CN114605216B - Method for oxidative coupling of methane - Google Patents

Method for oxidative coupling of methane Download PDF

Info

Publication number
CN114605216B
CN114605216B CN202011442333.1A CN202011442333A CN114605216B CN 114605216 B CN114605216 B CN 114605216B CN 202011442333 A CN202011442333 A CN 202011442333A CN 114605216 B CN114605216 B CN 114605216B
Authority
CN
China
Prior art keywords
cerium oxide
methane
catalyst
water
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011442333.1A
Other languages
Chinese (zh)
Other versions
CN114605216A (en
Inventor
王峰
王业红
张志鑫
张健
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN202011442333.1A priority Critical patent/CN114605216B/en
Publication of CN114605216A publication Critical patent/CN114605216A/en
Application granted granted Critical
Publication of CN114605216B publication Critical patent/CN114605216B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a method for oxidative coupling of methane. The method adopts methane as a reactant and water as an oxidant, and prepares ethylene through oxidative coupling reaction under the catalysis of a cerium-based catalyst. The reaction conditions are as follows: the reaction is carried out in a fixed bed reactor, the reaction is carried out under normal pressure, the reaction temperature is 450-800 ℃, the feeding airspeed of methane is 20000-30000 mL/(g.h), CH 4 :H 2 O=2:1 to 4:1. The catalyst is simple to prepare and high in efficiency to catalyze the reaction, water is used for replacing oxygen in the prior art to serve as an oxygen source, excessive oxidation is avoided, the selectivity of a product is improved, and the selectivity of ethylene is 77%.

