CN104477845A - Method for preparing synthesis gas by reforming glycerinum by virtue of plasmas - Google Patents
Method for preparing synthesis gas by reforming glycerinum by virtue of plasmas Download PDFInfo
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- CN104477845A CN104477845A CN201410754139.5A CN201410754139A CN104477845A CN 104477845 A CN104477845 A CN 104477845A CN 201410754139 A CN201410754139 A CN 201410754139A CN 104477845 A CN104477845 A CN 104477845A
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000002407 reforming Methods 0.000 title claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title abstract description 10
- 238000003786 synthesis reaction Methods 0.000 title abstract description 10
- 210000002381 plasma Anatomy 0.000 title 1
- 235000011187 glycerol Nutrition 0.000 claims abstract description 31
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 2
- 238000010891 electric arc Methods 0.000 claims 2
- 229910000906 Bronze Inorganic materials 0.000 claims 1
- 239000010974 bronze Substances 0.000 claims 1
- 235000009508 confectionery Nutrition 0.000 claims 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 16
- 239000003225 biodiesel Substances 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011810 insulating material Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Plasma Technology (AREA)
Abstract
本发明公开一种等离子体重整甘油制合成气方法，将甘油雾化后切向引入包括中心电极、聚四氟乙烯层、外电极、圆筒外壁、进料口及出气口的等离子体发生器；对等离子体发生器内的电极施以高电压，产生非热电弧等离子体，等离子体诱发甘油发生重整化学反应，产生合成气。本发明的主要部件是金属和绝缘材料，设备投入少，以生物柴油副产物甘油为原料，实现废物资源化利用，制氢成本低，同时提升了生物柴油副产物甘油的利用空间。The invention discloses a method for preparing synthesis gas from glycerin by plasma reforming. Glycerin is atomized and then tangentially introduced into a plasma generator comprising a central electrode, a polytetrafluoroethylene layer, an outer electrode, an outer wall of a cylinder, a feed inlet and a gas outlet. ; Apply a high voltage to the electrodes in the plasma generator to generate a non-thermal arc plasma, which induces a reforming chemical reaction of glycerin to generate synthesis gas. The main components of the invention are metals and insulating materials, and the investment in equipment is small, and glycerin, a by-product of biodiesel, is used as a raw material to realize the resource utilization of waste, and the cost of hydrogen production is low, and at the same time, the utilization space of glycerin, a by-product of biodiesel, is improved.
Description
技术领域 technical field
本发明涉及制氢技术，特别是涉及一种等离子体重整甘油制合成气方法。 The invention relates to hydrogen production technology, in particular to a method for producing synthesis gas by plasma reforming glycerin.
背景技术 Background technique
随着石油资源的日益枯竭，能量需求量的不断增加，全世界逐渐面临能源短缺的危机。生物柴油作为一种可再生能源，受到各国的重视并大力加以发展。但在制备生物柴油的过程中，每生产10吨生物柴油会产约1吨的甘油副产物，副产物甘油的有效利用已成为影响生物柴油企业发展的重要因素。以甘油为原材料制取合成气(氢气和一氧化碳混合气)，合成气是一种化工原料，也可以作为燃料，进而提升了甘油的利用空间。目前利用甘油制合成器的主要方法是催化重整，存在催化剂中毒的问题。 With the depletion of oil resources and the increasing demand for energy, the world is gradually facing the crisis of energy shortage. Biodiesel, as a renewable energy source, has been valued and vigorously developed by various countries. However, in the process of preparing biodiesel, about 1 ton of glycerol by-product will be produced for every 10 tons of biodiesel produced, and the effective utilization of by-product glycerol has become an important factor affecting the development of biodiesel enterprises. Glycerin is used as a raw material to produce synthesis gas (a mixture of hydrogen and carbon monoxide). Synthesis gas is a chemical raw material and can also be used as a fuel, thereby increasing the utilization space of glycerin. At present, the main method of using glycerol to make synthesizers is catalytic reforming, which has the problem of catalyst poisoning.
发明内容 Contents of the invention
为解决上述问题，本发明提出一种等离子体重整甘油制合成气方法。 In order to solve the above problems, the present invention proposes a method for producing synthesis gas from glycerin by plasma reforming.
