WO2019183842A1 - Composite catalyst, preparation method therefor and method for preparing ethylene - Google Patents

Composite catalyst, preparation method therefor and method for preparing ethylene Download PDF

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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
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molecular sieve
composite catalyst
gas
zirconium
catalyst according
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PCT/CN2018/080924
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French (fr)
Chinese (zh)
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刘世平
朱文良
刘中民
倪友明
刘红超
刘勇
马现刚
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中国科学院大连化学物理研究所
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Priority to PCT/CN2018/080924 priority Critical patent/WO2019183842A1/en
Priority to RU2020135262A priority patent/RU2767667C1/en
Publication of WO2019183842A1 publication Critical patent/WO2019183842A1/en
Priority to ZA2020/06131A priority patent/ZA202006131B/en

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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
    • 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.

Abstract

A composite catalyst, a preparation method therefor and a method for preparing ethylene. The composite catalyst comprises a zirconium-based oxide and a modified acidic molecular sieve, wherein the zirconium-based oxide has a mass content of 10 wt%-90 wt%, and the modified acidic molecular sieve has a mass content of 10 wt%-90 wt%; and the preparation method therefor is simple. The composite catalyst is used for preparing ethylene to break ASF distribution law for hydrocarbon in the Fischer-Tropsch (F-T) synthesis, wherein the selectivity of ethylene reaches 86%.

Description

一种复合催化剂、其制备方法和乙烯的制备方法Composite catalyst, preparation method thereof and preparation method of ethylene 技术领域Technical field
本申请涉及一种复合催化剂、其制备方法和乙烯的制备方法，属于合成气制低碳烯烃领域。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.
背景技术Background technique
乙烯是全球生产和消费量最大的基础化工产品，随着中国经济发展，国内乙烯需求将继续增加，但现有产能远远不能满足需求。目前乙烯主要经过石脑油裂解而获得，而中国的资源禀赋是“富煤、贫油、少气”，这严重制约了下游产业的发展并对国家能源安全构成严重威胁。因此，开发基于煤等非石油资源制取乙烯的方法具有一定现实意义。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.
目前，合成气制取乙烯的成熟方法是间接法。合成气先转化为甲醇，甲醇经过MTO过程生成混合低碳烯烃(C2-C4烯烃)。该路径在中国已经步入工业化，并且取得了巨大成功。与合成气经甲醇制取烯烃间接途径相比，合成气一步直接制取乙烯具有工艺简单、设备少的优势。合成气可以经过经典的Fischer-Tropsch过程直接制取烯烃，该过程中的催化剂为负载型金属催化剂。通常该过程C2-C4烃类最高选择性不超过58％，汽油馏分C5-C11最高选择性为45％，同时大量甲烷和高碳烷烃生成。因此如何高选择性地生成低碳烯烃一直是该领域难以克服的核心问题。经过国内外的研究人员多年持续不断的探索、改进，该领域已经取得了巨大进展，但低碳烯烃最高选择性依然不超过61％(H.M.Torres Galvis et al.,Science 2012,335,835–838)。At present, 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). The path has entered industrialization in China and has achieved great success. Compared with the indirect route of syngas to olefin by methanol, 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. Generally, 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).
由于合成气经甲醇制备低碳烯烃取得巨大成功，近期研究人员尝试将甲醇合成和甲醇制烯烃这两反应进行耦合，并且取得了成功。虽然甲醇反应与甲醇制烯烃反应进行耦合可以显著提高低碳烯烃选择性，但现有技术中获得的乙烯在烃类物种的选择性依然较低，其乙烯选择性不会超过25％。因此将合成气直接定向转化为乙烯挑战极大。Due to the great success of syngas in the preparation of low-carbon olefins from methanol, recent researchers have attempted to couple the two reactions of methanol synthesis and methanol to olefins with success. Although the coupling of the methanol reaction with the methanol to olefin reaction can significantly improve the selectivity of the lower olefins, the ethylene obtained in the prior art is still less selective in hydrocarbon species and does not have an ethylene selectivity of more than 25%. Therefore, the direct conversion of syngas to ethylene is extremely challenging.
发明内容Summary of the invention
根据本申请的一个方面，提供了一种复合催化剂，该复合催化剂应用于合成气一步高选择性制取乙烯，打破Fischer-Tropsch(F-T)合成中的烃类Anderson-Schulz-Flory(ASF)分布规律，其中乙烯选择性达到86％。According to an aspect of the present application, there is provided 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%.
所述复合催化剂，其特征在于，含有锆基氧化物和改性酸性分子筛；其组分按质量百分比包括：锆基氧化物的质量含量为10wt.％～90wt.％，改性酸性分子筛的质量含量为10wt.％～90wt.％；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.%;
其中，所述改性酸性分子筛为经过预吸附碱处理的酸性分子筛。Wherein, the modified acidic molecular sieve is an acidic molecular sieve treated by a pre-adsorbed alkali.
可选地，所述锆基氧化物的质量含量上限选自11wt.％、20wt.％、30wt.％、33.3wt.％、40wt.％、50wt.％、60wt.％、66.7wt.％、70wt.％、80wt.％或90wt.％；下限选自10wt.％、20wt.％、30wt.％、33.3wt.％、40wt.％、50wt.％、60wt.％、66.7wt.％、70wt.％、80wt.％或89wt.％。Optionally, 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.%.
可选地，所述改性酸性分子筛的质量含量上限选自11wt.％、20wt.％、30wt.％、33.3wt.％、40wt.％、50wt.％、60wt.％、66.7wt.％、70wt.％、80wt.％或90wt.％；下限选自10wt.％、20wt.％、30wt.％、33.3wt.％、40wt.％、50wt.％、60wt.％、66.7wt.％、70wt.％、80wt.％或89wt.％。Optionally, 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.%.
优选地，所述预吸附碱处理的步骤至少包括：将所述酸性分子筛与含有有机碱的气体接触进行预吸附碱处理。Preferably, 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.
优选地，预吸附碱处理的温度上限选自160℃、200℃、250℃、300℃或350℃；下限选自150℃、200℃、250℃、300℃或340℃。Preferably, 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.
可选地，预吸附碱处理的时间上限选自0.6h、1h、2h、3h或4h；下限选自0.5h、1h、2h、3h或3.9h。Optionally, 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.
优选地，所述预吸附碱处理的温度为150～350℃，预吸附碱处理的时间为0.5～4h。Preferably, 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.
可选地，所述含有有机碱的气体的质量空速上限选自400mL·g -1·h -1、500mL·g -1·h -1、1000mL·g -1·h -1、2000mL·g -1·h -1、3000mL·g -1·h -1、4000mL·g -1·h -1、5000mL·g -1·h -1或6000mL·g -1·h -1；下限选自300mL·g -1·h -1、500mL·g -1·h -1、1000mL·g -1·h -1、2000mL·g -1·h -1、3000mL·g -1·h -1、4000mL·g -1·h -1、4900mL·g -1·h -1或5000mL·g -1·h -1。 Optionally, 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 mL·g -1 ·h -1 .