Description

Method for oxidative coupling of methane
Technical Field
The invention relates to a method for oxidative coupling of methane, in particular to a technology for preparing ethylene by using methane and water as reactants through oxidative coupling.
Background
Ethylene is an important basic organic chemical raw material, and the production yield, the production technology and the application thereof are marks for measuring the national chemical level. Ethylene is currently produced industrially by naphtha cracking. The oil gas resources in China are deficient, and the ethylene source mainly depends on import and pyrolysis of naphtha. Thus, the development of process routes for the production of ethylene in a non-petroleum route is a major trend in the future. With the breakthrough of shale gas and combustible ice exploitation technology, natural gas with relatively abundant reserves, wide distribution and low price is used for replacing ethylene which is a basic organic chemical raw material for petroleum production, and the natural gas becomes a worldwide research hot spot in recent years. Methane is the main component of natural gas, combustible ice and shale gas, and is cleaner and richer in source than other petrochemical resources such as petroleum and coal. The synthesis of high-value chemical platform molecular ethylene by using methane as a raw material is increasingly attracting attention in the industry. Among them, the oxidative coupling of methane to ethylene is a major approach, and its key point is the design and development of efficient catalysts.
At present, catalytic systems for preparing ethylene by catalytic oxidative coupling of methane are mainly divided into three types: alkali metal-alkaline earth metal oxide catalysts, rare earth oxide catalysts, and transition metal oxide catalysts; although the catalytic system has a lot of catalytic research at present, the method has some disadvantages: for example, the catalyst activity is relatively low, the conversion of methane is less than 50%, the selectivity of ethylene is less than 60%, i.e., the yield of ethylene is less than 30% (-25%); in addition, oxygen acts as an oxidant, resulting in uncontrolled reactions, and excessive oxidation is likely to occur, yielding carbohydrates. Therefore, the new methane oxidative coupling process is explored, and the design and preparation of the efficient catalytic system have important significance.
Disclosure of Invention
The invention has the significance of overcoming the defects existing in the current process of preparing ethylene by oxidative coupling of methane. The catalyst has high catalytic activity, high stability, simple reaction process, high ethylene yield and no side product.
The preparation of ethylene by oxidative coupling of methane according to the present invention is prepared by the following scheme. The process of the oxidative coupling of methane is as follows: methane and water are used as raw materials, the raw materials are reacted in a fixed bed reactor, a catalyst reducible oxide catalyst is filled in a reaction tube, and the reaction tube is placed in the fixed bed reactor, wherein the reaction temperature is 400-850 ℃. The cerium oxide-based catalyst comprises a cerium oxide matrix and a metal auxiliary agent; the metal auxiliary agent is as follows: one, two or more of iron, nickel, cobalt, zinc and copper; the cerium oxide matrix in the cerium oxide-based catalyst is coordination unsaturated cerium oxide (CeO) x ,1.5<x<2) The method comprises the steps of carrying out a first treatment on the surface of the The metals are preferably: one, two or more of iron, zinc and copper; the preparation of the cerium oxide matrix in the cerium oxide-based catalyst can adopt a precipitation method, a hydrothermal method, a solvothermal method and a solid-phase thermal decomposition method; wherein the degree of coordination unsaturation (1.5<x<2) Adopts an in-situ reduction method and post-treatmentOriginal method control; the loading of the metal auxiliary agent is 1-10wt% (based on the weight ratio of the cerium oxide matrix); co-precipitation or impregnation may be employed; the preferable loading of the metal auxiliary agent is 2-5 wt%; the preferable reaction temperature is 400-600 ℃, the feeding airspeed of methane is 10000-30000 mL/(g.h), CH 4 :H 2 O=2:1 to 4:1; the optimal reaction temperature is 500-600 ℃, the feeding airspeed of methane is 20000-25000 mL/(g.h), CH 4 :H 2 O＝2:1～4:1。
The method for oxidative coupling of methane disclosed by the invention has the following characteristics: (1) Water is used as an oxidant to replace oxygen in the traditional process, so that excessive oxidation of oxygen is avoided, and the selectivity of ethylene is improved; (2) The catalyst adopts a coordinated unsaturated cerium oxide-based catalyst to construct a cooperative double-site cooperative catalytic system: dissociation of the vacancy properties activates water molecules. The adsorption and activation of water molecules by utilizing the oxygen vacancy property can be carried out at the temperature of more than 400 ℃, so that the reaction temperature of the catalytic reaction can be obviously reduced, the energy consumption is reduced, and the problems of catalyst sintering and the like caused by high-temperature reaction are avoided; the coupled alkane adsorbs the activated site, activate C-H bond, in the invention, the activated site of said adsorption is one, two or more than two of iron, nickel, cobalt, zinc, copper.
