CN102285864A - Method for producing methanol by catalytic oxidation of methane - Google Patents
Method for producing methanol by catalytic oxidation of methane Download PDFInfo
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- CN102285864A CN102285864A CN2010102017297A CN201010201729A CN102285864A CN 102285864 A CN102285864 A CN 102285864A CN 2010102017297 A CN2010102017297 A CN 2010102017297A CN 201010201729 A CN201010201729 A CN 201010201729A CN 102285864 A CN102285864 A CN 102285864A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 97
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 230000003647 oxidation Effects 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims abstract 2
- 230000007062 hydrolysis Effects 0.000 claims abstract 2
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims 3
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 3
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims 2
- 241000370738 Chlorion Species 0.000 claims 1
- 150000004054 benzoquinones Chemical class 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- VMVNZNXAVJHNDJ-UHFFFAOYSA-N methyl 2,2,2-trifluoroacetate Chemical compound COC(=O)C(F)(F)F VMVNZNXAVJHNDJ-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 12
- -1 dichlorobipyridyl palladium Chemical compound 0.000 abstract description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- YSVZGWAJIHWNQK-UHFFFAOYSA-N [3-(hydroxymethyl)-2-bicyclo[2.2.1]heptanyl]methanol Chemical compound C1CC2C(CO)C(CO)C1C2 YSVZGWAJIHWNQK-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- HKOAFLAGUQUJQG-UHFFFAOYSA-N 2-pyrimidin-2-ylpyrimidine Chemical compound N1=CC=CN=C1C1=NC=CC=N1 HKOAFLAGUQUJQG-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HSNVNALJRSJDHT-UHFFFAOYSA-N P(=O)(=O)[Mo] Chemical compound P(=O)(=O)[Mo] HSNVNALJRSJDHT-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
Classifications
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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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供了一种甲烷催化氧化生产甲醇的方法，属于化工技术领域。其特征是：在三氟乙酸与水组成的混合溶剂中，以氧气为氧化剂，用二氯联吡啶钯、苯醌和磷钼钒酸为催化剂，将甲烷催化氧化为三氟乙酸甲酯和甲醇，三氟乙酸甲酯水解即得甲醇。在该方法中，水与三氟乙酸的体积比为0～1∶2；甲烷和氧气的总压力为2.0～5.0MPa，甲烷与氧气的分压比为(1.6～12.5)∶1；在40～120℃下反应1～12h，生成三氟乙酸甲酯和甲醇。有水存在时，本发明所采用的催化剂具有更高的催化活性。The invention provides a method for producing methanol by catalytic oxidation of methane, which belongs to the technical field of chemical industry. It is characterized in that: in a mixed solvent composed of trifluoroacetic acid and water, oxygen is used as an oxidant, and dichlorobipyridyl palladium, benzoquinone and phosphomolybdovanadic acid are used as catalysts to catalyze the oxidation of methane into methyl trifluoroacetate and methanol , Methanol can be obtained by hydrolysis of methyl trifluoroacetate. In this method, the volume ratio of water and trifluoroacetic acid is 0～1:2; the total pressure of methane and oxygen is 2.0～5.0MPa, and the partial pressure ratio of methane and oxygen is (1.6～12.5): 1; at 40 React at ~120°C for 1~12h to generate methyl trifluoroacetate and methanol. In the presence of water, the catalyst used in the present invention has higher catalytic activity.
Description
技术领域 technical field
本发明涉及一种甲烷催化氧化生产甲醇的方法，属于化工技术领域。The invention relates to a method for producing methanol by catalytic oxidation of methane, which belongs to the technical field of chemical industry.
背景技术 Background technique
由甲烷生产甲醇时，通常采用两步法，即首先采用蒸汽裂解的方法生产合成气(CO+H2)，再由合成气通过费-托合成反应生产甲醇。但是甲烷转化为合成气的过程能耗很高，因此迫切需要开发较低温度下甲烷直接催化氧化生产甲醇新方法。When methanol is produced from methane, a two-step process is usually adopted, that is, first, steam cracking is used to produce synthesis gas (CO+H 2 ), and then methanol is produced from the synthesis gas through Fischer-Tropsch synthesis. However, the process of converting methane into synthesis gas consumes a lot of energy, so it is urgent to develop a new method of direct catalytic oxidation of methane to produce methanol at a lower temperature.
