WO2019183842A1 - Catalyseur composite, son procédé de préparation et procédé de préparation d'éthylène - Google Patents

Catalyseur composite, son procédé de préparation et procédé de préparation d'éthylène Download PDF

Info

Publication number
WO2019183842A1
WO2019183842A1 PCT/CN2018/080924 CN2018080924W WO2019183842A1 WO 2019183842 A1 WO2019183842 A1 WO 2019183842A1 CN 2018080924 W CN2018080924 W CN 2018080924W WO 2019183842 A1 WO2019183842 A1 WO 2019183842A1
Authority
WO
WIPO (PCT)
Prior art keywords
molecular sieve
composite catalyst
gas
zirconium
catalyst according
Prior art date
Application number
PCT/CN2018/080924
Other languages
English (en)
Chinese (zh)
Inventor
刘世平
朱文良
刘中民
倪友明
刘红超
刘勇
马现刚
Original Assignee
中国科学院大连化学物理研究所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国科学院大连化学物理研究所 filed Critical 中国科学院大连化学物理研究所
Priority to RU2020135262A priority Critical patent/RU2767667C1/ru
Priority to PCT/CN2018/080924 priority patent/WO2019183842A1/fr
Publication of WO2019183842A1 publication Critical patent/WO2019183842A1/fr
Priority to ZA2020/06131A priority patent/ZA202006131B/en