作为一种实施方式，所述含有有机碱的气体包括载气和有机碱。As an embodiment, the organic base-containing gas includes a carrier gas and an organic base.
优选地，所述有机碱选自三甲胺、二乙胺、三乙胺、吡啶、哒嗪、嘧啶、吡嗪、吡啶、咪唑、N-甲基咪唑、N-乙基咪唑、N--丙基咪唑、N-异丙基咪唑中的至少一种。Preferably, 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.
优选地，所述载气选自氮气、氦气、CO 2、氩气、氢气中的至少一种。 Preferably, the carrier gas is at least one selected from the group consisting of nitrogen, helium, CO 2 , argon, and hydrogen.
可选地，所述含有有机碱的气体中有机碱的体积分数上限选自0.2％、0.5％、1％、2％、3％、4％、5％、6％、7％、8％、9％或10％；下限选自0.1％、0.5％、1％、2％、3％、4％、5％、6％、7％、8％、9％或9.9％。Optionally, 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%.
进一步优选地，所述含有有机碱的气体中有机碱的体积分数为0.1％～10％。Further preferably, the volume fraction of the organic base in the organic base-containing gas is from 0.1% to 10%.
优选地，所述预吸附碱处理的步骤至少包括：将所述酸性分子筛在非活性气体氛中进行活化，然后将温度调至预吸附碱处理温度，与含有有机碱的气体接触进行预吸附碱处理，吸附饱和后，吹扫，降至室温，得到改性酸性分子筛。Preferably, 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.
可选地，所述活化的温度上限选自320℃、350℃、400℃、450℃或480℃；下限选自300℃、350℃、400℃、450℃或500℃。Optionally, 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.
可选地，所述活化的时间上限选自3.2h、3.5h、4h、4.5h或5h；下限选自3h、3.5h、4h、4.5h或4.8h。Optionally, 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.
优选地，所述活化的温度为300～500℃，活化的时间为3～5h。Preferably, the activation temperature is 300 to 500 ° C, and the activation time is 3 to 5 hours.
作为一种具体的实施方式，所述酸性分子筛进行预吸附碱处理的步骤至少包括：所述酸性分子筛需要经过在一定空速、温度下，载气携带有机碱进行预吸附有机碱处理一定时间；其中，所述有机碱在混合气中体积分数为0.1％～10％，载气可选为氮气、氦气、CO 2、氩气、氢气中的任意一种或者任意几种的混合物，预处理气体质量空速范围为300～5000mL·g -1·h -1；所述有机碱为三甲胺、二乙胺、三乙胺、哒嗪、嘧啶、吡嗪、吡啶、咪唑、N-甲基咪唑、N-乙基咪唑、N--丙基咪唑、N-异丙基咪唑中的任意一种或者几种的混合物；所述有机碱预处理温度范围为150～350℃，预处理时间为0.5～4h。 As a specific embodiment, 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; Wherein, the volume fraction of the organic base in the mixed gas is 0.1% to 10%, and 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-isopropylimidazole; the organic base pretreatment temperature ranges from 150 to 350 ° C, and the pretreatment time is 0.5 to 4h.
优选地，所述酸性分子筛选自具有MOR拓扑结构的分子筛、具有FER拓扑结构的分子筛、含有MOR拓扑结构和FER拓扑结构的共晶分子筛、含有MOR拓扑结构和FER拓扑结构的混晶分子筛中的至少一种。Preferably, 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.
优选地，所述具有MOR拓扑结构的分子筛为骨架原子Si/Al比为4～60的H-MOR分子筛。Preferably, the molecular sieve having the MOR topology is an H-MOR molecular sieve having a skeleton atom Si/Al ratio of 4 to 60.
优选地，所述具有FER拓扑结构的分子筛为骨架原子Si/Al比为5～50的H-ZSM-35分子筛。Preferably, 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.
优选地，所述酸性分子筛为H-MOR、H-ZSM-35、氢型MOR与ZSM-35的共晶分子筛、氢型MOR与ZSM-35的混晶分子筛中的至少一种。Preferably, 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.
优选地，所述锆基氧化物选自具有式(I)所述化学式的化合物中的至少一种：Preferably, the zirconium-based oxide is selected from at least one of the compounds having the formula of formula (I):
X aM b(ZrO 2) 1-a-b 式(I) X a M b (ZrO 2 ) 1-ab formula (I)
其中，式(I)中X为Si、Al、Ti、Ce、La中至少一种元素的氧化物；M为Cu、Ag、Zn、Mn、Y、Nb、Ga、In、Cr中至少一种元素的氧化物；Wherein 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;
其中，a为0.02～0.9，b为0.0～0.8。Among them, a is 0.02 to 0.9, and b is 0.0 to 0.8.
所述a、b为相应氧化物在全组分中的摩尔占比。The a, b are the molar proportions of the corresponding oxides in the total composition.
优选地，所述锆基氧化物为锆基金属氧化物中的至少一种。Preferably, the zirconium-based oxide is at least one of zirconium-based metal oxides.
可选地，所述a的上限选自0.1、0.4、0.5、0.6、0.8或0.9；下限选自0.02、0.1、0.4、0.5、0.6、或0.8。优选地，a为0.1～0.9之间的某一值。Alternatively, 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. Preferably, a is a value between 0.1 and 0.9.
可选地，所述b的上限选自0.02、0.05、0.1、0.4、0.5或0.8；下限选自0、0.02、0.05、0.1、0.4或0.5。优选地，b为0.1～0.8之间的某一值。Optionally, 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. Preferably, b is a value between 0.1 and 0.8.
本申请的另一方面，提供了所述的复合催化剂的制备方法，至少包括以下步骤：In another aspect of the present application, there is provided a method of preparing the composite catalyst comprising at least the following steps:
(1)获得锆基氧化物；(1) obtaining a zirconium-based oxide;
(2)获得改性酸性分子筛；(2) obtaining a modified acidic molecular sieve;
(3)将含有步骤(1)中的锆基氧化物和步骤(2)中改性酸性分子筛的各组分采用超声辅助化学复合法和/或物理复合法进行复合，得到所述复合催化剂。(3) The components comprising the zirconium-based oxide in the step (1) and the modified acidic molecular sieve in the step (2) are combined by ultrasonic assisted chemical compounding and/or physical compounding to obtain the composite catalyst.
优选地，步骤(1)中所述锆基氧化物的获得方法包括：通过共沉淀法、浸渍法、机械混合法中的至少一种进行制备。Preferably, 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.
作为一种实施方式，所述共沉淀法至少包括以下步骤：将含有X元素、M'元素和Zr元素的溶液与含有沉淀剂的溶液在搅拌的条件下以并流的方 式混合，控制体系pH值为7～9，沉淀结束后经老化，固液分离，洗涤、干燥和焙烧固相，得到所述锆基氧化物。As an embodiment, 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.
