WO2019183841A1 - 一种复合催化剂、其制备方法和乙烯的制备方法 - Google Patents

一种复合催化剂、其制备方法和乙烯的制备方法 Download PDF

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WO2019183841A1
WO2019183841A1 PCT/CN2018/080923 CN2018080923W WO2019183841A1 WO 2019183841 A1 WO2019183841 A1 WO 2019183841A1 CN 2018080923 W CN2018080923 W CN 2018080923W WO 2019183841 A1 WO2019183841 A1 WO 2019183841A1
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composite catalyst
molecular sieve
organic base
gas
mor molecular
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PCT/CN2018/080923
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English (en)
French (fr)
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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/CN2018/080923 priority Critical patent/WO2019183841A1/zh
Publication of WO2019183841A1 publication Critical patent/WO2019183841A1/zh

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00Aliphatic unsaturated hydrocarbons
    • C07C11/02Alkenes
    • C07C11/04Ethylene
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/40Ethylene production

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 methanol and 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 (C 2 -C 4 olefin).
  • C 2 -C 4 olefin mixed low olefin
  • the path has entered industrialization in China and has achieved great success.
  • ethylene is not highly selective in hydrocarbon species, and typically has an ethylene selectivity of no more than 40%. Therefore, how to convert the methanol/dimethyl ether orientation into high selectivity into ethylene is extremely difficult.
  • a composite catalyst for use in the high selectivity of methanol/dimethyl ether carbonylation hydrogenation to produce ethylene having an ethylene selectivity of 86%.
  • the composite catalyst comprises a CO hydrogenation catalyst, a modified H-MOR molecular sieve and graphite;
  • the modified H-MOR molecular sieve is a H-MOR molecular sieve treated by a pre-adsorbed organic base.
  • the CO hydrogenation catalyst is an oxide.
  • the step of pre-adsorbing the organic base treatment comprises at least: contacting the H-MOR molecular sieve with a gas containing an organic base for pre-adsorption organic alkali treatment.
  • the pre-adsorption organic base treatment temperature is 150-350 ° C
  • the pre-adsorption organic alkali treatment time is 0.5-4 h.
  • the upper temperature limit of the pre-adsorption organic base 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 organic 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 mass of the organic base-containing gas has a mass space velocity of 300 to 6000 mL ⁇ g -1 ⁇ h -1 .
  • 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 alkali-containing gas includes a carrier gas and an organic base; and the carrier gas is at least one selected from the group consisting of nitrogen, helium, CO 2 , argon, and hydrogen;
  • the organic base is at least one selected from the group consisting of trimethylamine, diethylamine, triethylamine, pyridine, pyridazine, pyrimidine, and pyrazine;
  • the volume fraction of the organic base in the organic base-containing gas is from 0.1% to 10%.
  • 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 H-MOR molecular sieve is activated in an inert atmosphere prior to contact with a gas containing an organic base;
  • the activation temperature is 300 to 500 ° C, and the activation time is 3 to 5 h.
  • the upper limit of the activation temperature is selected from 320 ° C, 350 ° C, 400 ° C, 450 ° C, 480 ° C or 500 ° C; the lower limit is selected from 300 ° C, 350 ° C, 400 ° C, 450 ° C, 480 ° 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 step of pre-adsorbing the organic base treatment comprises at least: activating the H-MOR molecular sieve in an inert atmosphere; then adjusting the temperature to a pre-adsorbed organic base treatment temperature to contact the gas containing the organic base.
  • the pre-adsorbed organic alkali treatment was carried out, and the mixture was purged and cooled to room temperature to obtain a modified H-MOR molecular sieve.
  • the purge is purged with at least one of nitrogen, helium, CO 2 , argon, and hydrogen.
  • the purged gas is the same as the carrier gas.
  • the step of pre-adsorbing the organic base treatment comprises at least: activating the acid-treated H-MOR molecular sieve in an inert gas atmosphere, and then adjusting the temperature to a pre-adsorbed organic base treatment temperature, and containing the organic base.
  • the gas is contacted with a pre-adsorbed organic base, and after adsorption is saturated, it is purged and lowered to room temperature to obtain a modified acidic molecular sieve.
  • the step of pre-adsorbing the organic base by the H-MOR comprises at least: the H-MOR molecular sieve needs to carry out pre-adsorption of the organic base 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, and hydrogen, or any one of
  • the pretreatment gas mass space velocity ranges from 300 to 5000 mL ⁇ g -1 ⁇ h -1
  • the organic base is any one of trimethylamine, diethylamine, triethylamine, pyridine, pyridazine, pyrimidine and pyrazine.
  • the organic base pretreatment temperature ranges from 150 to 350 ° C
  • the pretreatment time is from 0.5 to 4 h.
  • the mass ratio of the CO hydrogenation catalyst, the modified H-MOR molecular sieve, and the graphite in the composite catalyst is satisfied:
  • the H-MOR molecular sieve has a silicon to aluminum atomic ratio of 5 to 60.
