WO2019088703A2 - Procédé de production sélective d'éthylène - Google Patents

Procédé de production sélective d'éthylène Download PDF

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WO2019088703A2
WO2019088703A2 PCT/KR2018/013117 KR2018013117W WO2019088703A2 WO 2019088703 A2 WO2019088703 A2 WO 2019088703A2 KR 2018013117 W KR2018013117 W KR 2018013117W WO 2019088703 A2 WO2019088703 A2 WO 2019088703A2
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catalyst
propylene
ethylene
acid
zsm
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Korean (ko)
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WO2019088703A3 (fr
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전종원
김태완
김철웅
김주완
최원춘
강나영
박용기
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한국화학연구원
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/08—Propane
    • 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 process for selectively producing ethylene, and more particularly to a process for preparing ethylene with high selectivity from propylene under ZSM-5 catalysts treated with an acid and having a specific acidity.
  • ethylene more than 50% of ethylene is used in the production of polyethylene and ethylene copolymers in the world.
  • ethylene there are various types of ethylene, hydrogenation, hydrogenation, alkylation, hydration, oligomerization, Chemical reactions are very important for the chemical industry and are supplied as various raw materials.
  • C4 olefins, BTX aromatic oils and other fuels can be obtained as light olefins, ethylene and propylene by-products, , And a yield of about 16% of propylene.
  • the amount of ethylene produced in the petroleum-derived naphtha cracking process which is the most commonly used process for producing olefins, is about two times higher than the amount of propylene produced.
  • the type of hydrocarbon feedstock used and the process applied because of the different types of industries producing light products using light olefins, the price gap between ethylene and propylene will inevitably vary depending on local demand and supply, such as the US, Europe, China, and Asia.
  • Ethylene-to-propylene (ETP) processes have been extensively studied from ethylene due to the expectation that propylene prices and demand will be relatively high in comparison with ethylene in general in the olefin interconversion studies.
  • PTE propylene-to-ethylene
  • triolefin process using olefin metathesis reaction was developed and commercialized in the 1960s.
  • This metathesis reaction employs a heterogeneous catalyst in which tungsten oxide is supported on a silica carrier, and two moles of propylene are theoretically converted into one ethylene and two-butene, respectively.
  • the one-pass selectivity is less than 35.3% and the selectivity of ethylene is not high.
  • the propylene as the raw material and the metathesis reactors of butene, the main by-product, and the reactor for decomposing the various hydrocarbons produced must be constituted in series. Commercialization of ethylene production selectively from propylene through a metathesis path has been discontinued for reasons such as the above.
  • zeolites have been used as solid acid catalysts in many catalytic processes in the chemical industry due to their unique shape selectivity and controllable acid sites. In particular, these features have led to high efficiencies in oil refineries and petrochemical processes. For example, zeolite catalysts exhibit high catalytic activity and production selectivity in a series of catalytic reactions such as cracking, isomerization, aromatization, disproportionation, alkylation. Most of the zeolites as catalysts in ethylene production have been used in additional processes of the overall process to improve the yield of light olefins and ethylene is obtained through catalytic cracking of olefins and hydrocarbons as reaction intermediates. The selectivity of ethylene in this catalytic cracking was reported to be as low as 12 ⁇ 30%.
  • the process for producing selective ethylene according to the present invention comprises contacting propylene with a ZSM-5 catalyst treated with an acid having a weak acidity of not more than 0.145 mmol / g-catalyst and a strong acidity of not more than 0.410 mmol / g- .
  • a process for producing selective ethylene comprises the steps of: a) dehydrogenating a feedstock comprising propane under a chromium or platinum-based catalyst to obtain a propylene-containing mixture; And b) contacting the propylene-containing mixture obtained in the above step with an acid-treated ZSM-5 catalyst having a weak acidity of 0.145 mmol / g-catalyst and a strong acidity of 0.410 mmol / g-catalyst or less to convert propylene to ethylene ; ≪ / RTI >
  • a method for producing selective ethylene according to an embodiment of the present invention includes: a chromium-based or platinum-based catalyst; And an acid-treated ZSM-5 catalyst having a weak acidity of not more than 0.145 mmol / g-catalyst and a strong acidity of not more than 0.410 mmol / g-catalyst, wherein the feedstock comprising propane is added to the reactor containing the propane And contacting the feedstock with the chromium-based or platinum-based catalyst and the acid-treated ZSM-5 catalyst to produce ethylene.
  • the acid-treated ZSM-5 catalyst may be treated with a phosphoric acid compound to support 0.5 to 5% by weight of phosphorus.
  • the phosphoric acid compound is selected from phosphoric acid, ammonium monophosphate, ammonium dibasic phosphate, (C1-C10) alkylphosphoric acid and (C1- One or two or more.
  • the acid-treated ZSM-5 catalyst may be treated with one or two acids selected from hydrochloric acid, ammonium hexafluorosilicate, oxalic acid and ammonium fluoride have.