作为一种实施方式，所述浸渍法至少包括以下步骤：将氧化锆粉末浸渍于含有X元素和M'元素的盐溶液中或者将氧化锆粉末和X的氧化物浸渍于含有M'元素的盐溶液中或者将氧化锆粉末和M'的氧化物浸渍于含有X元素的盐溶液中；浸渍后经去除溶剂、干燥、焙烧，得到所述锆基氧化物。As an embodiment, 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'选自Cu、Ag、Zn、Mn、Y、Nb、Ga、In、Cr中至少一种。M' is at least one selected from the group consisting of Cu, Ag, Zn, Mn, Y, Nb, Ga, In, and Cr.
优选地，所述共沉淀法中搅拌的老化的时间为2～4h；焙烧的条件为400～600℃焙烧1～6h。Preferably, 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.
所述共沉淀法中的搅拌为剧烈搅拌。优选地，所述共沉淀法中搅拌的速度为250～5000rpm/min。The agitation in the coprecipitation method is vigorous stirring. Preferably, the speed of stirring in the coprecipitation method is from 250 to 5000 rpm/min.
优选地，所述浸渍法中浸渍的时间为1～6h；干燥的条件为60～200℃干燥1～10h；焙烧的条件为400～600℃焙烧1～6h。Preferably, 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.
优选地，所述溶液中的X元素、M'元素和Zr元素独立地来自X元素、M元素和Zr元素的硝酸盐、盐酸盐、醋酸盐、乙酰丙酮盐、硫酸盐中的至少一种。Preferably, 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. Kind.
优选地，所述沉淀剂为碱液。进一步优选地，所述碱液选自氨水、碳酸铵、碳酸钠、尿素、NaOH、KOH中的至少一种。Preferably, the precipitating agent is an alkali solution. Further preferably, the alkali liquid is at least one selected from the group consisting of ammonia water, ammonium carbonate, sodium carbonate, urea, NaOH, and KOH.
作为一种具体的实施方式，所述共沉淀法包括以下步骤：将含有X元素的化合物中的至少一种、含有M'元素的化合物中的至少一种与Zr盐配成水溶液，记为溶液A；将氨水、碳酸铵、碳酸钠、尿素、NaOH或者KOH一种或者任意几种配成水溶液B；在激烈搅拌条件下，将溶液A与溶液B以并流的方式混合，调节溶液A和溶液B的流量大小，控制混合液体pH范围为7～9；沉淀结束后，老化2～4h，过滤，洗涤，干燥；之后在400～600℃的温度范围焙烧1～6h。As a specific embodiment, 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. 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.
作为一种具体的实施方式，所述浸渍法包括以下步骤：将含有X元素的化合物中的至少一种和含有M'元素的化合物中的至少一种，加去离子水或醇溶液中，配成溶液C，将氧化锆粉末浸入到溶液C中，浸渍1～6h之后，缓慢蒸干溶剂，初步干燥之后再于烘箱中于60～200℃范围内干燥1～10h； 干燥后的粉末在400～600℃的温度范围焙烧1～6h。As a specific embodiment, 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.
优选地，步骤(3)中所述超声辅助化学复合法至少包括：将含有锆基氧化物和改性酸性分子筛的溶液超声后，经固液分离，干燥和焙烧固相，得到所述复合催化剂；Preferably, 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. ;
所述物理复合法至少包括：将含有锆基氧化物和改性酸性分子筛的混合物通过机械混合、球磨、振荡中的至少一种方式复合，得到所述复合催化剂。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.
优选地，所述超声辅助化学复合法中超声的时间为10min～3h；干燥的温度为60～150℃；焙烧的温度为300～650℃。Preferably, 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.
作为一种具体的实施方式，所述超声辅助化学复合法，是将锆基氧化物和改性酸性分子筛粉体分散于水或者醇溶液中，超声10min～3h，两者充分混合均匀后；再经过滤、干燥、焙烧得到复合催化剂；干燥温度范围为60～150℃，焙烧温度范围为300～650℃。As a specific embodiment, 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.
作为一种具体的实施方式，所述物理复合法，是指通过机械混合、球磨、振荡混合等混合方式将锆基氧化物与改性酸性分子筛催化剂进行复合。As a specific embodiment, 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.
作为一种具体的实施方式，所述复合催化剂的制备方法，至少包括如下步骤：As a specific embodiment, the preparation method of the composite catalyst includes at least the following steps:
(1)制备锆基金属氧化物；(1) preparing a zirconium-based metal oxide;
(2)将分子筛进行铵交换，制备成氢型分子筛，对氢型分子筛进行预吸附碱处理；(2) The molecular sieve is subjected to ammonium exchange to prepare a hydrogen type molecular sieve, and the hydrogen type molecular sieve is pre-adsorbed alkali;
(3)将步骤(1)和(2)中的产物采用超声辅助化学复合法或者物理复合法进行复合，制备成合成气一步制乙烯催化剂。(3) The products in the steps (1) and (2) are combined by ultrasonic assisted chemical compounding or physical compounding to prepare a one-step ethylene catalyst for syngas.
所述复合催化剂和/或根据所述方法制备得到的复合催化剂用于合成气一步法制备乙烯。The composite catalyst and/or the composite catalyst prepared according to the method is used for one-step synthesis of ethylene by synthesis gas.
本申请中的再一方面，提供了一种乙烯的制备方法，至少包括以下步骤：In still another aspect of the present application, a method for preparing ethylene is provided, comprising at least the following steps:
将含有合成气的原料气通过装有复合催化剂的反应器，反应得到乙烯；The raw material gas containing the synthesis gas is passed through a reactor equipped with a composite catalyst to obtain ethylene;
其中，所述复合催化剂选自所述的复合催化剂和/或根据所述的方法制备得到的复合催化剂中的至少一种；Wherein the composite catalyst is selected from at least one of the composite catalyst and/or the composite catalyst prepared according to the method;
其中，所述合成气包括CO、H 2、CO 2，摩尔比满足： Wherein, the syngas comprises CO, H 2 , CO 2 , and the molar ratio satisfies:
CO：H 2：CO 2＝1：0.2～4：0～1。 CO: H 2 : CO 2 = 1: 0.2 to 4: 0 to 1.
可选地，所述反应的温度上限选自280℃、300℃、320℃、350℃或380℃；下限选自250℃、280℃、300℃、320℃或350℃。Optionally, 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.
可选地，所述反应压力上限选自2.0MPa、2.5MPa、3.0MPa、5.0MPa、6.0MPa或8.0MPa；下限选自1.0MPa、2.0MPa、2.5MPa、3.0MPa、5.0MPa或6.0MPa。Optionally, 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.