Links

Classifications

    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • 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 application relates to a composite catalyst, a preparation method thereof and a preparation method of ethylene, and belongs to the field of synthesis gas to produce low carbon olefins.
  • Ethylene is the world's largest production and consumption of basic chemical products. With the development of China's economy, domestic ethylene demand will continue to increase, but the existing production capacity is far from meeting demand. At present, ethylene is mainly obtained by cracking naphtha, and China's resource endowment is “rich coal, lean oil, and less gas”, which seriously restricts the development of downstream industries and poses a serious threat to national energy security. Therefore, the development of a method based on non-petroleum resources such as coal to produce ethylene has certain practical significance.
  • the mature method for producing ethylene from syngas is an indirect method.
  • the syngas is first converted to methanol, and the methanol is subjected to an MTO process to produce a mixed low olefin (C2-C4 olefin).
  • C2-C4 olefin mixed low olefin
  • the path has entered industrialization in China and has achieved great success.
  • the direct synthesis of ethylene from syngas has the advantages of simple process and less equipment.
  • Syngas can be directly produced from olefins by a classical Fischer-Tropsch process in which the catalyst is a supported metal catalyst.
  • the maximum selectivity of the C2-C4 hydrocarbons is not more than 58%, and the maximum selectivity of the gasoline fraction C5-C11 is 45%, while a large amount of methane and high-carbon alkanes are formed. Therefore, how to selectively produce low-carbon olefins has always been a core problem that is difficult to overcome in this field. After years of continuous exploration and improvement by researchers at home and abroad, great progress has been made in this field, but the highest selectivity for low-carbon olefins is still no more than 61% (H.M.Torres Galvis et al., Science 2012, 335, 835-838).
  • a composite catalyst which is applied to the synthesis of ethylene in one step and high selectivity for syngas, and breaks the distribution of hydrocarbon Anderson-Schulz-Flory (ASF) in Fischer-Tropsch (FT) synthesis. Regularity, in which the selectivity of ethylene reaches 86%.
  • ASF Anderson-Schulz-Flory
  • FT Fischer-Tropsch
  • the composite catalyst is characterized in that it comprises a zirconium-based oxide and a modified acidic molecular sieve; the composition thereof comprises, by mass percentage, the mass content of the zirconium-based oxide is 10 wt.% to 90 wt.%, and the quality of the modified acidic molecular sieve The content is 10wt.% to 90wt.%;
  • the modified acidic molecular sieve is an acidic molecular sieve treated by a pre-adsorbed alkali.
  • the upper limit of the mass content of the zirconium-based oxide is selected from the group consisting of 11 wt.%, 20 wt.%, 30 wt.%, 33.3 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 66.7 wt.%, 70 wt.%, 80 wt.% or 90 wt.%; lower limit selected from 10 wt.%, 20 wt.%, 30 wt.%, 33.3 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 66.7 wt.%, 70 wt. .%, 80 wt.% or 89 wt.%.
  • the upper limit of the mass content of the modified acidic molecular sieve is selected from the group consisting of 11 wt.%, 20 wt.%, 30 wt.%, 33.3 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 66.7 wt.%, 70 wt.%, 80 wt.% or 90 wt.%; lower limit selected from 10 wt.%, 20 wt.%, 30 wt.%, 33.3 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 66.7 wt.%, 70 wt. .%, 80 wt.% or 89 wt.%.
  • the step of pre-adsorbing alkali treatment comprises at least contacting the acidic molecular sieve with a gas containing an organic base for pre-adsorption alkali treatment.
  • the upper temperature limit of the pre-adsorption alkali treatment is selected from 160 ° C, 200 ° C, 250 ° C, 300 ° C or 350 ° C; the lower limit is selected from 150 ° C, 200 ° C, 250 ° C, 300 ° C or 340 ° C.
  • the upper time limit of the pre-adsorption base treatment is selected from 0.6 h, 1 h, 2 h, 3 h or 4 h; the lower limit is selected from 0.5 h, 1 h, 2 h, 3 h or 3.9 h.
  • the pre-adsorption alkali treatment has a temperature of 150 to 350 ° C, and the pre-adsorption alkali treatment has a time of 0.5 to 4 h.
  • the upper limit of the mass space velocity of the organic base-containing gas is selected from the group consisting of 400 mL ⁇ g -1 ⁇ h -1 , 500 mL ⁇ g -1 ⁇ h -1 , 1000 mL ⁇ g -1 ⁇ h -1 , 2000 mL ⁇ g -1 ⁇ h -1 , 3000mL ⁇ g -1 ⁇ h -1 , 4000mL ⁇ g -1 ⁇ h -1 , 5000mL ⁇ g -1 ⁇ h -1 or 6000mL ⁇ g -1 ⁇ h -1 ; From 300 mL ⁇ g -1 ⁇ h -1 , 500 mL ⁇ g -1 ⁇ h -1 , 1000 mL ⁇ g -1 ⁇ h -1 , 2000 mL ⁇ g -1 ⁇ h -1 , 3000 mL ⁇ g -1 ⁇ h -1 4000 mL ⁇ g -1 ⁇ h -1 , 4900 mL ⁇ g -1 ⁇ h -1 or 5000
  • the organic base-containing gas includes a carrier gas and an organic base.
  • the organic base is selected from the group consisting of trimethylamine, diethylamine, triethylamine, pyridine, pyridazine, pyrimidine, pyrazine, pyridine, imidazole, N-methylimidazole, N-ethylimidazole, N-propyl At least one of a group of imidazoles and N-isopropylimidazole.