  • the acid-treated ZSM-5 catalyst may be treated with 0.005 to 0.5 mol of an acid.
  • the weak acidity may be 0.040 to 0.110 mmol / g-catalyst and the strong acidity may be 0.200 to 0.410 mmol / g-catalyst.
  • the acid-treated ZSM-5 catalyst may have a strong acidity / weak acidity of 1.0 to 8.0.
  • the acid-treated ZSM-5 catalyst may have a Si / Al 2 molar ratio of 23 to 280.
  • the treatment with the acid ZSM-5 catalyst and the contact of the propylene is 550 to a temperature of 600 °C, from 1 to 15KPa atmospheric pressure, of 0.1 to 10 hours -1
  • the step b) is performed at a temperature of 550 to 610 ° C, an atmospheric pressure of 0.01 to 1 MPa, a weight hourly space velocity of propylene of 0.1 to 10 hours -1 , Lt; / RTI > and an inert gas dilution ratio of from 0.001 to 0.125.
  • the step 550 to a temperature of 610 °C, 0.01 to 1 weight hourly space velocity and the pressure of 1MPa, in the range of 0.1 to 10 hours -1 of propane: 0.5 Lt; / RTI > and an inert gas dilution ratio of 1.5.
  • the chromium-based catalyst may be Cr 2 O 3 / Al 2 O 3
  • the platinum-based catalyst may be Pt-Sn / Al 2 O 3 .
  • the contacting can be carried out in a fixed-bed reactor or a fluidized-bed reactor.
  • the selective ethylene production method according to the present invention is very high in propylene conversion and ethylene selectivity using an acid-treated ZSM-5 catalyst treated with an acid.
  • the selective ethylene production method of the present invention significantly improves the selectivity of ethylene to be produced by reacting a catalyst with propylene under a specific controlled reaction condition of a ZSM-5 catalyst having a specific range of acidity and controlled, thereby increasing the conversion of propylene.
  • the selective ethylene production method according to the present invention can produce ethylene from propane by a series or cascade method, and use ethylene-treated ZSM-5 having a specific range of acidity as a catalyst to produce ethylene with excellent selectivity can do. Therefore, the process for producing selective ethylene from propane of the present invention is very economical because it can produce ethylene at a high price from low cost propane at high selectivity and yield.
  • Example 1 is a graph showing the yield of ethylene in Example 6 and Comparative Example 1 of the present invention.
  • Example 2 is a graph showing propylene conversion and ethylene selectivity of Example 6 and Comparative Example 1 of the present invention.
  • Example 3 is a graph showing the selectivity of ethylene according to the Si / Al2 molar ratio in Example 7 of the present invention.
  • Example 4 is a graph showing the conversion of propylene and the selectivity of ethylene according to the temperature of Example 8 of the present invention.
  • Example 5 is a graph showing the conversion of propylene and the selectivity of ethylene according to the partial pressure of Example 9 of the present invention.
  • FIG. 6 is a graph showing the conversion of propylene and the selectivity of ethylene in the presence of the acid-treated ZSM-5 prepared in Examples 2 to 5 of the present invention.
  • FIG. 7 is a schematic diagram of a reaction apparatus for producing selective ethylene from propane of the present invention.
  • Example 8 is a graph showing propane conversion and ethylene selectivity of Example 11 and Comparative Examples 2 to 3 of the present invention.
  • Example 9 is a graph showing propane conversion and ethylene selectivity according to the temperature of Example 12 of the present invention.
  • Example 10 is a graph showing propane conversion and ethylene selectivity according to the temperature of Example 13 and Example 14 of the present invention.
  • Example 11 is a graph showing propane conversion and ethylene selectivity according to the space velocity in Example 15 of the present invention.
  • Example 12 is a graph showing propylene conversion and ethylene selectivity according to the partial pressure of Example 16 of the present invention.
  • Example 13 is a graph showing the conversion of propylene and the selectivity of ethylene according to Example 13, Example 17, and Comparative Example 4 of the present invention.
  • the alkyl described in the present invention includes both straight chain or branched chain and means a hydrocarbon radical having 1 to 10 carbon atoms, preferably a hydrocarbon radical having 1 to 5 carbon atoms.
  • the present invention provides a process for preparing ethylene with high selectivity from propylene in the presence of ZSM-5 having acidity controlled by acid treatment.
  • propylene may be produced by dehydrogenation reaction of propane.
  • the present invention relates to a process for producing ethylene from propane in the presence of ZSM-5 in which acidity is controlled by treating with a dehydrogenation catalyst and an acid .
  • the production of ethylene from propane involves one aspect of the series described below and another aspect of the cascade.
  • the present invention can not necessarily be limited to the production of ethylene using a reaction product containing propylene produced by dehydrogenation reaction of propane.
