苯的 三种异构体的沸点相差很小， 采用通常的蒸熘技术不能得到高纯度对二甲苯， 而必须 采用昂贵的吸附分离工艺。
随着石油资源的日益短缺， 国内外许多研究机构积极开发增产芳烃新技术， 如甲 醇制芳烃以及液化气制芳烃等。 甲醇制芳烃技术是由煤或天然气制备芳烃的新途径， 通过甲醇或二甲醚在金属与分子筛复合的催化剂上直接芳构化制备芳烃。
1977年， Mobil公司的 Chang等人 (Journal of Catalysis, 1977, 47, 249) 报道了在 ZSM-5分子筛催化剂上甲醇及其含氧化合物转化制备芳烃等碳氢化合物的方法。研究 表明，在金属组分作用下，烷烃、烯烃在一定条件下能够转化为芳烃。因此，对 ZSM-5 进行金属组分改性， 从而在甲醇转化过程中生成更多的芳烃， 成为该过程研究的主要 方向。
目前对 ZSM-5的改性研究主要集中在 Zn、 Ga改性， 另外其它金属如 Ag、 Cu等 金属改性也有报道。 日本的 Ono等人 （J Chem. Soc, Faraday Trans. 1, 1988, 84(4), 1091; Microporous Materials, 1995, 4， 379) 利用离子交换法将 Zn和 Ag引入到 ZSM-5 分子筛中， 考察了甲醇制芳烃 （MTA) 的催化性能。 将 Zn引入后， 产物中芳烃的含 量有所提高， 能达到 67.4%左右 （C%；)， 引入 Ag后芳烃收率可达到 80 %左右。
中国专利 CN 101244969公开了一种 d-C2烃类或甲醇芳构化与催化剂再生的流 化床装置， 利用该装置及催化剂， 可随时调节芳构化反应器内的催化剂的结焦状态， 从而达到连续高效转化 d-C2烃类或甲醇并高选择性生成芳烃的目的。
中国专利 CN 1880288公开了一种甲醇转化制芳烃工艺，在改性 ZSM-5分子筛催 化剂上， 甲醇催化转化为以芳烃为主的产物， 具有芳烃的总选择性高， 工艺操作灵活 的优点。
美国专利 US 4615995公开了一种担载了 Zn和 Mn的 ZSM-5分子筛催化剂， 用 于甲醇转化制备烯烃和芳烃， 通过调变催化剂中 Zn和 Mn的含量可以改变产物中低 碳烯烃 /芳烃化合物的比值。
利用石油炼厂副产的液化石油气芳构化制备芳烃也是增加芳烃来源的有效途径， 一方面液化气芳构化可以制备高品质汽油， 另一方面液化气芳构化可以直接得到苯、 甲苯和二甲苯 （BTX) 产品。 USP 4642402曾公开了由 UOP公司开发轻烃转化制芳烃 工艺过程， 采用 Ga改性的 ZSM-5分子筛催化剂， 将碳三和碳四轻烃芳构化转化为 BTX芳烃， 其芳烃收率约 60%。
中国专利 CN 1023633C公开了一种低碳链烃芳构化用镓、 锌、 铂改性 HZSM-5 催化剂，适用于 C5-C8烷烃尤其适用于烯烃芳构化反应制备苯、 甲苯和二甲苯混合芳 烃， 总芳烃收率为 50重量％左右。
中国专利 CN 1660724A曾公开了一种液化气芳构化生产苯、 甲苯和二甲苯的流 化床工艺， 采用 DLC-2催化剂， 其混合三苯收率达到 65重量％左右。
上述甲醇转化制备芳烃和液化石油气芳构化制备芳烃均是以单一原料制备苯、 甲 苯和二甲苯 （BTX) 混合芳烃为目的产物， 市场价值较低， 因而经济效益较差。 发明内容
本发明的一个目的在于提供一种由甲醇和 /或二甲醚与 C4液化气相互转化高收率 制备芳烃的催化剂及其制备方法和应用， 即催化剂用于高收率制备芳烃的方法。 该方 法在原料上将来自煤炭资源的甲醇和来自石油炼厂副产的液化气资源有机结合，可以 最大限度获得芳烃产品。 同时， 甲醇芳构化和液化气芳构化反应过程有机结合， 可以 有效提高芳烃的收率。
