CN102285865A - Method for preparing methanol by directly oxidizing methane in ionic liquid under action of microwaves - Google Patents

Method for preparing methanol by directly oxidizing methane in ionic liquid under action of microwaves Download PDF

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Publication number
CN102285865A
CN102285865A CN2011101753122A CN201110175312A CN102285865A CN 102285865 A CN102285865 A CN 102285865A CN 2011101753122 A CN2011101753122 A CN 2011101753122A CN 201110175312 A CN201110175312 A CN 201110175312A CN 102285865 A CN102285865 A CN 102285865A
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ionic liquid
methyl alcohol
under
reaction
methane
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CN102285865B (en
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宋云保
马英冲
付泉
于长顺
王少君
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DALIAN TIANBAO CHEMISTRY INDUSTRY Co Ltd
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DALIAN TIANBAO CHEMISTRY INDUSTRY Co Ltd
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    • 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
    • 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
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention discloses a method for preparing methanol by directly oxidizing methane in ionic liquid under the action of microwaves, which comprises the following steps: placing a three-neck flask filled with ionic liquid, trifluoroacetic acid, trifluoroaceticanhydride, potassium persulfate and catalyst in a microwave reactor, introducing methane into the liquid at a certain speed with stirring by a magnetic force, heating at 80 to 110 DEG C for 30 to 120 minutes by microwaves to obtain methyl trifluoroacetate, and hydrolyzing the methyl trifluoroacetate to obtain methanol. In the invention, the ionic liquid is used as a solvent and microwave heating is combined, so the reaction time is reduced and the reaction yield and conversion rate are improved. The ionic liquid used as the solvent can be reclaimed, the operation is convenient and the cost is low.