可选地，所述原料气的质量空速上限选自400mL·g -1·h -1、500mL·g -1·h -1、1000mL·g -1·h -1、4000mL·g -1·h -1、8000mL·g -1·h -1或10000mL·g -1·h -1；下限选自300mL·g -1·h -1、400mL·g -1·h -1、500mL·g -1·h -1、1000mL·g -1·h -1、4000mL·g -1·h -1或8000mL·g -1·h -1。 Optionally, 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 .
优选地，所述反应的温度为250～380℃，压力为1.0～8.0MPa，气体质量空速为300～10000mL·g -1·h -1。 Preferably, the reaction temperature is 250 to 380 ° C, the pressure is 1.0 to 8.0 MPa, and the gas mass space velocity is 300 to 10000 mL·g -1 ·h -1 .
所述乙烯的制备方法为合成气一步高选择性制取乙烯，乙烯选择性达到86％。The preparation method of the ethylene is that the synthesis gas is ethylene in one step and the selectivity is 86%.
优选地，所述原料气中还包括非活性气体。Preferably, the feed gas further includes an inert gas.
优选地，所述非活性气体选自氮气、氩气、氦气、甲烷中的至少一种。Preferably, the inert gas is selected from at least one of nitrogen, argon, helium, and methane.
优选地，所述非活性气体在混合气体中的体积含量≤10％。Preferably, the volume content of the inert gas in the mixed gas is ≤10%.
可选地，所述非活性气体在混合气体中的体积含量上限选自1％、3％、5％、8％或10％；下限选自0％、1％、3％、5％或8％。Optionally, 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 %.
优选地，所述非活性气体在混合气体中的体积含量为0％～10％。Preferably, the inert gas has a volume content of 0% to 10% in the mixed gas.
可选地，所述CO和H 2的摩尔比上限选自1/0.3、1/0.5、1/1、1/3或1/4；下限选自1/0.2、1/0.3、1/0.5、1/1或1/3。 Optionally, 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.
优选地，所述反应器为固定床反应器、流化床反应器、移动床反应器中的至少一种。Preferably, the reactor is at least one of a fixed bed reactor, a fluidized bed reactor, and a moving bed reactor.
作为一种具体的实施方式，所述复合催化剂用于合成气一步制乙烯的方法，至少包括以下步骤：将含有合成气的原料气通过装有复合催化剂的反应器，在一定反应条件下，一步合成乙烯；所述合成气为CO、H 2和CO 2和其他气体，其中，CO、H 2和CO 2的摩尔比为：CO/H 2/CO 2＝1/X’/Y’(其中X’＝0.2～4；Y’＝0～1)；反应温度优选为250～380℃；其他气体选自惰性 气氮气、氩气、氦气、甲烷中的一种或者多种，其在原料气中的体积含量低于10％；反应压力优选为1.0～8.0MPa，气体速优选为300～10000mL·g -1·h -1。 As a specific embodiment, 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. Synthetic ethylene; the synthesis gas is CO, H 2 and CO 2 and other gases, wherein the molar ratio of CO, H 2 and CO 2 is: CO/H 2 /CO 2 =1/X'/Y' (wherein X'=0.2～4;Y′=0～1); the reaction temperature is preferably 250-380° C.; other gases are selected from one or more of inert gas nitrogen, argon, helium and methane, which are in the raw materials. 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 .
本申请中的合成气一步法制取乙烯得到乙烯的选择性大于40％。The synthesis gas in the present application produces ethylene in a one-step process to give an ethylene selectivity of greater than 40%.
本申请中，“H-MOR分子筛”是指氢型丝光沸石分子筛，可通过本领域中常规的制备方法对分子筛进行氢化反应制备。In the present application, "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.
本申请中，“H-ZSM-35分子筛”是指氢型ZSM-35分子筛，可通过本领域中常规的制备方法对分子筛进行氢化反应制备。In the present application, "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.
本申请中，所有涉及数值范围的条件均可独立地选自所述数值范围内的任意中间范围。In the present application, all conditions relating to the numerical range may be independently selected from any intermediate range within the stated numerical range.
本申请中，如无特别说明，所有涉及数值范围的条件均包含端点值。In the present application, all conditions involving numerical ranges include endpoint values unless otherwise stated.
本申请能产生的有益效果包括：The beneficial effects that can be produced by this application include:
1、本申请中将甲醇合成催化剂与羰基化催化剂进行复合，该复合催化剂具有乙烯选择性高(可达到86％)、甲烷和高碳烃生成少等突出特点。1. In the present application, 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.
2、本申请中的催化剂制备过程简单，容易获得。2. The preparation process of the catalyst in the present application is simple and easy to obtain.
3、本申请中提供的合成气一步制备乙烯过程具有反应条件温和，工艺简单等优点，具有大规模工业化的潜力。3. 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.
具体实施方式detailed description
下面结合实施例详述本申请，但本申请并不局限于这些实施例。The present application is described in detail below with reference to the embodiments, but the application is not limited to the embodiments.
如无特别说明，本申请中的原料均为通过商业购买，未经处理直接使用。Unless otherwise stated, the raw materials in this application are all commercially available and used without treatment.
实施例中，样品的元素分析XRF采用Magix(PHILIPS)型X荧光分析仪，通过IQ +无标定量分析程序，将标准样品的荧光强度和其标准组成相对应，扣除了干扰谱线的影响。 In the examples, 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.
实施例中转化率、选择性计算如下：The conversion and selectivity in the examples are calculated as follows:
CO的转化率的计算方法为：X(CO)＝1-F(CO) outlet/F(CO) inlet,其中F(CO) outlet是反应器出口CO流量，F(CO) inlet是反应器入口CO流量。 The CO conversion rate is calculated as: X(CO)=1-F(CO) outlet /F(CO) inlet , where F(CO) outlet is the reactor outlet CO flow and F(CO) inlet is the reactor inlet CO flow.
烃类选择性的计算方法为：S(C nH m)＝n*C nH m/Σ(n*C nH m)，C nH m是烃 类物种的在反应器出口的浓度，n是烃类物种中C原子数，m是H原子数。 The hydrocarbon selectivity is calculated as: S(C n H m )=n*C n H m /Σ(n*C n H m ), and C n H m is the concentration of the hydrocarbon species at the outlet of the reactor, n is the number of C atoms in the hydrocarbon species, and m is the number of H atoms.