  • the carrier gas is at least one selected from the group consisting of nitrogen, helium, CO 2 , argon, and hydrogen.
  • the upper limit of the volume fraction of the organic base in the organic base-containing gas is selected from the group consisting of 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%; the lower limit is selected from 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 9.9%.
  • the volume fraction of the organic base in the organic base-containing gas is from 0.1% to 10%.
  • the step of pre-adsorbing alkali treatment comprises at least: activating the acidic molecular sieve in an inert gas atmosphere, then adjusting the temperature to a pre-adsorption alkali treatment temperature, and contacting the gas containing the organic base to pre-adsorb the alkali. After the treatment, the adsorption is saturated, and the mixture is purged to room temperature to obtain a modified acidic molecular sieve.
  • the upper temperature limit of activation is selected from 320 ° C, 350 ° C, 400 ° C, 450 ° C or 480 ° C; the lower limit is selected from 300 ° C, 350 ° C, 400 ° C, 450 ° C or 500 ° C.
  • the upper limit of the time of activation is selected from 3.2 h, 3.5 h, 4 h, 4.5 h or 5 h; the lower limit is selected from 3 h, 3.5 h, 4 h, 4.5 h or 4.8 h.
  • the activation temperature is 300 to 500 ° C, and the activation time is 3 to 5 hours.
  • the step of performing the pre-adsorption alkali treatment on the acidic molecular sieve comprises at least: the acidic molecular sieve needs to be subjected to pre-adsorption organic alkali treatment for a certain time by carrying the organic base at a certain space velocity and temperature;
  • the volume fraction of the organic base in the mixed gas is 0.1% to 10%
  • the carrier gas may be any one of nitrogen, helium, CO 2 , argon, hydrogen, or a mixture of any of them, pretreatment
  • the gas mass space velocity ranges from 300 to 5000 mL ⁇ g -1 ⁇ h -1 ;
  • the organic base is trimethylamine, diethylamine, triethylamine, pyridazine, pyrimidine, pyrazine, pyridine, imidazole, N-methyl a mixture of any one or a combination of imidazole, N-ethylimidazole, N-propylimidazole, N-isopropylim
  • the acidic molecule is screened from a molecular sieve having a MOR topology, a molecular sieve having a FER topology, a eutectic molecular sieve containing a MOR topology and a FER topology, a mixed crystal molecular sieve containing a MOR topology and a FER topology. At least one.
  • the molecular sieve having the MOR topology is an H-MOR molecular sieve having a skeleton atom Si/Al ratio of 4 to 60.
  • the molecular sieve having the FER topology is an H-ZSM-35 molecular sieve having a skeleton atom Si/Al ratio of 5 to 50.
  • the acidic molecular sieve is at least one of a eutectic molecular sieve of H-MOR, H-ZSM-35, hydrogen type MOR and ZSM-35, and a mixed crystal molecular sieve of hydrogen type MOR and ZSM-35.
  • the zirconium-based oxide is selected from at least one of the compounds having the formula of formula (I):
  • X in the formula (I) is an oxide of at least one of Si, Al, Ti, Ce, and La; and M is at least one of Cu, Ag, Zn, Mn, Y, Nb, Ga, In, and Cr. Oxide of the element;
  • a 0.02 to 0.9
  • b 0.0 to 0.8
  • the a, b are the molar proportions of the corresponding oxides in the total composition.
  • the zirconium-based oxide is at least one of zirconium-based metal oxides.
  • the upper limit of a is selected from 0.1, 0.4, 0.5, 0.6, 0.8 or 0.9; the lower limit is selected from 0.02, 0.1, 0.4, 0.5, 0.6, or 0.8.
  • a is a value between 0.1 and 0.9.
  • the upper limit of b is selected from 0.02, 0.05, 0.1, 0.4, 0.5 or 0.8; the lower limit is selected from 0, 0.02, 0.05, 0.1, 0.4 or 0.5.
  • b is a value between 0.1 and 0.8.
  • the method for obtaining the zirconium-based oxide in the step (1) comprises: preparing by at least one of a coprecipitation method, a dipping method, and a mechanical mixing method.
  • the coprecipitation method includes at least the steps of: mixing a solution containing an element X element, an M' element, and a Zr element with a solution containing a precipitant in a cocurrent manner under stirring to control the pH of the system.
  • the value is 7 to 9, and after aging, the solid phase is separated, washed, dried and calcined to obtain the zirconium-based oxide.
  • the dipping method includes at least the steps of immersing the zirconia powder in a salt solution containing the X element and the M' element or immersing the zirconia powder and the oxide of X in a salt containing the M' element.
  • the zirconia powder and the oxide of M' are immersed in the salt solution containing the X element in the solution; after the immersion, the solvent is removed, dried, and calcined to obtain the zirconium-based oxide.
  • M' is at least one selected from the group consisting of Cu, Ag, Zn, Mn, Y, Nb, Ga, In, and Cr.
  • the aging time of the stirring in the coprecipitation method is 2 to 4 hours; and the baking condition is 400 to 600 ° C for 1 to 6 hours.
  • the agitation in the coprecipitation method is vigorous stirring.
