WO2017206468A1 - 一种常压下使用氧气为氧化剂催化氧化褐煤的方法 - Google Patents

一种常压下使用氧气为氧化剂催化氧化褐煤的方法 Download PDF

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WO2017206468A1
WO2017206468A1 PCT/CN2016/108846 CN2016108846W WO2017206468A1 WO 2017206468 A1 WO2017206468 A1 WO 2017206468A1 CN 2016108846 W CN2016108846 W CN 2016108846W WO 2017206468 A1 WO2017206468 A1 WO 2017206468A1
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acid
oxygen
lignite
catalyst
oxidant
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梁静
杨会会
魏贤勇
宗志敏
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China University of Mining and Technology CUMT
China University of Mining and Technology Beijing CUMTB
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China University of Mining and Technology CUMT
China University of Mining and Technology Beijing CUMTB
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Priority to RU2018145388A priority patent/RU2700265C1/ru
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Definitions

  • the invention relates to a method for gently oxidizing brown coal, in particular to a method for catalytically oxidizing brown coal by using oxygen as an oxidant under normal pressure.
  • China's lignite resources are abundant, about 13% of total coal reserves.
  • the degree of coalification is low, and there are shortcomings such as high water content, high ash content, low calorific value, low thermal efficiency obtained by direct combustion, and serious environmental pollution. It is regarded as inferior fuel, so some new technologies are needed to be limited and high.
  • Lignite is utilized in added value.
  • high value-added products can be obtained from coal as a raw material by oxidation reaction, and on the other hand, structures which may exist in coal can be reversed by the identification of the product structure.
  • the oxidation of coal can be divided into hydrogen peroxide oxidation method, oxidative acid oxidation method, oxygen (air) alkali oxidation method, osmium tetroxide oxidation method, sodium hypochlorite oxidation method and the like according to the oxidant.
  • the air/oxygen oxidation method of coal is the most studied among many oxidation methods, mainly because air or oxygen is cheap and easy to obtain, and the yield of organic acid in the product is high.
  • Kotani Kazuo In order to increase the yield of benzenecarboxylic acid, Kotani Kazuo first performs heat treatment followed by alkali-oxygen oxidation.
  • the heat treatment temperature is 300 to 500 °C.
  • the experimental results show that the yield of benzene carboxylic acid in Australian lignite after heat treatment is improved, and the highest yield can be increased to 30%.
  • Pan Qichen et al. carried out a series of experiments on alkali oxidation of lignite to benzene carboxylic acid and benzene carboxylic acid reforming to terephthalic acid. Taking Huolinhe lignite as raw material, they investigated the effects of several reaction conditions on the yield of coal acid, and obtained the optimal reaction conditions: reaction temperature 240 ° C, initial oxygen pressure 5.5 Mpa, alkali coal ratio 3:1, reaction time 0.5 h, the obtained coal acid yield was 35.2%, and the yield of benzene polycarboxylic acid reached 22.52%.
  • the reaction conditions selected by different researchers in the oxidation of alkali-O 2 vary within a narrow range, using the bases: Na 2 CO 3 , NaOH and KOH, and the oxidant is cheap air or O.
  • the temperature range is 220 ° C ⁇ 300 ° C
  • the pressure is often 3 ⁇ 10Mpa
  • the resulting product is mainly benzene acid
  • the alkali-oxygen oxidation method requires high temperature and high pressure conditions, and requires a large amount of alkali.
  • the object of the present invention is to provide a low-cost, environmentally friendly, mild and efficient method for catalytic oxidation of lignite using oxygen as an oxidant at atmospheric pressure.
  • the object of the present invention is achieved by the method of using a nitrogen-oxygen radical type catalyst and a metal salt or a metal oxide promoter to gently oxidize brown coal with oxygen as an oxidant;
  • the specific process is as follows: the lignite is pulverized to below 200 mesh, and the pulverized coal sample is vacuum dried at 80 ° C for 10 h, and the treated coal sample is weighed 0.5 g, 10 ml of acetic acid, 0.5 mmol of catalyst, and 0.15 to 0.25 mmol of cocatalyst. Add to the round bottom flask, connect the tee to the condensing tube, replace the oxygen three times in vacuum, fill the round bottom flask with oxygen, maintain the oxygen pressure at 0.1 MPa, and react at 80 °C ⁇ 120 °C for 4 ⁇ 12 h to observe the reaction.
  • Oxygen is an oxidant, catalytically oxidizes brown coal at a pressure of 0.1 MPa; after the reaction is filtered; the filtrate is decompressed to remove acetic acid, dissolved in a small amount of ethyl acetate, and then esterified with an excess of CH 2 N 2 /ether solution at room temperature for 10 h. The mixture was filtered through a 0.45 um filter paper, and the esterified product was analyzed by gas chromatography-mass spectrometry (GC/MS).
  • GC/MS gas chromatography-mass spectrometry
  • Gas chromatographic conditions the carrier gas is helium, the flow rate is 1.0mL/min, the split ratio is 20:1; the inlet temperature is 280°C; the heating procedure is: the initial temperature is 70°C, and the temperature is raised to 280°C at 20°C/min. 1 min, running time 14.5 min; mass spectrometry conditions: ion source temperature 280 ° C, transmission line temperature 280 ° C, relative molecular mass detection range 50 ⁇ 650 amu.
  • the catalyst is a nitrogen oxide radical type catalyst
  • the nitroxide type catalyst is N-hydroxy sulfonyl benzoimide, N, N-dihydroxybenzene tetramethylene diimide, 1, 3, 5-trihydroxyisocyanuric acid, N-hydroxy-N-methylbenzamide, 3,5-dinitro-N-hydroxy-N-methylbenzamide, 1-hydroxy-2,2-diphenyl
  • the structure of the catalyst is as follows:
  • the cocatalyst is a metal salt or a metal oxide
  • the metal salt or metal oxide is one of cobalt acetate, manganese acetate, copper acetate, iron acetate, and manganese dioxide.