本发明的另一目的在于提供一种由甲醇和 /或二甲醚与 C4液化气相互转化高选择 性制备对二甲苯的方法。采用双金属和硅联合改性制备的具有择形功能的分子筛催化 剂， 可以使甲醇和 /或二甲醚与 C4液化气芳构化和择形烷基化转化为对二甲苯产品。 为实现上述目的， 在一方面， 本发明提供一种用于甲醇和 /或二甲醚与 C4液化气 相互转化制备对二甲苯的催化剂，所述催化剂是采用双金属和硅氧烷基化合物联合改 性制备的具有择形功能的芳构化分子筛催化剂， 其中所述的双金属为锌和镓。
在本发明的一个优选的实施方案中， 所述的硅氧烷基化合物由式 I所示： ,
Figure imgf000004_0001
(式 I)
其中， R 、 R2、 R3和 独立地选自 d-do烷基。
在本发明的一个更优选的实施方案中， 所述硅氧烷基化合物为硅酸四乙酯。
在本发明的另一个优选的实施方案中，所述的双金属改性和硅氧烷基化合物联合 改性包括如下步骤： （1) 使用锌和镓中的一种的可溶性盐溶液浸渍分子筛， 过滤、 烘 干并焙烧， 得到一种金属改性的分子筛； （2) 使用锌和镓中的另一种的可溶性盐溶液 浸渍步骤 (1)得到的金属改性的分子筛，过滤、烘干并焙烧，得到双金属改性的分子筛； 和 (3) 使用硅氧烷基化合物浸渍上述双金属改性的分子筛， 过滤、 烘干并焙烧， 得到 双金属和硅氧烷基化合物联合改性的分子筛。
在本发明的另一个优选的实施方案中，所述的具有择形功能的芳构化分子筛催化 剂中的分子筛选自由 HZSM-5分子筛和 HZSM-11分子筛组成的组中的一种或两种。
在本发明的另一个优选的实施方案中，所述锌和镓的担载量分别为催化剂总质量 的 0.5-8重量％，硅氧烷基化合物以氧化硅计的担载量为催化剂总重量的 0.5-10重量％。
再另一方面， 本发明提供一种制备上述所述的催化剂的方法， 所述方法包括以下 步骤：
(1) 使用锌和镓中的一种的可溶性盐溶液浸渍分子筛， 过滤、 烘干并焙烧， 得到 一种金属改性的分子筛；
(2) 使用锌和镓中的另一种的可溶性盐溶液浸渍步骤 (1)得到的金属改性的分子 筛， 过滤、 烘干并焙烧， 得到双金属改性的分子筛； 和
(3) 使用硅氧烷基化合物浸渍上述双金属改性的分子筛， 过滤、 烘干并焙烧， 得 到双金属和硅氧烷基化合物联合改性的分子筛。
再另一方面， 本发明提供一种甲醇和 /或二甲醚与 C4液化气相互转化制备对二甲 苯的方法， 所述方法包括以下步骤： 将含有甲醇和 /或二甲醚与 C4液化气的混合气通 过装有上述的催化剂的反应器， 在反应温度 350-550°C、 反应压力为常压 -5MPa、 并 且原料进料重量空速为 O. l^Oh—1的条件下发生芳构化反应生成对二甲苯。
在本发明的甲醇和 /或二甲醚与 C4液化气芳构化转化的非水产物中， 芳烃收率大 于 70重量％， 其中对二甲苯在芳烃组分中选择性大于 80重量％， 对二甲苯在二甲苯 异构体中选择性大于 99重量％。
在本发明的一个优选的实施方案中， 所述方法在固定床或流化床中进行。 具体实施方式
具体地， 本发明提供一种用于甲醇和 /或二甲醚与 C4液化气相互转化制备对二甲 苯的催化剂，所述催化剂是采用双金属和硅氧烷基化合物联合改性制备的具有择形功 能的芳构化分子筛催化剂， 其中所述的双金属为锌和镓。
本发明所用的双金属和硅烷化联合改性的分子筛催化剂是按照包括下述步骤的 方法制备得到的：
1、 将沸石分子筛原粉经 H4 +离子交换、 焙烧制备成酸性沸石分子筛；