实施例1Example 1
称取21.46g Zr(NO 3) 4·5H 2O，11.90g Zn(NO 3) 2·6H 2O和4.34g Ce(NO 3) 3·6H 2O于烧杯中，加入150mL去离子水，搅拌得到盐溶液A。称取23.55g碳酸铵于烧杯中，加入150mL去离子水，充分搅拌，得到沉淀剂碱溶液B。在激烈搅拌条件下，将盐溶液A和沉淀剂碱溶液B以并流的方式混合，调节溶液A和B的相对流速确保沉淀混合液pH保持在7～8之间。共沉淀结束后，老化2h。之后在100℃烘箱中，干燥6h，在于500℃的马弗炉中焙烧4 h，得到锆基金属氧化物。经XRF元素分析，锆基氧化物组成为(ZnO) 0.4(CeO 2) 0.1(ZrO 2) 0.5。 Weigh 21.46g Zr(NO 3 ) 4 ·5H 2 O, 11.90g Zn(NO 3 ) 2 ·6H 2 O and 4.34g Ce(NO 3 ) 3 ·6H 2 O in a beaker, add 150mL deionized water, The salt solution A was obtained by stirring. 23.55 g of ammonium carbonate was weighed into a beaker, 150 mL of deionized water was added, and the mixture was thoroughly stirred to obtain a precipitating agent alkali solution B. The salt solution A and the precipitant alkali solution B were mixed in a cocurrent manner under vigorous stirring, and the relative flow rates of the solutions A and B were adjusted to ensure that the pH of the precipitation mixture was maintained between 7 and 8. After the end of the coprecipitation, it was aged for 2 h. Thereafter, it was dried in an oven at 100 ° C for 6 hours, and calcined in a muffle furnace at 500 ° C for 4 hours to obtain a zirconium-based metal oxide. The composition of the zirconium-based oxide was (ZnO) 0.4 (CeO 2 ) 0.1 (ZrO 2 ) 0.5 by XRF elemental analysis.
将H-MOR(Si/Al＝10)酸性分子筛装填于反应器中，在氮气气氛中升温到450℃活化4h，然后降温至250℃。用氮气携带吡啶(混合气中吡啶的体积分数为1％，混合气的质量空速为6000mL·g -1·h -1)的方式对H-MOR进行预吸附吡啶处理。吸附吡啶2h后，再用氮气吹扫4h，之后降至室温。取出处理过的H-MOR分子筛，得到经过预吸附碱处理的酸性分子筛。 H-MOR (Si/Al = 10) acidic molecular sieves were packed in a reactor, heated to 450 ° C for 4 h in a nitrogen atmosphere, and then cooled to 250 ° C. 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.
利用球磨机将上述得到的锆基金属氧化物粉末(3.0g)与预吸附吡啶后的H-MOR分子筛(1.5g)充分研磨，混合。将混合后的粉体压片、破碎、筛分，得到20～40目的颗粒催化剂，该催化剂记为1#。1#复合催化剂中锆基金属氧化物含量为66.7wt.％，分子筛质量含量为33.3wt.％。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.%.
取3g 1#催化剂装填于反应器中，在如下条件下进行合成气制备乙烯反应：反应温度300℃，反应压力5.0MPa，CO/H 2为3/1，原料气质量空速(GHSV)为2300mL·g -1·h -1。反应产物采用气相色谱仪在线分析，分析结果见表1。 3g 1# catalyst was charged into the reactor, and the synthesis gas was used to prepare ethylene reaction under the following conditions: reaction temperature 300 ° C, reaction pressure 5.0 MPa, CO/H 2 was 3/1, and raw material gas mass space velocity (GHSV) was 2300 mL·g -1 ·h -1 . The reaction product was analyzed online by gas chromatography, and the analysis results are shown in Table 1.
表1 实施例1催化剂反应结果Table 1 Example 1 catalyst reaction results
催化剂编号Catalyst number CO转化率(％)CO conversion rate (%) 乙烯选择性(％)Ethylene selectivity (%) 乙烷选择性(％)Ethane selectivity (%) 甲烷选择性(％)Methane selectivity (%)
1#1# 15.215.2 8181 3.03.0 1.21.2
实施例2Example 2
采用与实施例1中相同的制备方法和制备条件获得锆基氧化物。改性 H-MOR分子筛的具体制备条件如下表2所示，其余操作与实施例1相同。CO加氢催化剂与改性H-MOR分子筛制备复合催化剂的方法和条件与实施例1相同。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.
表2Table 2
Figure PCTCN2018080924-appb-000001
Figure PCTCN2018080924-appb-000001
催化剂4#：与实施例1的区别在于，改性H-MOR分子筛制备过程中载气为CO 2。 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 .
催化剂5#：与实施例1的区别在于，改性H-MOR分子筛制备过程中载气为氢气。Catalyst 5#: The difference from Example 1 is that the carrier gas during the preparation of the modified H-MOR molecular sieve is hydrogen.
其中，催化剂2#～5#采用实施例1所述的方法和条件进行甲醇羰化加氢制取乙烯反应，得到的乙烯选择性高、甲烷和高碳烃生成少。Among them, 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.
实施例3Example 3
采用浸渍法制备锆基金属氧化物，具体步骤如下：称取11.90g Zn(NO 3) 2·6H 2O于烧杯中，加入150mL去离子水，搅拌得到盐溶液C，将6.16g氧化锆粉末和0.79g氧化钛浸入到溶液C中，浸渍5h后，缓慢蒸干溶剂，初步干燥之后在烘箱中于100℃范围内干燥10h。干燥后的固体粉末在550℃的温度范围焙烧4h。得到锆基金属氧化物，其组成为(ZnO) 0.4(TiO 2) 0.1(ZrO 2) 0.5。 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 .
除锆基氧化物制备方法与实施例1不同之外，其余步骤都与实施例1保持一致，最后得到的催化剂记为6#。在实施例1相同的反应条件下，对6#催化剂进行评价，反应产物采用气相色谱仪在线分析，分析结果见表3。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.
表3 实施例3催化剂反应评价结果Table 3 Example 3 catalyst reaction evaluation results
催化剂编号Catalyst number CO转化率(％)CO conversion rate (%) 乙烯选择性(％)Ethylene selectivity (%) 乙烷选择性(％)Ethane selectivity (%) 甲烷选择性(％)Methane selectivity (%)
6#6# 12.512.5 80.080.0 3.03.0 2.42.4
实施例4Example 4
采用共沉淀法或浸渍法制备不同金属组成和不同含量的锆基金属氧化物，其中锆基氧化物的组成与实施例1和实施例3不同，共沉淀法的其余操作及条件同实施例1，浸渍法的其余操作及条件同实施例3。将获得的催化剂分别记为7#～17#，各催化剂具体组成见表4。在实施例1相同的反应条件下，对7#～17#号催化剂进行评价，反应产物采用气相色谱仪在线分析，分析结果见表4。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.
表4 实施例4催化剂反应结果Table 4 Example 4 catalyst reaction results
Figure PCTCN2018080924-appb-000002
Figure PCTCN2018080924-appb-000002
锆基氧化物样品的组成由XRF测得。The composition of the zirconium-based oxide sample was measured by XRF.
实施例5Example 5
考察分子筛拓扑结构、分子筛Si/Al、预吸附碱的种类和锆基金属氧 化物与酸性分子筛在复合催化剂中质量含量对合成气制乙烯反应的影响。锆基金属氧化物的组成和制备方式与实施例1相同，复合催化剂的制备和评价条件与实施例1保持一致。反应产物采用气相色谱仪在线分析，结果见表5。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.