  • the speed of stirring in the coprecipitation method is from 250 to 5000 rpm/min.
  • the immersion time in the dipping method is 1 to 6 hours; the drying condition is 60 to 200 ° C for 1 to 10 hours; and the firing condition is 400 to 600 ° C for 1 to 6 hours.
  • the X element, the M' element and the Zr element in the solution are independently derived from at least one of a nitrate, a hydrochloride, an acetate, an acetylacetonate, and a sulfate of the X element, the M element, and the Zr element.
  • a nitrate a hydrochloride, an acetate, an acetylacetonate, and a sulfate of the X element, the M element, and the Zr element.
  • the precipitating agent is an alkali solution.
  • the alkali liquid is at least one selected from the group consisting of ammonia water, ammonium carbonate, sodium carbonate, urea, NaOH, and KOH.
  • the coprecipitation method includes the steps of: formulating at least one of the compound containing the X element, at least one of the compounds containing the M' element, and the Zr salt into an aqueous solution, which is referred to as a solution.
  • solution A one or any of ammonia, ammonium carbonate, sodium carbonate, urea, NaOH or KOH is formulated into aqueous solution B; under intense stirring, solution A and solution B are mixed in a cocurrent manner to adjust solution A and The flow rate of the solution B is controlled to be in the range of 7 to 9 in the mixed liquid; after the completion of the precipitation, the mixture is aged for 2 to 4 hours, filtered, washed, and dried; then calcined at a temperature ranging from 400 to 600 ° C for 1 to 6 hours.
  • the impregnation method comprises the steps of: adding at least one of a compound containing an X element and a compound containing an M' element to a deionized water or an alcohol solution, Into solution C, the zirconia powder is immersed in the solution C, after immersion for 1 to 6 hours, the solvent is slowly evaporated to dryness, and then dried in an oven at 60 to 200 ° C for 1 to 10 hours; the dried powder is 400.
  • the temperature range of -600 ° C is calcined for 1 to 6 hours.
  • the ultrasonic assisted chemical compounding method in the step (3) comprises at least: ultrasonically separating a solution containing a zirconium-based oxide and a modified acidic molecular sieve, solid-liquid separation, drying and calcining the solid phase to obtain the composite catalyst. ;
  • the physical compounding method at least comprises: compounding a mixture containing a zirconium-based oxide and a modified acidic molecular sieve by at least one of mechanical mixing, ball milling, and shaking to obtain the composite catalyst.
  • the ultrasonic assisted chemical compounding method has an ultrasonic time of 10 min to 3 h; a drying temperature of 60 to 150 ° C; and a calcination temperature of 300 to 650 ° C.
  • the ultrasonic assisted chemical compounding method disperses the zirconium-based oxide and the modified acidic molecular sieve powder in water or an alcohol solution, and ultrasonically mixes for 10 min to 3 h, and the two are sufficiently mixed;
  • the composite catalyst is obtained by filtration, drying and calcination; the drying temperature ranges from 60 to 150 ° C, and the calcination temperature ranges from 300 to 650 ° C.
  • the physical compounding method refers to compounding a zirconium-based oxide with a modified acidic molecular sieve catalyst by a mixing method such as mechanical mixing, ball milling, and shaking mixing.
  • the preparation method of the composite catalyst includes at least the following steps:
  • the composite catalyst and/or the composite catalyst prepared according to the method is used for one-step synthesis of ethylene by synthesis gas.
  • a method for preparing ethylene comprising at least the following steps:
  • the raw material gas containing the synthesis gas is passed through a reactor equipped with a composite catalyst to obtain ethylene;
  • the composite catalyst is selected from at least one of the composite catalyst and/or the composite catalyst prepared according to the method;
  • the syngas comprises CO, H 2 , CO 2 , and the molar ratio satisfies:
  • the upper temperature limit of the reaction is selected from 280 ° C, 300 ° C, 320 ° C, 350 ° C or 380 ° C; the lower limit is selected from 250 ° C, 280 ° C, 300 ° C, 320 ° C or 350 ° C.
  • the upper limit of the reaction pressure is selected from 2.0 MPa, 2.5 MPa, 3.0 MPa, 5.0 MPa, 6.0 MPa, or 8.0 MPa; and the lower limit is selected from 1.0 MPa, 2.0 MPa, 2.5 MPa, 3.0 MPa, 5.0 MPa, or 6.0 MPa.
  • the upper limit of the mass space velocity of the raw material gas is selected from the group consisting of 400 mL ⁇ g -1 ⁇ h -1 , 500 mL ⁇ g -1 ⁇ h -1 , 1000 mL ⁇ g -1 ⁇ h -1 , 4000 mL ⁇ g -1 ⁇ h -1 , 8000mL ⁇ g -1 ⁇ h -1 or 10000mL ⁇ g -1 ⁇ h -1 ; lower limit is selected from 300mL ⁇ g -1 ⁇ h -1 , 400mL ⁇ g -1 ⁇ h -1 , 500mL ⁇ g -1 ⁇ h -1 , 1000 mL ⁇ g -1 ⁇ h -1 , 4000 mL ⁇ g -1 ⁇ h -1 or 8000 mL ⁇ g -1 ⁇ h -1 .
  • the reaction temperature is 250 to 380 ° C
  • the pressure is 1.0 to 8.0 MPa
  • the gas mass space velocity is 300 to 10000 mL ⁇ g -1 ⁇ h -1 .
