CN1683828A - Method for treating solid organic waste substance using high frequency plasma - Google Patents
Method for treating solid organic waste substance using high frequency plasma Download PDFInfo
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- CN1683828A CN1683828A CN 200410026856 CN200410026856A CN1683828A CN 1683828 A CN1683828 A CN 1683828A CN 200410026856 CN200410026856 CN 200410026856 CN 200410026856 A CN200410026856 A CN 200410026856A CN 1683828 A CN1683828 A CN 1683828A
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
- Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
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Abstract
The method of treating solid organic waste with HF plasma features the spouted bed comprising double stage one plasma area. The method includes the following steps: generating the first plasma area and the second plasma area at low voltage condition, comprising one spouted bed with the first plasma area and the second plasma area, adopting water vapor as plasma work gas and feeding the solid material to the second plasma area. The present invention is superior to available technology, has excellent operation stability and continuity, capacity of treating large grains and lumps of solid matter and high efficiency of obtaining valuable synthetic gas.
Description
Technical Field
The invention relates to the technical field of solid waste treatment, in particular to a technology for pyrolyzing and gasifying solid organic waste by utilizing high-frequency plasma in the electrical field.
Background
The solid organic waste comprises municipal domestic waste, high-molecular waste such as plastics and rubber, and certain agricultural and forestry production waste and industrial waste and the like. In recent years, national economy is rapidly developed, the production of solid organic wastes is greatly increased, the production of waste plastics in China reaches 370 ten thousand tons and the production of waste rubber reaches 85 thousand tons in 2000, and increasingly serious problems of white pollution, black pollution and the like are caused. At present, the treatment technology of solid waste at home and abroad mainly comprises landfill, incineration, mechanical or chemical recovery. For example, a small part of waste plastics in China is recycled at present, but most recycled products are low in grade, and the market demand is not large. Most waste plastic products in the garbage are still treated together with the garbage according to landfill, and as the plastic has light weight and large volume, the landfill occupies a large area, large molecules of the plastic can not be automatically degraded and can not rot for a long time, not only resources are wasted, but also the land is damaged and the underground water is polluted. The incineration treatment method has better volume reduction and decrement effects, but the incineration of the waste plastics often generates a large amount of smoke containing toxic pollutants to cause serious air pollution. Recently, chemical recycling methods such as the method of producing gasoline and diesel oil by catalytic cracking of waste plastics have also received great attention. The oil preparation by cracking waste plastics needs to be carried out under the conditions of 0.2-0.5MPa pressure, 500-800 ℃ temperature and catalyst action, the waste plastic raw material is converted into low molecular fuel oil by thermal cracking reaction and catalytic cracking reaction under the action of catalyst and heat, and products similar to gasoline and diesel oil are obtained after fractional distillation and condensation. The main problems of the prior technology for producing oil by cracking waste plastics are that the product quality is difficult to control to achieve the aim of generating gasoline and diesel oil which meet the national standard, and the catalyst has poor reaction effect, low oil yield and high energy consumption.
The plasma is excited ionized gas, which is composed of negatively charged particles such as electrons, positively charged particles such as positive ions, and neutral particles such as atoms, etc., and the number of positive and negative charges in the ionized gas is equal, and the whole body remains electrically neutral and has conductivity. Plasma can provide a reaction environment with concentrated energy and high temperature, which not only can greatly improve the chemical reaction rate, but also can generate chemical reactions which are difficult to occur in other reaction systems, so that the plasma technology is gradually applied to a plurality of industrial fields such as chemical industry, metallurgy, electronics, energy sources, materials and the like recently. In the aspects of energy and environmental protection, the plasma pyrolysis gasification technology of solid waste is also reported more.
The technology of treating solid organic waste by using DC arc plasma can be found in Chinese patents 01129931 and 02250661And the like. The working gas is ionized into high-temperature plasma in a direct current arc plasma generator and is injected into a plasma gasification reactor to form 3000-10000K high-temperature environment; the solid organic waste is carried by carrier gas through a screw feeder and sprayed into a pyrolysis area of the plasma gasification reactor to form a high-temperature reaction environment in which a large amount of active ions exist; solid organic wasteAnd carrying out fast pyrolysis gasification reaction in a high-temperature region of the reactor to generate chemical synthesis gas with recycling value. The current application of dc arc plasma to treat solid organic waste has some technical limitations, such as: (1) the direct current arc discharge is a large current strong discharge, the electrode is easy to be ablated, the service life is short, and when inert gases (Ar, He) and reducing gases (H) are used2) Or neutral gas (N)2) When used as a working gas, the electrode life is generally 600 hours; when using oxidizing gases (O)2H, air, H2O), the electrode life is only about 200 hours. (2) The temperature of the direct current arc plasma is as high as 3000-10000K, and the reactor wall material is difficult to bear for a long time. (3) The solid materials can only be introduced at the downstream of the plasma jet flow and are difficult to enter a plasma central area, the plasma gasification reactor adopts a carrier bed mode, the residence time of reactants is short (0.2-2 ms), and the pyrolysis gasification is incomplete.