  • the mass ratio of the CO hydrogenation catalyst, the modified H-MOR molecular sieve, and the graphite in the composite catalyst is satisfied:
  • the H-MOR molecular sieve has a silicon to aluminum atomic ratio of 5 to 60.
  • the upper limit of the mass content of the CO hydrogenation catalyst is selected from the group consisting of 11 wt.%, 20 wt.%, 30 wt.%, 33.3 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 65.2 wt.%, 65.4 wt.%, 66.7 wt.%, 70 wt.%, 80 wt.% or 90 wt.%; the lower limit is selected from 10 wt.%, 20 wt.%, 30 wt.%, 33.3 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 65.2 wt.%, 65.4 wt.%, 66.7 wt.%, 70 wt.%, 80 wt.% or 89 wt.%.
  • the upper limit of the mass content of the modified H-MOR molecular sieve is selected from the group consisting of 7.8 wt.%, 10 wt.%, 11 wt.%, 20 wt.%, 30 wt.%, 32.6 wt.%, 33.3 wt.%, 40 wt.
  • the lower limit is selected from 7 wt.%, 7.8 wt.%, 10 wt.%, 20 wt.%, 30 wt.%, 32.6 wt.%, 33.3 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 64.5 wt.%, 66.7 wt.%, 70 wt.%, 80 wt. %, 87.8 wt.% or 90 wt.%; the lower limit is selected from 7 wt.%, 7.8 wt.%, 10 wt.%, 20 wt.%, 30 wt.%, 32.6 wt.%, 33.3 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 64.5 wt.%, 66.7 wt.%, 70 wt.%, 80 wt. %, 87.8 wt.% or 89 wt.%
  • the mass ratio of the CO hydrogenation catalyst, the modified H-MOR molecular sieve, and the graphite in the composite catalyst is satisfied:
  • the mass ratio of the CO hydrogenation catalyst, the modified H-MOR molecular sieve, and the graphite in the composite catalyst is satisfied:
  • the upper limit of the mass content of the graphite is selected from 2 wt.%, 2.2 wt.% or 5 wt.%; and the lower limit is selected from 1 wt.%, 2 wt.% or 2.2 wt.%.
  • the upper limit of the silicon to aluminum atomic ratio of the H-MOR molecular sieve is selected from 10, 30, 40, 50 or 60; and the lower limit is selected from 5, 10, 30, 40 or 50.
  • the CO hydrogenation catalyst is selected from at least one of the compounds having the formula of formula (I):
  • M is an oxide of at least one of Zr, Cr, and Ce; a is 0.1 to 0.9, and b is 0.05 to 0.8.
  • the a, b are the molar proportions of the corresponding oxides in the total composition.
  • the upper limit of the range of a in the formula (I) is selected from 0.1, 0.4, 0.5, 0.6, 0.8 or 0.9; the lower limit is selected from 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 0.05, 0.1, 0.4, 0.5, 0.6, or 0.8; and the lower limit is selected from 0.05, 0.1, 0.4, 0.5 or 0.6.
  • b is a value between 0.05 and 0.8.
  • a method of preparing the composite catalyst characterized in that it comprises at least:
  • the method for obtaining the CO hydrogenation catalyst in the step (1) includes at least a coprecipitation method or a dipping method.
  • the coprecipitation method comprises at least the steps of: mixing a salt solution containing a Zn element, an M′ element, and an Al element with a solution containing a precipitant in a cocurrent manner under stirring to control the pH of the system.
  • the value is 7-9, after aging, the solid-liquid separation, washing, drying and calcining the solid phase to obtain the CO hydrogenation catalyst;
  • the dipping method includes at least: immersing the alumina powder in a salt solution containing the Zn element and the M' element or immersing the oxide of the alumina and the M' element in a salt solution containing the Zn element; removing the solvent after the immersion Drying and calcining to obtain the CO hydrogenation catalyst;
  • M' is selected from at least one of Zr, Cr, and Ce.
  • the aging time in the coprecipitation method is 2 to 4 hours, and the firing condition is 400 to 600 ° C roasting for 1 to 6 hours;
  • 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 Zn element, the M' element, and the Al element in the solution are independently derived from at least one of a nitrate, a hydrochloride, an acetate, an acetylacetonate, and a sulfate of a Zn element, an M' element, and an Al element.
  • the conditions for drying in the coprecipitation are dried at 100 ° C for 6 hours.
  • the agitation in the coprecipitation method is vigorous agitation.
  • the stirring speed in the coprecipitation method is from 250 to 5000 rpm/min.
  • 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 comprises the steps of: arranging at least one of the compounds containing the M' element with an aqueous solution of Zn and Al, and recording it as solution A; and ammonia, ammonium carbonate, and carbonic acid.