The invention has the following advantages: (1) The reaction process is simple, and the activity and stability of the catalyst are high; (2) the reaction condition is relatively mild and the energy consumption is low.
Detailed Description
Example 1
Preparing a coordination unsaturated iron-loaded cerium oxide catalyst by coprecipitation coupling liquid-phase in-situ reduction: 2wt% Fe/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of ferric nitrate nonahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of the nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; redispersing in 100mL water, adding hydrazine hydrate as liquid phase reducer, and hydratingThe molar ratio of hydrazine to nitrate (comprising cerium nitrate and ferric nitrate) is 5, the reaction is carried out for 1 hour at room temperature, the filtration and the vacuum drying at 100 ℃ are carried out, and the coordination unsaturated cerium oxide-based catalyst 2wt% Fe/CeO is obtained x ,x＝1.75；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1 (molar ratio, the same applies below). After reacting at 650 ℃ for 400 minutes, the conversion of methane is 38% and the selectivity of ethylene is: 77%.
Example 2
Preparing a coordination unsaturated iron-loaded cerium oxide catalyst by coprecipitation coupling liquid-phase in-situ reduction: 2wt% Fe/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of ferric nitrate nonahydrate, dissolving in 100mL of water, adding a certain amount of citric acid, wherein the mass ratio of the citric acid to nitrate (cerium nitrate to ferric nitrate) is 2:1, stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of nitrate under stirring, placing the obtained precipitate into a synthesis kettle, crystallizing at 100deg.C for 24 hr, cooling, filtering, washing with water for three times, and vacuum drying at 100deg.C to obtain 2wt% Fe/CeO x X=1.87 catalyst;
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion rate of methane is 35% by on-line chromatography analysis, and the selectivity of ethylene is: 75%.
Example 3
Preparing a coordination unsaturated zinc-loaded cerium oxide catalyst by coprecipitation coupling liquid-phase in-situ reduction: 2wt% Zn/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of zinc nitrate hexahydrate, dissolving in 100mL of water, adding a certain amount of zinc nitrate hexahydrateThe ratio of the content of citric acid to the content of nitrate (comprising cerium nitrate and zinc nitrate) is 2:1, stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of nitrate under stirring, placing the obtained precipitate into a synthesis kettle, crystallizing at 100deg.C for 24 hr, cooling, filtering, washing with water for three times, and vacuum drying at 100deg.C to obtain 2wt% Zn/CeO x X=1.92 catalyst;
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion rate of methane is 30% by on-line chromatography analysis, and the selectivity of ethylene is: 71%.
Example 4
Preparing a coordination unsaturated zinc-loaded cerium oxide catalyst by coprecipitation coupling liquid-phase in-situ reduction: 2wt% Zn/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of zinc nitrate hexahydrate, dissolving in 100mL of water, adding a certain amount of citric acid, and the ratio of the citric acid to nitrate (comprising cerium nitrate and zinc nitrate) is 2:1, stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of nitrate under stirring, placing the obtained precipitate into a synthesis kettle, crystallizing at 100deg.C for 24 hr, cooling, filtering, washing with water for three times, and vacuum drying at 100deg.C to obtain 2wt% Zn/CeO x X=1.94 catalyst;
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion rate of methane is 30% by on-line chromatography analysis, and the selectivity of ethylene is: 71%.
Example 5
Preparing a copper-loaded cerium oxide catalyst with unsaturated coordination through coprecipitation coupling liquid phase in-situ reduction: 2wt% Cu/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of copper nitrate hexahydrate, dissolving in 100mL of water, adding a certain amount of citric acid, and the ratio of the mass of the citric acid to the mass of nitrate (comprising cerium nitrate and copper nitrate) is 2:1, stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of nitrate under stirring, placing the obtained precipitate into a synthesis kettle, crystallizing at 100deg.C for 24 hr, cooling, filtering, washing with water for three times, and vacuum drying at 100deg.C to obtain 2wt% Cu/CeO x X=1.75 catalyst;
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion of methane was 33% and the selectivity of ethylene was: 69%.
Example 6
Coprecipitation coupled with gas phase post treatment reduction to prepare a coordinated unsaturated iron-loaded cerium oxide catalyst: 2wt% Fe/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of ferric nitrate nonahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of the nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; drying at 100 ℃, roasting at 500 ℃ for 4 hours, reducing with hydrogen at 350 ℃ for 4 hours, and obtaining 2wt% Fe/CeO of the coordination unsaturated cerium oxide-based catalyst, wherein the flow rate of the hydrogen is 30mL/min 2 ,x＝1.78；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O＝4:1。After reacting at 650 ℃ for 400 minutes, the conversion of methane is 40% and the selectivity of ethylene is: 70%.
Example 7