表5 实施例5催化剂评价结果Table 5 Example 5 catalyst evaluation results
Figure PCTCN2018080924-appb-000003
Figure PCTCN2018080924-appb-000003
其中，所述FER型拓扑结构分子筛为H-ZSM-35分子筛。Wherein, the FER type topological molecular sieve is H-ZSM-35 molecular sieve.
实施例6Example 6
本实施例中锆基氧化物的组成与制备方法与实施例相同。The composition and preparation method of the zirconium-based oxide in this embodiment are the same as those in the examples.
将MOR(Si/Al＝10)分子筛装填于反应器中，在氮气气氛中升温到450℃活化4h，然后降温至250℃。用氮气携带吡啶(混合气中吡啶的体积分数为1％，混合气的质量空速为6000mL·g -1·h -1)的方式对H-MOR进行预吸附吡啶处理。吸附吡啶2h后，再用氮气吹扫4h，之后降至室温。取出处理过的H-MOR分子筛，得到经过预吸附碱处理的分子筛。 MOR (Si/Al = 10) molecular sieves were packed in a reactor, heated to 450 ° C for 4 h in a nitrogen atmosphere, and then cooled to 250 ° C. 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.
复合催化剂的制备过程中将实施例1中的改性H-MOR分子筛替换为上述经过预吸附碱处理的分子筛，其余与实施例1相同，得到复合催化剂28#。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#.
取3g 28#催化剂装填于反应器中，在如下条件下进行合成气制备乙烯反应：反应温度300℃，反应压力5.0MPa，CO/H 2为3/1，原料气质量空 速(GHSV)为2300mL·g -1·h -1。反应产物采用气相色谱仪在线分析，分析结果见表6。 3g 28# catalyst was charged into the reactor, and the synthesis gas was used to prepare ethylene reaction under the following conditions: reaction temperature 300 ° C, reaction pressure 5.0 MPa, CO/H 2 was 3/1, and raw material gas mass space velocity (GHSV) was 2300 mL·g -1 ·h -1 . The reaction product was analyzed online by gas chromatography, and the analysis results are shown in Table 6.
表6 实施例6催化剂反应结果Table 6 Example 6 catalyst reaction results
催化剂编号Catalyst number CO转化率(％)CO conversion rate (%) 乙烯选择性(％)Ethylene selectivity (%) 乙烷选择性(％)Ethane selectivity (%) 甲烷选择性(％)Methane selectivity (%)
28#28# 13.213.2 70.170.1 2.82.8 1.51.5
实施例7Example 7
考察复合催化剂中锆基金属氧化物与酸性分子筛氧化物含量对合成气制乙烯反应的影响。除了改变锆基金属氧化物和分子筛的相对含量，其他条件包括锆基金属氧化物组成、制备过程和复合成催化剂的评价条件与实施例1一致，反应产物采用气相色谱仪在线分析，结果如表7所示。The effect of the content of zirconium-based metal oxides and acidic molecular sieve oxides on the synthesis of ethylene in synthesis gas was investigated. In addition to changing the relative content of zirconium-based metal oxides and molecular sieves, other conditions including zirconium-based metal oxide composition, preparation process, and evaluation conditions for composite catalysts are consistent with Example 1, and the reaction products are analyzed by gas chromatography on-line. 7 is shown.
表7 实施例7不同催化剂反应评价结果Table 7 Example 7 Different Catalyst Reaction Evaluation Results
Figure PCTCN2018080924-appb-000004
Figure PCTCN2018080924-appb-000004
实施例8Example 8
考察1#复合催化剂在250℃、280℃、320℃、380℃反应温度下的催化性能，除了反应温度外，其他评价条件与实施例1一致。反应产物采用气相色谱仪在线分析，结果见表8。The catalytic performance of the 1# composite catalyst at a reaction temperature of 250 ° C, 280 ° C, 320 ° C, and 380 ° C was examined, and other evaluation conditions were in accordance with Example 1 except for the reaction temperature. The reaction product was analyzed online by gas chromatography, and the results are shown in Table 8.
表8 1#催化剂在不同温度下评价结果Table 8 Evaluation results of 1# catalyst at different temperatures
Figure PCTCN2018080924-appb-000005
Figure PCTCN2018080924-appb-000005
实施例9Example 9
考察原料摩尔组成对合成气制乙烯反应的影响，除了改变气体的摩尔比之外，其他评价条件与实施例1一致。原料气摩尔比为CO/H 2/CO 2＝1/X'/Y'，X'与Y'值及其相应条件下的评价结果列于表9中。 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 raw material gas molar ratio is CO/H 2 /CO 2 =1/X'/Y', and the X' and Y' values and their evaluation results under the respective conditions are shown in Table 9.
表9 不同原料气条件合成气制乙烯反应结果Table 9 Results of ethylene production from syngas with different feed gas conditions
Figure PCTCN2018080924-appb-000006
Figure PCTCN2018080924-appb-000006
实施例10Example 10
在1.0、2.5、3.0、6.0和8.0MPa的不同反应总压条件下，考察反应压力对合成气制乙烯反应的影响，催化剂为1#催化剂，除反应压力外，其他条件与实施例1一致，反应产物采用气相色谱仪在线分析，结果列于表10中。Under the conditions of different reaction total pressures of 1.0, 2.5, 3.0, 6.0 and 8.0 MPa, the influence of reaction pressure on the reaction of synthesis gas to ethylene was investigated. The catalyst was 1# catalyst, and other conditions were the same as those in Example 1 except for the reaction pressure. The reaction products were analyzed on-line by gas chromatography, and the results are shown in Table 10.
表10 不同反应压力下合成气制乙烯反应的结果Table 10 Results of ethylene reaction from synthesis gas at different reaction pressures
Figure PCTCN2018080924-appb-000007
Figure PCTCN2018080924-appb-000007
实施例11Example 11
分别在300、4000、8000和10000mL/g cat·h不同反应气体空速下，考察气体空速对合成气制乙烯反应的影响，催化剂为1#，除气体空速外，其他条件与实施例1一致，反应产物采用气相色谱仪在线分析，结果列于表11中。 Under the different reaction gas space velocities of 300, 4000, 8000 and 10000 mL/g cat · h, the effects of gas space velocity on the synthesis gas production of ethylene were investigated. The catalyst was 1#, except for gas space velocity, other conditions and examples. 1 Consistent, the reaction products were analyzed online by gas chromatography, and the results are shown in Table 11.
表11 不同反应空速下合成气制乙烯反应结果Table 11 Results of ethylene production from synthesis gas at different reaction space velocities
Figure PCTCN2018080924-appb-000008
Figure PCTCN2018080924-appb-000008
实施例12Example 12
催化剂为1#样品，反应器分别为流化床反应器和移动床反应器，其他条件同实施例1。反应产物采用气相色谱仪在线分析，结果见表12。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.