  • One or any of sodium, urea, NaOH or KOH is formulated into aqueous solution B; under intense stirring, solution A and solution B are mixed in a cocurrent manner, and the flow rates of solution A and solution B are adjusted to control the mixed liquid.
  • the pH ranges from 7 to 9; after the precipitation is completed, it 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 soluble salt and soluble Zn salt of the compound containing M' element to deionized water or alcohol solution to prepare solution C,
  • the alumina powder is immersed in the solution C, and 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 at a temperature of 400 to 600 ° C. The range is calcined for 1 to 6 hours.
  • the step (3) comprises at least: mixing the components of the CO hydrogenation catalyst containing the CO in the step (1) and the modified H-MOR molecular sieve in the step (2) by ball milling to the mixed Graphite is added to the composition and subjected to sheet molding to obtain the composite catalyst.
  • the preparation method of the composite catalyst includes at least the following steps:
  • the molecular sieve is subjected to ammonium exchange to prepare a hydrogen type molecular sieve, acid-treated H-MOR, and then subjected to pre-adsorption organic alkali treatment;
  • the composite catalyst and/or the composite catalyst prepared according to the method is used for the hydrogenation of methanol/dimethyl ether to produce ethylene.
  • a method for preparing ethylene comprises at least the following steps:
  • the feed gas containing methanol/dimethyl ether, CO and H 2 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 the composite catalyst prepared according to the method;
  • the raw material gas composition molar ratio satisfies:
  • the reaction temperature is 200-350 ° C
  • the pressure is 1.0-8.0 MPa
  • the mass velocity of the feed gas is 300-10000 mL ⁇ g -1 ⁇ h -1 .
  • the upper temperature limit of the reaction is selected from 220 ° C, 280 ° C, 300 ° C, 320 ° C or 350 ° C; the lower limit is selected from 200 ° C, 220 ° C, 280 ° C, 300 ° C or 320 ° C.
  • the upper limit of the reaction pressure is selected from the group consisting of 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 , 2300 mL ⁇ g -1 ⁇ h -1 , 4000mL ⁇ 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 , 1000mL ⁇ g -1 ⁇ h -1 , 2300mL ⁇ g -1 ⁇ h -1 , 4000mL ⁇ g -1 ⁇ h -1 or 8000mL ⁇ g -1 ⁇ h -1 .
  • the raw material 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 feed gas is ⁇ 10%.
  • the upper limit of the volume content of the inert gas in the raw material gas is selected from 1%, 3%, 5%, 8% or 10%; and the lower limit is selected from 0%, 1%, 3%, 5% or 8 %.
  • the volume of the inert gas in the feed gas is from 0% to 10%.
  • composition gas molar ratio (methanol / dimethyl ether: CO: H 2 ) is selected from 0.1:1:1, 0.05:1:1, 0.3:1:2, 0.5:1:3 or 0.1:1:1.
  • the upper limit of the molar ratio of methanol/dimethyl ether to CO is selected from 0.06/1, 0.25/1 or 0.5/1; and the lower limit is selected from 0.05/1, 0.2/1 or 0.4/1.
  • the upper limit of the molar ratio of CO and H 2 is selected from 1/1, 1/3 or 1/4; and the lower limit is selected from 1/0.5, 1/1 or 1/3.
  • the reactor is selected from 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 the hydrogenation of methanol/dimethyl ether to ethylene, and at least comprises the steps of: charging a raw material gas containing methanol/dimethyl ether, CO and H 2 ; a reactor having a composite catalyst, which synthesizes ethylene under certain reaction conditions; the combined feed gas is methanol/dimethyl ether, CO and H 2 and other gases; the reaction temperature is preferably 200-350 ° C; the other gases are selected from inert One or more of nitrogen, argon, helium and methane, wherein the volume content in the raw material 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 preparation method of the ethylene is methanol/dimethyl ether carbonylation hydrogenation and high selectivity to produce ethylene, and the ethylene selectivity reaches 86%.
  • 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.
  • a CO hydrogenation 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 methanol/dimethyl ether carbonylation hydrogenation to ethylene process 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
  • X (MeOH / DME) 1 - F (MeOH / DME) outlet / F (MeOH / DME) inlet , where F (MeOH / DME) outlet is the reactor outlet MeOH or DME flow, The F (MeOH/DME) inlet is the reactor inlet MeOH or DME flow.
  • the salt solution A and the precipitant alkali solution B were mixed in a cocurrent manner, and the relative flow rates of the solutions A and B were adjusted to ensure that the pH of the precipitation mixture was maintained at 7-8. between.
  • the coprecipitation 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 CO hydrogenation catalyst.
  • the composition of the CO hydrogenation catalyst was (ZnO) 0.4 (ZrO 2 ) 0.5 (Al 2 O 3 ) 0.1 by XRF elemental analysis.