  • the preparation method of the ethylene is that the synthesis gas is ethylene in one step and the selectivity is 86%.
  • the feed gas further includes an inert gas.
  • the inert gas is selected from at least one of nitrogen, argon, helium, and methane.
  • the volume content of the inert gas in the mixed gas is ⁇ 10%.
  • the upper limit of the volume content of the inert gas in the mixed gas is selected from 1%, 3%, 5%, 8% or 10%; and the lower limit is selected from 0%, 1%, 3%, 5% or 8 %.
  • the inert gas has a volume content of 0% to 10% in the mixed gas.
  • the upper limit of the molar ratio of CO and H 2 is selected from 1/0.3, 1/0.5, 1/1, 1/3 or 1/4; the lower limit is selected from 1/0.2, 1/0.3, 1/0.5 , 1/1 or 1/3.
  • the reactor is at least one of a fixed bed reactor, a fluidized bed reactor, and a moving bed reactor.
  • the composite catalyst is used for a method for synthesizing ethylene into one step, and at least comprises the steps of: passing a raw material gas containing synthesis gas through a reactor equipped with a composite catalyst, under a certain reaction condition, one step.
  • the volume content in the gas is less than 10%;
  • the reaction pressure is preferably 1.0 to 8.0 MPa, and the gas velocity is preferably 300 to 10000 mL ⁇ g -1 ⁇ h -1 .
  • the synthesis gas in the present application produces ethylene in a one-step process to give an ethylene selectivity of greater than 40%.
  • H-MOR molecular sieve means a hydrogen type mordenite molecular sieve which can be produced by hydrogenating a molecular sieve by a conventional production method in the art.
  • H-ZSM-35 molecular sieve means a hydrogen type ZSM-35 molecular sieve which can be produced by hydrogenating a molecular sieve by a conventional preparation method in the art.
  • a methanol synthesis catalyst is combined with a carbonylation catalyst, which has outstanding characteristics such as high ethylene selectivity (up to 86%), and low generation of methane and high carbon hydrocarbons.
  • the one-step preparation of ethylene in the synthesis gas provided in the present application has the advantages of mild reaction conditions, simple process, and the like, and has the potential of large-scale industrialization.
  • the elemental analysis of the sample XRF was performed by a Magix (PHILIPS) type X-ray fluorescence analyzer, and the fluorescence intensity of the standard sample was correlated with its standard composition by an IQ + non-standard quantitative analysis program, and the influence of the interference line was subtracted.
  • PHILIPS Magix type X-ray fluorescence analyzer
  • the composition of the zirconium-based oxide was (ZnO) 0.4 (CeO 2 ) 0.1 (ZrO 2 ) 0.5 by XRF elemental analysis.
  • the H-MOR was pre-adsorbed with pyridine in a manner of carrying pyridine with nitrogen (the volume fraction of pyridine in the mixed gas was 1%, and the mass space velocity of the mixed gas was 6000 mL ⁇ g -1 ⁇ h -1 ). After pyridine was adsorbed for 2 h, it was purged with nitrogen for 4 h and then cooled to room temperature.
  • the treated H-MOR molecular sieve was taken out to obtain an acidic molecular sieve treated with a pre-adsorbed alkali.
  • the zirconium-based metal oxide powder (3.0 g) obtained above and the H-MOR molecular sieve (1.5 g) pre-adsorbed with pyridine were sufficiently ground and mixed by a ball mill.
  • the mixed powder was tableted, crushed, and sieved to obtain a particulate catalyst of 20 to 40 mesh, and the catalyst was designated as ##.
  • the content of the zirconium-based metal oxide in the 1# composite catalyst was 66.7 wt.%, and the molecular sieve mass content was 33.3 wt.%.
  • reaction product was analyzed online by gas chromatography, and the analysis results are shown in Table 1.
  • a zirconium-based oxide was obtained by the same preparation method and preparation conditions as in Example 1.
  • the specific preparation conditions of the modified H-MOR molecular sieve are shown in Table 2 below, and the rest of the operations were the same as in Example 1.
  • the method and conditions for preparing the composite catalyst by the CO hydrogenation catalyst and the modified H-MOR molecular sieve are the same as in the first embodiment.
  • Catalyst 4# The difference from Example 1 is that the carrier gas during the preparation of the modified H-MOR molecular sieve is CO 2 .
  • Catalyst 5# The difference from Example 1 is that the carrier gas during the preparation of the modified H-MOR molecular sieve is hydrogen.
  • the catalysts 2# to 5# were subjected to methanol carbonylation hydrogenation to obtain ethylene by the method and conditions described in Example 1, and the obtained ethylene had high selectivity and less generation of methane and high carbon hydrocarbons.
  • the zirconium-based metal oxide is prepared by the impregnation method. The specific steps are as follows: 11.90 g of Zn(NO 3 ) 2 ⁇ 6H 2 O is weighed into a beaker, 150 mL of deionized water is added, and the salt solution C is stirred to obtain 6.16 g of zirconia powder. And 0.79 g of titanium oxide was immersed in the solution C, and after immersing for 5 hours, the solvent was slowly evaporated to dryness, and after preliminary drying, it was dried in an oven at 100 ° C for 10 hours. The dried solid powder was calcined at a temperature of 550 ° C for 4 h. A zirconium-based metal oxide having a composition of (ZnO) 0.4 (TiO 2 ) 0.1 (ZrO 2 ) 0.5 was obtained .