表12 1#复合催化剂不同反应器中的反应结果Table 12 Reaction results in different reactors of 1# composite catalyst
反应器类型Reactor type CO转化率(％)CO conversion rate (%) 乙烯选择性(％)Ethylene selectivity (%) 乙烷选择性(％)Ethane selectivity (%) 甲烷选择性(％)Methane selectivity (%)
流化床Fluidized bed 14.314.3 80.280.2 4.44.4 2.32.3
移动床Moving bed 16.316.3 81.281.2 3.53.5 3.43.4
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。The above description is only a few examples of the present application, and is not intended to limit the scope of the application. However, the present application is disclosed in the preferred embodiments, but is not intended to limit the application, any person skilled in the art, It is within the scope of the technical solution to make a slight change or modification with the technical content disclosed above, which is equivalent to the equivalent embodiment, without departing from the technical scope of the present application.

Claims (20)

  1. 一种复合催化剂，其特征在于，含有锆基氧化物和改性酸性分子筛；A composite catalyst comprising a zirconium-based oxide and a modified acidic molecular sieve;
    所述锆基氧化物的质量含量为10wt.％～90wt.％，所述改性酸性分子筛的质量含量为10wt.％～90wt.％；The zirconium-based oxide has a mass content of 10 wt.% to 90 wt.%, and the modified acidic molecular sieve has a mass content of 10 wt.% to 90 wt.%;
    其中，所述改性酸性分子筛为经过预吸附碱处理的酸性分子筛。Wherein, the modified acidic molecular sieve is an acidic molecular sieve treated by a pre-adsorbed alkali.
  2. 根据权利要求1所述的复合催化剂，其特征在于，所述预吸附碱处理的步骤至少包括：将所述酸性分子筛与含有有机碱的气体接触进行预吸附碱处理。The composite catalyst according to claim 1, wherein 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.
  3. 根据权利要求1或2所述的复合催化剂，其特征在于，所述预吸附碱处理的温度为150～350℃，预吸附碱处理的时间为0.5～4h，所述含有有机碱的气体的质量空速为300～6000mL·g -1·h -1。 The composite catalyst according to claim 1 or 2, wherein the pre-adsorption alkali treatment temperature is 150 to 350 ° C, and the pre-adsorption alkali treatment time is 0.5 to 4 h, and the mass of the organic alkali-containing gas is used. The space velocity is 300 to 6000 mL·g -1 ·h -1 .
  4. 根据权利要求2所述的复合催化剂，其特征在于，所述含有有机碱的气体包括载气和有机碱；The composite catalyst according to claim 2, wherein the organic base-containing gas comprises a carrier gas and an organic base;
    所述载气选自氮气、氦气、CO 2、氩气、氢气中的至少一种； The carrier gas is selected from at least one of nitrogen, helium, CO 2 , argon, and hydrogen;
    所述有机碱选自三甲胺、二乙胺、三乙胺、哒嗪、嘧啶、吡嗪、吡啶、咪唑、N-甲基咪唑、N-乙基咪唑、N--丙基咪唑、N-异丙基咪唑中的至少一种；The organic base is selected from the group consisting of trimethylamine, diethylamine, triethylamine, pyridazine, pyrimidine, pyrazine, pyridine, imidazole, N-methylimidazole, N-ethylimidazole, N-propylimidazole, N- At least one of isopropyl imidazole;
    所述含有有机碱的气体中有机碱的体积分数为0.1％～10％。The volume fraction of the organic base in the organic base-containing gas is from 0.1% to 10%.
  5. 根据权利要求2所述的复合催化剂，其特征在于，所述预吸附碱处理的步骤至少包括：将所述酸性分子筛在非活性气体氛中进行活化；然后将温度调至预吸附碱处理温度，与含有有机碱的气体接触进行预吸附碱处理；吸附饱和后，吹扫，降至室温，得到改性酸性分子筛。The composite catalyst according to claim 2, wherein the step of pre-adsorbing alkali treatment comprises at least: activating the acidic molecular sieve in an inert gas atmosphere; and then adjusting the temperature to a pre-adsorption alkali treatment temperature, The pre-adsorption alkali treatment is carried out in contact with a gas containing an organic base; after the adsorption is saturated, the mixture is purged to room temperature to obtain a modified acidic molecular sieve.
  6. 根据权利要求5所述的复合催化剂，其特征在于，所述活化的温度为300～500℃，活化的时间为3～5h。The composite catalyst according to claim 5, wherein the activation temperature is 300 to 500 ° C, and the activation time is 3 to 5 hours.
  7. 根据权利要求1所述的复合催化剂，其特征在于，所述酸性分子筛选自具有MOR拓扑结构的分子筛、具有FER拓扑结构的分子筛、含有MOR拓扑结构和FER拓扑结构的共晶分子筛、含有MOR拓扑结构和FER拓扑结构的混晶分子筛中的至少一种。The composite catalyst according to claim 1, wherein the acidic molecule is selected 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, and a MOR topology. At least one of a mixed crystal molecular sieve of a structure and an FER topology.
  8. 根据权利要求7所述的复合催化剂，其特征在于，所述具有MOR拓扑结构的分子筛为骨架原子Si/Al比为4～60的H-MOR分子筛；The composite catalyst according to claim 7, wherein the molecular sieve having a MOR topology is an H-MOR molecular sieve having a skeleton atom Si/Al ratio of 4 to 60;
    所述具有FER拓扑结构的分子筛为骨架原子Si/Al比为5～50的H-ZSM-35分子筛。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.
  9. 根据权利要求1所述的复合催化剂，其特征在于，所述锆基氧化物选自具有式(I)所述化学式的化合物中的至少一种：The composite catalyst according to claim 1, wherein the zirconium-based oxide is at least one selected from the group consisting of compounds having the chemical formula of the formula (I):
    X aM b(ZrO 2) 1-a-b式 (I) X a M b (ZrO 2 ) 1-ab formula (I)
    其中，式(I)中X为Si、Al、Ti、Ce、La中至少一种元素的氧化物；M为Cu、Ag、Zn、Mn、Y、Nb、Ga、In、Cr中至少一种元素的氧化物；Wherein 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;
    其中，a为0.02～0.9，b为0.0～0.8。Among them, a is 0.02 to 0.9, and b is 0.0 to 0.8.
  10. 权利要求1至9任一项所述的复合催化剂的制备方法，其特征在于，至少包括以下步骤：The method for preparing a composite catalyst according to any one of claims 1 to 9, characterized in that it comprises at least the following steps:
    (1)获得锆基氧化物；(1) obtaining a zirconium-based oxide;
    (2)获得改性酸性分子筛；(2) obtaining a modified acidic molecular sieve;
    (3)将含有步骤(1)中的锆基氧化物和步骤(2)中改性酸性分子筛的各组分采用超声辅助化学复合法和/或物理复合法进行复合，得到所述复合催化剂。(3) The components comprising the zirconium-based oxide in the step (1) and the modified acidic molecular sieve in the step (2) are combined by ultrasonic assisted chemical compounding and/or physical compounding to obtain the composite catalyst.