Coprecipitation coupled with gas phase post treatment reduction to prepare a coordinated unsaturated iron-loaded cerium oxide catalyst: 2wt% Fe/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of ferric nitrate nonahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of the nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; drying at 100 ℃, roasting at 500 ℃ for 4 hours, reducing with hydrogen at 350 ℃ for 4 hours, and obtaining 2wt% Fe/CeO of the coordination unsaturated cerium oxide-based catalyst, wherein the flow rate of the hydrogen is 30mL/min 2 ,x＝1.80；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 10000 mL/(g.h), and oxidant water is pumped into the reaction tube by a microscale sample injection pump and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion of methane was 42% and the selectivity of ethylene was: 71%.
Example 8
Coprecipitation coupled with gas phase post treatment reduction to prepare a coordinated unsaturated iron-loaded cerium oxide catalyst: 2wt% Fe/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of ferric nitrate nonahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of the nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; drying at 100 ℃, roasting at 500 ℃ for 4 hours, reducing with hydrogen at 350 ℃ for 4 hours, and obtaining 2wt% Fe/CeO of the coordination unsaturated cerium oxide-based catalyst, wherein the flow rate of the hydrogen is 30mL/min 2 ,x＝1.79；
Weighing 200mg of the catalyst, molding and screening the catalyst with 14-25 meshes, filling the catalyst into a reaction tube, and standingUnder reduced pressure, the airspeed of methane is 48000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample pump, CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion of methane was 32% and the selectivity of ethylene was: 71%.
Example 9
Coprecipitation coupled with gas phase post treatment reduction to prepare a coordinated unsaturated iron-loaded cerium oxide catalyst: 2wt% Fe/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of ferric nitrate nonahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of the nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; drying at 100 ℃, roasting at 500 ℃ for 4 hours, reducing with hydrogen at 350 ℃ for 4 hours, and obtaining 2wt% Fe/CeO of the coordination unsaturated cerium oxide-based catalyst, wherein the flow rate of the hydrogen is 30mL/min 2 ,x＝1.81；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. After reacting at 800 ℃ for 400 minutes, the conversion rate of methane is 50% by on-line chromatographic analysis, and the selectivity of ethylene is: 50%.
Example 10
Coprecipitation coupled with gas phase post treatment reduction to prepare a coordinated unsaturated iron-loaded cerium oxide catalyst: 2wt% Fe/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of ferric nitrate nonahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of the nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; drying at 100 ℃, roasting at 500 ℃ for 4 hours, reducing with hydrogen at 350 ℃ for 4 hours, and obtaining 2wt% Fe/CeO of the coordination unsaturated cerium oxide-based catalyst, wherein the flow rate of the hydrogen is 30mL/min 2 ,x＝1.87；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. After reacting at 450 ℃ for 400 minutes, the conversion rate of methane is 32% by on-line chromatography analysis, and the selectivity of ethylene is: 66%.
Example 11
Coprecipitation coupled with gas phase post treatment reduction to prepare a coordinated unsaturated iron-loaded cerium oxide catalyst: 2wt% Fe/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of ferric nitrate nonahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of the nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; drying at 100 ℃, roasting at 500 ℃ for 4 hours, reducing with hydrogen at 350 ℃ for 4 hours, and obtaining 2wt% Fe/CeO of the coordination unsaturated cerium oxide-based catalyst, wherein the flow rate of the hydrogen is 30mL/min 2 ,x＝1.87；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=2:1. After reacting at 650 ℃ for 400 minutes, the conversion of methane is 38% and the selectivity of ethylene is: 72%.
Example 12
Coprecipitation coupled with gas phase post treatment reduction to prepare a coordinated unsaturated iron-loaded cerium oxide catalyst: 2wt% Fe/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of ferric nitrate nonahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of the nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; drying at 100deg.C, 500 deg.CRoasting for 4 hours, reducing the mixture for 4 hours at 350 ℃ with hydrogen flow rate of 30mL/min to obtain 2wt% Fe/CeO of the coordination unsaturated cerium oxide-based catalyst 2 x＝1.86；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=1:1. After reacting at 650 ℃ for 400 minutes, the conversion rate of methane is 35% by on-line chromatography analysis, and the selectivity of ethylene is: 71%.
Example 13
Precipitation coupling impregnation and reduction to prepare the coordination unsaturated iron-loaded cerium oxide catalyst: 2wt% Fe/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of ferric nitrate nonahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of the nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; redispersing in 100mL of water, adding a certain amount of hydrazine hydrate as a liquid phase reducing agent, reducing for 3 hours at room temperature with a molar ratio of hydrazine hydrate to nitrate (comprising cerium nitrate and ferric nitrate) of 5, filtering, and vacuum drying at 100 ℃ to obtain 2wt% Fe/CeO of a coordination unsaturated cerium oxide-based catalyst 2 x＝1.77；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion of methane is 38% and the selectivity of ethylene is: 77%.