  • the process for producing the selective ethylene from propylene of the present invention comprises:
  • the process for producing selective ethylene of the present invention is a process for producing ethylene selectively from propylene using a ZSM-5 catalyst controlled to have an acidity in a specific range by treatment with acid as an acid, ZSM-5 catalyst can be contacted with propylene to produce ethylene with high conversion and selectivity, and ethylene can be obtained with high selectivity from propylene, rather than the production of olefins obtained from various byproducts by thermal decomposition of olefins .
  • the process for producing selective ethylene from propylene according to the present invention is characterized in that the ZSM-5 catalyst is treated with a specific acid to selectively deal with the weak acid point by dealumination of the ZSM-5 catalyst to increase the conversion of propylene, Can be improved.
  • zeolite including ZSM-5 catalyst, has strong and strong electron-dense and low-density portions, but as the Si / Al 2 molar ratio is low, It is difficult to form strong acid sites, and the acidity is weak.
  • the inventors of the present invention have found that when ZSM-5 catalyst is treated with an acid to deal with the density of isolated Si-O-Al, and thus weak acidity selectively decreases, ethylene is produced from propylene with high conversion and selectivity And the invention was completed.
  • the selective ethylene production method of the present invention can produce ethylene with high yield and selectivity by selectively controlling the acidity and strong acidity by treating the ZSM-5 catalyst with an acid.
  • the process for producing the selective ethylene of the present invention is surprisingly improved in comparison with the process for producing propylene from an ethylene which is very economical because it can obtain ethylene with remarkably improved selectivity and simple process unlike the conventional process, Conversion rate and selectivity, and by this selective preparation of ethylene according to the present invention, supply imbalance of ethylene and propylene can be solved.
  • the acid-treated ZSM-5 catalyst can be described in two modes depending on the type of acid to be treated.
  • phosphorus is supported on ZSM-5, which is a specific zeolite catalyst, so that slight dealumination proceeds to weaken the strong acid point due to mutual attractive force between the zeolite framework and aluminum, so as to have controlled weak acidity and strong acidity , It is possible to greatly increase the selectivity of ethylene in a series or cascade process, particularly a cascade process, which will be described later, and is more suitable for a process using propane as a raw material gas.
  • These acids may be one or more selected from ammonium hexafluorosilicate (AHFS) and phosphate compounds.
  • the acid treated in the acid treated ZSM-5 catalyst is one or more selected from ammonium hexafluorosilicate (AHFS) and phosphoric acid compounds
  • AHFS ammonium hexafluorosilicate
  • the dealumination of the ZSM- 5 catalyst it is considered that the strong acid point of the ZSM-5 catalyst is adjusted to the intermediate acid point to increase the conversion to ethylene and the selectivity to ethylene.
  • the ZSM-5 catalyst treated with the phosphoric acid compound according to an embodiment of the present invention is improved in hydrothermal stability of the aluminum in the ZSM-5 catalytic structure by treating the ZSM-5 catalyst with the phosphoric acid compound, It is anticipated that some of the strong acid points will become acidic centers of the middle century, thereby increasing the selectivity and conversion of ethylene.
  • the position of phosphorus (P) differs slightly depending on the type of the phosphoric acid compound, but in general, the particle size of the phosphoric acid compound is relatively in comparison with the pore size of the crystalline zeolite Relatively large amounts of phosphorus (P) are present on the outer surface of the zeolite catalyst, since the degree of penetration of the phosphate compound into the pores of the crystalline zeolite is smaller than that on the outer surface of the zeolite.
  • the Brensted acid point which is the strong acid point of the ZSM-5 catalyst. It is considered that both the outer surface and the inner pore surface of the catalyst are present. If the reaction occurs at the active surface of the outer surface, 5 catalyst, and it is considered that this is a factor that lowers the selectivity of ethylene produced.
  • the ZSM-5 catalyst is treated with a phosphate compound to remove the external acid sites, which are external catalyst active sites, to cause the reaction only at the internal acid sites of the ZSM-5 catalyst, .
  • the external acid sites are appropriately deactivated and the reaction mainly occurs at the acid sites in the pores of the ZSM-5 catalyst, thereby increasing the selectivity of ethylene.
  • the phosphoric acid compound treatment on ZSM-5 in this respect is preferably phosphoric acid (H 3 PO 4), the first phosphoric acid ammonium salts ((NH 4) H 2 PO 4), the second phosphate salt ( (NH 4 ) 2 HPO 4 ), (C 1 -C 10) alkyl phosphites and (C 1 -C 10) alkyl phosphates, more preferably phosphoric acid (H 3 PO 4 ), a monobasic ammonium salt ((NH 4 ) H 2 PO 4 ) and a dibasic ammonium salt ((NH 4 ) 2 HPO 4 ).
  • the acid-treated ZSM-5 catalyst may be treated with a phosphoric acid compound to support 0.5 to 5% by weight, preferably 0.75 to 1.5% by weight of phosphorus.
