CN111763136A - Application of sulfonyl-containing ionic liquid in reaction system for preparing methanol and ethanol from methane - Google Patents
Application of sulfonyl-containing ionic liquid in reaction system for preparing methanol and ethanol from methane Download PDFInfo
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- CN111763136A CN111763136A CN202010551923.1A CN202010551923A CN111763136A CN 111763136 A CN111763136 A CN 111763136A CN 202010551923 A CN202010551923 A CN 202010551923A CN 111763136 A CN111763136 A CN 111763136A
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- ionic liquid
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- ethanol
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 81
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 42
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 27
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- -1 N-butylpyridinium bis (trifluoromethanesulfonyl) imide salt Chemical class 0.000 claims description 4
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical class CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 2
- ZDMWZUAOSLBMEY-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butyl-1-methylpiperidin-1-ium Chemical class CCCC[N+]1(C)CCCCC1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F ZDMWZUAOSLBMEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- HKOAFLAGUQUJQG-UHFFFAOYSA-N 2-pyrimidin-2-ylpyrimidine Chemical compound N1=CC=CN=C1C1=NC=CC=N1 HKOAFLAGUQUJQG-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052924 anglesite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XHIHMDHAPXMAQK-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F XHIHMDHAPXMAQK-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0222—Sulfur-containing compounds comprising sulfonyl groups
- B01J31/0224—Sulfur-containing compounds comprising sulfonyl groups being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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 an application of sulfonyl-containing ionic liquid in a reaction system for preparing methanol and ethanol from methane. Adding a certain amount of sulfonyl-containing ionic liquid, solvent water and a catalyst into a reaction system, then introducing methane gas and air, and reacting for a period of time under certain temperature and pressure conditions to obtain products of oxygen-containing compounds such as methanol, ethanol and the like. Compared with the existing reaction system for preparing methanol, ethanol and the like by directly oxidizing methane, the method effectively improves the yield of alcohol products in the reaction system by adding the sulfonyl-containing ionic liquid into the reaction system. The scheme has simple process and is easy to popularize and apply.
Description
Technical Field
The invention relates to the technical field of methanol and ethanol preparation by direct oxidation of methane, in particular to application of an ionic liquid containing sulfonyl in a reaction system for preparing methanol and ethanol from methane.
Background
The natural gas has been found to have a natural reserve far exceeding that of petroleum, and is one of the most promising energy sources in the world today, and the composition of the natural gas is methane up to 90%. Today, extensive attention is being given to the research of the preparation of hydrocarbons and oxygenates by activation and functionalization of methane. Methanol is a core product of C1 chemistry, mainly used for heating and automobile fuel, while ethanol has wider application in medicine and industry, and the conversion of methane into methanol and ethanol is one of the most important industrial processes.
At present, the high-efficiency utilization of methane is mainly realized by converting methane into synthesis gas through an indirect way under the conditions of high temperature and high pressure, and then methanol is generated through a Fischer-Tropsch synthesis reaction. The indirect conversion process has the problems of long process flow and high energy consumption, and from the perspective of sustainable development, the direct conversion of methane can be carried out at lower temperature and pressure, so that the intermediate step of preparing synthesis gas is directly omitted, and the problems are effectively solved, thus the process has application prospects.
In recent years, the direct catalytic oxidation of methane to produce alcohol products has been widely studied, and among them, the reaction system using strong acid such as concentrated sulfuric acid and fuming sulfuric acid as media has better operation performance. For example, Periana et al (Science, 1993, 259(5093)340) reported the complex Pt (bpym) Cl2As a catalyst, the conversion rate of the liquid phase catalytic oxidation of methane in a fuming sulfuric acid solvent is 81 percent, and the selectivity of methanol is more than 90 percent. Later, the domestic researchers adopted HgSO4、Ag2SO4、La2(SO4)3And PbSO4And a series of metal sulfates are used as catalysts, and concentrated sulfuric acid is used as a solvent, so that better catalytic reaction performance is obtained. However, such strong acid based catalytic systems are limited by high cost, high corrosiveness, etc. Recently, the subject group realizes the direct oxidation of methane to methanol (CN 110038591A; CN 110639547A) in an aqueous medium by the design of an iridium-based composite oxide catalyst, but the catalytic reaction efficiency needs to be further improved.