2、 使用一种金属可溶性盐溶液对酸性沸石分子筛进行浸渍改性， 得到金属改性 沸石分子筛；
3、 使用另一种金属可溶性盐溶液对步骤 2得到的金属改性沸石分子筛再次进行 浸渍改性， 得到双金属改性的沸石分子筛；
4、 使用硅氧烷基试剂对步骤 3得到的双金属改性的沸石分子筛进行浸渍改性， 调变催化剂外表面酸性和孔结构， 得到双金属和硅烷化联合改性催化剂； 和
5、 将步骤 4制备改性制备催化剂压片或喷雾干燥成型后使用。
所述双金属为锌和镓。
本文中， 硅氧烷基化合物改性也称作硅烷化改性。
在分子筛是 H型分子筛的情况下， 可以省去步骤 1。 另外， 硅烷化改性也可以在 双金属改性之前进行。
所述硅氧烷基化合物的结构通式如式 I所示： OR,
I
(！) R;j
(式 I)
其中， R2、 R3和 均选自 d-do烷基。
所述 d-d。烷基的实例包括甲基、 乙基、 正丙基、 异丙基、 正丁基、 异丙基、 叔 丁基、 戊基、 己基、 庚基、 壬基和癸基。 在所述基团具有异构体的情况下， 包括各种 异构的基团。 例如， 丙基包括正丙基和异丙基， 并且丁基包括正丁基、 异丙基和叔丁 基。
所述硅氧烷基化合物优选在室温为液体。在所述硅氧烷基化合物在室温下为固体 的情况下， 将其加热成为液体， 然后用于浸渍。
所述的改性分子筛催化剂中，金属的担载量分别为催化剂总质量的 0.5-8重量％， 硅氧烷基化合物以氧化硅计的担载量为催化剂总重量的 0.5-10重量％。
所述分子筛具体可为 ZSM-5分子筛或 ZSM-11分子筛， 优选 ZSM-5分子筛； 所 述硅氧烷基化合物具体可为硅酸乙酯 （Ri、 R2、 R3和 均为乙基；)。
本发明以甲醇和 /或二甲醚与 C4液化气混合物料为原料， 其中甲醇可以为含水甲 醇， 甲醇质量浓度为 50-100%; 其中甲醇和 /或二甲醚与 C4液化气混合物进料可以采 用任意比例， 即可以甲醇单一进料反应、 可以二甲醚单一进料反应、 可以 C4液化气 单一进料反应以及甲醇、 二甲醚和 C4液化气任意比例混合进料， 但为了获得更高的 芳烃收率， 甲醇和 /或二甲醚与 C4液化气进料优选比例为 (10-90) ： (90- 10)， 优选为 (30-70)： (70- 30) (重量比）。
本发明所述甲醇和 /或二甲醚与 C4液化气转化反应的反应方式为固定床或流化床 的任一种形式。 反应温度为 350-550°C， 优选 400-500°C ; 反应压力为常压 -5MPa， 优 选常压 -2MPa; 原料进料重量空速为 O. l^Oh—1, 优选为 l-10h—
具体实施方式
下面通过实施例详述本发明， 但本发明不局限于以下实施例。
下述实施例中所述试剂和材料，如无特殊说明，均可从商业途径获得；实施例中"重 量％ "表示重量百分含量。除非另外指出，本申请中的份、百分含量和比例都按重量计。 实施例 1、 固定床催化剂制备
1) 将 500g ZSM-5沸石分子筛原粉 （南开大学催化剂厂） (SiO2/Al2O3=50) 在 550°C 下焙烧去除模板剂， 在 80°C水浴中用 0.5mol/L硝酸铵溶液进行交换 4次， 交换后在 120°C空气中烘干， 550°C下焙烧 3小时， 得到 HZSM-5沸石分子筛。
2) 取步骤 1) 制备的 HZSM-5 沸石分子筛各 20g， 用 5%质量浓度的硝酸锌 [Zn(N03)2]溶液常温浸渍 4 小时， 倾出上层液体后 120°C烘干， 然后 550°C空气中焙烧 6小时， 得到锌改性的 HZSM-5沸石分子筛。