Description

Under the microwave action in the ionic liquid directly oxidizing methane prepare the method for methyl alcohol
Technical field
The direct oxidation that the present invention relates to methane belongs to organic chemistry filed.The methyl alcohol preparation process that particularly relates to directly oxidizing methane in a kind of ion liquid solvent system under the microwave action.
Background technology
Methane is important chemical material, is rich natural resource as the main component of Sweet natural gas.Yet because transporting methane gas or natural gas liquids are very expensive, methane is difficult to be utilized usually.Methane is converted into the liquid fuel being convenient to transport and useful chemical is very important.
The conversion of methane mainly is divided into indirect reformer and directly transforms two big classes.At present the technology of methane conversion synthesizing methanol mostly is the indirect reformer method, promptly adopts the method for steam cracking to make the synthetic gas of certain ratio of carbon-hydrogen, and industrial chemicals such as methyl alcohol are produced in synthetic gas regeneration.Though this technology is comparatively ripe, need under high temperature (being higher than 900 ℃), condition of high voltage, carry out the methane cracking reaction, condition comparatively harshness and energy consumption is very high, so methane directly transforms the extremely concern of Chinese scholars of research work of synthesizing methanol.
The method that methane directly transforms synthesizing methanol is divided into homogeneous gas-phase oxidation, gas-solid heterogeneous catalytic oxidation and liquid phase catalytic oxidation 3 big classes, and wherein, the industrial applications of homogeneous gas-phase oxidation and gas-solid heterogeneous catalytic oxidation is still unrealistic.The direct synthesizing methanol of methane liquid phase catalytic oxidation is the direction at the early-stage of nearly twenty or thirty year, and the many employings of reaction precious metal is a catalyzer, at CF 3The aqueous solution of COOH and H 2SO 4React in the solution, the reaction times is longer, and temperature is higher.
The material that is made of ion fully that ionic liquid promptly is in a liquid state under room temperature and adjacent temperature (30～250 ℃), it generally is made up of organic cation and inorganic anion.As a kind of novel organic solvent, ionic liquid relies on its special nature, demonstrates good prospect in fields such as organic synthesis, organic catalysis, inorganic synthetic, electrochemistry, Green Chemistry and chemical separations.Ionic liquid is used for the existing relevant report of conversion of methane as solvent.Because ionic liquid has very strong polarity, can well absorb microwave, be that solvent react under microwave condition and can play quick heating with the ionic liquid, reduce the reaction times, advantages such as raising reaction efficiency.Therefore, directly oxidizing methane prepares methyl alcohol in the ionic liquid under microwave action, may obtain better reaction effect under the short reaction times.
Summary of the invention
The purpose of this invention is to provide a kind of under microwave action in the ionic liquid directly oxidizing methane prepare methanol process, this method environmental protection, solvent is recyclable, low cost, short productive rate height of reaction times.
The technical solution adopted in the present invention, concrete preparation process is as follows:
The first step, in there-necked flask, add ionic liquid, trifluoroacetic acid, trifluoroacetic anhydride, Potassium Persulphate and catalyzer successively, its mass ratio is 10: 77: 22.3: 13.3: 0.1, there-necked flask is packed in the microwave reactor, and with the homogeneous reaction liquid of magnetic agitation;
Second step, will be used for feeding under the liquid level of polyfluortetraethylene pipe insertion reaction liquid of methane, with power microwave heating to 80～110 of 100～600W ℃;
The 3rd step, feed methane with the speed of 10ml～60ml/min, reaction 30～120min;
Behind the 4th step, the stopped reaction, reaction solution adds the 20ml deionized water, at 25 ℃ of following hydrolysis 30min;
The 5th step, distillation hydrolyzed solution, the cut that gets 90 ℃ is a product methyl alcohol.
Ionic liquid of the present invention is made up of positively charged ion and negatively charged ion, and positively charged ion is that substituting group is hydrogen, C 1～C 4Alkyl; Negatively charged ion is Cl -, Br -In a kind of.
Catalyzer of the present invention is the nanometer gold that is carried on silicon oxide, and wherein silicon oxide is a carrier, and nanometer gold is an activeconstituents, and its building-up process is, with ionic liquid 1-methyl-3-hexyl imidazoles hexafluorophosphate [C 6Mim] PF 6, butyl silicate, water and hydrochloro-auric acid HAuCl 4With mol ratio 1: 5: 5: 0.01 thorough mixing.Ageing at room temperature is 12 hours then, adds and hydrochloro-auric acid HAuCl again 41: 1 formaldehyde of mol ratio reduction two hours gets purple gel, through filtration under diminished pressure, and drying, after the roasting, the purple powdery product that obtains is catalyzer.