The technology of treating solid organic waste by using high frequency plasma is represented by chinese patent 93102963. The high-frequency plasma is generated by high-frequency coupling electrodeless discharge, and is divided into capacitive coupling plasma and inductive coupling plasma according to different coupling modes, if the energy coupling in the plasma is generated by static charge (generated by the voltage of a radio-frequency antenna/electrode), the coupling mode is capacitive coupling, and the generated plasma is Capacitive Coupling Plasma (CCP); if the energy coupling in the plasma is mainly generated by (moving charges) generated by the magnetic field of the radio frequency antenna/electrode, the corresponding coupling mode is inductive coupling, and the generated plasma is Inductively Coupled Plasma (ICP). High-frequency plasmas have many advantages, such as: (1) other plasma torches must use an inert gas as the working gas to prevent erosion of the electrode, while highfrequency plasma can work in air or oxygen conditions, resulting in significant savings in operating costs. (2) The high-frequency plasma area is large, the air flow speed is low, the powder is easy to supply in the center, the retention time of the powder in the high-temperature area is long, and the plasma torch has a long high-temperature jet flow tail flame. (3) The high-frequency plasma can be annular due to the skin effect of the high-frequency current, the carrier gas can form a channel in the center of the plasma, and the solid powder is rapidly decomposed under the action of the annular high-temperature plasma.
The electrodeless plasma jet device proposed in chinese patent 93102963 is mainly used for dissociating harmful waste materials, and uses a radio frequency plasma jet tube to excite free electrons, the waste materials are combined with a controllable free electron source, and the collision and ultraviolet radiation generated by electrons and molecules are utilized to make the free electrons dissociate the waste materials, and become a simple compound which can be discharged safely and is harmless to the environment. In particular, the dissociation process adopts a non-heating mode, depends on the bond cleavage of excited electrons, the dissociation degree of the waste is influenced by the density and the temperature of free electrons and the residence time of the waste in plasma, the electron density can be controlled by the flow of carrier gas, and the temperature can be controlled by changing the radio frequency power. The inventors have proposed that the apparatus can be scaled up to radio frequency power MW level, with a waste treatment rate of 500kg/h scale. But the main problems to be improved are: (1) the temperature of the rf plasma torch operating at atmospheric pressure is still high and requires external water cooling. (2) The radio frequency plasma jet tube is sensitive to external interference, and when the solid material supply amount is increased, plasma is unstable and easy to extinguish. (3) The solid material to be treated must be in powder form, while large-particle, lumpy material is difficult to treat.
Disclosure of Invention
The invention aims to overcome the limitations of the prior art and provide a method for pyrolyzing and gasifying solid organic wastes by utilizing high-frequency plasma, which has good operation stability and continuity, can treat large particles and massive solid materials and can obtain valuable synthesis gas with high efficiency.
First, high frequency plasma state parameters (such as electron density, electron temperature, gas temperature) are greatly affected by the operating pressure, and if the discharge is performed under a high pressure condition close to atmospheric pressure, electrons, ions, and neutral particles will exchange energy sufficiently by violent collisions, thereby causing the plasma to reach or approach a thermal equilibrium state; on the contrary, the low-pressure plasma of hundreds or thousands of pascals is often in a non-thermal equilibrium state, at this time, the number density of gas particles is low, the collision probability of electrons and ions or neutral particles is very small, the difference between the electron temperature and the heavy particle temperature is large, the electron temperature can reach tens of thousands of degrees, and the heavy particle temperature is only hundreds of degrees. Our experimental results show that: for a radio frequency plasma torch tube with the inner diameter of 30mm, when the pressure of working gas in the torch tube is 50Pa (absolute pressure), the high-frequency power required by plasma ignition is 50W, and the temperature measured by a thermocouple is 150 ℃; when the gas pressure is 3000Pa, the ignition power is 700W, and the temperature measured by a thermocouple is 500 ℃; when the gas pressure is 10000Pa for 5000-. When the high-frequency plasma is used for pyrolysis and gasification of solid organic wastes such as plastics and rubber, the preferred operating pressure is 5000-10000Pa and the temperature is 1000-1500 ℃.