  • Example 1 Except that the preparation method of the zirconium-based oxide was different from that of Example 1, the other steps were the same as those of Example 1, and the catalyst obtained finally was recorded as 6#. Under the same reaction conditions as in Example 1, the 6# catalyst was evaluated, and the reaction product was analyzed by gas chromatography on-line, and the analysis results are shown in Table 3.
  • the zirconium-based metal oxides of different metal compositions and different contents are prepared by a coprecipitation method or a dipping method, wherein the composition of the zirconium-based oxide is different from that of the first embodiment and the third embodiment, and the remaining operations and conditions of the coprecipitation method are the same as those in the first embodiment.
  • the remaining operations and conditions of the impregnation method are the same as those in Example 3.
  • the obtained catalysts were respectively referred to as 7# to 17#, and the specific compositions of the respective catalysts are shown in Table 4. Under the same reaction conditions as in Example 1, the catalyst No. 7#-17# was evaluated, and the reaction product was analyzed by gas chromatography on-line, and the analysis results are shown in Table 4.
  • composition of the zirconium-based oxide sample was measured by XRF.
  • the molecular sieve topology, the molecular sieve Si/Al, the type of pre-adsorbed alkali and the effect of the mass content of zirconium-based metal oxide and acidic molecular sieve on the synthesis gas to ethylene were investigated.
  • the composition and preparation of the zirconium-based metal oxide were the same as in Example 1, and the preparation and evaluation conditions of the composite catalyst were in accordance with Example 1.
  • the reaction product was analyzed by gas chromatography on-line, and the results are shown in Table 5.
  • the FER type topological molecular sieve is H-ZSM-35 molecular sieve.
  • composition and preparation method of the zirconium-based oxide in this embodiment are the same as those in the examples.
  • the H-MOR was pre-adsorbed with pyridine in a manner of carrying pyridine with nitrogen (the volume fraction of pyridine in the mixed gas was 1%, and the mass space velocity of the mixed gas was 6000 mL ⁇ g -1 ⁇ h -1 ). After pyridine was adsorbed for 2 h, it was purged with nitrogen for 4 h and then cooled to room temperature.
  • the treated H-MOR molecular sieve was taken out to obtain a molecular sieve subjected to pre-adsorption alkali treatment.
  • Example 1 In the preparation of the composite catalyst, the modified H-MOR molecular sieve of Example 1 was replaced with the above-mentioned pre-adsorbed alkali-treated molecular sieve, and the rest was the same as in Example 1 to obtain a composite catalyst 28#.
  • reaction product was analyzed online by gas chromatography, and the analysis results are shown in Table 6.
  • the effect of the molar composition of the raw materials on the ethylene reaction of the synthesis gas was examined, and the evaluation conditions were the same as those in Example 1 except that the molar ratio of the gas was changed.
  • the catalyst was a ## sample, and the reactors were a fluidized bed reactor and a moving bed reactor, respectively, and the other conditions were the same as in Example 1.
  • the reaction product was analyzed online by gas chromatography, and the results are shown in Table 12.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un catalyseur composite, son procédé de préparation et un procédé de préparation d'éthylène. Le catalyseur composite comprend un oxyde à base de zirconium et un tamis moléculaire acide modifié, l'oxyde à base de zirconium ayant une teneur en masse de 10% en poids à 90% en poids, et le tamis moléculaire acide modifié a une teneur en masse de 10% en poids à 90% en poids; et le procédé de préparation de celui-ci est simple. Le catalyseur composite est utilisé pour préparer de l'éthylène pour rompre la loi de distribution ASF pour un hydrocarbure dans la synthèse Fischer-Tropsch (F-T), la sélectivité de l'éthylène atteignant 86 %.
PCT/CN2018/080924 2018-03-28 2018-03-28 Catalyseur composite, son procédé de préparation et procédé de préparation d'éthylène WO2019183842A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
RU2020135262A RU2767667C1 (ru) 2018-03-28 2018-03-28 Композиционный катализатор, способ его получения и способ получения этилена
PCT/CN2018/080924 WO2019183842A1 (fr) 2018-03-28 2018-03-28 Catalyseur composite, son procédé de préparation et procédé de préparation d'éthylène
ZA2020/06131A ZA202006131B (en) 2018-03-28 2020-10-02 Composite catalyst, method for preparing the same, and method for producing ethylene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2018/080924 WO2019183842A1 (fr) 2018-03-28 2018-03-28 Catalyseur composite, son procédé de préparation et procédé de préparation d'éthylène