  • Another aspect of the present invention is to provide a method of treating a ZSM-5 catalyst, which is a specific zeolite catalyst, with a specific acid to dealuminate the ZSM-5 catalyst to remove weak acid sites so that the ZSM-5 catalyst has controlled acidity and acidity
  • This catalyst is more advantageous for the step of reacting the propylene-containing raw material (g) with the catalyst (step b) of the series process to be described later).
  • the acid treated with such a ZSM-5 catalyst may be one or more selected from ammonium hexafluorosilicate, hydrochloric acid, oxalic acid and ammonium fluoride, specifically ammonium hexafluorosilicate, oxalic acid and ammonium fluoride.
  • a process for the selective production of ethylene from propane in accordance with an embodiment of the present invention is characterized in that the ZSM-5 catalyst is treated with a ZSM-5 catalyst when treated with one or more selected acids selected from ammonium hexafluorosilicate, hydrochloric acid, oxalic acid and ammonium fluoride It is possible to selectively remove weak acid sites by dealumination, thereby increasing the conversion of propylene and improving the selectivity of ethylene.
  • the zeolite including the ZSM-5 catalyst exhibits strong and strong electron-dense and low-density portions.
  • the Si / Al 2 molar ratio is low, the electron dense and the electron dense are close to each other It is difficult to form strong acid sites, and the acidity is weak.
  • the inventors of the present invention have found that by treating ZSM-5 with one or more acids selected from a phosphate compound, hydrochloric acid, ammonium hexafluorosilicate, oxalic acid and ammonium fluoride to control the acidity and weak acidity, It has been found that ethylene can be prepared from propylene.
  • the acid-treated ZSM-5 catalyst according to an embodiment of the present invention is prepared by treating 0.005 to 0.5 mol, preferably 0.05 to 0.25 mol of one or two acids selected from ammonium hexafluorosilicate, hydrochloric acid, oxalic acid and ammonium fluoride .
  • the acid may preferably be ammonium hexafluorosilicate in order to have a well-controlled acidity and to increase ethylene selectivity.
  • the acid treated ZSM-5 catalyst may be treated with 0.05 to 0.25 moles of ammonium hexafluorosilicate in order to have good propylene conversion and ethylene selectivity.
  • the acid treatment of ZSM-5 can be carried out by any of the conventional treatment method impregnation methods recognizable to those skilled in the art.
  • ion-exchange method, incipient wetness method, , Solution impregnation method and the like are all applicable.
  • the specific catalyst used in the preparation of the selective ethylene of the present invention is ZSM-5.
  • ZSM-5 Unlike ZSM-11, ZSM-22, HY, SSZ-13, SAPO-34, SAPO-11, mordenite and beta, which are common zeolite catalysts, ZSM-5 surprisingly shows propylene conversion and ethylene selectivity by acidity control. And particularly when the acidity is controlled by treatment with ammonium hexafluorosilicate or phosphoric acid compounds, the conversion and selectivity can be further improved.
  • the present invention can further include a step of obtaining propylene by contacting propane with a dehydrogenation catalyst (PDH process catalyst) (step of obtaining propylene), wherein the product of the step of obtaining propylene is reacted with acid-treated ZSM-5 To produce ethylene.
  • PDH process catalyst dehydrogenation catalyst
  • the process for producing ethylene according to an embodiment of the present invention includes a cascade process in which the step of obtaining propylene and the step of preparing ethylene are sequentially performed in a single reactor, or the production of propylene in the upstream reactor is performed using two independent reactors And a series process in which the reaction product of the upstream reactor is fed to the downstream reactor to produce ethylene in the downstream reactor.
  • one embodiment comprises a propylene-containing mixture obtained as a by-product of a PDH (Propane De-Hydrogenation) process as illustrated on the right hand side of FIG. 7 and reacting it with a propylene- (Ethylene) from ethylene.
  • PDH Process De-Hydrogenation
  • Ether propylene-
  • the PDH process and the PTE process can be performed in separate reactors.
  • a feedstock comprising propane is sequentially contacted with a PDH process catalyst and a PTE process catalyst in a reactor (a single reactor) comprising a PDH process catalyst and a PTE process catalyst as illustrated in the left side of Figure 7 Is a cascade process for the selective production of ethylene from propane.
  • a process for producing selective ethylene according to an embodiment of the present invention using propane as a starting material is a serise process
  • Another aspect of the method for producing selective ethylene according to one embodiment of the present invention using propane as a starting material is a cascade process
  • Chromium or platinum-based catalysts and feedstock comprising propane added to the reactor containing an acid-treated ZSM-5 catalyst having a weak acidity of 0.145 mmol / g-catalyst and a strong acidity of 0.410 mmol / Contacting the alumina chromium catalyst and the acid treated ZSM-5 catalyst to produce ethylene from propane.