本发明为达到以上目的，是通过以下的技术方案来实现的： In order to achieve the above object, the present invention is achieved through the following technical solutions:
提供一种等离子体重整甘油制合成气方法：1)将甘油通过雾化后引入等离子体发生器；2)对等离子体发生器内的电极施以高电压，中心电极与外电极在高压电作用下，中心电极尖端与外电极最窄处产生击穿电弧，其在旋流的甘油喷雾推动下边高速旋转横扫电极间区域边向发生器下游移动，直至电弧过长淬灭，上述过程不断循环，产生非热电弧等离子体，等离子体诱发甘油发生重整化学反应，产生合成气。 Provide a method for plasma reforming glycerol to synthesize gas: 1) introduce glycerin into a plasma generator after atomization; 2) apply high voltage to the electrodes in the plasma generator, and the central electrode and the outer electrode Under the action, a breakdown arc is generated at the narrowest point between the tip of the center electrode and the outer electrode, which is driven by the swirling glycerin spray to rotate at a high speed and sweep across the area between the electrodes while moving downstream of the generator until the arc is too long and quenched. The above process continues to cycle , to generate non-thermal arc plasma, which induces a chemical reaction of reforming glycerin to generate synthesis gas.
所述的等离子体发生器，包括中心电极、聚四氟乙烯层、外电极、圆筒外壁、进料口及出气口；发生器的中心电极、聚四氟乙烯层、外电极、圆筒外壁及出气口轴线均位于圆筒外壁轴线上，其中中心电极为一带有尖端的铜棒，外电极为一铜缩放喷管，圆筒外壁为不锈钢管；中心电极与外电极通过聚四氟乙烯层隔开，两电极之间最窄距离0.5-5mm；甘油通过固定在圆筒外壁上的进料口切向进入等离子体发生器。 The plasma generator includes a central electrode, a polytetrafluoroethylene layer, an outer electrode, a cylinder outer wall, a feed inlet and a gas outlet; the central electrode of the generator, a polytetrafluoroethylene layer, an outer electrode, and a cylinder outer wall and the axis of the gas outlet are located on the axis of the outer wall of the cylinder. The central electrode is a copper rod with a tip, the outer electrode is a copper zoom nozzle, and the outer wall of the cylinder is a stainless steel tube; the central electrode and the outer electrode are separated by a polytetrafluoroethylene layer. Open, the narrowest distance between the two electrodes is 0.5-5mm; glycerin enters the plasma generator tangentially through the feed port fixed on the outer wall of the cylinder.
因甘油中碳氧比为1∶1，所以甘油转化为合成气可以需要额外的氧元素(如 水或者氧气)： Since the ratio of carbon to oxygen in glycerol is 1:1, the conversion of glycerol to syngas may require additional oxygen elements (such as water or oxygen):
C3H8O3→4H2+3CO C 3 H 8 O 3 →4H 2 +3CO
等离子体重整甘油的主要气态产物为H2和CO。少量的CO2、CH4、C2H2、C2H4、C2H6、少量的液态产物和碳黑也会在重整过程中产生。 The main gaseous products of plasma reforming glycerol are H2 and CO. Small amounts of CO 2 , CH 4 , C 2 H 2 , C 2 H 4 , C 2 H 6 , small amounts of liquid products, and carbon black are also produced during the reforming process.
本发明具有体积小，效率高，稳定性好，可靠性高和成本较低等优点，可有效的进行等离子体重整可再生原料甘油制取富氢气。 The invention has the advantages of small size, high efficiency, good stability, high reliability and low cost, etc., and can effectively carry out plasma reformation of renewable raw material glycerin to produce hydrogen-rich gas.
附图说明 Description of drawings
图1为本发明的结构示意图。 Fig. 1 is a structural schematic diagram of the present invention.
图1中：1中心电极，2聚四氟乙烯层，3外电极，4圆筒外壁，5进料口，6出气口。 In Fig. 1: 1 center electrode, 2 polytetrafluoroethylene layer, 3 outer electrode, 4 cylinder outer wall, 5 feed inlet, 6 gas outlet.