  • the amount of the catalyst is 0.5mmol
  • the molar ratio of the promoter based on the catalyst is 30% to 50%
  • the total yield of coal acid is 66.21% to 85.47%
  • the yield of the benzenecarboxylic acid is 22.58% to 28.85. %.
  • the beneficial effect is that, by adopting the above scheme, low-cost, environmentally-friendly oxygen is used as an oxidant, a nitroxide-type compound is used as a catalyst, a metal salt or a metal oxide is used as a co-catalyst, and a lignite oxidation product is identified by GC/MS.
  • Compounds including 40 monocarboxylic acid compounds (MCAs), 14 dicarboxylic acid compounds (DCAs), 4 tricarboxylic acid compounds (ATCAs), 21 benzene carboxylic acid compounds (BCAs), 23 alkane compounds (HCs), 15 other compounds (OCs) and 6 heteroatom compounds.
  • the monocarboxylic acid compound (MCAs) accounts for a large proportion of the oxidation products, and its content is as high as 28.34% to 36.08%, and the highest content is 7-carbonyloctanoic acid, and others such as 3-hydroxypropionic acid, 2-hydroxyacetic acid, 2
  • the content of -hydroxypropionic acid, decanoic acid, 2-ethyl-3-carbonylbutyric acid, and (Z)-octadeca-11-enoic acid is also high.
  • the dibasic acid in the oxidation product is mainly short-chain, and the longest chain hydrocarbon is undecanedioic acid.
  • the unsubstituted white gum, suberic acid, fatty acid and other compounds are detected by GC/MS.
  • a dibasic acid compound of a substituent such as a compound such as methylglutaric acid, hydroxy-succinic acid or methyl adipic acid.
  • the total content of the dibasic acid compound is 10.26% to 18.34%, and the highest content is 2,4-dimethyladipate, followed by malic acid, succinic acid, and 2-hydroxysuccinic acid.
  • the total content of the tribasic acid in the oxidation product is from 3.15% to 7.82%, including 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, 2-hydroxy-1,3,5-pentanetricarboxylic acid. , 1,3,6-hexanetricarboxylic acid, the three kinds of tribasic acid compounds, of which the highest relative content is 1,3,6-hexanetricarboxylic acid.
  • benzene carboxylic acid compounds there are 21 kinds of benzene carboxylic acid compounds in the oxidation product, the total content is 22.58% ⁇ 28.85%, including 3 kinds of tribasic acid compounds, 1 dibasic acid compound, 17 kinds of monobasic acid compounds, which can be seen to generate more kinds of one yuan.
  • the highest content of the benzenecarboxylic acid compound is benzene-1,3,5-tricarboxylic acid, followed by benzoic acid, 4-methoxybenzoic acid, and benzene-1,2,4-tricarboxylic acid.
  • the invention Compared with the traditional alkali-O 2 oxidation method, the invention has the essential feature that although the oxygen is used as the oxidant, the reaction condition of the method is mild, and the normal temperature (oxygen pressure is maintained at 0.1 MPa) medium temperature (80-120 ° C). Under conditions, the brown coal can be oxidized gently and efficiently, avoiding the use of high temperature and high pressure equipment and reducing energy consumption; and the oxidation efficiency is high, the total yield of coal acid is 66.21% ⁇ 85.47%, and the yield of benzenecarboxylic acid reaches 22.58% ⁇ 28.85. % is a mild and efficient method of oxidation of lignite.
  • the reaction is a catalytic oxidation process, and the amount of the catalyst and the cocatalyst is small.
  • the amount of lignite is 0.5 g
  • the amount of the catalyst is 0.5 mmol
  • the amount of the cocatalyst is 0.15 to 0.25 mmol;
  • the reaction conditions are mild, the reaction is carried out under normal pressure (0.1MPa) and medium temperature (80 ⁇ 120 °C), the equipment requirements are low, avoiding the disadvantages that must be carried out under high temperature and high pressure when using oxygen for oxidation in the past, reducing the energy Consumption
  • the reaction is highly efficient, the total yield of coal acid is 66.21% ⁇ 85.47%, of which the yield of benzenecarboxylic acid reaches 22.58% ⁇ 28.85%, compared with the traditional alkali-O 2 oxidation method, coal acid and benzene carboxylic acid The rate is higher.
  • the catalytic oxidation system From the oxidation product, the catalytic oxidation system not only has a good oxidation effect on the aromatic side chain, but also has a good oxidation effect on the chain hydrocarbon material.
  • Figure 1 is a total ion chromatogram of the lignite oxidation product of the present invention.
  • the method gently oxidizes brown coal with oxygen as an oxidant under the action of a nitrogen oxide radical catalyst and a metal salt or a metal oxide promoter;
  • the specific process is as follows: the lignite is pulverized to below 200 mesh, and the pulverized coal sample is vacuum dried at 80 ° C for 10 h, and the treated coal sample is weighed 0.5 g, 10 ml of acetic acid, 0.5 mmol of catalyst, and 0.15 to 0.25 mmol of cocatalyst. Add to the round bottom flask, connect the tee to the condensing tube, replace the oxygen three times in vacuum, fill the round bottom flask with oxygen, maintain the oxygen pressure at 0.1 MPa, and react at 80 °C ⁇ 120 °C for 4 ⁇ 12 h to observe the reaction.
  • Oxygen is an oxidant, which catalyzes the oxidation of lignite at a pressure of 0.1 MPa.
  • Oxygen is an oxidant, catalytically oxidizes lignite at a pressure of 0.1 MPa; after the reaction is completed, the filtrate is filtered, the acetic acid is removed under reduced pressure, and a small amount of ethyl acetate is added to dissolve, and then esterified with an excess of CH 2 N 2 /ether solution at room temperature for 10 h.