Example 14
Preparing a coordination unsaturated iron-loaded cerium oxide catalyst by coprecipitation coupling liquid-phase in-situ reduction: 1wt% Fe/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of ferric nitrate nonahydrate, dissolving in 100mL of water, and stirring at room temperature; measuring 50mL of the massAqueous ammonia with a concentration of 25% was dispersed in 50mL of water to prepare a solution having a volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of the nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; redispersing in 100mL of water, adding a certain amount of hydrazine hydrate as a liquid phase reducing agent, reducing the mixture for 3 hours at room temperature with the molar ratio of hydrazine hydrate to nitrate (comprising cerium nitrate and ferric nitrate) being 8, filtering, and vacuum drying at 100 ℃ to obtain a coordinated unsaturated cerium oxide-based catalyst 1wt% Fe/CeO 2 x＝1.69；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion of methane was 34% and the selectivity of ethylene was: 77%.
Example 15
Preparing a coordination unsaturated iron-loaded cerium oxide catalyst by coprecipitation coupling liquid-phase in-situ reduction: 5wt% Fe/CeO 2 : weighing 5g of cerium nitrate hexahydrate and a certain amount of ferric nitrate nonahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of the nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; redispersing in 100mL of water, adding a certain amount of hydrazine hydrate as a liquid phase reducing agent, reducing the mixture for 1 hour at room temperature with the molar ratio of hydrazine hydrate to nitrate (comprising cerium nitrate and ferric nitrate) being 3, filtering, and vacuum drying at 100 ℃ to obtain 5wt% Fe/CeO of a coordination unsaturated cerium oxide-based catalyst 2 x＝1.93；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. Reacting at 650 deg.c for 400 min, and on-line chromatographic analysis to convert methaneThe conversion was 41% and the selectivity for ethylene was: 70%.
Example 16
Preparing the coordination unsaturated iron-loaded cerium oxide catalyst by coupling solid-phase thermal decomposition and impregnation with liquid-phase in-situ reduction: 2wt% Fe/CeO 2 : weighing 5g of ammonium ceric nitrate, and roasting for 4 hours at 400 ℃ in air to obtain cerium oxide; the iron-loaded cerium oxide catalyst is prepared by adopting an impregnation method: taking a certain amount of 10mmol/L ferric nitrate aqueous solution, stirring at room temperature, adding 2g of cerium oxide matrix, continuously stirring for 4 hours, evaporating to dryness at 100 ℃, and roasting at 300 ℃ for 4 hours to obtain 2wt% Fe/CeO with saturated coordination 2 . Redispersing in 100mL of water, adding a certain amount of hydrazine hydrate as a liquid phase reducing agent, reducing the mixture for 1 hour at room temperature with the molar ratio of hydrazine hydrate to nitrate (comprising cerium nitrate and ferric nitrate) being 10, filtering, and vacuum drying at 100 ℃ to obtain 2wt% Fe/CeO of a coordination unsaturated cerium oxide-based catalyst 2 x＝1.79；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion of methane is 40% and the selectivity of ethylene is: 68%.
Example 17
Preparing the coordination unsaturated iron-loaded cerium oxide catalyst by coupling solid-phase thermal decomposition and impregnation with liquid-phase in-situ reduction: 2wt% Fe/CeO 2 : weighing 5g of ammonium ceric nitrate, and roasting for 4 hours at 600 ℃ in air to obtain cerium oxide; the method comprises the steps of carrying out a first treatment on the surface of the The iron-loaded cerium oxide catalyst is prepared by adopting an impregnation method: taking a certain amount of 10mmol/L ferric nitrate aqueous solution, stirring at room temperature, adding 2g of cerium oxide matrix, continuously stirring for 4 hours, evaporating to dryness at 100 ℃, and roasting at 300 ℃ for 4 hours to obtain 2wt% Fe/CeO with saturated coordination 2 . Redispersing in 100mL water, adding hydrazine hydrate as liquid phase reducer, reducing at room temperature for 1 hr with the molar ratio of hydrazine hydrate to nitrate (including cerium nitrate and ferric nitrate) of 5, filtering, and vacuum drying at 100deg.C to obtain the final product2wt% Fe/CeO of a cerium oxide-based catalyst with site unsaturation 2 x＝1.94；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion of methane is 38% and the selectivity of ethylene is: 67%.
Example 18
Preparing the coordination unsaturated iron-loaded cerium oxide catalyst by coupling solid-phase thermal decomposition and impregnation with gas-phase aftertreatment reduction: 2wt% Fe/CeO 2 : weighing 5g of ammonium ceric nitrate, and roasting for 4 hours at 400 ℃ in air to obtain cerium oxide; the method comprises the steps of carrying out a first treatment on the surface of the The iron-loaded cerium oxide catalyst is prepared by adopting an impregnation method: taking a certain amount of 10mmol/L ferric nitrate aqueous solution, stirring at room temperature, adding 2g of cerium oxide matrix, continuously stirring for 4 hours, evaporating to dryness at 100 ℃, and roasting at 300 ℃ for 4 hours to obtain 2wt% Fe/CeO with saturated coordination 2 . Then placing the catalyst in hydrogen atmosphere, reducing the catalyst for 4 hours at 450 ℃ and the hydrogen flow rate is 30mL/min to obtain 2wt% Fe/CeO of the coordination unsaturated cerium oxide-based catalyst 2 ,x＝1.88；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion of methane was 43% and the selectivity of ethylene was: 70%.