  • the pre-adsorption pyridine treatment was carried out in such a manner that pyridine was carried by nitrogen (the volume fraction of pyridine in the mixed gas was 0.2%, 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 to obtain a modified H-MOR molecular sieve.
  • the CO hydrogenation catalyst (30.0 g) obtained above and the modified H-MOR molecular sieve (15.0 g) were sufficiently ground and mixed by a ball mill. Graphite was added and tableted to obtain a composite catalyst, and the catalyst was designated as ##.
  • the mass content of the CO hydrogenation catalyst in the 1# composite catalyst was 65.2 wt.%
  • the mass of the modified H-MOR molecular sieve was 32.6 wt.%
  • the mass content of the graphite was 2.2%.
  • the CO hydrogenation catalyst 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 are the same as in the first embodiment.
  • 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 CO hydrogenation catalyst is prepared by the impregnation method, and 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 7.6 g of chromium oxide powder and 2.04 g of alumina was immersed in solution C, and after immersion 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 CO hydrogenation catalyst having a composition of (ZnO) 0.4 (Cr 2 O 3 ) 0.5 (Al 2 O 3 ) 0.1 was obtained .
  • Example 3 Except that the CO hydrogenation catalyst preparation method was different from that of Example 1, the remaining steps were consistent with Example 1, and the finally obtained catalyst 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 CO hydrogenation catalyst sample composition was measured by XRF.
  • the molecular sieve Si/Al, the type of pre-adsorbed organic base and the effect of methanol/dimethyl ether carbonylation hydrogenation to ethylene were investigated.
  • the composition and preparation method of the CO hydrogenation catalyst were the same as in Example 1, and the preparation and evaluation conditions of the composite catalyst were consistent with those of Example 1.
  • the reaction product was analyzed by gas chromatography on-line, and the results are shown in Table 5.
  • composition and preparation method of the CO hydrogenation catalyst in this embodiment are the same as those in the examples.
  • the pre-adsorption pyridine treatment was carried out in such a manner that pyridine was carried by nitrogen (the volume fraction of pyridine in the mixed gas was 0.2%, 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 to obtain a modified MOR molecular sieve.
  • Example 1 In the preparation of the composite catalyst, the modified H-MOR molecular sieve of Example 1 was replaced with a modified MOR molecular sieve, and the rest was the same as in Example 1, to obtain a composite catalyst 26#.
  • 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

一种复合催化剂、其制备方法和乙烯的制备方法。复合催化剂由CO加氢催化剂和改性 H-MOR分子筛复合而成;将复合催化剂用于甲醇/二甲醚羰化加氢制乙烯,其中乙烯选择性达到86%。

Description

一种复合催化剂、其制备方法和乙烯的制备方法 技术领域
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,属于甲醇与合成气制低碳烯烃领域。
背景技术