  • the esterified product was analyzed by gas chromatography-mass spectrometry GC/MS using a 0.45 um filter paper.
  • Gas chromatographic conditions the carrier gas is helium, the flow rate is 1.0mL/min, the split ratio is 20:1; the inlet temperature is 280°C; the heating procedure is: the initial temperature is 70°C, and the temperature is raised to 280°C at 20°C/min. 1 min, running time 14.5 min; mass spectrometry conditions: ion source temperature 280 ° C, transmission line temperature 280 ° C, relative molecular mass detection range 50 ⁇ 650 amu.
  • the catalyst is a nitrogen oxide radical type catalyst
  • the nitroxide type catalyst is N-hydroxy sulfonyl benzoimide, N, N-dihydroxybenzene tetramethylene diimide, 1, 3, 5-trihydroxyisocyanuric acid, N-hydroxy-N-methylbenzamide, 3,5-dinitro-N-hydroxy-N-methylbenzamide, 1-hydroxy-2,2-diphenyl One of the ketones;
  • the cocatalyst is a metal salt or a metal oxide
  • the metal salt or metal oxide is one of cobalt acetate, manganese acetate, copper acetate, iron acetate, and manganese dioxide.
  • the lignite is 0.5g
  • the amount of the catalyst is 0.5mmol
  • the molar ratio of the promoter based on the catalyst is 30% to 50%
  • the total yield of coal acid is 66.21% to 85.47%
  • the yield of the benzenecarboxylic acid is 22.58% to 28.85%. .
  • Example 1 The smashed lignite was pulverized to below 200 mesh, and the pulverized coal sample was vacuum dried at 80 ° C for 10 h, and the treated coal sample was weighed 0.5 g, 10 ml of acetic acid, N-hydroxy sulfonyl benzoimide. 0.5mmol, manganese acetate 0.15mmol was added to the round bottom flask in turn, and the tee was connected to the condensing tube, and the oxygen was replaced three times in vacuum, so that the round bottom flask was filled with oxygen, the oxygen pressure was maintained at 0.1 MPa, and the reaction was carried out at 120 ° C for 4 h. Observe the reaction. After the reaction was completed, it was filtered.
  • the filtrate was evaporated under reduced pressure of acetic acid, dissolved with a small portion of ethyl acetate, and then esterified with an excess of CH 2 N 2 / diethyl ether solution at room temperature for 10 h, filtered over 0.45 um filter paper, and the product after esterification was analyzed by GC/MS.
  • Agilent 7890/5975 gas chromatography-mass spectrometry was used to analyze the distribution of oxidation products. A total of 123 compounds were identified, including 40 monocarboxylic acid compounds (MCAs) with a total content of 28.34%; 14 dicarboxylic acids.
  • MCAs monocarboxylic acid compounds
  • DCAs Compound (DCAs), total content 11.68%; 4 tricarboxylic acid compounds (ATCAs), total content 7.82%; 21 benzene carboxylic acid compounds (BCAs), total content 24.35%; 23 alkane compounds (HCs) , the total content of 11.75%; 15 other compounds (OCs), the total content of 13.98%; 6 kinds of heteroatom compounds, the total content of 2.08%; the total yield of coal acid reached 72.19%, of which the yield of benzenecarboxylic acid reached 24.35% .
  • ATCAs tricarboxylic acid compounds
  • BCAs tricarboxylic acid compounds
  • HCs alkane compounds
  • OCs alkane compounds
  • 6 kinds of heteroatom compounds the total content of 2.08%
  • the total yield of coal acid reached 72.19%, of which the yield of benzenecarboxylic acid reached 24.35% .
  • Example 2 The smashed lignite was pulverized to below 200 mesh, and the pulverized coal sample was vacuum dried at 80 ° C for 10 h, and the treated coal sample was weighed 0.5 g, 10 ml of acetic acid, N,N-dihydroxytetraphenyltetramethylene. 0.5 mmol of imide and 0.20 mmol of copper acetate were sequentially added to the round bottom flask, and the tee was connected to the condensing tube, and the oxygen was replaced three times in vacuum to make the round bottom flask filled with oxygen, maintaining the oxygen pressure at 0.1 MPa at 80 ° C. The reaction was carried out for 12 hours, and the reaction was observed. After the reaction was completed, it was filtered.
  • the filtrate was evaporated under reduced pressure of acetic acid, dissolved with a small portion of ethyl acetate, and then esterified with an excess of CH 2 N 2 / diethyl ether solution at room temperature for 10 h, filtered over 0.45 um filter paper, and the product after esterification was analyzed by GC/MS.
  • Agilent 7890/5975 gas chromatography-mass spectrometry was used to analyze the distribution of oxidation products. A total of 123 compounds were identified, including 40 monocarboxylic acid compounds (MCAs) with a total content of up to 30.22%; 14 dicarboxylic acid compounds.
  • MCAs monocarboxylic acid compounds
  • DCAs total content 10.26%
  • ATCAs tricarboxylic acid compounds
  • BCAs tricarboxylic acid compounds
  • HCs alkane compounds
  • the total content is 25.20%; 15 other compounds (OCs), the total content is 7.61%; 6 kinds of heteroatom compounds, the total content is 0.98%; the total yield of coal acid is 66.21%, and the yield of benzenecarboxylic acid reaches 22.58%.
  • Example 3 The smashed lignite was pulverized to below 200 mesh, and the pulverized coal sample was vacuum dried at 80 ° C for 10 h, and the treated coal sample was weighed 0.5 g, 10 ml of acetic acid, 1,3,5-trihydroxyisocyanuric acid. 0.5mmol, 0.25mmol of manganese dioxide, added to the round bottom flask in turn, connected to the tee on the condensation tube, replaced the oxygen three times in vacuum, filled the round bottom flask with oxygen, maintained the oxygen pressure to 0.1MPa, and reacted at 100 ° C 10h, observe the reaction. After the reaction was completed, it was filtered.