Publications (1)

Publication Number Publication Date
WO2019183842A1 true WO2019183842A1 (fr) 2019-10-03

Family

ID=68062495

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/080924 WO2019183842A1 (fr) 2018-03-28 2018-03-28 Catalyseur composite, son procédé de préparation et procédé de préparation d'éthylène

Country Status (3)

Country Link
RU (1) RU2767667C1 (fr)
WO (1) WO2019183842A1 (fr)
ZA (1) ZA202006131B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113351199A (zh) * 2021-05-26 2021-09-07 陕西延长石油（集团）有限责任公司 酸性多相催化剂、制备方法及一步法制备乳酸工艺
CN113979448A (zh) * 2020-07-27 2022-01-28 中国石油化工股份有限公司 含氟zsm-35分子筛及其制备方法
CN114369002A (zh) * 2020-10-14 2022-04-19 中国石油天然气股份有限公司 一种合成气合成线性α-烯烃的方法
CN114588937A (zh) * 2022-03-16 2022-06-07 浙江大学 一种哒嗪掺杂改性c3n4光催化剂的制备方法及应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113979444B (zh) * 2020-07-27 2023-11-24 中国石油化工股份有限公司 一种具有fer结构的分子筛的制备方法和fer结构的分子筛

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0071382A2 (fr) * 1981-07-23 1983-02-09 The British Petroleum Company p.l.c. Procédé de production de catalyseurs à base d'aluminosilicates cristallins et l'utilisation des catalyseurs ainsi préparés
CN103962177A (zh) * 2013-01-31 2014-08-06 中国石油化工股份有限公司 一种含分子筛的催化剂的制备方法
CN104028314A (zh) * 2014-05-09 2014-09-10 神马实业股份有限公司 一种分子筛催化剂的制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2050730A1 (fr) * 2007-10-17 2009-04-22 BP Chemicals Limited Procédé de préparation d'éthène
US8535629B2 (en) * 2010-12-02 2013-09-17 Johnson Matthey Public Limited Company Zeolite catalyst containing metal
JP6030812B1 (ja) * 2015-03-24 2016-11-24 株式会社アシックス 上衣