Example 19
Preparing the coordination unsaturated zinc-loaded cerium oxide catalyst by coupling solid-phase thermal decomposition and impregnation with gas-phase aftertreatment reduction: 2wt% Zn/CeO 2 : weighing 5g of ammonium ceric nitrate, and roasting for 4 hours at 400 ℃ in air to obtain cerium oxide; the method comprises the steps of carrying out a first treatment on the surface of the The zinc-loaded cerium oxide catalyst is prepared by adopting an impregnation method: taking a certain amount of 10mmol/L zinc nitrate aqueous solution, stirring at room temperature, adding 2g of the cerium oxide matrix, continuously stirring for 4 hours, evaporating at 100 ℃,roasting for 4 hours at 300 ℃ to obtain 2wt% Zn/CeO with saturated coordination 2 . Then placing the catalyst in hydrogen atmosphere, reducing the catalyst for 4 hours at 550 ℃, and obtaining 2wt% Zn/CeO of the coordination unsaturated cerium oxide-based catalyst, wherein the flow rate of the hydrogen is 30mL/min 2 ,x＝1.63；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion of methane was 41% and the selectivity of ethylene was: 67%.
Example 20
Preparing the coordination unsaturated copper-loaded cerium oxide catalyst by coupling solid-phase thermal decomposition and impregnation with gas-phase aftertreatment reduction: 2wt% Cu/CeO 2 : weighing 5g of ammonium ceric nitrate, and roasting for 4 hours at 400 ℃ in air to obtain cerium oxide; the method adopts an impregnation method to prepare a copper-loaded cerium oxide catalyst: taking a certain amount of copper nitrate aqueous solution with the concentration of 10mmol/L, stirring at room temperature, adding 2g of cerium oxide matrix, continuously stirring for 4 hours, evaporating to dryness at 100 ℃, and roasting at 300 ℃ for 4 hours to obtain 2wt% Cu/CeO with saturated coordination 2 . Then placing the catalyst in hydrogen atmosphere, reducing for 4 hours at 350 ℃, and obtaining 2wt% Cu/CeO of the coordination unsaturated cerium oxide-based catalyst, wherein the flow rate of the hydrogen is 30mL/min 2 x＝1.92；
200mg of the catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a microscale sample injection pump, and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion of methane was 44% and the selectivity of ethylene was: 68%.
Comparative example 1
Weighing 5g of cerium nitrate hexahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of cerium nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; redispersing the mixture in 100mL of water, adding a certain amount of hydrazine hydrate as a liquid phase reducing agent, reducing the mixture for 1 hour at room temperature, filtering the mixture, and drying the mixture in vacuum at 100 ℃ to obtain a coordinated unsaturated cerium oxide catalyst, wherein x=1.97;
200mg of the coordination unsaturated cerium oxide catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the reaction is carried out under normal pressure, the airspeed of methane is 18000 mL/(g.h), and oxidant water is pumped into the reaction tube by a microscale sample pump and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion of methane is 8% and the selectivity of ethylene is: 50%.
Comparative example 2
Weighing 5g of cerium nitrate hexahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of cerium nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; vacuum drying at 100 ℃ to obtain a coordination saturated cerium oxide catalyst;
200mg of the coordination saturated cerium oxide catalyst is weighed, 14-25 meshes of catalyst is sieved by a forming sieve and is filled into a reaction tube, the mixture is reacted under normal pressure, the airspeed of methane is 18000 mL/(g.h), and oxidant water is pumped into the reaction tube by a microscale sample pump and CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion rate of methane is 2% by on-line chromatography analysis, and the selectivity of ethylene is: 40%.
Comparative example 3
Weighing 5g of cerium nitrate hexahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of 25% ammonia water by mass concentration is measured and dispersed in 50mL of water to prepare the water with the volume ratio of 1:1 in aqueous ammonia; dropwise adding the ammonia water solution into the aqueous solution of cerium nitrate under the stirring condition, continuously stirring for 4 hours, filtering, and washing for three times; vacuum drying at 100 ℃ to obtain a coordination saturated cerium oxide catalyst; iron-supported cerium oxide catalysis prepared by impregnation methodAgent (2 wt% Fe/CeO) 2 ): taking a certain amount of 10mmol/L ferric nitrate aqueous solution, stirring at room temperature, adding 2g of cerium oxide matrix, continuously stirring for 4 hours, evaporating to dryness at 100 ℃, and roasting at 300 ℃ for 4 hours to obtain 2wt% Fe/CeO with saturated coordination 2 。
200mg of the above 2wt% Fe/CeO was weighed 2 The catalyst is formed and sieved, the catalyst with 14-25 meshes is filled into a reaction tube, and reacts under normal pressure, the airspeed of methane is 18000 mL/(g.h), and oxidant water is pumped into the reaction tube by a microscale sample injection pump, CH 4 :H 2 O=4:1. After reacting at 650 ℃ for 400 minutes, the conversion of methane is 10% and the selectivity of ethylene is: 42%.