近年来，人们提出了一系列甲烷直接催化氧化的高效催化剂。一些过渡金属化合物具有较高的催化活性。以联嘧啶(bmpy)为配体的铂配合物催化剂Pt(bpym)Cl2，是迄今为止最高效的催化剂。该催化剂在102％的发烟硫酸中能够在较低温度下将甲烷催化氧化为硫酸甲酯，硫酸甲酯水解即可得到甲醇(R.A.Periana，D.J.Taube，S.Gamble，et al.PlatinumCatalysts for the High-Yield Oxidation of Methane to a Methanol Derivative.Science，1998年，280卷，560～564页)。但是，该催化剂价格昂贵；更重要的是，反应过程生成的水份使催化剂活性显著下降，给工业应用带来很大困难。In recent years, a series of highly efficient catalysts for the direct catalytic oxidation of methane have been proposed. Some transition metal compounds have high catalytic activity. Pt(bpym)Cl 2 , a platinum complex catalyst with bipyrimidine (bmpy) as a ligand, is the most efficient catalyst so far. The catalyst can catalyze the oxidation of methane into methyl sulfate at a relatively low temperature in 102% oleum, and methyl sulfate can be hydrolyzed to obtain methanol (RAPeriana, DJTaube, S.Gamble, et al.PlatinumCatalysts for the High- Yield Oxidation of Methane to a Methanol Derivative. Science, 1998, Vol. 280, pp. 560-564). However, the catalyst is expensive; more importantly, the moisture generated in the reaction process significantly reduces the activity of the catalyst, which brings great difficulties to industrial applications.
有人研究了在三氟乙酸与水的混合溶剂中，以金属钯和氯化铜的混合物为催化剂，将甲烷氧化为三氟乙酸甲酯和甲醇，取得了较高的转化率(M.Lin，T.Hogan，A.Sen.A Highly Catalytic Bimetallic System for theLow-Temperature Selective Oxidation of Methane and Lower Alkanes withDioxygen as the Oxidant.Journal of the American Chemical Society，1997年，119卷，6048～6053页)。但是，该催化反应以一氧化碳和氧气为氧化剂，而一氧化碳对人体有毒。Someone has studied that in the mixed solvent of trifluoroacetic acid and water, the mixture of metal palladium and cupric chloride is used as a catalyst to oxidize methane into methyl trifluoroacetate and methyl alcohol, and obtain a higher conversion rate (M.Lin, T. Hogan, A. Sen. A Highly Catalytic Bimetallic System for the Low-Temperature Selective Oxidation of Methane and Lower Alkanes with Dioxygen as the Oxidant. Journal of the American Chemical Society, 1997, Volume 119, Pages 6048-6053). However, this catalytic reaction uses carbon monoxide and oxygen as oxidants, and carbon monoxide is toxic to humans.
发明内容 Contents of the invention
本发明提供了一种甲烷催化氧化生产甲醇的方法，其特征在于：在三氟乙酸与水组成的混合溶剂中，以氧气为氧化剂，用二氯联吡啶钯、苯醌和磷钼钒酸的混合物为催化剂，将甲烷催化氧化为三氟乙酸甲酯和甲醇，三氟乙酸甲酯水解即得甲醇；有水存在时，本发明所采用的催化剂具有更高的催化活性。The invention provides a method for producing methanol by catalytic oxidation of methane, which is characterized in that: in a mixed solvent composed of trifluoroacetic acid and water, oxygen is used as an oxidant, and dichlorobipyridyl palladium, benzoquinone and phosphomolybdovanadic acid are used The mixture is a catalyst, and the methane is catalyzed and oxidized into methyl trifluoroacetate and methanol, and the methyl trifluoroacetate is hydrolyzed to obtain methanol; when there is water, the catalyst adopted in the present invention has higher catalytic activity.