Aiming at the problems of large harm of a solvent in a strong acid medium to the environment, poor catalyst stability, low reaction efficiency in a water isothermal reaction medium and the like in the reaction system for preparing alcohols by directly oxidizing methane, the invention provides the reaction system for realizing the high catalytic performance of the catalyst under the mild condition, which is of great significance for preparing methanol and ethanol by directly oxidizing methane.
Disclosure of Invention
Aiming at the problems of the reaction system for preparing the alcohols by directly oxidizing the methane, the method for introducing the sulfonyl-containing ionic liquid into the reaction system for preparing the alcohol products by directly oxidizing the methane in the aqueous medium is provided, so that the efficient preparation of the methanol and the ethanol by directly oxidizing the methane is realized.
The invention aims to provide application of sulfonyl-containing ionic liquid in a reaction system for preparing methanol and ethanol from methane.
The sulfonyl group-containing ionic liquid refers to ionic liquids such as 1-ethyl-3 methylimidazolium bis (trifluoromethanesulfonyl) imide salt (IL-1), N-butylpyridinium bis (trifluoromethanesulfonyl) imide salt (IL-2), and N-butyl-N-methylpiperidinium bis (trifluoromethanesulfonyl) imide salt (IL-3) having a sulfonyl group in the structure.
The reaction system for preparing methanol and ethanol from methane containing sulfonyl ionic liquid comprises methane gas, air, solvent water, a catalyst and sulfonyl ionic liquid, and oxygen-containing compounds such as methanol, ethanol and the like are generated after reaction.
The reaction system for preparing methanol and ethanol from methane containing sulfonyl ionic liquid, the added ionic liquid containing sulfonyl and solvent H2The volume ratio of O is 1: 10-1: 1000, preferably 1: 10-1: 100.
The reaction system for preparing methanol and ethanol from methane containing sulfonyl ionic liquid has CH under the initial reaction condition4The molar ratio of the air to the air is 1: 1-50: 1, preferably 1: 1-30: 1, and the reaction pressure is 1-30 atm.
In the reaction system for preparing methanol and ethanol from methane by using the ionic liquid containing sulfonyl group, the adopted catalyst and dosage can be directly selected from the catalysts and dosages disclosed in documents and patents.
Based on the technical scheme, preferably, the ionic liquid added into the solvent is one or a mixture of more of 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt (IL-1), N-butylpyridinium bis (trifluoromethanesulfonyl) imide salt (IL-2) and N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt (IL-3).
Compared with the prior art, the invention has the following beneficial effects: compared with a reaction system using water as a solvent, the catalytic activity of the catalyst is higher.
Detailed Description
The present invention is further described in detail below with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
10 mg of IrO prepared by the preparation method described in CN110038591A were each obtained2The catalyst/CuO was placed in a high-pressure reactor (inner liner volume 100 mL) to conduct the experiment. The experimental conditions were as follows: adding 30 mL of water into a reaction kettle, introducing a certain amount of ionic liquid containing sulfonic groups, and introducing CH4And air, reacting at a reaction pressure and a reaction temperature of 150 DEG CoC, the reaction time is 3 hours, and the stirring speed of the reaction kettle is 800 r/min. After the reaction is finished, carrying out qualitative and quantitative analysis on the liquid product, and calculating the yield of the total alcohol and the selectivity of the methanol and the ethanol. The results of activity evaluation are shown in Table 1.
Example 1:
adding 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt (IL-1), IL-1 and H into the reaction system2The volume ratio of O is 1: 30, introduction of CH4And air at a molar ratio of 3:1, and a test pressure of 4 atm.
Comparative example 1:
adding no ionic liquid into the reaction system, and introducing CH4And air at a molar ratio of 3:1, and a test pressure of 4 atm.
Example 2:
adding N-butylpyridinium bis (trifluoromethanesulfonyl) imide (IL-2), IL-2 and H into the reaction system2The volume ratio of O is 1: 50, introduction of CH4And mole of airThe ratio is 5:1, and the test pressure is 6 atm.
Example 3:
adding N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt (IL-3), IL-3 and H into the reaction system2The volume ratio of O is 1: 20, introduction of CH4And air at a molar ratio of 3:1, and a test pressure of 4 atm.