  11. 根据权利要求10所述的复合催化剂的制备方法，其特征在于，步骤(1)中所述锆基氧化物的获得方法包括：通过共沉淀法、浸渍法、机械混合法中的至少一种进行制备。The method for preparing a composite catalyst according to claim 10, wherein the method for obtaining the zirconium-based oxide in the step (1) comprises: performing at least one of a coprecipitation method, a dipping method, and a mechanical mixing method. preparation.
  12. 根据权利要求11所述的复合催化剂的制备方法，其特征在于，所述共沉淀法至少包括以下步骤：将含有X元素、M'元素和Zr元素的溶 液与含有沉淀剂的溶液在搅拌的条件下以并流的方式混合，控制体系pH值为7～9，沉淀结束后经老化，固液分离，洗涤、干燥和焙烧固相，得到所述锆基氧化物；The method for producing a composite catalyst according to claim 11, wherein the coprecipitation method comprises at least the following steps: stirring a solution containing a X element, an M' element, and a Zr element with a solution containing a precipitating agent The mixture is mixed in a cocurrent manner, the pH of the control system is 7-9, and after aging, the solid phase is separated, washed, dried and calcined to obtain the zirconium-based oxide;
    所述浸渍法至少包括以下步骤：将氧化锆粉末浸渍于含有X元素和M'元素的盐溶液中或者将氧化锆粉末和X的氧化物浸渍于含有M'元素的盐溶液中或者将氧化锆粉末和M'的氧化物浸渍于含有X元素的盐溶液中；浸渍后经去除溶剂、干燥、焙烧，得到所述锆基氧化物；The impregnation 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 solution containing the M' element or zirconia The powder and the oxide of M' are immersed in a salt solution containing X element; after immersion, the solvent is removed, dried, and calcined to obtain the zirconium-based oxide;
    其中，M'选自Cu、Ag、Zn、Mn、Y、Nb、Ga、In、Cr中至少一种。Wherein M' is at least one selected from the group consisting of Cu, Ag, Zn, Mn, Y, Nb, Ga, In, and Cr.
  13. 根据权利要求12所述的复合催化剂的制备方法，其特征在于，所述共沉淀法中老化的时间为2～4h，焙烧的条件为400～600℃焙烧1～6h；The method for preparing a composite catalyst according to claim 12, wherein the aging time in the coprecipitation method is 2 to 4 hours, and the firing condition is 400 to 600 ° C for 1 to 6 hours;
    所述浸渍法中浸渍的时间为1～6h，干燥的条件为60～200℃干燥1～10h，焙烧的条件为400～600℃焙烧1～6h。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.
  14. 根据权利要求12所述的复合催化剂的制备方法，其特征在于，所述溶液中的X元素、M'元素和Zr元素独立地来自X元素、M'元素和Zr元素的硝酸盐、盐酸盐、醋酸盐、乙酰丙酮盐、硫酸盐中的至少一种。The method for preparing a composite catalyst according to claim 12, wherein the X element, the M' element and the Zr element in the solution are independently derived from the nitrate, hydrochloride of the X element, the M' element and the Zr element. At least one of acetate, acetylacetonate, and sulfate.
  15. 根据权利要求10所述的复合催化剂的制备方法，其特征在于，步骤(3)中所述超声辅助化学复合法至少包括：将含有锆基氧化物和改性酸性分子筛的溶液超声后，经固液分离，干燥和焙烧固相，得到所述复合催化剂；The method for preparing a composite catalyst according to claim 10, wherein the ultrasonic assisted chemical compounding method in the step (3) comprises at least: ultrasonically modifying a solution containing a zirconium-based oxide and a modified acidic molecular sieve, and solidifying Separating, drying and calcining the solid phase to obtain the composite catalyst;
    所述物理复合法至少包括：将含有锆基氧化物和改性酸性分子筛的混合物通过机械混合、球磨、振荡中的至少一种方式复合，得到所述复合催化剂。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.
  16. 根据权利要求15所述的复合催化剂的制备方法，其特征在于，所述超声辅助化学复合法中超声的时间为10min～3h；干燥的温度为60～150℃；焙烧的温度为300～650℃。The method for preparing a composite catalyst according to claim 15, wherein the ultrasonic assisted chemical compounding method has a time of 10 min to 3 h; a drying temperature of 60 to 150 ° C; and a calcination temperature of 300 to 650 ° C. .
  17. 一种乙烯的制备方法，其特征在于，至少包括以下步骤：A method for preparing ethylene, characterized in that it comprises at least the following steps:
    将含有合成气的原料气通过装有复合催化剂的反应器，反应得到乙烯；The raw material gas containing the synthesis gas is passed through a reactor equipped with a composite catalyst to obtain ethylene;
    其中，所述复合催化剂选自权利要求1至9任一项所述的复合催化剂和/或根据权利要求10至16任一项所述的方法制备得到的复合催化剂中的至少一种；Wherein the composite catalyst is at least one selected from the group consisting of the composite catalyst according to any one of claims 1 to 9 and/or the composite catalyst prepared according to the method according to any one of claims 10 to 16;
    其中，所述合成气包括CO、H 2、CO 2，摩尔比满足： Wherein, the syngas comprises CO, H 2 , CO 2 , and the molar ratio satisfies:
    CO：H 2：CO 2＝1：0.2～4：0～1。 CO: H 2 : CO 2 = 1: 0.2 to 4: 0 to 1.
  18. 根据权利要求17所述的乙烯的制备方法，其特征在于，所述反应的温度为250～380℃，压力为1.0～8.0MPa，气体质量空速为300～10000mL·g -1·h -1。 The method for preparing ethylene according to claim 17, wherein the reaction temperature is 250 to 380 ° C, the pressure is 1.0 to 8.0 MPa, and the gas mass space velocity is 300 to 10000 mL·g -1 · h -1 .
  19. 根据权利要求17所述的乙烯的制备方法，其特征在于，所述原料气中还包括非活性气体；The method for preparing ethylene according to claim 17, wherein the raw material gas further comprises an inert gas;
    所述非活性气体选自氮气、氩气、氦气、甲烷中的至少一种；The inert gas is selected from at least one of nitrogen, argon, helium, and methane;
    所述非活性气体在混合气中的体积含量≤10％。The volume content of the inert gas in the mixed gas is ≤10%.
  20. 根据权利要求17所述的乙烯的制备方法，其特征在于，所述反应器为固定床反应器、流化床反应器、移动床反应器中的至少一种。The method for producing ethylene according to claim 17, wherein the reactor is at least one of a fixed bed reactor, a fluidized bed reactor, and a moving bed reactor.
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