  • a process for producing selective ethylene according to an embodiment of the present invention using propane as a starting material is a process for preparing a propylene-containing mixture produced in a PDH process for producing propylene from a conventional propane or a mixture prepared through a PDH process in one reactor It is possible to produce ethylene with surprisingly improved selectivity and yield with high propane conversion by conversion to ethylene by contacting with a particular catalyst having a range of acidity.
  • the method of preparing selective ethylene according to an embodiment of the present invention using propane as a starting material may be performed by combining a PTE process using an acid-treated ZSM-5 catalyst as described above before the PDH process, Including the PTE process described above prior to the process does not require additional new process equipment and is very economical.
  • the process for producing selective ethylene according to an embodiment of the present invention using propane as a starting material is a process for producing propylene from a low-cost natural gas (mostly propane) using a propylene produced by a PDH process, which is an on- Can solve the imbalance between demand and supply of local propylene and ethylene.
  • the Bronsted acidity and Lewis acidity of the present invention are measured by FT-IR analysis after adsorption of pyridine (after desorption of physically adsorbed pyridine at 150 DEG C after adsorption at 50 DEG C, and acidity measurement using the value of pyridine adsorbed at the acid site) .
  • the strong acidity and weak acidity of the present invention are values obtained by measuring ammonia adsorption at 25 ° C using an NH 3 -TPD equipment and measuring the temperature desorption (120 ° C. to 800 ° C.).
  • the acid-treated ZSM-5 catalyst may have a Si / Al 2 molar ratio of 23 to 280.
  • the Si / Al 2 molar ratio of the better acid treated ZSM-5 can range from 30 to 100, more preferably from 30 to 80.
  • the acidity of the acid-treated ZSM-5 catalyst is 0.040 to 0.110 mmol / g-catalyst and the acidity of acidity is 0.200 to 0.410 mmol / g-catalyst.
  • the acidity of the acid-treated ZSM-5 catalyst is 0.040 to 0.080 mmol / g-catalyst and the acidity of the acid is 0.200 to 0.410 mmol / g- More preferably, the weak acidity is from 0.040 to 0.070 mmol / g-catalyst and the strong acidity is from 0.200 to 0.410 mmol / g-catalyst.
  • the acidity of the acid-treated ZSM-5 catalyst is 0.040 to 0.110 mmol / g-catalyst and the acidity of the acid is 0.200 to 0.390 mmol / g- More preferably, the weak acidity is from 0.045 to 0.110 mmol / g-catalyst and the strong acidity is from 0.200 to 0.390 mmol / g-catalyst.
  • the process for preparing selective ethylene according to an embodiment of the present invention using propane as a starting material is a process catalyst for selectively producing ethylene from propylene of a mixture containing propylene prepared by a PDH process, Using ZSM-5 catalysts controlled to have acidity, ethylene can be produced with surprisingly improved conversion and selectivity.
  • the acid-treated ZSM-5 catalyst may have a ratio of strong acidity to weak acidity, that is, a ratio of strong acidity to weak acidity of 1.0 to 8.0.
  • the acid-treated ZSM-5 catalyst may have an overall acidity of 0.20 to 0.50 mmol / g-catalyst, advantageously 0.240 to 0.480 mmol / g-catalyst.
  • the acidity of the acid treated ZSM-5 catalyst is less than 0.200 mmol / g-catalyst
  • the Lewis acidity is less than 0.010 mmol / g-catalyst
  • the total acidity is from 0.20 to 0.50 mmol / g catalyst, advantageously a Bronsted acidity of from 0.100 to 0.160 mmol / g-catalyst and a Lewis acidity of from 0.05 to 0.008 mmol / g-catalyst
  • the overall acidity may be from 0.20 to 0.50 mmol / g-catalyst, advantageously from 0.240 to 0.480 mmol / g-catalyst.
  • the ZSM-5 catalyst according to an embodiment of the present invention may be H-ZSM-5, and ZSM-5 may be one selected from the group consisting of La, Zn, Ni, Fe, Ga, Cu, Pd, Al, Co, Cr, Au, Pt, Re, Ru, and Ir.
  • the process for preparing the selective ethylene from propylene of the present invention can be carried out in a fixed bed reactor or a fluidized bed reactor.
  • an inert gas (unreactive gas) used as a diluting gas may mean a gas phase of a Group 18 element as well as a gas not participating in the reaction.
  • the inert gas may be nitrogen, argon, helium or a mixed gas thereof; Steam (steam); And light hydrocarbons such as methane, ethane, and the like, and more specifically nitrogen, argon, helium, or a mixed gas thereof.
  • the dilution ratio suggested may mean a mixing ratio (dilution ratio) based on the volume ratio.
  • a control reaction for the production of optionally ethylene from propylene is 550 to 600 °C temperature, of from 1 to 10KPa pressure, 0.1 to 10 weight hourly space velocity of propylene in the time 1 and 1: 1 (1 to 30) dilution ratio (volume ratio) of propylene (1) and inert gas (1 to 30).