3) 取步骤 2) 制备的锌改性的 HZSM-5 沸石分子筛用 8%质量浓度的硝酸镓 [Ga(N03)3]溶液常温浸渍 4 小时， 倾出上层液体后 120°C烘干， 然后 550°C空气中焙烧 6小时， 得到锌和镓双金属改性的 HZSM-5沸石分子筛。
4) 采用正硅酸乙酯 （TEOS) 将步骤 3) 得到的锌和镓双金属改性的 HZSM-5沸石 分子筛常温浸渍 24小时， 倾出上层液体后 120°C烘干、 550°C空气中焙烧 6小时， 得 到锌镓双金属与硅烷化联合改性的 HZSM-5催化剂， 元素分析催化剂中锌含量为 2.8 重量％、镓含量为 3.6重量％、硅烷化以氧化硅计的担载量为催化剂总质量的 7.9重量％， 催化剂命名为 CPX-01。 实施例 2、 固定床催化剂制备
1) 取实施例 1 制备的 HZSM-5 沸石分子筛各 20g， 用 10%质量浓度的硝酸镓 [Ga(N03)3]溶液常温浸渍 4小时， 倾出上层液体后 120°C烘干， 然后 550°C空气中焙烧 6小时， 得到镓改性的 HZSM-5沸石分子筛。
2) 取步骤 1) 制备的镓改性的 HZSM-5 沸石分子筛用 8%质量浓度的硝酸锌 [Zn(N03)2]溶液常温浸渍 4小时， 倾出上层液体后 120°C烘干， 然后 550°C空气中焙烧 6小时， 得到镓和锌双金属改性的 HZSM-5沸石分子筛。
4) 采用正硅酸乙酯 （TEOS) 将步骤 2) 得到的镓和锌双金属改性的 HZSM-5沸石 分子筛常温浸渍 24小时， 倾出上层液体后 120°C烘干、 550°C空气中焙烧 6小时， 得 到锌镓双金属与硅烷化联合改性的 HZSM-5催化剂， 元素分析催化剂中锌含量为 3.7 重量％、镓含量为 5.2重量％、硅烷化以氧化硅计的担载量为催化剂总质量的 6.7重量％， 催化剂命名为 CPX-02。 实施例 3、 流化床催化剂的制备
1) 取实施例 1 制备的 HZSM-5 沸石分子筛 200g， 用 10%质量浓度的硝酸锌 [Zn(N03)2]溶液常温浸渍 4小时， 倾出上层液体后 120°C烘干， 然后 550°C空气中焙烧 6小时， 得到锌改性的 HZSM-5沸石分子筛。
2) 取步骤 1) 制备的锌改性的 HZSM-5 沸石分子筛用 15%质量浓度的硝酸镓 [Ga(N03)3]溶液常温浸渍 4小时， 倾出上层液体后 120°C烘干， 然后 550°C空气中焙烧 6小时， 得到锌和镓双金属改性的 HZSM-5沸石分子筛。
3) 采用正硅酸乙酯 （TEOS) 将步骤 3) 得到的锌和镓双金属改性的 HZSM-5沸石 分子筛常温浸渍 24小时， 倾出上层液体后 120°C烘干、 550°C空气中焙烧 6 小时， 得 到锌镓双金属与硅烷化联合改性的 HZSM-5沸石分子筛。
4) 将步骤 3) 得到的锌镓双金属与硅烷化联合改性的 HZSM-5沸石分子筛与高岭 土， 硅溶胶， 铝溶胶以及去离子水混合成浆料， 分子筛与高岭土、 硅溶胶、 铝溶胶的 干基质量比为 30: 32： 26： 12， 浆料的固含量约为 35重量％。 浆料在室温老化 5小时 并通过胶体磨胶膜后喷雾成型， 得到粒径为 20-100μιη 的微球催化剂。 元素分析催化 剂中锌含量为 2.3重量％、 镓含量为 3.1重量％， 硅烷化以氧化硅计的担载量为催化剂 总质量的 5.3重量％， 催化剂命名为 CPX-03。 实施例 4、 固定床反应评价