Claims (5)

1. A method for oxidative coupling of methane, which is characterized by comprising the following steps:
the process of the oxidative coupling of methane is as follows: methane and water are used as raw materials, the raw materials are reacted in a fixed bed reactor, a cerium oxide-based catalyst is filled in a reaction tube, and then the reaction tube is placed in the fixed bed reactor, wherein the reaction temperature is 450-800 ℃; the cerium oxide-based catalyst comprises a cerium oxide matrix and a metal auxiliary agent; the metal auxiliary agent is as follows: one, two or more of iron, zinc and copper;
the cerium oxide matrix in the cerium oxide-based catalyst is cerium oxide CeO with unsaturated coordination x , 1.5<x<2; the loading capacity of the metal auxiliary agent is 1wt% -10 wt%; the loading of the metal promoter is based on the weight ratio of the cerium oxide matrix.
2. A method according to claim 1, characterized in that:
the loading capacity of the metal auxiliary agent is 2wt% -5 wt%.
3. A method according to claim 1, characterized in that:
the reaction temperature is 450-600 ℃, the feeding airspeed of methane is 20000-30000 mL/(g.h), CH 4 : H 2 Molar ratio of o=2:1 to 4:1.
4. A method according to claim 1 or 3, characterized in that:
the reaction temperature is 500-600 ℃, the feeding airspeed of methane is 22000-28000 mL/(g.h), CH 4 : H 2 Molar ratio of o=3:1 to 4:1.
5. A method according to claim 1, characterized in that:
the coordination unsaturation degree of the cerium oxide matrix is controlled by adopting an in-situ reduction method and/or a post-treatment reduction method;
the in-situ reduction method comprises the following steps: mixing cerium oxide with a precursor salt solution of a metal auxiliary agent, and adding a reducing agent, wherein the molar ratio of the reducing agent to metal ions is 2: 1-10: 1, a step of;
and/or, the post-treatment reduction method comprises the following steps: drying the cerium oxide catalyst into which the additive metal is introduced, and then reducing the cerium oxide catalyst in a hydrogen atmosphere, wherein the reduction temperature is as follows: 300-600 ℃.
CN202011442333.1A 2020-12-08 2020-12-08 Method for oxidative coupling of methane Active CN114605216B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011442333.1A CN114605216B (en) 2020-12-08 2020-12-08 Method for oxidative coupling of methane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011442333.1A CN114605216B (en) 2020-12-08 2020-12-08 Method for oxidative coupling of methane