  • This reaction condition is more favorable when propylene is diluted with an inert gas and supplied as a raw material.
  • the conversion of propylene may be 60% or more, the selectivity of ethylene may be 50% or more, and the conversion of propylene may be 70% or more , And the selectivity of ethylene may be 60% or more.
  • the conversion of propylene into ethylene is limited to a specific value or higher and is a value obtained by the formula, and these formulas are described in the following examples.
  • the preparation process according to an embodiment of the present invention simultaneously satisfies ZSM-5, a specific catalyst having an acidity of such a controlled specific range, and a specific range of reaction conditions, thereby greatly improving the propylene conversion and ethylene selectivity.
  • the gas containing propylene is supplied together with other reaction by-products by the PDH process of propane,
  • the reaction conditions during the production of ethylene may differ from the reaction conditions described above.
  • step b) is carried out at a temperature of 550 to 610 ⁇ ⁇ , an atmospheric pressure of 1 to 1 MPa, a pressure of 0.1 to 10 the weight hourly space velocity of -1 hour propylene and 1: 0.001 to 0.125 propylene (1) and inert gas (0.001 to 0.125), can be carried out in a dilution ratio (volume ratio).
  • step b) thus controlled can produce ethylene with higher selectivity and conversion rates in combination with the PDH process of step a).
  • the dehydrogenation step (a) can be carried out at a reaction temperature of 500-610 DEG C with a weight hourly space velocity (WHSV) of 1 to 15 h < -1 > have.
  • WHSV weight hourly space velocity
  • a process for producing selective ethylene from propane in accordance with an embodiment of the present invention comprises:
  • the propylene-containing mixture obtained in the above step is treated with an acid-treated ZSM-5 catalyst having a weak acidity of not more than 0.145 mmol / g-catalyst and a strong acidity of not more than 0.410 mmol / g-catalyst and a temperature of 550 to 600 ° C, Under conditions of a weight hourly space velocity of propylene of from 0.1 to 10 hr -1 and a propylene dilution ratio (volume ratio) of from 1: 0.001 to 0.125 to convert propylene to ethylene.
  • the process for the production of the selective ethylene from propane in accordance with an embodiment of the present invention can be carried out continuously in each of the different reactors in series form a) and b).
  • the PDH process and the PTE process are performed in one reactor, and preferably 550 to 610 ° C Atmospheric pressure of 0.01 to 1 MPa, weight hourly space velocity of propane at 0.1 to 10 hours -1 and propane and inert gas dilution ratios (volume ratio) of 1: 0.50 to 1.50.
  • the process for producing selective ethylene according to an embodiment of the present invention using propane as a starting material may be a propane conversion rate of 60% or more, an ethylene selectivity of 25% or more, and a propane conversion rate of 65% or more , And the selectivity of ethylene may be 30% or more.
  • the process for selectively producing ethylene from propane has significantly improved conversion and selectivity compared to conventional processes, such as propane cracking and the like.
  • a chromium-based or platinum-based catalyst is usually used in a chromium-based catalyst or a PDH process used in a Lummus process But it may be Cr 2 O 3 / Al 2 O 3 or Pt-Sn / Al 2 O 3 in a preferred combination with an acid-treated ZSM-5 catalyst.
  • the pyridine adsorption experiment was performed in a high-temperature chamber with a diffuse reflectance equipped with a window (Spectra-Tech).
  • the chamber may be connected to a gas system to allow gas to flow through the chamber and to leave the chamber free of gas.
  • the sample was pulverized into fine powder and made into pellets and placed in a chamber for measurement.
  • the sample was first heated to 250 DEG C and held at 250 DEG C for at least 1 hour while passing inert gas through the chamber. After cooling to 50 < 0 > C, the pyridine inert gas mixture was passed through the chamber for about 5 minutes. Thereafter, the flow of the pyridine was stopped, while the flow of the inert gas was continued, and the amount of pyridine passed through the chamber for 5 minutes was measured. After that, the flow of inert gas was heated to 150 DEG C over about 12 hours, , And the amount of chemically desorbed pyridine was measured.
  • the pyridine absorbed at 50 ⁇ ⁇ by the amount of pyridine absorbed in the Bronsted acid and Lewis acid sites was measured by using the pyrimidinium-band and the pyridine-Lewis acid band corresponding to the known extinction coefficient, Using the difference.
  • the analytical techniques used to measure the acidity and weak acidity of the catalysts were determined from NH 3 -TPD (temperature-programmed desorption) and acid intensity distributions by ammonia desorption desorption.
  • a sample was prepared as in the above-mentioned Bronsted acidity and Lewis acidity measurement, and the sample was pre-treated by heating at 500 ° C. for 60 minutes. After ammonia adsorption for 30 minutes at 100 ° C., / min and ammonia desorbed was measured using a TCD detector (thermal conductivity detector).