该方法包括以下步骤：将二氯联吡啶钯、苯醌和磷钼钒酸按一定比例加入三氟乙酸与水组成的混合溶剂中，其中水与三氟乙酸的体积比为0～1∶2；二氯联吡啶钯的浓度为0.1～3mM；反应体系中氯离子与二氯联吡啶钯的摩尔比为0～100；磷钼钒酸为1～4个钒原子取代的Keggin结构的磷钼钒酸，磷钼钒酸的浓度为0.05～3mM；通入总压力为2.0～5.0MPa的甲烷和氧气，其中甲烷与氧气的分压比为(1.6～12.5)∶1；搅拌，在40～120℃恒温反应1～12h，生成三氟乙酸甲酯和甲醇；三氟乙酸甲酯水解即得甲醇。The method comprises the following steps: adding dichlorobipyridyl palladium, benzoquinone and phosphomolybdovanadic acid in a certain proportion to a mixed solvent composed of trifluoroacetic acid and water, wherein the volume ratio of water to trifluoroacetic acid is 0-1:2 ; The concentration of dichlorobipyridyl palladium is 0.1 ~ 3mM; the molar ratio of chloride ion to dichlorobipyridyl palladium in the reaction system is 0 ~ 100; phosphomolybdovanadic acid is phosphomolybdenum of Keggin structure replaced by 1 ~ 4 vanadium atoms Vanadic acid, the concentration of phosphomolybdovanadic acid is 0.05 ~ 3mM; feed the methane and oxygen with a total pressure of 2.0 ~ 5.0MPa, wherein the partial pressure ratio of methane and oxygen is (1.6 ~ 12.5): 1; stirring, at 40 ~ React at a constant temperature of 120°C for 1 to 12 hours to generate methyl trifluoroacetate and methanol; hydrolyze methyl trifluoroacetate to obtain methanol.
有水存在时，本发明所采用的催化剂具有更高的催化活性。In the presence of water, the catalyst used in the present invention has higher catalytic activity.
具体实施方式 Detailed ways
实施例1Example 1
首先将二氯联吡啶钯(0.30mM)、苯醌(1.20mM)和磷钼钒酸H5PMo10V2O40(0.05mM)置于装有玻璃内衬的不锈钢高压反应釜(50mL)内，其中反应溶剂为10mL三氟乙酸。封釜，用甲烷排除釜内空气，最后通入2.5MPa甲烷和0.5MPa氧气，关闭进气阀，开动磁力搅拌，于100℃反应8h。反应停止后，将高压釜置于冰水混合物中冷却至3℃左右，取出反应液，利用气相色谱仪分析液相中三氟乙酸甲酯和甲醇的浓度。测得三氟乙酸甲酯和甲醇的总浓度为1.12mM。First, dichlorobipyridyl palladium (0.30mM), benzoquinone (1.20mM) and phosphomolybdovanadate H 5 PMo 10 V 2 O 40 (0.05mM) were placed in a glass-lined stainless steel autoclave (50mL) In, the reaction solvent is 10mL trifluoroacetic acid. Seal the kettle, remove the air in the kettle with methane, finally introduce 2.5MPa methane and 0.5MPa oxygen, close the inlet valve, start magnetic stirring, and react at 100°C for 8h. After the reaction stopped, the autoclave was placed in an ice-water mixture and cooled to about 3°C, the reaction solution was taken out, and the concentrations of methyl trifluoroacetate and methanol in the liquid phase were analyzed by gas chromatography. The total concentration of methyl trifluoroacetate and methanol was measured to be 1.12 mM.
实施例2Example 2
首先将二氯联吡啶钯(0.25mM)、苯醌(1.00mM)和磷钼钒酸H5PMo10V2O40(0.04mM)置于装有玻璃内衬的不锈钢高压反应釜(50mL)内，其中反应溶剂为10mL三氟乙酸和2mL水。封釜，用甲烷排除釜内空气，最后通入2.5MPa甲烷和0.5MPa氧气，关闭进气阀，开动磁力搅拌，于100℃反应8h。反应停止后，将高压釜置于冰水混合物中冷却至3℃左右，取出反应液，利用气相色谱仪分析液相中三氟乙酸甲酯和甲醇的浓度。测得三氟乙酸甲酯和甲醇的总浓度为3.58mM。First, dichlorobipyridyl palladium (0.25mM), benzoquinone (1.00mM) and phosphomolybdovanadate H 5 PMo 10 V 2 O 40 (0.04mM) were placed in a glass-lined stainless steel autoclave (50mL) In, the reaction solvent is 10mL trifluoroacetic acid and 2mL water. Seal the kettle, remove the air in the kettle with methane, finally introduce 2.5MPa methane and 0.5MPa oxygen, close the inlet valve, start magnetic stirring, and react at 100°C for 8h. After the reaction stopped, the autoclave was placed in an ice-water mixture and cooled to about 3°C, the reaction solution was taken out, and the concentrations of methyl trifluoroacetate and methanol in the liquid phase were analyzed by gas chromatography. The total concentration of methyl trifluoroacetate and methanol was found to be 3.58 mM.