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。
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(C 2-C 4烯烃)。该路径在中国已经步入工业化,并且取得了巨大成功。但在现有的MTO过程中,乙烯在烃类物种中的选择性不高,通常乙烯选择性不超过40%。因此如何将甲醇/二甲醚定向高选择性转化为乙烯难度极大。
发明内容
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甲醇/二甲醚羰基化加氢高选择性制取乙烯,其中乙烯选择性达到86%。
所述复合催化剂包含CO加氢催化剂、改性H-MOR分子筛和石墨;
其中,所述改性H-MOR分子筛为经过预吸附有机碱处理的H-MOR分子筛。
可选地,所述CO加氢催化剂为氧化物。
可选地,所述预吸附有机碱处理的步骤至少包括:将所述H-MOR分子筛与含有有机碱的气体接触进行预吸附有机碱处理。
可选地,所述预吸附有机碱处理的温度为150~350℃,预吸附有机碱处理的时间为0.5~4h。
可选地,预吸附有机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℃。
可选地,预吸附有机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。
可选地,所述含有有机碱的气体的质量空速为300~6000mL·g -1·h -1
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
可选地,所述含有有机碱的气体包括载气和有机碱;所述载气选自氮气、氦气、CO 2、氩气、氢气中的至少一种;
所述有机碱选自三甲胺、二乙胺、三乙胺、吡啶、哒嗪、嘧啶、吡嗪中的至少一种;
所述含有有机碱的气体中有机碱的体积分数为0.1%~10%。
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%。
可选地,所述H-MOR分子筛与含有有机碱的气体接触之前在非活性气氛中进行活化;
所述活化的温度为300~500℃,活化的时间为3~5h。
可选地,所述活化的温度上限选自320℃、350℃、400℃、450℃、480℃或500℃;下限选自300℃、350℃、400℃、450℃、480℃或500℃。
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。
可选地,所述预吸附有机碱处理的步骤至少包括:将所述H-MOR分子筛在非活性气氛中进行活化;然后将温度调至预吸附有机碱处理温度,与含有有机碱的气体接触进行预吸附有机碱处理,吹扫,降至室温,得到改性H-MOR分子筛。
可选地,所述吹扫为氮气、氦气、CO 2、氩气、氢气中的至少一种进行吹扫。
可选地,所述吹扫的气体与载气相同。
可选地,所述预吸附有机碱处理的步骤至少包括:将所述酸处理H-MOR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有机碱处理温度,与含有有机碱的气体接触进行预吸附有机碱处理,吸附饱和后,吹扫,降至室温,得到改性酸性分子筛。
作为一种具体的实施方式,所述H-MOR进行预吸附有机碱处理的步骤至少包括:所述H-MOR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、吡啶、哒嗪、嘧啶、吡嗪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。
可选地,所述复合催化剂中CO加氢催化剂、改性H-MOR分子筛和石墨的质量比满足:
CO加氢催化剂:改性H-MOR分子筛:石墨=10~90:7~90:1~5;
所述H-MOR分子筛的硅铝原子比为5~60。
可选地,所述复合催化剂中CO加氢催化剂、改性H-MOR分子筛和石墨的质量比满足:
CO加氢催化剂:改性H-MOR分子筛:石墨=10~90:10~90:1~5;
所述H-MOR分子筛的硅铝原子比为5~60。
可选地,所述CO加氢催化剂的质量含量上限选自11wt.%、20wt.%、30wt.%、33.3wt.%、40wt.%、50wt.%、60wt.%、65.2wt.%、65.4wt.%、66.7wt.%、70wt.%、80wt.%或90wt.%;下限选自10wt.%、20wt.%、30wt.%、33.3wt.%、40wt.%、50wt.%、60wt.%、65.2wt.%、65.4wt.%、66.7wt.%、70wt.%、80wt.%或89wt.%。
可选地,所述改性H-MOR分子筛的质量含量上限选自7.8wt.%、10wt.%、11wt.%、20wt.%、30wt.%、32.6wt.%、33.3wt.%、40wt.%、50wt.%、60wt.%、64.5wt.%、66.7wt.%、70wt.%、80wt.%、87.8wt.%或90wt.%;下限选自7wt.%、7.8wt.%、10wt.%、20wt.%、30wt.%、32.6wt.%、33.3wt.%、 40wt.%、50wt.%、60wt.%、64.5wt.%、66.7wt.%、70wt.%、80wt.%、87.8wt.%或89wt.%。
可选地,所述复合催化剂中CO加氢催化剂、改性H-MOR分子筛和石墨的质量比满足:
CO加氢催化剂:改性H-MOR分子筛:石墨=65.4:32.6:2。
可选地,所述复合催化剂中CO加氢催化剂、改性H-MOR分子筛和石墨的质量比满足:
CO加氢催化剂:改性H-MOR分子筛:石墨=65.2:32.6:2.2。
可选地,所述石墨的质量含量上限选自2wt.%、2.2wt.%或5wt.%;下限选自1wt.%、2wt.%或2.2wt.%。
可选地,所述H-MOR分子筛的硅铝原子比上限选自10、30、40、50或60;下限选自5、10、30、40或50。
可选地,所述CO加氢催化剂选自具有式(I)所述化学式的化合物中的至少一种:
(ZnO) aM b(Al 2O 3) 1-a-b  式(I)
其中,M为Zr、Cr、Ce中至少一种元素的氧化物;a为0.1~0.9,b为0.05~0.8。
所述a、b为相应氧化物在全组分中的摩尔占比。
可选地,式(I)中所述a的范围上限选自0.1、0.4、0.5、0.6、0.8或0.9;下限选自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。
可选地,所述b的上限选自0.05、0.1、0.4、0.5、0.6、或0.8;下限选自0.05、0.1、0.4、0.5或0.6。优选地,b为0.05~0.8之间的某一值。
本申请的另一方面,提供了所述的复合催化剂的制备方法,其特征在于,至少包括:
(1)获得CO加氢催化剂;
(2)获得改性H-MOR分子筛;
(3)将石墨加入到含有步骤(1)中的CO加氢催化剂和步骤(2)中改性H-MOR分子筛的混合物中,成型,得到所述复合催化剂。
可选地,步骤(1)中所述CO加氢催化剂的获得方法至少包括:共 沉淀法或浸渍法。