  • the filtrate was evaporated under reduced pressure of acetic acid, dissolved with a small portion of ethyl acetate, and then esterified with an excess of CH 2 N 2 / diethyl ether solution at room temperature for 10 h, filtered over 0.45 um filter paper, and the product after esterification was analyzed by GC/MS.
  • Agilent 7890/5975 gas chromatography-mass spectrometry was used to analyze the distribution of oxidation products. A total of 123 compounds were identified, including 40 monocarboxylic acid compounds (MCAs) with a total content of up to 32.25%; 14 dicarboxylic acid compounds.
  • MCAs monocarboxylic acid compounds
  • DCAs total content 13.46%
  • ATCAs tricarboxylic acid compounds
  • BCAs tricarboxylic acid compounds
  • HCs alkane compounds
  • Example 4 The smashed lignite was pulverized to below 200 mesh, and the pulverized coal sample was vacuum dried at 80 ° C for 10 h, and the treated coal sample was weighed 0.5 g, 10 ml of acetic acid, N-hydroxy-N-methylbenzamide. 0.5 mmol, 0.2 mmol of iron acetate was added to the round bottom flask in turn, and the tee was connected to the condensing tube, and the oxygen was replaced three times in vacuum to make the round bottom flask filled with oxygen, maintaining the oxygen pressure at 0.1 MPa, and reacting at 90 ° C for 11 h. Observe the reaction. After the reaction was completed, it was filtered.
  • the filtrate was evaporated under reduced pressure of acetic acid, dissolved with a small portion of ethyl acetate, and then esterified with an excess of CH 2 N 2 / diethyl ether solution at room temperature for 10 h, filtered over 0.45 um filter paper, and the product after esterification was analyzed by GC/MS.
  • Agilent 7890/5975 gas chromatography-mass spectrometry was used to analyze the distribution of oxidation products.
  • a total of 123 compounds were identified, including 40 monocarboxylic acid compounds (MCAs) with a total content of up to 30.85%; 14 dicarboxylic acids Acid compounds (DCAs) with a total content of 18.34%; four tricarboxylic acid compounds (ATCAs) with a total content of 3.83%; 21 benzene carboxylic acid compounds (BCAs) with a total content of 25.76%; 23 alkane compounds (HCs) ), the total content of 12.15%; 15 other compounds (OCs), the total content of 6.95%; 6 kinds of heteroatom compounds, the total content of 2.12%; the total yield of coal acid reached 78.78%, of which the yield of benzenecarboxylic acid reached 25.76 %.
  • Example 5 The smashed lignite was pulverized to below 200 mesh, and the pulverized coal sample was vacuum dried at 80 ° C for 10 h, and the treated coal sample was weighed 0.5 g, 10 ml of acetic acid, 3,5-dinitro-N-hydroxyl -N-methylbenzamide 0.5mmol, cobalt acetate 0.15mmol was added to the round bottom flask in turn, the tee was connected to the condensing tube, and the oxygen was replaced three times in vacuum, so that the round bottom flask was filled with oxygen, and the oxygen pressure was maintained at 0.1 MPa. The reaction was carried out at 110 ° C for 9 h, and the reaction was observed. After the reaction was completed, it was filtered.
  • the filtrate was evaporated under reduced pressure of acetic acid, dissolved with a small portion of ethyl acetate, and then esterified with an excess of CH 2 N 2 / diethyl ether solution at room temperature for 10 h, filtered over 0.45 um filter paper, and the product after esterification was analyzed by GC/MS.
  • Agilent 7890/5975 gas chromatography-mass spectrometry was used to analyze the distribution of oxidation products. A total of 123 compounds were identified, including 40 monocarboxylic acid compounds (MCAs) with a total content of up to 36.08%.
  • MCAs monocarboxylic acid compounds
  • DCAs dicarboxylic acid compounds
  • ATCAs ternary carboxylic acid compounds
  • BCAs benzene carboxylic acid compounds
  • HCs 23 alkane compounds
  • the total content is 7.62%
  • 15 other compounds (OCs) the total content is 5.05%
  • 6 kinds of heteroatom compounds the total content is 1.86%
  • the total yield of coal acid is 85.47%, of which the yield of benzenecarboxylic acid reaches 28.85%.
  • Example 6 The smashed lignite was pulverized to below 200 mesh, and the pulverized coal sample was vacuum dried at 80 ° C for 10 h, and the treated coal sample was weighed 0.5 g, 10 ml of acetic acid, 1-hydroxy-2,2-diphenyl. ⁇ ketone 0.5mmol, cobalt acetate 0.15mmol was added to the round bottom flask in turn, the tee was connected to the condensing tube, and the oxygen was replaced three times in vacuum, so that the round bottom flask was filled with oxygen, and the oxygen pressure was maintained at 0.1 MPa. The reaction was carried out at 100 ° C for 10 h, and the reaction was observed. After the reaction was completed, it was filtered.
  • the filtrate was evaporated under reduced pressure of acetic acid, dissolved with a small portion of ethyl acetate, and then esterified with an excess of CH 2 N 2 / diethyl ether solution at room temperature for 10 h, filtered over 0.45 um filter paper, and the product after esterification was analyzed by GC/MS.
  • Agilent 7890/5975 gas chromatography-mass spectrometry was used to analyze the distribution of oxidation products. A total of 123 compounds were identified, including 40 monocarboxylic acid compounds (MCAs) with a total content of up to 32.74%; 14 dicarboxylic acid compounds.
  • MCAs monocarboxylic acid compounds
  • DCAs total content 12.83%
  • ATCAs tricarboxylic acid compounds
  • BCAs benzene carboxylic acid compounds
  • HCs alkane compounds
  • 15 other compounds (OCs) the total content of 11.80%
  • 6 kinds of heteroatom compounds the total content of 2.53%
  • the total yield of coal acid reached 76.54%, of which the yield of benzenecarboxylic acid reached 25.12%.