具体实施方式 Detailed ways
实施例 Example
如附图1所示，本发明包括中心电极1、聚四氟乙烯层2、外电极3、圆筒外壁4、进料口5及出气口6；装置的中心电极1、聚四氟乙烯层2、外电极3、圆筒外壁4及出气口6轴线均位于圆筒外壁3轴线上，其中中心电极1为一带有尖端的铜棒(直径10mm)，外电极3为一铜缩放喷管(长110mm，喉部直径11mm)，圆筒外壁为不锈钢管(直径48mm，长300mm)；中心电极1与外电极3通过聚四氟乙烯层2隔开，两电极之间最窄距离1.8mm。)将甘油雾化后通过进料口5引入等离子体发生器；2)对等离子体发生器内的电极施以12kV交流高压电，中心电极与外电极在高电压作用下，中心电极1尖端与外电极3最窄处产生击穿电弧，其在旋流的甘油喷雾推动下边高速旋转横扫电极间区域边向发生器下游移动，直至电弧过长淬灭，上述过程不断循环，产生非热电弧等离子体，等离子体诱发甘油发生重整化学反应，产生富氢合成气由出气口6排出，主要产物包括H2和CO，H2与CO的比率约为1.33，且合成气的选择性可高于80％。合成气浓度高于94％。表明甘油分解是等离子环境中的主要反应。使用纯甘油时能源效率高于50％，若能优化电源和装置几何结构、结合余热回收技术，可进一步提高能源效率。 As shown in accompanying drawing 1, the present invention comprises central electrode 1, polytetrafluoroethylene layer 2, outer electrode 3, cylinder outer wall 4, feed inlet 5 and air outlet 6; Central electrode 1 of device, polytetrafluoroethylene layer 2. The axes of the outer electrode 3, the outer wall of the cylinder 4 and the air outlet 6 are all located on the axis of the outer wall of the cylinder 3, wherein the central electrode 1 is a copper rod with a tip (diameter 10 mm), and the outer electrode 3 is a copper scaling nozzle ( Length 110mm, throat diameter 11mm), the outer wall of the cylinder is a stainless steel tube (diameter 48mm, length 300mm); the central electrode 1 and the outer electrode 3 are separated by a polytetrafluoroethylene layer 2, and the narrowest distance between the two electrodes is 1.8mm. ) Atomize the glycerin and introduce it into the plasma generator through the feed port 5; 2) Apply a 12kV AC high voltage to the electrodes in the plasma generator, and the center electrode and the outer electrode are under high voltage, and the tip of the center electrode 1 A breakdown arc is generated at the narrowest part of the outer electrode 3, which is driven by the swirling glycerin spray and moves to the downstream of the generator while sweeping across the area between the electrodes at a high speed until the arc is too long and quenched. The above process continues to circulate, generating a non-thermal arc Plasma, plasma induces a chemical reaction of reforming glycerin to produce hydrogen-rich synthesis gas, which is discharged from the gas outlet 6. The main products include H2 and CO. The ratio of H2 to CO is about 1.33, and the selectivity of the synthesis gas can be high at 80%. The syngas concentration is higher than 94%. It is shown that glycerol decomposition is the main reaction in the plasma environment. The energy efficiency is higher than 50% when pure glycerin is used. If the power supply and device geometry can be optimized, combined with waste heat recovery technology, the energy efficiency can be further improved.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101164865A (en) * | 2007-09-28 | 2008-04-23 | 中国科学院广州能源研究所 | Reactor using with plasma diffraction to produce hydrogen |
| CN101279715A (en) * | 2008-05-29 | 2008-10-08 | 中山大学 | A device that uses non-equilibrium plasma to eliminate volatile organic compounds and simultaneously produce hydrogen |
| CN103204471A (en) * | 2013-04-08 | 2013-07-17 | 浙江大学 | Method for preparing synthesis gas by using hot plasma pyrolysis glycerin |
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2014
- 2014-12-02 CN CN201410754139.5A patent/CN104477845A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101164865A (en) * | 2007-09-28 | 2008-04-23 | 中国科学院广州能源研究所 | Reactor using with plasma diffraction to produce hydrogen |
| CN101279715A (en) * | 2008-05-29 | 2008-10-08 | 中山大学 | A device that uses non-equilibrium plasma to eliminate volatile organic compounds and simultaneously produce hydrogen |
| CN103204471A (en) * | 2013-04-08 | 2013-07-17 | 浙江大学 | Method for preparing synthesis gas by using hot plasma pyrolysis glycerin |
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