Secondly, the stability problem of the high frequency plasma is mainly caused by the influence of the difference of the properties of the plasma working gas and the solid material to be processed on the high frequency energy coupling process. This patent uses a two-stage plasma as follows to improve the high frequency plasma stability: (1) a first plasma torch tube with a smaller diameter is used, plasma working gas is introduced into the first plasma torch tube, a first plasma area is generated through a first inductive coupling coil, and a high-temperature jet tail flame enters a second plasma area from the outlet of the first plasma torch tube. (2) And a second plasma torch tube with a larger diameter is used, and a second plasma area is generated through a second inductive coupling coil under the auxiliary action of the high-temperature jet tail flame of the first plasma torch tube. (3) The solid material is supplied to the second plasma area and pyrolyzed and gasified in the plasma high-temperature reaction atmosphere. In the double-stage plasma, the first plasma area is not influenced by solid materials, and stable operation is easy to maintain; when the second plasma area is affected by the supply of solid materials and is unstable, the high-temperature jet tail flame of the first plasma torch tube contains various active particles such as high-energy electrons, ions, excited atoms, molecules, free radicals and the like, so that the second plasma torch tube is not easy to extinguish arc under the combined action of the second inductive coupling coil.
Thirdly, in order to process large particles and massive solid materials, the first plasma area and the second plasma area form a spouted bed mode, and the method comprises the following steps: a semi-cone type air distribution plate is arranged at the lower part of the second plasma area, the bottom of the semi-cone type air distribution plate is connected with the outlet of the first plasma torch pipe, the high-temperature jet tail flame of the first plasma torch pipe becomes the central spouted air flow of the spouted bed of the second plasma area, and the corresponding partial area of the second plasma on the semi-cone type air distribution plate becomes the downward reflux area of the spouted bed; after the solid material is supplied to the second plasma area, the solid material is carried by the central spout airflow to spout upwards, and then coarse particles are separated from the jet flow due to the action of gravity, return to the downward reflux area and enter the next spout circulation. Therefore, large particles and blocky solid materials have enough residence time in the spouted bed until pyrolysis gasification reaction is completed to form small particle ash, and the small particle ash reaches an ash removal system along with air flow.
Fourthly, in order to fully utilize the organic components of the solid waste to prepare the synthesis gas, the plasma working gas can adopt superheated steam or a mixture of the superheated steam and air, oxygen or other gases. The water vapor and oxygen are dissociated into O, OH radicals by the high-frequency plasma, so that the pyrolysis gasification reaction of the solid waste is essentially oxidation reaction property in the method. Active particles such as high-energy electrons and ions contained in the plasma also have a bond cleavage effect on the high molecular organic matter. The total package reaction formula for preparing the synthesis gas by reacting the organic components of the solid waste with superheated steam is as follows: . When the plasma workinggas contains air and oxygen, part of organic components also participate in oxidation reaction: thereby providing part of the energy required for pyrolysis gasification.
Based on the above points, the present patent proposes a method for treating solid organic waste by using high frequency plasma, which comprises the following steps:
(1) under the condition of low pressure, a first plasma area is generated through a first inductive coupling coil, and a high-temperature jet flow tail flame enters a second plasma area;
(2) generating a second plasma area through a second inductive coupling coil under the auxiliary action of the first plasma high-temperature jet flow tail flame;
(3) the first plasma area and the second plasma area form a spouted bed, wherein the high-temperature jet tail flame of the first plasma is the central spouted air flow of the second plasma area, and the other areas of the second plasma are downward reflux areas of the spouted bed;
(4) and solid materials are supplied to the second plasma area, and pyrolysis and gasification reactions are completed under the action of the plasma.
Wherein, the preferable operating pressure of the first plasma area and the second plasma area is 5000-10000Pa, and the temperature is 1000-1500 ℃; the plasma working gas adopts superheated steam, or a mixture of the superheated steam and air or oxygen, or other gases and mixtures thereof.
Compared with the prior art, the invention has the following outstanding advantages: (1) due to the low pressure operation condition, the temperature of the high frequency plasma can be controlled below 1500 ℃, the plasma reactor can be manufactured by using conventional materials (such as casting ceramic), and the long-time continuous operation of the device is facilitated. (2) Because of the adoption of the two-stage plasma, the stability of the high-frequency plasma is greatly improved, and the plasma ignition process is easier. (3) Due to the spouted bed form, large particles and lumpy solid materials can also be treated. (4) The plasma working gas mainly adopts water vapor, which is beneficial to preparing synthesis gas from organic components of solid waste.