Beneficial effect of the present invention: adopt catalytic methane conversion preparation methyl alcohol in the microwave-assisted ionic liquid, production process obviously shortens, and process energy consumption and process cost are low.
Embodiment
Embodiment 1
In there-necked flask, add ionic liquid [C successively 4Mim] Cl, K 2S 2O 8, TFA, TFAA, Au/SiO 2After (mass ratio is 10: 77: 22.3: 13.3: 0.1), place microwave reactor, microwave reactor power 300W feeds the speed of methane gas with 10ml/min in the liquid, under 80 ℃, and reaction 30min.Behind the stopped reaction, reaction solution adds the 20ml deionized water, at 25 ℃ of following hydrolysis 30min.The distillation hydrolyzed solution, the cut that gets 90 ℃ is a product methyl alcohol.Methane conversion 5.1%, methyl alcohol yield 4.8%.
Embodiment 2
In there-necked flask, add ionic liquid [C successively 1Mim] Cl, K 2S 2O 8, TFA, TFAA, Au/SiO 2After (mass ratio is 10: 77: 22.3: 13.3: 0.1), place microwave reactor, microwave reactor power 100W feeds the speed of methane gas with 20ml/min in the liquid, under 80 ℃, and reaction 30min.Behind the stopped reaction, reaction solution adds the 20ml deionized water, at 25 ℃ of following hydrolysis 30min.The distillation hydrolyzed solution, the cut that gets 90 ℃ is a product methyl alcohol.Methane conversion 4.7%, methyl alcohol yield 4.6%.
Embodiment 3
In there-necked flask, add ionic liquid [C successively 1Mim] Cl, K 2S 2O 8, TFA, TFAA, Au/SiO 2After (mass ratio is 10: 77: 22.3: 13.3: 0.1), place microwave reactor, microwave reactor power 300W feeds the speed of methane gas with 20ml/min in the liquid, under 80 ℃, and reaction 30min.Behind the stopped reaction, reaction solution adds the 20ml deionized water, at 25 ℃ of following hydrolysis 30min.The distillation hydrolyzed solution, the cut that gets 90 ℃ is a product methyl alcohol.Methane conversion 4.8%, methyl alcohol yield 4.6%.
Embodiment 4
In there-necked flask, add ionic liquid [C successively 2Mim] Cl, K 2S 2O 8, TFA, TFAA, Au/SiO 2After (mass ratio is 10: 77: 22.3: 13.3: 0.1), place microwave reactor, microwave reactor power 400W feeds the speed of methane gas with 40ml/min in the liquid, under 90 ℃, and reaction 30min.Behind the stopped reaction, reaction solution adds the 20ml deionized water, at 25 ℃ of following hydrolysis 30min.The distillation hydrolyzed solution, the cut that gets 90 ℃ is a product methyl alcohol.Methane conversion 4.3%, methyl alcohol yield 4.3%.
Embodiment 5
In there-necked flask, add ionic liquid [C successively 3Mim] Cl, K 2S 2O 8, TFA, TFAA, Au/SiO 2After (mass ratio is 10: 77: 22.3: 13.3: 0.1), place microwave reactor, microwave reactor power 500W feeds the speed of methane gas with 60ml/min in the liquid, under 100 ℃, and reaction 30min.Behind the stopped reaction, reaction solution adds the 20ml deionized water, at 25 ℃ of following hydrolysis 30min.The distillation hydrolyzed solution, the cut that gets 90 ℃ is a product methyl alcohol.Methane conversion 3.9%, methyl alcohol yield 3.8%.
Embodiment 6
In there-necked flask, add ionic liquid [C successively 4Mim] Cl, K 2S 2O 8, TFA, TFAA, Au/SiO 2After (mass ratio is 10: 77: 22.3: 13.3: 0.1), place microwave reactor, microwave reactor power 600W feeds the speed of methane gas with 10ml/min in the liquid, under 110 ℃, and reaction 30min.Behind the stopped reaction, reaction solution adds the 20ml deionized water, at 25 ℃ of following hydrolysis 30min.The distillation hydrolyzed solution, the cut that gets 90 ℃ is a product methyl alcohol.Methane conversion 5.2%, methyl alcohol yield 5.0%.
Embodiment 7
In there-necked flask, add ionic liquid [C successively 4Mim] Cl, K 2S 2O 8, TFA, TFAA, Au/SiO 2After (mass ratio is 10: 77: 22.3: 13.3: 0.1), place microwave reactor, microwave reactor power 300W feeds the speed of methane gas with 10ml/min in the liquid, under 80 ℃, and reaction 60min.Behind the stopped reaction, reaction solution adds the 20ml deionized water, at 25 ℃ of following hydrolysis 30min.The distillation hydrolyzed solution, the cut that gets 90 ℃ is a product methyl alcohol.Methane conversion 5.1%, methyl alcohol yield 4.8%.
Embodiment 8
In there-necked flask, add ionic liquid [C successively 4Mim] Cl, K 2S 2O 8, TFA, TFAA, Au/SiO 2After (mass ratio is 10: 77: 22.3: 13.3: 0.1), place microwave reactor, microwave reactor power 300W feeds the speed of methane gas with 10ml/min in the liquid, under 80 ℃, and reaction 90min.Behind the stopped reaction, reaction solution adds the 20ml deionized water, at 25 ℃ of following hydrolysis 30min.The distillation hydrolyzed solution, the cut that gets 90 ℃ is a product methyl alcohol.Methane conversion 5.5%, methyl alcohol yield 5.4%.
Embodiment 9
In there-necked flask, add ionic liquid [C successively 4Mim] Cl, K 2S 2O 8, TFA, TFAA, Au/SiO 2After (mass ratio is 10: 77: 22.3: 13.3: 0.1), place microwave reactor, microwave reactor power 300W feeds the speed of methane gas with 10ml/min in the liquid, under 80 ℃, and reaction 120min.Behind the stopped reaction, reaction solution adds the 20ml deionized water, at 25 ℃ of following hydrolysis 30min.The distillation hydrolyzed solution, the cut that gets 90 ℃ is a product methyl alcohol.Methane conversion 5.4%, methyl alcohol yield 5.4%.