可选地,所述共沉淀法至少包括以下步骤:在搅拌的条件下,将含有Zn元素、M'元素和Al元素的盐溶液与含有沉淀剂的溶液以并流的方式混合,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CO加氢催化剂;
所述浸渍法至少包括:将氧化铝粉末浸渍于含有Zn元素和M'元素的盐溶液中或者将氧化铝和M'元素的氧化物浸渍于含有Zn元素的盐溶液中;浸渍后经去除溶剂、干燥、焙烧,得到所述CO加氢催化剂;
其中,所述M'选自Zr、Cr、Ce中至少一种。
可选地,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;
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;
所述溶液中的Zn元素、M'元素和Al元素独立地来自Zn元素、M'元素和Al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。
可选地,所述共沉淀中干燥的条件为100℃干燥6小时。
可选地,所述共沉淀法中的搅拌为剧烈搅拌。
可选地,所述共沉淀法中搅拌的速度为250~5000rpm/min。
可选地,所述沉淀剂为碱液。
可选地,所述碱液选自氨水、碳酸铵、碳酸钠、尿素、NaOH、KOH中的至少一种。
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M'元素的化合物中的至少一种与Zn、Al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。
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M'元素的化合物中的至少一种可溶性盐和可溶性Zn盐,加去离子水或醇溶液中, 配成溶液C,将氧化铝粉末浸入到溶液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。
可选地,所述步骤(3)至少包括:将含有步骤(1)中的CO加氢催化剂和步骤(2)中的改性H-MOR分子筛各组分通过球磨充分混合,向混合后的组分中加入石墨,进行打片成型,得到所述复合催化剂。
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:
(1)制备CO加氢催化剂;
(2)将分子筛进行铵交换,制备成氢型分子筛,酸处理H-MOR,之后进行预吸附有机碱处理;
(3)将步骤(1)和(2)中的产物通过球磨混合,加入石墨,打片制备成甲醇/二甲醚羰化加氢制乙烯复合催化剂。
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甲醇/二甲醚羰化加氢制备乙烯。
本申请的再一方面,提供了一种乙烯的制备方法,其特征在于,至少包括以下步骤:
将含有甲醇/二甲醚、CO和H 2的原料气通过装有复合催化剂的反应器,反应得到乙烯;
其中,所述复合催化剂选自所述复合催化剂、根据所述的方法制备得到的复合催化剂中的至少一种;
其中,所述原料气组成摩尔比满足:
甲醇/二甲醚:CO:H 2=0.05~0.5:1:0.5~4。
可选地,所述反应的温度为200~350℃,压力为1.0~8.0MPa,原料气质量空速为300~10000mL·g -1·h -1
可选地,所述反应的温度上限选自220℃、280℃、300℃、320℃或350℃;下限选自200℃、220℃、280℃、300℃或320℃。
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。
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、2300mL·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、2300mL·g -1·h -1、4000mL·g -1·h -1或8000mL·g -1·h -1
可选地,所述原料气中还包括非活性气体;
所述非活性气体选自氮气、氩气、氦气、甲烷中的至少一种;
所述非活性气体在原料气中的体积含量≤10%。
可选地,所述非活性气体在原料气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%。
可选地,所述非活性气体在原料气中的体积含量为0%~10%。
可选地,所述原料气中组成摩尔比(甲醇/二甲醚:CO:H 2)选自0.1:1:1、0.05:1:1、0.3:1:2、0.5:1:3或0.1:1:1。
可选地,所述甲醇/二甲醚与CO的摩尔比上限选自0.06/1、0.25/1或者0.5/1;下限选自0.05/1、0.2/1或者0.4/1。
可选地,所述CO和H 2的摩尔比上限选自1/1、1/3或1/4;下限选自1/0.5、1/1或1/3。
可选地,所述反应器选自固定床反应器、流化床反应器、移动床反应器中的至少一种。
作为一种具体的实施方式,所述复合催化剂用于甲醇/二甲醚羰化加氢制乙烯的方法,至少包括以下步骤:将含有甲醇/二甲醚、CO和H 2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,合成乙烯;所述合原料气为甲醇/二甲醚、CO和H 2和其他气体;反应温度优选为200~350℃;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
所述乙烯的制备方法为甲醇/二甲醚羰基化加氢高选择性制取乙烯,乙烯选择性达到86%。
本申请中的甲醇/二甲醚羰化加氢制取乙烯得到乙烯的选择性大于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。
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。
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。
本申请能产生的有益效果包括:
1、本申请中将CO加氢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。
2、本申请中的催化剂制备过程简单,容易获得。
3、本申请中甲醇/二甲醚羰化加氢制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。
具体实施方式
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。
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。
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。
实施例中转化率、选择性计算如下:
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。
甲醇/二甲醚转化率:X(MeOH/DME)=1-F(MeOH/DME) outlet/F(MeOH/DME) inlet,其中F(MeOH/DME) outlet是反应器出口MeOH或者DME流量,F(MeOH/DME) inlet是反应器入口MeOH或者DME流量。