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Abstract

一种常压下使用氧气为氧化剂催化氧化褐煤的方法，属于温和氧化褐煤的方法。该方法在氮氧自由基型催化剂及金属盐或金属氧化物助催化剂的作用下，以氧气为氧化剂温和氧化褐煤；工艺：将褐煤粉碎至200目以下，粉碎后的煤样于80℃下真空干燥10h，称取处理后的煤样0.5g，10ml乙酸，催化剂0.5mmol，助催化剂0.15～0.25mmol依次加入圆底烧瓶中，在冷凝管上口接三通，真空置换氧气三次，使圆底烧瓶内充满氧气，维持氧气压为0.1MPa，在80℃～120℃下反应4～12h；反应结束后过滤；滤液减压除去乙酸，加入少量乙酸乙酯溶解，然后用过量的CH2N2/乙醚溶液室温下酯化10h后，用0.45um的滤纸过滤，通过气相色谱-质谱联用仪分析酯化后的产物。该方法以氧气为氧化剂，价格低廉且无毒环保，条件温和。

Description

一种常压下使用氧气为氧化剂催化氧化褐煤的方法 技术领域
本发明涉及一种温和氧化褐煤的方法，特别是一种常压下使用氧气为氧化剂催化氧化褐煤的方法。
背景技术
我国褐煤资源丰富，约为煤炭总储量的13％。但煤化程度低，存在水分高、灰分高、热值低等缺点，直接燃烧获得的热效率低，且会带来严重的环境污染，被视为劣质燃料，因此需要一些新技术来有限度和高附加值地利用褐煤。通过氧化反应一方面可以以煤炭为原料获得高附加值产品，另一方面可以通过对产物结构的鉴定反推煤中可能存在的结构。煤的氧化按氧化剂可分为双氧水氧化法、氧化性酸氧化法、氧气(空气)碱氧化法、四氧化钌氧化法、次氯酸钠氧化法等。
其中煤的空气/氧气氧化法是诸多氧化法中研究最多的，主要是因为空气或氧气廉价易得，而且产物中有机酸收率较高。
Kamiya等以日本烟煤为原料，研究O2/Na2CO3体系和O2/K2CO3体系中的氧化反应。反应温度设定在250-280℃，氧化时间120分钟，氧气初压3MPa，反应结束后，过滤掉煤渣，用硫酸酸化，过滤掉再生腐殖酸，再用2-丁酮萃取滤液。实验结果表明氧化温度、碱用量及搅拌速度对产物收率有明显的影响，煤酸收率最高的反应条件是：反应温度270℃，煤:Na2CO3＝l:3，氧气初压1.5Mpa，揽拌速度85r/min，反应时间2h，煤酸收率达65％。
神谷佳男等为提高苯羧酸的收率，先采用热处理再进行碱-氧气氧化。热处理的温度在300～500℃。实验结果显示，热处理后的澳大利亚褐煤的苯羧酸收率有一定的提高，最高收率可增至30％。
潘琪琨等进行了一系列碱氧化褐煤制苯羧酸及苯羧酸重整制对苯二甲酸的实验。以霍林河褐煤为原料，他们考察了几种反应条件对煤酸收率的影响，得到最佳反应条件：反应温度240℃，氧气初压5.5Mpa，碱煤比3:1，反应时间0.5h，得到的煤酸收率为35.2％，其中苯多羧酸收率达到22.52％。
由上述可见，不同研究者在进行碱-O2氧化时所选的反应条件在一个较窄的范围内变化，采用的碱有：Na2CO3、NaOH和KOH，氧化剂为廉价的空气或者O2，温度范围为220℃～300℃，压力往往在3～10Mpa，所得的产物主要以苯多酸为主，除此之外溶液中尚存在多种小分子脂肪酸，包括甲酸、草酸、乙酸、丙二酸、丙酮酸等。碱-氧气氧化方法需要高温、高压的条件，且需碱量较大，这些缺点一直制约着这种方法的实际利用。
发明内容
本发明的目的是要提供一种价格低廉、环境友好、温和高效的常压下使用氧气为氧化剂催化氧化褐煤的方法。
本发明的目的是这样实现的：该方法在氮氧自由基型催化剂及金属盐或金属氧化物助催化剂的作用下，以氧气为氧化剂温和氧化褐煤；
具体工艺过程如下：将褐煤粉碎至200目以下，粉碎后的煤样于80℃下真空干燥10h，称取处理后的煤样0.5g，10ml乙酸，催化剂0.5mmol，助催化剂0.15～0.25mmol依次加入圆底烧瓶中，在冷凝管上口接三通，真空置换氧气三次，使圆底烧瓶内充满氧气，维持氧气压为0.1MPa，在80℃～120℃下反应4～12h，观察反应情况；氧气为氧化剂，在0.1MPa常压下催化氧化褐煤；反应结束后过滤；滤液减压除去乙酸，加入少量乙酸乙酯溶解，然后用过量的CH2N2/乙醚溶液室温下酯化10h后，用0.45um的滤纸过滤，通过气相色谱-质谱联用仪(GC/MS)分析酯化后的产物。
气相色谱条件：载气为氦气，流量1.0mL/min，分流比为20:1；进样口温度280℃；升温程序为：初始温度70℃，以20℃/min升至280℃，保持1min，运行时间14.5min；质谱条件：离子源的温度280℃，传输线的温度280℃，相对分子质量检测范围50～650amu。
所述的催化剂为氮氧自由基型催化剂，氮氧自由基型催化剂为N-羟基邻磺酰苯甲酰亚胺、N,N-二羟基均苯四甲二酰亚胺、1,3,5-三羟基异氰尿酸、N-羟基-N-甲基苯甲酰胺、3,5-二硝基-N-羟基-N-甲基苯甲酰胺、1-羟基-2，2-二苯基-3-吲哚酮中的一种；所述的催化剂的结构如下：
Figure PCTCN2016108846-appb-000001
所述的助催化剂为金属盐或金属氧化物，所述的金属盐或金属氧化物为乙酸钴、乙酸锰、乙酸铜、乙酸铁、二氧化锰中的一种。
褐煤为0.5g时，催化剂的用量为0.5mmol，助催化剂基于催化剂的摩尔比为30％～50％，煤酸总收率为66.21％～85.47％，其中苯羧酸收率达22.58％～28.85％。
有益效果，由于采用了上述方案，使用价格低廉、环境友好的氧气为氧化剂，氮氧自由基型化合物为催化剂，金属盐或金属氧化物为助催化剂，褐煤氧化产物通过GC/MS共鉴定出123种化合物，包括40种一元羧酸化合物(MCAs)，14种二元羧酸化合物(DCAs)，4种三元羧酸化合物(ATCAs)，21种苯羧酸化合物(BCAs)，23种烷烃化合物(HCs)，15种其他化合物(OCs)和6种杂原子化合物。
其中一元羧酸化合物(MCAs)在氧化产物中占的比例较大，其含量高达28.34％～36.08％，含量最高的是7-羰基辛酸，其他如3-羟基丙酸、2-羟基乙酸、2-羟基丙酸、壬烷酸、2-乙基-3-羰基丁酸、(Z)-十八碳-11-烯酸的含量也较高。
氧化产物中二元酸主要是以短链为主，最长的链烃是十一烷二酸，通过GC/MS检测到无取代基的胶酸、辛二酸、肥酸等化合物和带有取代基的二元酸化合物，如甲基戊二酸、羟基-琥珀酸、甲基己二酸等化合物。二元酸化合物总含量为10.26％～18.34％，相对含量最高的是2,4-二甲基己二酸，其次是缩苹果酸、琥珀酸、2-羟基琥珀酸。
氧化产物中三元酸的总含量为3.15％～7.82％，包括1,2,3-丙三酸，1,3,5-戊三酸，2-羟基-1,3,5-戊三酸，1,3,6-己三酸这4种三元酸化合物，其中相对含量最高的是1,3,6-己三酸。
氧化产物中共有21种苯羧酸化合物产生，总含量达22.58％～28.85％，其中包括3种三元酸化合物、1种二元酸化合物，17种一元酸化合物，可见生成较多种类的一元苯羧酸化合物，含量最高的是苯-1,3,5-三羧酸，其次是苯甲酸、4-甲氧基苯甲酸、苯-1,2,4-三羧酸。
本发明与传统的碱-O2氧化法相比其实质性的特点是：尽管都使用氧气为氧化剂，但本方法反应条件温和，在常压(氧气压维持0.1MPa)中温(80～120℃)条件下即可温和高效氧化褐煤，避免了高温高压设备的使用，降低了能耗；且氧化效率高，煤酸总收率达66.21％～85.47％，其中苯羧酸收率达到22.58％～28.85％，是一种温和高效的的褐煤氧化方法。
采用Agilent 7890/5975气相色谱-质谱联用仪分析检测氧化产物分布，共鉴定出123种化合物，其中包括40种一元羧酸化合物(MCAs)，总含量为28.34％～36.08％；14种二元羧酸化合物(DCAs)，总含量为10.26％～18.34％；4种三元羧酸化合物(ATCAs)，总含量为3.15％～7.82％；21种苯羧酸化合物(BCAs)，总含量22.58％～28.85％；23种烷烃化合物(HCs)，总含量7.62％～25.20％；15种其他化合物(OCs)，总含量5.05％～13.98；6种杂原子化合物，总含量为0.98％～2.53％；其中煤酸总收率共达66.21％～85.47％，苯羧酸收率达到22.58％～28.85％。
优点：
1、反应是一个催化氧化过程，催化剂和助催化剂的用量少，当褐煤用量为0.5g时，催化剂用量为0.5mmol，助催化剂用量为0.15～0.25mmol；
2、反应条件温和，反应在常压(0.1MPa)和中温(80～120℃)下进行，对设备要求低，避免了以往使用氧气进行氧化时必须在高温高压下进行的弊端，降低了能耗；
3、反应具有高效性，煤酸总收率达66.21％～85.47％，其中苯羧酸收率达到22.58％～28.85％，与传统的碱-O2氧化法相比，煤酸与苯羧酸收率都更高，从氧化产物看此催化氧化体系不仅对芳烃侧链具有较好的氧化效果，对于链烃物质也具有较好的氧化效果。
附图说明：
图1是本发明的褐煤氧化产物总离子流色谱图。
具体实施方式
该方法在氮氧自由基型催化剂及金属盐或金属氧化物助催化剂的作用下，以氧气为氧化剂温和氧化褐煤；
具体工艺过程如下：将褐煤粉碎至200目以下，粉碎后的煤样于80℃下真空干燥10h，称取处理后的煤样0.5g，10ml乙酸，催化剂0.5mmol，助催化剂0.15～0.25mmol依次加入圆底烧瓶中，在冷凝管上口接三通，真空置换氧气三次，使圆底烧瓶内充满氧气，维持氧气压为0.1MPa，在80℃～120℃下反应4～12h，观察反应情况；氧气为氧化剂，在0.1MPa常压下催化氧化褐煤。氧气为氧化剂，在0.1MPa常压下催化氧化褐煤；反应结束后过滤；滤液减压除去乙酸，加入少量乙酸乙酯溶解，然后用过量的CH2N2/乙醚溶液室温下酯化10h后，用0.45um的滤纸过滤，通过气相色谱-质谱联用仪GC/MS分析酯化后的产物。
气相色谱条件：载气为氦气，流量1.0mL/min，分流比为20:1；进样口温度280℃；升温程序为：初始温度70℃，以20℃/min升至280℃，保持1min，运行时间14.5min；质谱条件：离子源的温度280℃，传输线的温度280℃，相对分子质量检测范围50～650amu。
所述的催化剂为氮氧自由基型催化剂，氮氧自由基型催化剂为N-羟基邻磺酰苯甲酰亚胺、N,N-二羟基均苯四甲二酰亚胺、1,3,5-三羟基异氰尿酸、N-羟基-N-甲基苯甲酰胺、3,5-二硝基-N-羟基-N-甲基苯甲酰胺、1-羟基-2，2-二苯基-3-吲哚酮中的一种；
Figure PCTCN2016108846-appb-000002
所述的助催化剂为金属盐或金属氧化物，所述的金属盐或金属氧化物为乙酸钴、乙酸锰、乙酸铜、乙酸铁、二氧化锰中的一种。
褐煤为0.5g，催化剂的用量为0.5mmol，助催化剂基于催化剂的摩尔比为30％～50％，煤酸总收率为66.21％～85.47％，其中苯羧酸收率达22.58％～28.85％。
实施例1：将胜利褐煤粉碎至200目以下，粉碎后的煤样于80℃下真空干燥10h，称取处理后的煤样0.5g，10ml乙酸，N-羟基邻磺酰苯甲酰亚胺0.5mmol，乙酸锰0.15mmol依次加入圆底烧瓶中，在冷凝管上口接三通，真空置换氧气三次，使圆底烧瓶内充满氧气，维持氧气压为0.1MPa，在120℃下反应4h，观察反应情况。反应结束后过滤。滤液减压除去乙酸，加入少量乙酸乙酯溶解，然后用过量的CH2N2/乙醚溶液室温下酯化10h后，用0.45um的滤纸过滤，通过GC/MS分析酯化后的产物。
采用Agilent 7890/5975气相色谱-质谱联用仪分析检测氧化产物分布，共鉴定出123种化合物，其中包括40种一元羧酸化合物(MCAs)，总含量为28.34％；14种二元羧酸 化合物(DCAs)，总含量为11.68％；4种三元羧酸化合物(ATCAs)，总含量为7.82％；21种苯羧酸化合物(BCAs)，总含量24.35％；23种烷烃化合物(HCs)，总含量11.75％；15种其他化合物(OCs)，总含量13.98％；6种杂原子化合物，总含量为2.08％；煤酸总收率共达72.19％，其中苯羧酸收率达到24.35％。
实施例2：将胜利褐煤粉碎至200目以下，粉碎后的煤样于80℃下真空干燥10h，称取处理后的煤样0.5g，10ml乙酸，N,N-二羟基均苯四甲二酰亚胺0.5mmol，乙酸铜0.20mmol依次加入圆底烧瓶中，在冷凝管上口接三通，真空置换氧气三次，使圆底烧瓶内充满氧气，维持氧气压为0.1MPa，在80℃下反应12h，观察反应情况。反应结束后过滤。滤液减压除去乙酸，加入少量乙酸乙酯溶解，然后用过量的CH2N2/乙醚溶液室温下酯化10h后，用0.45um的滤纸过滤，通过GC/MS分析酯化后的产物。
采用Agilent 7890/5975气相色谱-质谱联用仪分析检测氧化产物分布，共鉴定出123种化合物，其中包括40种一元羧酸化合物(MCAs)，总含量高达30.22％；14种二元羧酸化合物(DCAs)，总含量为10.26％；4种三元羧酸化合物(ATCAs)，总含量为3.15％；21种苯羧酸化合物(BCAs)，总含量22.58％；23种烷烃化合物(HCs)，总含量25.20％；15种其他化合物(OCs)，总含量7.61％；6种杂原子化合物，总含量为0.98％；煤酸总收率共达66.21％，其中苯羧酸收率达到22.58％。
实施例3：将胜利褐煤粉碎至200目以下，粉碎后的煤样于80℃下真空干燥10h，称取处理后的煤样0.5g，10ml乙酸，1,3,5-三羟基异氰尿酸0.5mmol，二氧化锰0.25mmol，依次加入圆底烧瓶中，在冷凝管上口接三通，真空置换氧气三次，使圆底烧瓶内充满氧气，维持氧气压为0.1MPa，在100℃下反应10h，观察反应情况。反应结束后过滤。滤液减压除去乙酸，加入少量乙酸乙酯溶解，然后用过量的CH2N2/乙醚溶液室温下酯化10h后，用0.45um的滤纸过滤，通过GC/MS分析酯化后的产物。
采用Agilent 7890/5975气相色谱-质谱联用仪分析检测氧化产物分布，共鉴定出123种化合物，其中包括40种一元羧酸化合物(MCAs)，总含量高达32.25％；14种二元羧酸化合物(DCAs)，总含量为13.46％；4种三元羧酸化合物(ATCAs)，总含量为6.95％；21种苯羧酸化合物(BCAs)，总含量25.44％；23种烷烃化合物(HCs)，总含量13.85％；15种其他化合物(OCs)，总含量6.83％；6种杂原子化合物，总含量为1.22％；煤酸总收率共达78.10％，其中苯羧酸收率达到25.44％。
实施例4：将胜利褐煤粉碎至200目以下，粉碎后的煤样于80℃下真空干燥10h，称取处理后的煤样0.5g，10ml乙酸，N-羟基-N-甲基苯甲酰胺0.5mmol，乙酸铁0.2mmol依次加入圆底烧瓶中，在冷凝管上口接三通，真空置换氧气三次，使圆底烧瓶内充满氧气，维持氧气压为0.1MPa，在90℃下反应11h，观察反应情况。反应结束后过滤。滤液减压除去乙酸，加入少量乙酸乙酯溶解，然后用过量的CH2N2/乙醚溶液室温下酯化10h后，用0.45um的滤纸过滤，通过GC/MS分析酯化后的产物。
采用Agilent 7890/5975气相色谱-质谱联用仪分析检测氧化产物分布，共鉴定出123种化合物，其中包括40种一元羧酸化合物(MCAs)，总含量高达30.85％；14种二元羧 酸化合物(DCAs)，总含量为18.34％；4种三元羧酸化合物(ATCAs)，总含量为3.83％；21种苯羧酸化合物(BCAs)，总含量25.76％；23种烷烃化合物(HCs)，总含量12.15％；15种其他化合物(OCs)，总含量6.95％；6种杂原子化合物，总含量为2.12％；煤酸总收率共达78.78％，其中苯羧酸收率达到25.76％。
实施例5：将胜利褐煤粉碎至200目以下，粉碎后的煤样于80℃下真空干燥10h，称取处理后的煤样0.5g，10ml乙酸，3,5-二硝基-N-羟基-N-甲基苯甲酰胺0.5mmol，乙酸钴0.15mmol依次加入圆底烧瓶中，在冷凝管上口接三通，真空置换氧气三次，使圆底烧瓶内充满氧气，维持氧气压为0.1MPa，在110℃下反应9h，观察反应情况。反应结束后过滤。滤液减压除去乙酸，加入少量乙酸乙酯溶解，然后用过量的CH2N2/乙醚溶液室温下酯化10h后，用0.45um的滤纸过滤，通过GC/MS分析酯化后的产物。
采用Agilent 7890/5975气相色谱-质谱联用仪分析检测氧化产物分布，共鉴定出123种化合物，其中包括40种一元羧酸化合物(MCAs)，总含量高达36.08％；14种二元羧酸化合物(DCAs)，总含量为15.76％；4种三元羧酸化合物(ATCAs)，总含量为4.78％；21种苯羧酸化合物(BCAs)，总含量28.85％；23种烷烃化合物(HCs)，总含量7.62％；15种其他化合物(OCs)，总含量5.05％；6种杂原子化合物，总含量为1.86％；煤酸总收率共达85.47％，其中苯羧酸收率达到28.85％。
实施例6：将胜利褐煤粉碎至200目以下，粉碎后的煤样于80℃下真空干燥10h，称取处理后的煤样0.5g，10ml乙酸，1-羟基-2,2-二苯基-3-吲哚酮0.5mmol，乙酸钴0.15mmol依次加入圆底烧瓶中，在冷凝管上口接三通，真空置换氧气三次，使圆底烧瓶内充满氧气，维持氧气压为0.1MPa，在100℃下反应10h，观察反应情况。反应结束后过滤。滤液减压除去乙酸，加入少量乙酸乙酯溶解，然后用过量的CH2N2/乙醚溶液室温下酯化10h后，用0.45um的滤纸过滤，通过GC/MS分析酯化后的产物。
采用Agilent 7890/5975气相色谱-质谱联用仪分析检测氧化产物分布，共鉴定出123种化合物，其中包括40种一元羧酸化合物(MCAs)，总含量高达32.74％；14种二元羧酸化合物(DCAs)，总含量为12.83％；4种三元羧酸化合物(ATCAs)，总含量为5.85％；21种苯羧酸化合物(BCAs)，总含量25.12％；23种烷烃化合物(HCs)，总含量9.13％；15种其他化合物(OCs)，总含量11.80％；6种杂原子化合物，总含量为2.53％；煤酸总收率共达76.54％，其中苯羧酸收率达到25.12％。

Claims (3)

  1. 一种常压下使用氧气为氧化剂催化氧化褐煤的方法，其特征是：该方法在氮氧自由基型催化剂及金属盐或金属氧化物助催化剂的作用下，以氧气为氧化剂温和氧化褐煤；
    具体工艺过程如下：将褐煤粉碎至200目以下，粉碎后的煤样于80℃下真空干燥10h，称取处理后的煤样0.5g，10ml乙酸，催化剂0.5mmol，助催化剂0.15～0.25mmol依次加入圆底烧瓶中，在冷凝管上口接三通，真空置换氧气三次，使圆底烧瓶内充满氧气，维持氧气压为0.1MPa，在80℃～120℃下反应4～12h，观察反应情况；氧气为氧化剂，在0.1MPa常压下催化氧化褐煤；反应结束后过滤；滤液减压除去乙酸，加入少量乙酸乙酯溶解，然后用过量的CH2N2/乙醚溶液室温下酯化10h后，用0.45um的滤纸过滤，通过气相色谱-质谱联用仪分析酯化后的产物。
  2. 根据权利要求1所述的一种常压下使用氧气为氧化剂催化氧化褐煤的方法，其特征是：所述的催化剂为氮氧自由基型催化剂，氮氧自由基型催化剂为N-羟基邻磺酰苯甲酰亚胺、N,N-二羟基均苯四甲二酰亚胺、1,3,5-三羟基异氰尿酸、N-羟基-N-甲基苯甲酰胺、3,5-二硝基-N-羟基-N-甲基苯甲酰胺、1-羟基-2，2-二苯基-3-吲哚酮中的一种；所述的催化剂的结构如下：
    Figure PCTCN2016108846-appb-100001
    所述的助催化剂为金属盐或金属氧化物，所述的金属盐或金属氧化物为乙酸钴、乙酸锰、乙酸铜、乙酸铁、二氧化锰中的一种。
  3. 根据权利要求1所述的一种常压下使用氧气为氧化剂催化氧化褐煤的方法，其特征是：褐煤为0.5g，催化剂的用量为0.5mmol，助催化剂基于催化剂的用量摩尔比为30％～50％，煤酸总收率为66.21％～85.47％，其中苯羧酸收率达22.58％～28.85％。
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