以实施例 1和 2中制备的 CPX-01和 CPX-02催化剂作为反应催化剂， 将 5g催化 剂装入固定床反应器， 在 550°C空气气氛中处理 1 小时， 在氮气气氛下降温到反应温 度 450°C， 0.15MPa。通过进料泵将甲醇和 C4液化气泵入温度为 200°C汽化器中混合后 进入反应器与催化剂接触反应。 原料甲醇与 C4液化气进料重量比为 50:50， 进料总重 量空速为 21^。 反应原料组成与非水产物分布如表 1所示， 非水产物中芳烃收率分别 为 71.31重量％和 73.03重量％， 芳烃产物中对二甲苯含量分别为 87.17重量％和 86.67 重量％， 对二甲苯在二甲苯异构体中选择性分别为 99.41重量％和 99.32重量％。 表 1、 原料与产物分布
Figure imgf000009_0001
* C5 +: C5以上组分； C9 +: C9以上组分。 实施例 5、 固定床反应评价
以实施例 1和 2中制备的 CPX-01和 CPX-02催化剂作为反应催化剂， 将 5g催化 剂装入固定床反应器， 在 550°C空气气氛中处理 1 小时， 在氮气气氛下降温到反应温 度 450°C， 0.1MPa。 通过进料泵将甲醇和 C4液化气泵入温度为 200°C汽化器中混合后 进入反应器与催化剂接触反应。 原料甲醇与 C4液化气进料重量比为 30:70， 进料总重 量空速为 21^。 反应原料组成与非水产物分布如表 2所示， 非水产物中芳烃收率分别 为 75.21重量％和 79.01重量％， 芳烃产物中对二甲苯含量分别为 85.88重量％和 85.74 重量％， 对二甲苯在二甲苯异构体中选择性分别为 99.21重量％和 99.19重量％。
表 2、 原料与产物分布
Figure imgf000010_0001
* C5 +: C5以上组分； C9 +: C9以上组分。 实施例 6、 流化床反应评价
以实施例 3中制备的 CPX-03催化剂作为反应催化剂， 将 10g催化剂装入固定流 化床反应器， 在 550°C空气气氛中处理 1小时， 在氮气气氛下降温到反应温度 450°C， 0.1MPa。通过进料泵将二甲醚和 C4液化气泵入温度为 280°C预热器中混合后进入固定 流化床反应器与催化剂接触反应。 原料甲醇与 C4液化气进料重量比分别为 50:50 和 30:70, 进料总重量空速为 21^。 反应原料组成与非水产物分布如表 3所示， 非水产物 中芳烃收率分别为 70.12重量％和 72.87重量％，芳烃产物中对二甲苯含量分别为 84.47 重量％和 85.21重量％，对二甲苯在二甲苯异构体中选择性分别为 99.04重量％和 99.08 重量％。
表 3、 原料与产物分布
Figure imgf000011_0001
* C5 +: C5以上组分； C9 +: C9以上组分。

Claims

权利 要 求
1、一种用于甲醇和 /或二甲醚与 C4液化气相互转化制备对二甲苯的催化剂，所述 催化剂是采用双金属和硅氧烷基化合物联合改性制备的具有择形功能的芳构化分子 筛催化剂， 其中所述的双金属为锌和镓， 并且所述的硅氧烷基化合物由式 I所示： ,
Figure imgf000012_0001
(式 I)
其中， R 、 R2、 R3和 独立地选自 d-do烷基。
2、 根据权利要求 1所述的催化剂， 其中所述硅氧烷基化合物为硅酸四乙酯。
3、 根据权利要求 1所述的催化剂， 其中所述的具有择形功能的芳构化分子筛催 化剂中的分子筛选自由 HZSM-5分子筛和 HZSM-11分子筛组成的组中的一种或两种。
4、 根据权利要求 1所述的催化剂， 其中所述锌和镓的担载量分别为催化剂总质 量的 0.5-8重量％， 硅氧烷基化合物以氧化硅计的担载量为催化剂总重量的 0.5-10重 量0 /0。