Drawings
The following describes the substance of this patent in further detail with reference to the attached drawings.
The figure is a schematic view of the patent embodiment. In the figure: 1, a first plasma area, 2, a second plasma area, 3, a first inductive coupling coil, 4, a first plasma torch tube, 5, a semi-conical air distribution plate, 6, a second inductive coupling coil, 7, a second plasma torch tube, 8, a water vapor generator, 9, a spiral feeder, 10, a storage bin, 11, a first matching network, 12, a first crystal-controlled RF high-frequency power supply, 13, a second matching network, 14, a second crystal-controlled RF high-frequency power supply, 15, an ash removal system, 16, an ash bin, 17 and an air extraction system.
Detailed Description
Example one
As shown in the figure I, a water vapor generator (8) generates overheated water vapor, the overheated water vapor is supplied to a first plasma area (1) after being metered and regulated, and meanwhile, the overheated water vapor is supplied to a second plasma area (2) through a semi-conical air distribution plate (5) with a plurality of series of small air inlet holes uniformly distributed; the model of the firstcrystal control RF high-frequency power supply (12) is JG-2K-B, the output power is 0-2kW, and the output frequency is 13.56MHz of the industrial special high frequency; the model of the first matching network (11) is JG-2KW, and a forward power meter and a reverse power meter are equipped; the first inductive coupling coil (3) is wound by a copper pipe and spirally surrounds the outer wall of the first plasma torch pipe (4) cast by high-temperature resistant ceramic; the model of the second crystal-controlled RF high-frequency power supply (14) is JG-10K-B, the output power is 0-10kW, the frequency is 13.56MHz, and the model of the second matching network (13) is JG-10KW and is provided with a forward power meter and a reverse power meter; the second inductive coupling coil (6) is wound by a copper pipe and spirally surrounds the outer wall of a second plasma torch pipe (7) cast by high-temperature resistant ceramic; the air extraction system (17) is a water-ring vacuum pump, the air extraction rate is 12L/s, the limit pressure is 4000Pa, and the gas of the plasma reactor is extracted through the ash removal system (15) so that the pressure of the first plasma area and the pressure of the second plasma area are about 5000 Pa; starting a first crystal-controlled RF high-frequency power supply (12) and adjusting a first matching network (11) so that a first plasma region (1)1) Starting luminance; then starting a second crystal control RF high-frequency power supply (14), and adjusting a second matching network (13) to enable a second plasma area (2) to be ignited; adjusting the output power of crystal control RF high-frequency power supplies (12, 14) and matching networks (11, 13) to enable the temperature of the first plasma area and the second plasma area to reach more than 1000 ℃; starting a spiral feeder (9), adding the polypropylene PP plastic particles stored in a storage bin (10) into a plasma reactor, pyrolyzing and gasifying the polypropylene PP plastic particles under the action of high temperature ofplasma, discharging gas through an ash removal system (15) and an air extraction system (17), and analyzing the gas by chromatography after sampling, wherein the main component of the gas is H2、CO、CH4、C2H4、C2H2、CO2、C2H6、C3H6、C3H8Etc., gas heat value of about 22MJ/Nm3And is suitable for being used as chemical synthesis gas, raw material gas or fuel gas and the like. An ash bin (16) may collect a very small amount of ash.
Example two
As in the first embodiment, the pumping system (17) is adjusted so that the pressure in the first plasma region and the pressure in the second plasma region are approximately 10000 Pa; adjusting the output power of the crystal-controlled RF high-frequency power supply (12, 14) and the matching network (11, 13) to make the temperature of the first plasma area and the second plasma area be about 1300 ℃; the polypropylene PP plastic particles are pyrolyzed and gasified, and the gas is sampled and then is analyzed by chromatography, and the main component types are the same as the first embodiment.