  • TCD detector thermo conductivity detector
  • 0.1M oxalic acid 1 g
  • the prepared sample was heated at 60 ° C. for 5 hours at 550 ° C. to prepare a ZSM-5 catalyst treated with 0.1 M oxalic acid.
  • a ZSM-5 catalyst treated with 0.1 M ammonium fluoride was prepared in the same manner as in Example 2, except that ammonium fluoride was used instead of oxalic acid in Example 2, and the mixture was stirred for 72 hours at a final temperature of 500 ° C for 10 hours.
  • Example 2 hydrochloric acid instead of oxalic acid was used to conduct a reflux reaction at 85 ° C for 4 hours, followed by washing with distilled water and firing at 400 ° C for 6 hours. The procedure of Example 2 was repeated to prepare a ZSM- 5 catalyst.
  • ammonium hexafluorosilicate 0.05, 0.25 0.5M treated ZSM-5 catalyst was prepared with different moles of ammonium hexafluorosilicate at 0.05, 0.25, or 0.5M instead of ammonium hexafluorosilicate 0.1M .
  • Example 5 of the present invention 0.5 g of the ZSM-5 catalyst prepared in Example 5 of the present invention and 0.5 g of the ZSM-5 catalyst (Comparative Example 1) not treated with ammonium hexafluorosilicate were charged in a 0.5-inch fixed bed reactor, (WHSV) of 1.09 h -1 , a partial pressure of propylene of 0.0065 MPa, and a total flow rate (propylene + nitrogen) of 70.6 ml / min, at 550 ° C. and a reaction temperature of 0.1 MPa Ethylene was prepared, and the yield of ethylene was shown in FIG. 1, and the conversion of propylene and the selectivity of ethylene were shown in FIG.
  • WHSV 0.5-inch fixed bed reactor
  • the ZSM-5 catalyst of the present invention is superior to Comparative Example 1 (which is the leftmost bar graph in the graph of FIG. 1) in which ammonium hexafluorosilicate is not treated, And that the yield of ethylene is high at the same time.
  • a ZSM-5 catalyst treated with 0.1 M ammonium hexafluorosilicate (AHFS) as in Example 5 was used as a catalyst in Example 6 using ZSM-5 having a different Si / Al 2 molar ratio as shown in Table 2 below. The results are shown in Table 2 and FIG. 3, respectively.
  • 30, 50, 80, and 280 in the x-axis are Si / Al 2 molar ratios, fresh is the ZSM-5 catalyst not treated with AHFS, 0.1 M is treated with 0.1 M ammonium hexafluorosilicate (AHFS) Means one ZSM-5 catalyst.
  • Ethylene was prepared from propylene using ZSM-5 treated with AHFS in the same manner as in Example 6 except that the temperature was changed to 400 ° C., 450 ° C., 500 ° C., 550 ° C., 600 ° C. or 650 ° C. in Example 6 The results are shown in Fig.
  • ethylene was produced from propylene in the same manner as in Example 6 except that the partial pressure of propylene was changed as shown in Fig. 5. The results are shown in Fig.
  • the conversion of propylene and the selectivity of ethylene differ markedly according to the dilution ratio of propylene and nitrogen.
  • the dilution ratio of propylene and nitrogen is 1: 1 to 1: 30, The selectivity can be seen.
  • the nitrogen input amount is in the range of 10 to 150 ml / min, that is, the dilution ratio of propylene and nitrogen is 1: 1 to 30, preferably 1: : 4 to 16.5 shows better conversion and selectivity.
  • Example 3 (NH 4 F in FIG. 6) or Example 4 (HCl in FIG. 6) instead of the catalyst prepared in Example 5 (AHSF in FIG. 6)
  • Ethylene was prepared in the same manner as in Example 6 except that the ZSM-5 catalyst prepared in Example 1 was used. The results are shown in FIG.
  • ethylene can be selectively prepared from propylene under an acid-treated ZSM-5 catalyst treated with an acid. Further, among various acids, ZSM-5 treated with ammonium hexafluorosilicate Ethylene can be produced with the highest selectivity and yield under the catalyst.
  • the PDH catalyst, Cr 2 O 3 / Al 2 O 3, was prepared according to the method of Applied Catalysis A: General 233 (2002) 21-33 and used in the present invention.
  • FIG. 7 is a schematic diagram of a reaction apparatus for producing selective ethylene from propane.
  • a stainless steel reactor having a quartz reactor pretreated for 3 hours at 550 ° C with nitrogen gas (50 ml / min) as shown in FIG. 7 (left) was charged with Cr 2 O 3 / Al 2 O 3 (Rigas (purity 99.99%), 5.04 ml / min) as a reactant was injected into the reactor to fill the catalyst bed in the reactor with 0.5 g of the catalyst (PDH catalyst) and 0.5 g of the catalyst of Example 1 To allow the reaction to proceed.