实施例3Example 3
二氯联吡啶钯、苯醌、磷钼钒酸的浓度、反应溶剂的组成和总体积、操作过程均与实施例2完全相同。在反应体系中加入15mM氯化钠。后续步骤和实施例2完全相同。反应停止后，测得三氟乙酸甲酯的浓度为7.40mM。The concentration of dichlorobipyridyl palladium, benzoquinone, phosphomolybdovanadic acid, the composition and the total volume of the reaction solvent, and the operating process are all identical to those in Example 2. Add 15mM sodium chloride to the reaction system. Subsequent steps are exactly the same as in Example 2. After the reaction was stopped, the concentration of methyl trifluoroacetate was measured to be 7.40 mM.
实施例4Example 4
首先将二氯联吡啶钯(0.25mM)、苯醌(1.00mM)和磷钼钒酸H5PMo10V2O40(0.21mM)置于装有玻璃内衬的不锈钢高压反应釜(50mL)内，其中反应溶剂为10mL三氟乙酸和2mL水。封釜，用甲烷排除釜内空气，最后通入2.5MPa甲烷和0.5MPa氧气，关闭进气阀，开动磁力搅拌，于100℃反应8h。反应停止后，将高压釜置于冰水混合物中冷却至3℃左右，取出反应液，利用气相色谱仪分析液相中三氟乙酸甲酯和甲醇的浓度。测得三氟乙酸甲酯和甲醇的总浓度为12.90mM。First, dichlorobipyridyl palladium (0.25mM), benzoquinone (1.00mM) and phosphomolybdovanadate H 5 PMo 10 V 2 O 40 (0.21mM) were placed in a glass-lined stainless steel autoclave (50mL) In, the reaction solvent is 10mL trifluoroacetic acid and 2mL water. Seal the kettle, remove the air in the kettle with methane, finally introduce 2.5MPa methane and 0.5MPa oxygen, close the inlet valve, start magnetic stirring, and react at 100°C for 8h. After the reaction stopped, the autoclave was placed in an ice-water mixture and cooled to about 3°C, the reaction solution was taken out, and the concentrations of methyl trifluoroacetate and methanol in the liquid phase were analyzed by gas chromatography. The total concentration of methyl trifluoroacetate and methanol was measured to be 12.90 mM.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103949263A (en) * | 2014-04-27 | 2014-07-30 | 东北石油大学 | Perovskite composite oxide catalyst for preparing methyl alcohol from methane as well as preparation method of catalyst |
| CN103949257A (en) * | 2014-04-27 | 2014-07-30 | 东北石油大学 | Nuclear shell perovskite-type catalyst for producing controllable synthesis gas as well as application of catalyst |
| CN115093324A (en) * | 2022-02-22 | 2022-09-23 | 上海交通大学 | Preparation method of esterified alkane |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103949263A (en) * | 2014-04-27 | 2014-07-30 | 东北石油大学 | Perovskite composite oxide catalyst for preparing methyl alcohol from methane as well as preparation method of catalyst |
| CN103949257A (en) * | 2014-04-27 | 2014-07-30 | 东北石油大学 | Nuclear shell perovskite-type catalyst for producing controllable synthesis gas as well as application of catalyst |
| CN103949257B (en) * | 2014-04-27 | 2016-01-06 | 东北石油大学 | For the production of nucleocapsid perovskite type catalyst and the application of controllable synthesis gas |
| CN103949263B (en) * | 2014-04-27 | 2016-04-13 | 东北石油大学 | For the perovskite mixed oxides catalyst and preparation method thereof of methane methyl alcohol |
| CN115093324A (en) * | 2022-02-22 | 2022-09-23 | 上海交通大学 | Preparation method of esterified alkane |
| CN115093324B (en) * | 2022-02-22 | 2023-12-26 | 上海交通大学 | Preparation method of esterified alkane |
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