Example 4:
adding 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt (IL-1), IL-1 and H into the reaction system2The volume ratio of O is 1: 30, introduction of CH4And air at a molar ratio of 20:1, test pressure 21 atm.
TABLE 1 Activity evaluation results
| Example 1 | Comparative example 1 | Example 2 | Example 3 | Example 4 | |
| Alcohol yield (. mu.mol/g)cat） | 1554 | 909 | 1061 | 1290 | 1894 |
| Methanol/ethanol selectivity (%) | 76.2/23.8 | 94.3/4.5 | 87.5/12.5 | 80.3/19.7 | 75.7/24.3 |
It should be finally noted that the above examples are only intended to illustrate the technical solutions of the present invention, and not to limit the scope of the present invention, and that other variations and modifications based on the above description and thought may be made by those skilled in the art, and that all embodiments need not be exhaustive. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (5)
1. The application of the ionic liquid containing sulfonyl in a reaction system for preparing methanol and ethanol from methane is characterized in that a certain amount of ionic liquid containing sulfonyl is added into the reaction system for preparing methanol and ethanol by directly oxidizing heterogeneous methane.
2. The sulfonyl-containing ionic liquid according to claim 1, wherein the sulfonyl-containing ionic liquid is an ionic liquid such as 1-ethyl-3 methylimidazolium bis (trifluoromethanesulfonyl) imide salt (IL-1), N-butylpyridinium bis (trifluoromethanesulfonyl) imide salt (IL-2), and N-butyl-N-methylpiperidinium bis (trifluoromethanesulfonyl) imide salt (IL-3) having a sulfonyl group in the structure.
3. The system of claim 1, comprising methane gas, air, solvent water, catalyst and sulfonyl-containing ionic liquid, wherein oxygen-containing compounds such as methanol and ethanol are produced after the reaction.
4. The system of claims 1-3, wherein the ionic liquid containing sulfonic groups and the solvent H are added to form the methanol and ethanol from methane2The volume ratio of O is 1: 10-1: 1000, preferably 1: 10-1: 100.
5. The system of claims 1-4, wherein the initial reaction conditions are CH, under which the system is used to produce methanol and ethanol from methane containing sulfonyl ionic liquid4The molar ratio of the air to the air is 1: 1-50: 1, preferably 1: 1-30: 1, and the reaction pressure is 1-30 atm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998050333A1 (en) * | 1996-04-24 | 1998-11-12 | Catalytica, Inc. | Ligated platinum group metal catalyst complex and improved process for catalytically converting alkanes to esters and derivatives thereof |
| US20040059153A1 (en) * | 2002-05-23 | 2004-03-25 | Institut Francais Du Petrole | Process for carbonylating alcohols, employing a catalyst based on rhodium or iridium in a non-aqueous ionic liquid, with efficient catalyst recycling |
| CN109809966A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of method of alkane C-H partial oxidation in ionic liquid |
| CN110038591A (en) * | 2019-05-28 | 2019-07-23 | 中山大学 | A kind of copper for methane oxidation methanol-iridium composite oxide catalyst |
| CN110639547A (en) * | 2019-09-10 | 2020-01-03 | 中山大学 | Iridium-based multi-phase composite oxide catalyst for preparing alcohol products by methane oxidation and preparation method thereof |
-
2020
- 2020-06-17 CN CN202010551923.1A patent/CN111763136A/en active Pending
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|---|---|---|---|---|
| WO1998050333A1 (en) * | 1996-04-24 | 1998-11-12 | Catalytica, Inc. | Ligated platinum group metal catalyst complex and improved process for catalytically converting alkanes to esters and derivatives thereof |
| US20040059153A1 (en) * | 2002-05-23 | 2004-03-25 | Institut Francais Du Petrole | Process for carbonylating alcohols, employing a catalyst based on rhodium or iridium in a non-aqueous ionic liquid, with efficient catalyst recycling |
| CN109809966A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of method of alkane C-H partial oxidation in ionic liquid |
| CN110038591A (en) * | 2019-05-28 | 2019-07-23 | 中山大学 | A kind of copper for methane oxidation methanol-iridium composite oxide catalyst |
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Non-Patent Citations (1)
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