  • PDH catalyst 0.5 g of the catalyst
  • Example 1 To allow the reaction to proceed.
  • Cov. C3- denote conversion of C 3-;
  • Wt C3 to represent the weight of Propane at the initial time;
  • Wt C 3 - is the weight of C 3 - at the desired reaction time;
  • Example 11 The procedure of Example 11 was repeated except that the PTE catalyst was not used in Example 11 to proceed the dehydrogenation process. The results are shown in FIG.
  • Example 11 was prepared in the same manner as in Example 11 except that only the catalyst of Example 1 was filled and the PTE process was performed without using Cr 2 O 3 / Al 2 O 3 as the PDH catalyst in Example 11, Respectively.
  • Example 12 Production of ethylene from propane under phosphorus-supported ZSM-5 catalyst according to temperature in Example 11
  • Example 11 the reaction was carried out in the same manner as in Example 11 except that the reaction temperature was changed to 500 ° C., 580 ° C., and 610 ° C. Ethylene was produced from propane and the results are shown in FIG.
  • the model feeds from the PDH back-end gas were prepared with the compositions shown in Table 3 below, and 0.5 g of the catalyst of Example 1 was filled in a fixed-bed reactor equipped with a quartz reactor using a quartz reactor as shown in FIG. 7 And the propylene gas was passed through the catalyst layer in the reactor so that the reaction proceeded. 0.1 MPa pressure, the nitrogen feed rate was 5.04 ml / min, the weight hourly space velocity (WHSV) of the reactant was maintained at 1.2 h -1 , and the reaction temperature was 550 ° C. The results are shown in FIG.
  • Example 14 Production of ethylene from propane under phosphorus-supported ZSM-5 catalyst according to temperature in Example 13
  • Example 13 The same procedure as in Example 13 was conducted except that the reaction temperature was changed to 500 ° C, 580 ° C, or 610 ° C in Example 13, and ethylene was prepared from propane. The results are shown in FIG.
  • Example 15 In Example 13, preparation of ethylene from propane under phosphorus-supported ZSM-5 catalyst according to space velocity
  • Example 13 the reaction temperature was 550 DEG C and the weight hourly space velocity (WHSV) of the reaction product was 1.2, 5, 8.5, 12, and 15 h- 1 .
  • Ethylene was produced from propane, and the results are shown in FIG.
  • Example 16 Production of ethylene from propane under phosphorus-supported ZSM-5 catalyst according to partial pressure in Example 13
  • Ethylene was produced from propane in the same manner as in Example 13 except that the reaction temperature in Example 13 was 550 ° C and the partial pressure was changed (0.0077 to 0.0500 MPa) as shown in FIG. 12, Respectively.
  • the nitrogen input amount is in the range of 1 to 10 ml / min, that is, the dilution ratio of nitrogen and propylene is 1: 0.001 to 0.125, preferably 1: 0.025 to 0.10, It can be seen that a better conversion and selectivity are exhibited at 0.025 to 0.075.
  • Example 13 was prepared in the same manner as in Example 13 except that the catalyst prepared in Example 5 was used in place of the catalyst prepared in Example 1, and the results are shown in FIG.
  • Example 13 was prepared in the same manner as in Example 13, except that the H-ZSM-5 catalyst (the catalyst of Comparative Example 1) which was not subjected to the acid treatment was used instead of the catalyst prepared in Example 1. The results are shown in FIG. .

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Abstract

Un procédé de production selon la présente invention est un procédé de production sélective d'éthylène à partir de propylène. Plus spécifiquement, l'éthylène est produit à partir de propylène au moyen d'un procédé contrôlé et d'un catalyseur ZSM-5, qui est traité avec un acide et présente ainsi une acidité contrôlée. De plus, le taux de conversion du propylène et la sélectivité pour l'éthylène du procédé de production sont extrêmement élevés.
PCT/KR2018/013117 2017-11-01 2018-10-31 Procédé de production sélective d'éthylène WO2019088703A2 (fr)

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KR10-2017-0144800 2017-11-01
KR1020170144800A KR102049352B1 (ko) 2017-11-01 2017-11-01 산 처리된 zsm-5를 통한 프로필렌으로부터 선택적 에틸렌의 제조방법
KR10-2018-0055768 2018-05-16
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US5026935A (en) * 1989-10-02 1991-06-25 Arco Chemical Technology, Inc. Enhanced production of ethylene from higher hydrocarbons
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KR101279691B1 (ko) * 2011-11-29 2013-06-28 롯데케미칼 주식회사 미세 및 중형기공성 ｚｓｍ-5 촉매, 이의 제조방법 및 그 촉매를 이용한 탄화수소 혼합물의 촉매 접촉분해를 통한 경질 올레핀 제조방법

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