EXAMPLE III
As in the first embodiment, when the solid material is fed as crushed particles of waste tires, the gas-producing main component has H2、CO、CH4、C2H4、C2H2、CO2、C2H6、C3H6、C3H8Etc. and hydrogen sulfide H2S, gas heat value about 20MJ/Nm3. The ash bin (16) collects the solid product, i.e. pyrolytic carbon black, which has an elemental analysis of: 85% C, 0.5% H, 12% O, 0.4% N, 1.9% S; the ash content is 16.2 percent by industrial analysis, the heat value is 28500kJ/kg, the BET specific surface area is 70m2(ii)/g; scanning Electron Microscope (SEM) shows that the pyrolytic carbon black particles form a primary particle aggregate structure with the size of 50-2000 mu m; photoelectron Spectroscopy (XPS) showed that the carbon in the pyrolytic carbon black was mainly present as graphite-structured carbon, and that the sulfur morphology was associated with FeS2Similar to ZnS; nuclear magnetic resonance spectroscopy (NMR) showed that the main chemical property of the pyrolytic carbon black is an aromatic carbon C ═ C bond structure. Therefore, the solid products can be used as industrial semi-reinforcing carbon black and can also be used as activated carbon after further treatment.
Claims (6)
1. A method for treating solid organic waste by high-frequency plasma is characterized by comprising a spouted bed consisting of a two-stage plasma zone.
2. The method for treating solid organic waste with high frequency plasma as claimed in claim 1, wherein a spouted bed is constituted by a first plasma zone and a second plasma zone, wherein the first plasma high temperature jet tail flame is a central spout gas flow of the second plasma zone, and the other zone of the second plasma is a downward reflux zone of the spouted bed.
3. A method for treating solid organic waste with high frequency plasma as claimed in claim 2, wherein the solid material is supplied to the second plasma region.
4. The method for treating solid organic waste with high frequency plasma as claimed in claim 2, wherein the first plasma zone and the second plasma zone are generated under low pressure condition.
5. The method for treating solid organic waste with high frequency plasma as claimed in claim 4, wherein the pressure of the working gas is 5000-10000 Pa.
6. The method for treating solid organic waste with high frequency plasma as claimed in claim 2, wherein the plasma working gas is mainly water vapor.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100268562A CN1297781C (en) | 2004-04-14 | 2004-04-14 | Method for treating solid organic waste substance using high frequency plasma |
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| CNB2004100268562A CN1297781C (en) | 2004-04-14 | 2004-04-14 | Method for treating solid organic waste substance using high frequency plasma |
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| CN1683828A true CN1683828A (en) | 2005-10-19 |
| CN1297781C CN1297781C (en) | 2007-01-31 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7832344B2 (en) | 2006-02-28 | 2010-11-16 | Peat International, Inc. | Method and apparatus of treating waste |
| CN103241726A (en) * | 2013-05-09 | 2013-08-14 | 广州大学 | Method for preparing nano conductive carbon by cracking organic compound through hybrid plasma technology |
| US8671855B2 (en) | 2009-07-06 | 2014-03-18 | Peat International, Inc. | Apparatus for treating waste |
| CN113924162A (en) * | 2019-06-05 | 2022-01-11 | 国立大学法人金泽大学 | Fine particle manufacturing device and fine particle manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102022209215A1 (en) | 2022-09-05 | 2024-03-07 | Sms Group Gmbh | Process for processing plastic waste using plasmalysis |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0821609A (en) * | 1994-07-04 | 1996-01-23 | Satoru Yoshinaka | Incinerator and treating furnace |
| CN2469328Y (en) * | 2001-04-23 | 2002-01-02 | 王忠义 | Plasma incineration furnace for special garbage |
| CN1172110C (en) * | 2001-12-11 | 2004-10-20 | 北京机电研究所 | Plasma high temperature processing process and equipment for refuses |
| JP2003336818A (en) * | 2002-05-17 | 2003-11-28 | Hitachi Zosen Corp | Thermal decomposition furnace facility for waste |
| CN2593067Y (en) * | 2002-12-26 | 2003-12-17 | 中国科学院广州能源研究所 | Plasma pyrolytic gasifying apparatus for polymeric rejected material |
-
2004
- 2004-04-14 CN CNB2004100268562A patent/CN1297781C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7832344B2 (en) | 2006-02-28 | 2010-11-16 | Peat International, Inc. | Method and apparatus of treating waste |
| US8671855B2 (en) | 2009-07-06 | 2014-03-18 | Peat International, Inc. | Apparatus for treating waste |
| CN103241726A (en) * | 2013-05-09 | 2013-08-14 | 广州大学 | Method for preparing nano conductive carbon by cracking organic compound through hybrid plasma technology |
| CN103241726B (en) * | 2013-05-09 | 2015-03-11 | 广州大学 | Method for preparing nano conductive carbon by cracking organic compound through hybrid plasma technology |
| CN113924162A (en) * | 2019-06-05 | 2022-01-11 | 国立大学法人金泽大学 | Fine particle manufacturing device and fine particle manufacturing method |
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