5、 一种制备根据权利要求 1-4中任何一项所述的催化剂的方法，所述方法包括以 下步骤：
(1) 使用锌和镓中的一种的可溶性盐溶液浸渍分子筛， 过滤、 烘干并焙烧， 得到 一种金属改性的分子筛；
(2) 使用锌和镓中的另一种的可溶性盐溶液浸渍步骤 (1)得到的金属改性的分子 筛， 过滤、 烘干并焙烧， 得到双金属改性的分子筛； 和
(3) 使用硅氧烷基化合物浸渍上述双金属改性的分子筛， 过滤、 烘干并焙烧， 得 到双金属和硅氧烷基化合物联合改性的分子筛催化剂。
6、一种甲醇和 /或二甲醚与 C4液化气相互转化制备对二甲苯的方法，所述方法包 括以下步骤：
将含有甲醇和 /或二甲醚与 C4液化气的混合气通过装有根据权利要求 1-4中任何 一项所述的催化剂的反应器， 在反应温度 350-550°C、 反应压力为常压 -5MPa、 并且 原料进料重量空速为 O. l^Oh—1的条件下发生芳构化反应生成对二甲苯。 '、 根据权利要求 6所述的方法， 其中所述方法在固定床或流化床中进行。
PCT/CN2012/074709 2011-12-19 2012-04-26 甲醇和/或二甲醚与c4液化气相互转化制备对二甲苯的催化剂及其制备方法和应用 WO2013091337A1 (zh)

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JP2017518994A (ja) * 2014-06-04 2017-07-13 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ メタノール及び／又はジメチルエーテルからｐ−キシレン及びプロピレンを製造する方法
JP2017518995A (ja) * 2014-06-04 2017-07-13 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ 高選択率でｐ−キシレンを製造してプロピレンを併産する方法
CN112457149A (zh) * 2020-11-30 2021-03-09 陕西延长石油（集团）有限责任公司 一种油田伴生气芳构化一体化转化***及方法

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KR20140101812A (ko) 2014-08-20
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CN103157514A (zh) 2013-06-19
SG11201402787QA (en) 2014-09-26
US9968922B2 (en) 2018-05-15
AU2012357512A1 (en) 2014-06-19
JP2015504002A (ja) 2015-02-05
JP5873570B2 (ja) 2016-03-01
EP2803407A1 (en) 2014-11-19
CN103157514B (zh) 2015-02-04
EP2803407B1 (en) 2017-06-14
AU2012357512B2 (en) 2015-12-17
EP2803407A4 (en) 2015-10-21
MY168285A (en) 2018-10-22
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