烃类选择性的计算方法为:S(C nH mO L)=n*C nH mO L/Σ(n*C nH mO L),C nH mO L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。L是O原子数。
实施例1
称取21.46g Zr(NO 3) 4·5H 2O,11.90g Zn(NO 3) 2·6H 2O和7.5g Al(NO 3) 3·9H 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(搅拌速率为450rpm/min),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4h,得到CO加氢催化剂。经XRF元素分析,CO加氢催化剂组成为(ZnO) 0.4(ZrO 2) 0.5(Al 2O 3) 0.1
将H-MOR(Si/Al=10)分子筛装填于反应器中,在氮气气氛中升温到300℃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0.2%,混合气的质量空速为6000mL·g -1·h -1)的方式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,得到改性H-MOR分子筛。
利用球磨机将上述得到的CO加氢催化剂(30.0g)与改性H-MOR分子筛(15.0g)充分研磨混合。加入石墨,打片成型,得到复合催化剂,该催化剂记为1#。1#复合催化剂中CO加氢催化剂质量含量为65.2wt.%,改性H-MOR分子筛质量为32.6wt.%,石墨质量含量为2.2%。
取3g 1#催化剂装填于反应器中,在如下条件下进行甲醇羰化加氢制取乙烯反应:反应温度250℃,反应压力5.0MPa,甲醇/CO/H 2为0.1/1/1,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。
表1 实施例1催化剂反应结果
Figure PCTCN2018080923-appb-000001
实施例2
采用与实施例1中相同的制备方法和制备条件获得CO加氢催化剂。 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。
表2
Figure PCTCN2018080923-appb-000002
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
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。
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。
实施例3
采用浸渍法制备CO加氢催化剂,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7.6g氧化铬粉末和2.04g氧化铝浸入到溶液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CO加氢催化剂,其组成为(ZnO) 0.4(Cr 2O 3) 0.5(Al 2O 3) 0.1
除CO加氢催化剂制备方法与实施例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。
表3 实施例3催化剂反应评价结果
Figure PCTCN2018080923-appb-000003
实施例4
采用共沉淀法或浸渍法制备不同金属组成和不同含量CO加氢催化剂,其中CO加氢催化剂的组成与实施例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#~16#,各催化剂具体组成见表4。原料气组成为二甲醚/CO/H 2为0.1/1/1,在实施例1相同的反应条件下对7#~16#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。
表4 实施例4催化剂反应结果
Figure PCTCN2018080923-appb-000004
CO加氢催化剂样品组成由XRF测得。
实施例5
考察分子筛Si/Al、预吸附有机碱的种类和对甲醇/二甲醚羰化加氢制乙烯反应的影响。CO加氢催化剂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。
表5 实施例5催化剂评价结果
Figure PCTCN2018080923-appb-000005
实施例6
本实施例中CO加氢催化剂的组成与制备方法与实施例相同。
将MOR(Si/Al=10)分子筛装填于反应器中,在氮气气氛中升温到300℃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0.2%,混合气的质量空速为6000mL·g -1·h -1)的方式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,得到改性MOR分子筛。
复合催化剂的制备过程中将实施例1中的改性H-MOR分子筛替换为改性MOR分子筛,其余与实施例1相同,得到复合催化剂26#。
取3g 26#催化剂装填于反应器中,在如下条件下进行甲醇羰化加氢制取乙烯反应:反应温度250℃,反应压力5.0MPa,甲醇/CO/H 2为0.1/1/1,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。
表6 实施例6催化剂反应结果
催化剂编号 甲醇转化率 CO转化率 乙烯选择性 乙烷选择性 甲烷选择
(%) (%) (%) (%) 性(%)
26# 75.1 11.2 70.2 2.2 1.1
实施例7
考察复合催化剂中CO加氢催化剂与改性H-MOR分子筛含量对甲醇/二甲醚羰化加氢制乙烯反应的影响。除了改变CO加氢催化剂质量含量外,其他条件包括CO加氢催化剂组成、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。
表7 实施例7不同催化剂反应评价结果
Figure PCTCN2018080923-appb-000006
实施例8
考察1#复合催化剂在200℃、280℃、320℃、350℃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。
表8 1#催化剂在不同温度下评价结果
Figure PCTCN2018080923-appb-000007
实施例9
考察原料摩尔组成对甲醇/二甲醚羰化加氢制乙烯反应的影响,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。原料气摩尔比为二甲醚/CO/H 2=X'与Y'值及其相应条件下(如原料气中惰性气体的体积分数) 的评价结果列于表9中。
表9 不同原料气条件甲醇/二甲醚羰化加氢制乙烯反应结果