Publications (2)

Publication Number Publication Date
CN114605216A CN114605216A (en) 2022-06-10
CN114605216B true CN114605216B (en) 2023-06-27

Family

ID=81855745

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011442333.1A Active CN114605216B (en) 2020-12-08 2020-12-08 Method for oxidative coupling of methane

Country Status (1)

Country Link
CN (1) CN114605216B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017089937A2 (en) * 2015-11-24 2017-06-01 Sabic Global Technologies B.V. Systems and methods for producing c2 hydrocarbons and steam from the oxidative coupling of methane

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4443648A (en) * 1982-08-30 1984-04-17 Atlantic Richfield Company Methane conversion
US4499324A (en) * 1984-04-16 1985-02-12 Atlantic Richfield Company Methane conversion
DE3534530A1 (en) * 1985-09-27 1987-04-09 Manfred Prof Dr Baerns Continuous process for the oxidative coupling of methane to C2+ hydrocarbons in the presence of catalysts
CN106431845B (en) * 2015-08-11 2019-04-16 中国科学院大连化学物理研究所 A kind of method that doping type ceria catalysis acetone prepares phenolic compound
CN111333478B (en) * 2018-12-18 2021-11-16 中国科学院大连化学物理研究所 Method for preparing olefin, aromatic hydrocarbon and hydrogen by steam catalytic conversion of methane

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017089937A2 (en) * 2015-11-24 2017-06-01 Sabic Global Technologies B.V. Systems and methods for producing c2 hydrocarbons and steam from the oxidative coupling of methane

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen;Xiaoguang Guo et al.;《science》;第344卷(第6184期);第616-619页 *
二氧化铈催化 芳香伯醇氧化偶联制备 亚胺和α,β-不饱和酮;张志鑫等;《中国化学会第30 届学术年会》;第1-7页 *
低温甲烷氧化偶联制乙烯;申文杰;《物理化学学报》;第33卷(第12期);第2321-2322页 *
甲烷氧化偶联反应制乙烯的研究进展;张志翔;王凤荣;苑慧敏;王斯晗;张宝军;孟素凤;;现代化工(第03期);第20-25页 *

Also Published As

Publication number Publication date
CN114605216A (en) 2022-06-10

Similar Documents

Publication Publication Date Title
Xu et al. Advances in higher alcohol synthesis from CO2 hydrogenation
CN107497437B (en) For CO2Iron-based catalyst for preparing low-carbon olefin by hydrogenation and application thereof
CN112169799B (en) Method for synthesizing low-carbon olefin by carbon dioxide hydrogenation by iron-based catalyst
US20180273454A1 (en) Multicomponent heterogeneous catalysts for direct co2 hydrogenation to methanol
KR101437072B1 (en) Catalyst for efficient co2 conversion and method for preparing thereof
CN111036278B (en) Method for preparing low-carbon olefin from synthesis gas
CN102958869B (en) The catalyzer containing cobalt and manganese is used to prepare the method for alkene from synthetic gas
CN113385171A (en) Metal-based catalyst protected by few-layer carbon and application thereof in ethylene oxide carbonylation
CN113813953A (en) Preparation and application methods of cerium-zirconium composite oxide solid solution catalyst
CN112645787A (en) Method for preparing isoprene
JP3632071B2 (en) Carbon monoxide hydrogenation using sulfide catalyst
CN105251505A (en) Cobalt-based catalyst for producing C2+ oxygen-containing compound and co-producing olefin through synthetic gas, preparation method and applications thereof
CN114605216B (en) Method for oxidative coupling of methane
US20240083832A1 (en) Method for preparing acetic acid by catalyst
CN108855158B (en) Preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst
CN102039133B (en) Fischer-Tropsch synthesized Co-based fluidized bed catalyst and preparation method thereof
CN113813952B (en) Preparation and application methods of chlorine-modified cubic cerium oxide nanocrystalline catalyst
CN114605218B (en) Methane oxidative coupling method
CN114605215B (en) Method for preparing ethylene by oxidative coupling of methane
EP3023479A1 (en) Process for the deoxygenation of alcohols and use thereof
CN116328779A (en) Liquid state sunlight zero carbon emission methanol synthesis catalyst and preparation method and application thereof
CN112844390A (en) Iron-nickel bimetallic Fischer-Tropsch catalyst for preparing low-carbon olefin, preparation method and application
CN114682254A (en) Supported catalyst, catalyst composition comprising the same, method for preparing the same, and method for preparing propionaldehyde using the same
CN114605217B (en) Method for preparing ethylene by oxidative coupling of methane
CN114471744B (en) Pretreatment method of iron-based catalyst and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant