CN1375448A - Methane oxidization catalyzing method - Google Patents
Methane oxidization catalyzing method Download PDFInfo
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- CN1375448A CN1375448A CN 02116304 CN02116304A CN1375448A CN 1375448 A CN1375448 A CN 1375448A CN 02116304 CN02116304 CN 02116304 CN 02116304 A CN02116304 A CN 02116304A CN 1375448 A CN1375448 A CN 1375448A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005977 Ethylene Substances 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 11
- 239000011949 solid catalyst Substances 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000007084 catalytic combustion reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
本发明公开了一种甲烷催化氧化方法,是在含有甲烷和氧气的反应体系中加入50ppm以上的NO或/和NO2,从而使反应温度降低200－300℃。反应体系可以是甲烷气相氧化反应制备合成气的体系、利用甲烷制备甲醛或甲醇或乙烯的体系。本发明的方法具有反应温度低,H2/CO比合适等优点,同时避免了使用固体催化剂导致的积碳和甲烷深度氧化。
The invention discloses a method for catalytic oxidation of methane. More than 50 ppm of NO or/and NO 2 is added to a reaction system containing methane and oxygen, thereby reducing the reaction temperature by 200-300°C. The reaction system may be a system for preparing synthesis gas by methane gas-phase oxidation reaction, or a system for preparing formaldehyde, methanol or ethylene by using methane. The method of the present invention has the advantages of low reaction temperature, suitable H 2 /CO ratio, etc., and simultaneously avoids carbon deposition and deep oxidation of methane caused by the use of solid catalysts.
Description
技术领域：Technical field:
本发明涉及甲烷转化技术领域，尤其是一种不使用固体催化剂，通过甲烷直接气相氧化制备合成气或其他C1、C2化合物的方法。The invention relates to the technical field of methane conversion, in particular to a method for preparing synthesis gas or other C1 and C2 compounds through direct gas-phase oxidation of methane without using a solid catalyst.
背景技术：Background technique:
天然气是一种丰富、清洁的一次能源，可直接用于发电、工业和民用，同时也是近代化学工业的重要原料。随着石油短缺问题的日趋严重和人类对全球变暖的广泛关注，以甲烷为主要原料的天然气化工在世界范围内受到普遍的重视。到目前为止，甲烷转化主要有两种途径。一种是直接法，即甲烷通过一步反应得到所需的目的产物，如甲醇，甲醛(以MoO3/SiO2为催化剂)，乙烯(以V2O5/SiO2为催化剂)等。由于经济效益的问题，直接法目前仍处于实验室研究阶段。Natural gas is an abundant and clean primary energy that can be directly used for power generation, industry and civil use, and is also an important raw material for the modern chemical industry. With the increasingly serious problem of oil shortage and widespread concern about global warming, the natural gas chemical industry with methane as the main raw material has received widespread attention worldwide. So far, there have been two main pathways for methane conversion. One is the direct method, that is, the desired target products such as methanol, formaldehyde (with MoO 3 /SiO 2 as catalyst), ethylene (with V 2 O 5 /SiO 2 as catalyst) can be obtained through one-step reaction from methane. Due to the problem of economic benefits, the direct method is still in the stage of laboratory research.
另一种是目前工业上采用的间接法，即甲烷先转化为合成气，然后用合成气制备甲醇，如：
这种方法的缺点是H2/CO比高于合成甲醇需要的H2/CO比，而且设备投资大，能耗高。The disadvantage of this method is that the H 2 /CO ratio is higher than the H 2 /CO ratio required for methanol synthesis, and the equipment investment and energy consumption are high.
其他正在研究的路线还包括使用固体催化剂的甲烷-二氧化碳重整和甲烷部分氧化，它们的共同问题是催化剂上的积碳比较严重。Other routes under study include methane-carbon dioxide reforming and partial oxidation of methane using solid catalysts. Their common problem is that the carbon deposition on the catalyst is relatively serious.
发明内容：Invention content:
本发明的目的是提供一种不使用固体催化剂，在较低温度下转化甲烷的方法。该方法可避免使用固体催化剂带来的积碳、深度氧化等问题。The object of the present invention is to provide a method for converting methane at a lower temperature without using a solid catalyst. This method can avoid problems such as carbon deposition and deep oxidation caused by the use of solid catalysts.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
本发明的催化甲烷氧化的方法是，在含有甲烷和氧气的反应体系中加入50ppm以上的NO或/和NO2。The method for catalyzing methane oxidation of the present invention is to add more than 50 ppm of NO or/and NO 2 into the reaction system containing methane and oxygen.
所述反应体系为甲烷气相氧化反应制备合成气(CO+H2)的体系或者利用甲烷制备甲醛或甲醇或乙烯的体系。The reaction system is a system for preparing synthesis gas (CO+H 2 ) by gas-phase oxidation of methane or a system for preparing formaldehyde, methanol or ethylene by utilizing methane.
所述反应体系中甲烷的浓度为0.4％-60％。The concentration of methane in the reaction system is 0.4%-60%.
所述反应体系中甲烷与氧气的体积比为(0.2-5)∶1。The volume ratio of methane to oxygen in the reaction system is (0.2-5):1.
所述方法中，加入NO或/和NO2的浓度优选为200-2000ppm。In the method, the concentration of adding NO or/and NO2 is preferably 200-2000ppm.
利用甲烷气相氧化反应制备合成气，即Synthesis gas is produced by gas-phase oxidation of methane, namely
同时在CH4-O2体系中加入微量(50-2000ppm)的NOx(NO/NO2)，可以使反应温度降低200-300℃。改变反应条件(温度、CH4/O2比、流速等)，可改变产物中CO、H2、CH3OH、HCHO、C2H4的分布，从而得到一种或几种主要产物。由于是气相反应，此方法不存在积碳问题。At the same time, adding a small amount (50-2000ppm) of NO x (NO/NO 2 ) to the CH 4 -O 2 system can lower the reaction temperature by 200-300°C. Changing the reaction conditions (temperature, CH 4 /O 2 ratio, flow rate, etc.) can change the distribution of CO, H 2 , CH 3 OH, HCHO, and C 2 H 4 in the product, thereby obtaining one or several main products. Because it is a gas phase reaction, there is no carbon deposition problem in this method.
本发明的特点如下：Features of the present invention are as follows:
甲烷氧化反应在没有催化剂存在下在750℃以上才能发生。本发明不使用固体催化剂，通过在CH4-O2体系中加入微量(50-2000ppm)的NOx(NO/NO2)，使反应温度降低200-300℃。就甲烷部分氧化制合成气而言，在520℃左右开始生成CO和H2，650-700℃时甲烷转化率和CO选择性分别可达到50％和80％，产物中合成气的H2/CO为0.8-2.0。The methane oxidation reaction can only occur above 750°C in the absence of a catalyst. The invention does not use a solid catalyst, and reduces the reaction temperature by 200-300°C by adding a small amount (50-2000ppm) of NO x (NO/NO 2 ) into the CH 4 -O 2 system. As far as the partial oxidation of methane to synthesis gas is concerned, CO and H 2 start to be produced at around 520°C, and the methane conversion rate and CO selectivity can reach 50% and 80% respectively at 650-700°C, and the H 2 / CO is 0.8-2.0.
本发明的优点与积极效果：Advantage and positive effect of the present invention:
本发明利用甲烷气相氧化反应制备合成气，与传统的甲烷-水汽重整方法相比，具有反应温度低，H2/CO比适宜等优点。同时，与使用固体催化剂的甲烷部分氧化法相比，避免了积碳和甲烷的深度氧化(生成CO2)。The invention utilizes methane gas-phase oxidation reaction to prepare synthesis gas, and has the advantages of low reaction temperature, suitable H2 /CO ratio and the like compared with the traditional methane-steam reforming method. At the same time, compared with the partial oxidation of methane using a solid catalyst, carbon deposition and deep oxidation of methane (generating CO 2 ) are avoided.
本发明可用于甲烷部分氧化制备合成气，或用于甲烷-水汽重整体系，即在CH4-H2O体系中加入O2与NOx，以降低反应温度，改善H2/CO比。The invention can be used for the partial oxidation of methane to prepare synthesis gas, or for the methane-water vapor reformation system, that is, adding O 2 and NO x to the CH 4 -H 2 O system to lower the reaction temperature and improve the H 2 /CO ratio.
本发明还可用于合成其他甲烷部分氧化产物，如甲醛、甲醇等。与现有的方法相比，因为是气相反应，避免了这些物质在固体催化剂上的继续氧化(生成CO或CO2)，可提高对还原性物质的选择性。The invention can also be used to synthesize other methane partial oxidation products, such as formaldehyde, methanol and the like. Compared with the existing method, because it is a gas phase reaction, the continuous oxidation of these substances on the solid catalyst (generating CO or CO 2 ) is avoided, and the selectivity to reducing substances can be improved.
本发明是一种活化甲烷的方法，不仅可用于天然气化工，亦可用于其他甲烷参与的反应，如催化燃烧，甲烷裂解制碳纳米管，利用甲烷进行煤的液化等通常需要固体催化剂的体系，可解决传统方法中固-固反应效率低，产物与催化剂难以分离等问题。The invention is a method for activating methane, which can be used not only for natural gas chemical industry, but also for other reactions in which methane participates, such as catalytic combustion, methane cracking to produce carbon nanotubes, coal liquefaction using methane, and other systems that usually require solid catalysts. It can solve the problems of low solid-solid reaction efficiency and difficult separation of products and catalysts in traditional methods.
附图说明：Description of drawings:
图1为制备合成气条件下添加NO对CH4转化率和CO收率的影响示意图。Figure 1 is a schematic diagram of the effect of adding NO on the conversion of CH 4 and the yield of CO under the condition of producing syngas.
图2为催化燃烧条件下添加NO对CH4转化率和CO收率的影响示意图。Fig. 2 is a schematic diagram of the effect of adding NO on the conversion of CH4 and the yield of CO under catalytic combustion conditions.
图中，■和□分别表示无NO时的CH4转化率和CO收率；●和○分别表示添加600ppmNO时的CH4转化率和CO收率。In the figure, ■ and □ represent the CH conversion and CO yield without NO, respectively; ● and ○ represent the CH conversion and CO yield when 600 ppm NO is added, respectively.
图3为不同温度反应后产物的红外光谱图。a：550℃；b：600℃；c：700℃。Fig. 3 is the infrared spectrogram of the product after reacting at different temperatures. a: 550°C; b: 600°C; c: 700°C.
实施例：Example:
甲烷催化氧化反应在一内径为6mm的石英反应管内进行，反应管由电炉加热，加热段长度为20cm，反应温度由LU-900M型程序温度控制仪控制。反应气体(CH4，空气，NO)流量由质量流量计控制，预先混合后通入反应管内。反应产物中的O2，N2，H2等由两台气相色谱仪(分子筛柱，热导检测器)检测，CH4，CO，HCHO，CH3OH由一台布鲁克Vector22红外光谱仪(10cm气体池)在线检测，并由色谱校正浓度。1.甲烷转化制备合成气：The methane catalytic oxidation reaction is carried out in a quartz reaction tube with an inner diameter of 6 mm. The reaction tube is heated by an electric furnace, and the length of the heating section is 20 cm. The reaction temperature is controlled by a LU-900M program temperature controller. The flow rate of reaction gas (CH 4 , air, NO) is controlled by a mass flow meter, which is pre-mixed and then passed into the reaction tube. O 2 , N 2 , H 2 in the reaction product were detected by two gas chromatographs (molecular sieve column, thermal conductivity detector), CH 4 , CO, HCHO, CH 3 OH were detected by a Bruker Vector22 infrared spectrometer (10cm gas pool) detected online, and the concentration was calibrated by chromatography. 1. Methane conversion to produce synthesis gas:
反应条件：反应体系中CH4浓度为20％，O2浓度为10％，加入的NO浓度为600ppm，流速为40ml/min。Reaction conditions: the concentration of CH4 in the reaction system is 20%, the concentration of O2 is 10%, the concentration of NO added is 600ppm, and the flow rate is 40ml/min.
从图1中可以看出，在550℃就可观察到明显的反应，在700℃时，CH4转化率为38％，生成CO的选择性为91％，H2/CO为0.8。而不加NOx反应需要750℃才能发生。It can be seen from Figure 1 that an obvious reaction can be observed at 550°C, and at 700°C, the conversion of CH 4 is 38%, the selectivity to CO is 91%, and the H 2 /CO ratio is 0.8. The reaction without NOx
表1列出了不同反应条件(流速，温度，CH4/O2比)对CH4转化率、CO收率以及H2/CO比的影响。表1：CH4浓度 CH4/O2 流速 CO最高 甲烷转化率* H2/CO* 温度*(％) (ml/min) 收率(％) (％) (℃)10 1∶1 40 46 55 0.4 65020 2∶1 40 35 38 0.8 70020 5∶1 40 4 6.8 0.9 65020 2∶1 200 4 7.5 0.8 700*为CO最高收率时的数据2.甲烷催化燃烧：Table 1 lists the effects of different reaction conditions (flow rate, temperature, CH 4 /O 2 ratio) on CH 4 conversion, CO yield and H 2 /CO ratio. Table 1: CH 4 Concentration CH 4 /O 2 Flow Rate CO Maximum Methane Conversion * H 2 /CO * Temperature * (%) (ml/min) Yield (%) (%) (°C)10 1:1 40 46 55 0.4 65020 2∶1 40 35 38 0.8 70020 5∶1 40 4 6.8 0.9 65020 2∶1 200 4 7.5 0.8 700 * is the data at the highest yield of CO 2. Catalytic combustion of methane:
反应条件：反应体系中CH4浓度为0.4％，O2浓度为2％，其余为N2，加入的NO浓度为600ppm，流速为40ml/min。Reaction conditions: the concentration of CH 4 in the reaction system is 0.4%, the concentration of O 2 is 2%, the rest is N 2 , the concentration of NO added is 600ppm, and the flow rate is 40ml/min.
从图2可以看出，在催化燃烧条件(强氧化条件)下，加入NO可以使反应的初始温度由850℃降到550℃，在650℃左右CO收率可达到70％，高于700℃时，CH4接近完全转化。3.甲烷转化合成其他产物：It can be seen from Figure 2 that under catalytic combustion conditions (strong oxidation conditions), adding NO can reduce the initial temperature of the reaction from 850°C to 550°C, and the CO yield can reach 70% at around 650°C, which is higher than 700°C , CH 4 is nearly completely converted. 3. Methane conversion to other products:
反应条件：反应体系中CH4浓度为20％，O2浓度为10％，其余为N2，加入的NO浓度为600ppm，流速为40ml/min。Reaction conditions: the concentration of CH 4 in the reaction system is 20%, the concentration of O 2 is 10%, the rest is N 2 , the concentration of NO added is 600ppm, and the flow rate is 40ml/min.
对同样的反应体系(CH4-O2-NOx)，改变反应条件，可得到甲醛、甲醇、乙烯等产物。For the same reaction system (CH 4 -O 2 -NO x ), by changing the reaction conditions, products such as formaldehyde, methanol, and ethylene can be obtained.
图3是不同温度反应后产物的红外光谱图(局部)，a为550℃反应后产物的红外光谱图；b为600℃反应后产物的红外光谱图；c为700℃反应后产物的红外光谱图。可以看出在较低温度时有利于生成甲醛和甲醇，升高温度可得到乙烯。Figure 3 is the infrared spectrogram (partial) of the product after reaction at different temperatures, a is the infrared spectrum of the product after the reaction at 550 ° C; b is the infrared spectrum of the product after the reaction at 600 ° C; c is the infrared spectrum of the product after the reaction at 700 ° C picture. It can be seen that formaldehyde and methanol are favored at lower temperatures, and ethylene can be obtained at higher temperatures.
Claims (7)
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| CNB021163049A CN1172842C (en) | 2002-03-22 | 2002-03-22 | A method for catalytic methane oxidation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008006244A1 (en) * | 2006-07-04 | 2008-01-17 | Dalian Institute Of Chemical Physics Chinese Academy Of Sciences | Oxidation catalyst |
| CN101239316B (en) * | 2007-02-09 | 2010-05-19 | 中国石油化工股份有限公司 | Catalyst for methane selective oxidation for making formaldehyde and preparation and application thereof |
| CN102260148A (en) * | 2011-06-01 | 2011-11-30 | 北京大学 | Method for synthesizing mixed aldehyde by synthetic gas |
| CN111377797A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Process method for preparing methanol by methane oxidation |
-
2002
- 2002-03-22 CN CNB021163049A patent/CN1172842C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008006244A1 (en) * | 2006-07-04 | 2008-01-17 | Dalian Institute Of Chemical Physics Chinese Academy Of Sciences | Oxidation catalyst |
| CN101239316B (en) * | 2007-02-09 | 2010-05-19 | 中国石油化工股份有限公司 | Catalyst for methane selective oxidation for making formaldehyde and preparation and application thereof |
| CN102260148A (en) * | 2011-06-01 | 2011-11-30 | 北京大学 | Method for synthesizing mixed aldehyde by synthetic gas |
| CN102260148B (en) * | 2011-06-01 | 2013-11-06 | 北京大学 | Method for synthesizing mixed aldehyde by synthetic gas |
| CN111377797A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Process method for preparing methanol by methane oxidation |
| CN111377797B (en) * | 2018-12-28 | 2022-08-12 | 中国石油化工股份有限公司 | Process method for preparing methanol by methane oxidation |
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| Publication number | Publication date |
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| CN1172842C (en) | 2004-10-27 |
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