Figure PCTCN2018080923-appb-000008
实施例10
在1.0、2.5、3.0、6.0和8.0MPa的不同反应总压条件下,考察反应压力对甲醇/二甲醚羰化加氢制乙烯反应的影响,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。
表10 不同反应压力下甲醇/二甲醚羰化加氢制乙烯反应的结果
Figure PCTCN2018080923-appb-000009
实施例11
分别在300、4000、8000和10000mL/g cat·h不同反应气体空速下,考察气体空速对甲醇/二甲醚羰化加氢制乙烯反应的影响,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。
表11 不同反应空速下甲醇/二甲醚羰化加氢制乙烯反应结果
Figure PCTCN2018080923-appb-000010
实施例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。
表12 1#复合催化剂不同反应器中的反应结果
Figure PCTCN2018080923-appb-000011
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。

Claims (18)

  1. 一种复合催化剂,其特征在于,所述复合催化剂包含CO加氢催化剂、改性H-MOR分子筛和石墨;
    其中,所述改性H-MOR分子筛为经过预吸附有机碱处理的H-MOR分子筛。
  2. 根据权利要求1所述的复合催化剂,其特征在于,所述预吸附有机碱处理的步骤至少包括:将所述H-MOR分子筛与含有有机碱的气体接触进行预吸附有机碱处理。
  3. 根据权利要求2所述的复合催化剂,其特征在于,所述预吸附有机碱处理的温度为150~350℃,预吸附有机碱处理的时间为0.5~4h。
  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的质量空速为300~6000mL·g -1·h -1
  5. 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;
    所述载气选自氮气、氦气、CO 2、氩气、氢气中的至少一种;
    所述有机碱选自三甲胺、二乙胺、三乙胺、吡啶、哒嗪、嘧啶、吡嗪中的至少一种;
    所述含有有机碱的气体中有机碱的体积分数为0.1%~10%。
  6. 根据权利要求2所述的复合催化剂,其特征在于,所述H-MOR分子筛与含有有机碱的气体接触之前在非活性气氛中进行活化;
    所述活化的温度为300~500℃,活化的时间为3~5h。
  7. 根据权利要求2所述的复合催化剂,其特征在于,所述预吸附有机碱处理的步骤至少包括:将所述H-MOR分子筛在非活性气氛中进行活化;然后将温度调至预吸附有机碱处理温度,与含有有机碱的气体接触进行预吸附有机碱处理,吹扫,降至室温,得到改性H-MOR分子筛。
  8. 根据权利要求1所述的复合催化剂,其特征在于,所述复合催化剂中CO加氢催化剂、改性H-MOR分子筛和石墨的质量比满足:
    CO加氢催化剂:改性H-MOR分子筛:石墨=10~90:7~90:1~5;
    所述H-MOR分子筛的硅铝原子比为5~60。
  9. 根据权利要求1所述的复合催化剂,其特征在于,所述复合催化剂中CO加氢催化剂、改性H-MOR分子筛和石墨的质量比满足:
    CO加氢催化剂:改性H-MOR分子筛:石墨=65.2:32.6:2.2。
  10. 根据权利要求1所述的复合催化剂,其特征在于,所述CO加氢催化剂选自具有式(I)所述化学式的化合物中的至少一种:
    (ZnO) aM b(Al 2O 3) 1-a-b 式(I)
    其中,M为Zr、Cr、Ce中至少一种元素的氧化物;a为0.1~0.9,b为0.05~0.8。
  11. 权利要求1至10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:
    (1)获得CO加氢催化剂;
    (2)获得改性H-MOR分子筛;
    (3)将石墨加入到含有步骤(1)中的CO加氢催化剂和步骤(2)中改性H-MOR分子筛的混合物中,成型,得到所述复合催化剂。
  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,步骤(1)中所述CO加氢催化剂的获得方法至少包括:共沉淀法或浸渍法。
  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,所述共沉淀法至少包括以下步骤:在搅拌的条件下,将含有Zn元素、M'元素和Al元素的盐溶液与含有沉淀剂的溶液以并流的方式混合,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CO加氢催化剂;
    所述浸渍法至少包括:将氧化铝粉末浸渍于含有Zn元素和M'元素的 盐溶液中或者将氧化铝和M'元素的氧化物浸渍于含有Zn元素的盐溶液中;浸渍后经去除溶剂、干燥、焙烧,得到所述CO加氢催化剂;
    其中,所述M'选自Zr、Cr、Ce中至少一种。
  14. 根据权利要求13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;
    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;
    所述溶液中的Zn元素、M'元素和Al元素独立地来自Zn元素、M'元素和Al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。
  15. 一种乙烯的制备方法,其特征在于,至少包括以下步骤:
    将含有甲醇/二甲醚、CO和H 2的原料气通过装有复合催化剂的反应器,反应得到乙烯;
    其中,所述复合催化剂选自权利要求1至10任一项所述的复合催化剂、根据权利要求11至14任一项所述的方法制备得到的复合催化剂中的至少一种;
    其中,所述原料气组成摩尔比满足:
    甲醇/二甲醚:CO:H 2=0.05~0.5:1:0.5~4。
  16. 根据权利要求15所述的乙烯的制备方法,其特征在于,所述反应的温度为200~350℃,压力为1.0~8.0MPa,原料气质量空速为300~10000mL·g -1·h -1
  17. 根据权利要求15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;
    所述非活性气体选自氮气、氩气、氦气、甲烷中的至少一种;
    所述非活性气体在原料气中的体积含量≤10%。
  18. 根据权利要求15所述的乙烯的制备方法,其特征在于,所述反应器选自固定床反应器、流化床反应器、移动床反应器中的至少一种。
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