Claims (7)

  1. Under the microwave action in the ionic liquid directly oxidizing methane prepare the method for methyl alcohol, it is characterized in that concrete preparation process is as follows:
    The first step, in there-necked flask, add ionic liquid, trifluoroacetic acid, trifluoroacetic anhydride, Potassium Persulphate and catalyzer successively, its mass ratio is 10: 77: 22.3: 13.3: 0.1, there-necked flask is packed in the microwave reactor, and with the homogeneous reaction liquid of magnetic agitation;
    Second step, will be used for feeding under the liquid level of polyfluortetraethylene pipe insertion reaction liquid of methane, with power microwave heating to 80～110 of 100～600W ℃;
    The 3rd step, feed methane with the speed of 10ml～60ml/min, reaction 30～120min;
    Behind the 4th step, the stopped reaction, reaction solution adds the 20ml deionized water, at 25 ℃ of following hydrolysis 30min;
    The 5th step, distillation hydrolyzed solution, the cut that gets 90 ℃ is a product methyl alcohol.
  2. 2. under the microwave action according to claim 1 in the ionic liquid directly oxidizing methane prepare the method for methyl alcohol, the process that it is characterized in that preparing methyl alcohol is to carry out under microwave, microwave power is at 100～600W.
  3. 3. under the microwave action according to claim 1 in the ionic liquid directly oxidizing methane prepare the method for methyl alcohol, it is characterized in that using ionic liquid to be solvent.
  4. 4. under the microwave action according to claim 1 in the ionic liquid directly oxidizing methane prepare the method for methyl alcohol, it is characterized in that described ionic liquid is made up of positively charged ion and negatively charged ion, positively charged ion is that substituting group is hydrogen, C 1～C 4Alkyl; Negatively charged ion is Cl -, Br -In a kind of.
  5. 5. under the microwave action according to claim 1 in the ionic liquid directly oxidizing methane prepare the method for methyl alcohol, it is characterized in that 80～110 ℃ of described temperature of reaction.
  6. 6. under the microwave action according to claim 1 in the ionic liquid directly oxidizing methane prepare the method for methyl alcohol, it is characterized in that described catalyzer is the nanometer gold that is carried on silicon oxide, wherein silicon oxide is a carrier, nanometer gold is an activeconstituents.
  7. 7. under the microwave action according to claim 1 in the ionic liquid directly oxidizing methane prepare the method for methyl alcohol, the building-up process that it is characterized in that the nano catalyst that this is carried on silicon oxide is, with ionic liquid 1-methyl-3-hexyl imidazoles hexafluorophosphate, butyl silicate, water and hydrochloro-auric acid with mol ratio 1: 5: 5: 0.01 thorough mixing; Ageing at room temperature is 12 hours then, adds and 1: 1 formaldehyde of hydrochloro-auric acid mol ratio reduction two hours again, gets purple gel, through filtration under diminished pressure, and drying, after the roasting, product is the purple powder.
CN201110175312.2A 2010-11-16 2011-06-27 Method for preparing methanol by directly oxidizing methane in ionic liquid under action of microwaves Expired - Fee Related CN102285865B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103712838A (en) * 2013-12-31 2014-04-09 云南磷化集团有限公司 Detection pretreatment method of anion collecting agent for collophanite flotation

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Publication number Priority date Publication date Assignee Title
US6538162B2 (en) * 2001-01-30 2003-03-25 Exxonmobil Chemical Patents Inc. Method for converting alkanes to oxygenates
WO2009091913A1 (en) * 2008-01-16 2009-07-23 Periana Roy A Tridentate (nnc) catalysts for the selective oxidation of hydrocarbons
CN101704716A (en) * 2009-11-06 2010-05-12 华东理工大学 Method for directly preparing methanol by partially oxidizing methane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6538162B2 (en) * 2001-01-30 2003-03-25 Exxonmobil Chemical Patents Inc. Method for converting alkanes to oxygenates
WO2009091913A1 (en) * 2008-01-16 2009-07-23 Periana Roy A Tridentate (nnc) catalysts for the selective oxidation of hydrocarbons
CN101704716A (en) * 2009-11-06 2010-05-12 华东理工大学 Method for directly preparing methanol by partially oxidizing methane

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Title
HIDEAKI ITOH ET AL.,: "Synthesis of Gold Nanoparticles Modified with Ionic Liquid Based on the Imidazolium Cation", 《J. AM. CHEM. SOC.》, vol. 126, no. 10, 19 February 2004 (2004-02-19), pages 3026 - 3027, XP055254752, DOI: doi:10.1021/ja039895g *
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103712838A (en) * 2013-12-31 2014-04-09 云南磷化集团有限公司 Detection pretreatment method of anion collecting agent for collophanite flotation

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