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0071382A2 (fr) * 1981-07-23 1983-02-09 The British Petroleum Company p.l.c. Procédé de production de catalyseurs à base d'aluminosilicates cristallins et l'utilisation des catalyseurs ainsi préparés
CN103962177A (zh) * 2013-01-31 2014-08-06 中国石油化工股份有限公司 一种含分子筛的催化剂的制备方法
CN104028314A (zh) * 2014-05-09 2014-09-10 神马实业股份有限公司 一种分子筛催化剂的制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113979448A (zh) * 2020-07-27 2022-01-28 中国石油化工股份有限公司 含氟zsm-35分子筛及其制备方法
CN114369002A (zh) * 2020-10-14 2022-04-19 中国石油天然气股份有限公司 一种合成气合成线性α-烯烃的方法
CN113351199A (zh) * 2021-05-26 2021-09-07 陕西延长石油（集团）有限责任公司 酸性多相催化剂、制备方法及一步法制备乳酸工艺
CN114588937A (zh) * 2022-03-16 2022-06-07 浙江大学 一种哒嗪掺杂改性c3n4光催化剂的制备方法及应用

Also Published As

Publication number Publication date
ZA202006131B (en) 2022-01-26
RU2767667C1 (ru) 2022-03-18

Similar Documents

Publication Publication Date Title
CN108568313B (zh) 一种催化剂及一氧化碳加氢直接转化制低碳烯烃的方法
WO2019183842A1 (fr) Catalyseur composite, son procédé de préparation et procédé de préparation d'éthylène
CN101884926B (zh) 用于费托合成反应的沉淀铁催化剂、其制备方法及其应用
CN111346672B (zh) 一种掺杂杂原子分子筛催化合成气高选择性制低碳烯烃的方法
CN109745965B (zh) 一种含CeZr氧化物的催化剂及一氧化碳加氢直接转化制低碳烯烃的方法
CN106140266B (zh) 一种金属改性zsm-5分子筛催化剂及其制备方法和应用
WO2017031635A1 (fr) Catalyseur à base de fer préparé au moyen d'un procédé de coprécipitation-fusion, procédé de préparation associé et application associée
CN108940355B (zh) 一种碱修饰的催化剂及一氧化碳加氢反应制乙烯的方法
CN104525196A (zh) 负载于双氧化物复合载体的铂镓催化剂及其制备方法和应用
WO2020125487A1 (fr) Procédé de préparation d'une oléfine à faible teneur en carbone à haute sélectivité à partir d'un gaz de synthèse catalysé par un tamis moléculaire dopé par un hétéroatome
WO2021147213A1 (fr) Catalyseur à base de fer coeur-coquille utilisé pour la production directe d'hydrocarbures aromatiques à partir de gaz de synthèse, et son procédé de préparation et son application
CN108927132B (zh) 一种双功能催化剂及一氧化碳加氢制乙烯的方法
CN106890665B (zh) 一种二甲醚羰基化生产乙酸甲酯的催化剂及其应用
CN1589176A (zh) 含有水铁矿和铝的费托合成催化剂
CN110314696B (zh) 一种复合催化剂、其制备方法和乙烯的制备方法
CN112108180A (zh) 一种合成气直接转化制低碳烯烃的催化剂及其制备方法
RU2749513C1 (ru) Смешанный катализатор, модифицированный органическим основанием, и способ получения этилена путем гидрирования монооксида углерода
CN112973661A (zh) 烷烃脱氢催化剂及其制备方法与应用
CN110314695A (zh) 一种复合催化剂、其制备方法和乙烯的制备方法
CN112973779A (zh) 一种zsm-22分子筛的后处理方法及其在合成气一步法制液体燃料中的应用
WO2019183841A1 (fr) Catalyseur composite, son procédé de préparation et procédé de préparation d'éthylène
CN115155588A (zh) 一种用于二氧化碳直接加氢制备芳烃的串联催化剂及其制备方法和应用
CN109647492B (zh) 合成气直接生产低碳烯烃的催化剂
CN115196651A (zh) 一种无钠Cu-SSZ-13沸石的制备方法及其应用
CN111068770A (zh) 一种用于一氧化碳加氢制低碳烯烃的负载型催化剂及制备方法和应用

Legal Events

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

Ref document number: 18911805

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18911805

Country of ref document: EP

Kind code of ref document: A1