CN109316917B - Integrated biogas desulfurization device and method - Google Patents
Integrated biogas desulfurization device and method Download PDFInfo
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- CN109316917B CN109316917B CN201811346001.6A CN201811346001A CN109316917B CN 109316917 B CN109316917 B CN 109316917B CN 201811346001 A CN201811346001 A CN 201811346001A CN 109316917 B CN109316917 B CN 109316917B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
- B01D53/323—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 by electrostatic effects or by high-voltage electric fields
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/00—Sources of waste gases
- B01D2258/05—Biogas
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Abstract
The invention discloses an integrated methane desulfurization device and a method, belonging to the technical field of methane desulfurization, comprising a reaction tank for containing absorption liquid, wherein the upper side of the reaction tank is provided with a gas outlet, the lower side of the reaction tank is provided with a gas collection and distribution port, the gas collection and distribution port is connected with a fan outside the reaction tank, and the reaction tank is internally provided with a high-voltage electrode and a low-voltage end, wherein one end of the high-voltage electrode, which is not immersed in the liquid level, is connected with the positive pole of a high-voltage direct-current power supply control console through a high-voltage lead, and the other end of the low-voltage end, which is not extended into the liquid level, is connected with the negative pole of the high-voltage direct-current power supply control console.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of methane desulfurization, and relates to a desulfurization device and a desulfurization method combining discharge plasma and wet desulfurization, in particular to an integrated methane desulfurization device and an integrated methane desulfurization method.
[ background of the invention ]
The biogas is combustible gas with high heat value and can be used for driving a generator to generate electricity or dragging an air blower to supply air. But the biogas inevitably contains hydrogen sulfide, the current biogas emission is characterized by large gas amount and high hydrogen sulfide concentration which can reach 2% under extreme conditions, the hydrogen sulfide is toxic, flammable and explosive, and has extremely strong corrosivity, and how to purify the hydrogen sulfide in the biogas efficiently is related to the safe and efficient utilization of biogas energy. In the traditional methane desulfurization process, dry desulfurization mainly based on ferric oxide and wet desulfurization mainly based on alkali liquor absorption cannot purify methane efficiently for a long time, the corrosion of key equipment can greatly increase the operation cost, and the biological desulfurization method has the problems of long construction period, blockage of a reaction system, withering and death of microorganisms and the like. Therefore, the search for a novel efficient and economic biogas purification method is of great significance.
The discharge plasma technology is a novel pollutant treatment technology which is simple in process, good in treatment effect and free of secondary pollution and is established in recent years. Under the action of high voltage, a large amount of active substances are generated, wherein the active substances comprise active particles with strong oxidizability, such as hydroxyl radicals and ozone, and can quickly oxidize reducing substances, and no new pollutants are introduced in the whole process. In practical applications, in order to further improve the treatment efficiency and reduce the energy consumption, the discharge plasma is often combined with methods such as activated carbon, catalysts, electrocatalytic oxidation, and the like.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provide an integrated biogas desulfurization device and method, which overcome the technical difficulty of applying liquid-phase direct current glow discharge to biogas desulfurization and combine direct current glow discharge with wet desulfurization.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the utility model provides an integration marsh gas desulphurization unit, is including being used for holding the reaction tank of absorption liquid, and its upside is opened and is equipped with the gas outlet, and the gas collection gas distribution port has been seted up to the downside, and the gas collection gas distribution port is connected with the fan outside the reaction tank in the reaction tank, is equipped with high voltage electrode and low-voltage end in the reaction tank, and wherein high voltage electrode does not soak liquid level one end and links to each other with high voltage direct current power supply console positive pole through high-voltage wire, and the low-voltage end is not stretched into the one end of liquid level.
The invention further improves the following steps:
the high-voltage electrode is a needle-shaped high-voltage electrode, an insulating rubber sleeve is wrapped outside the high-voltage electrode, and a conductive copper rod is arranged at the low-voltage end of the high-voltage electrode.
The side surface of the lower side of the reaction tank, which is opposite to the gas collection and distribution port, is provided with a liquid inlet, and the outer side of the liquid inlet is sequentially connected with a circulating pump and a liquid storage tank.
The bottom of the reaction tank is provided with a filtering system for solid-liquid separation, the filtering system is divided into two branches outside the reaction tank, one end of the filtering system is connected with the solid tank, and the other end of the filtering system is connected with the circulating pump.
The surface of the reaction tank is coated with an epoxy resin insulating layer, the bottom of the reaction tank is provided with an insulating pad, and the side surface of the inner wall of the reaction tank is provided with a liquid level detector.
The high-voltage electrode is immersed below the absorption liquid level and does not exceed 3mm, and the low-voltage end extends below the liquid level.
An integrated biogas desulfurization method comprises the following steps,
step 1, methane enters a reaction tank from a gas collection and distribution port through a fan, and hydrogen sulfide in the methane is rapidly absorbed by absorption liquid;
and 2, starting the high-voltage direct-current power supply, directly discharging the high-voltage electrode to the liquid phase, generating strong oxidizing substances around the electrode, further deeply treating hydrogen sulfide, and discharging the treated methane from the gas outlet.
The further improvement is that:
the regeneration liquid stored in the liquid storage tank is blown into the reaction tank from the liquid inlet through a circulating pump so as to replenish the water lost due to evaporation in the step 2 and activate the absorption liquid inactivated due to reaction in the step 1; wherein the liquid level detector determines the amount of regeneration liquid that needs to be replenished.
And the desulfurized absorption liquid flows out from the bottom of the reaction tank, and is subjected to solid-liquid separation by a filtering system, the elemental sulfur enters a solid tank, and the residual absorption liquid returns to the reaction tank again.
The absorption liquid is oxidizing liquid containing ferric ions, and the regeneration liquid is hydrogen peroxide liquid.
Compared with the prior art, the invention has the following beneficial effects:
the invention applies the direct current glow discharge plasma technology to the methane desulfurization through reasonable design, the whole system works circularly, the voltage required by discharge is greatly reduced through a specially designed electrode structure and a discharge form that the electrode is in contact with the liquid level, and the Fe is added3+Adjusting the conductivity of the solution to achieve a DC discharge by bubbling H2O2The regeneration liquid is supplied for evaporation loss, the continuous and stable discharge is maintained, the whole process is efficient and safe, and no secondary pollution is generated.
Furthermore, the materials and medicines used in the construction and operation of the invention are low in price, the operation cost is not high, the treatment, regeneration and recovery are integrated into a whole, and the occupied area and the initial investment cost are both saved by more than half.
Furthermore, the yield of the treated methane is not affected, and sulfur simple substances with higher purity can be collected for recycling after reaction.
[ description of the drawings ]
FIG. 1 is an overall structure diagram of the integrated biogas desulfurization device of the present invention;
FIG. 2 is a reaction plan view of the integrated biogas desulfurization device of the present invention;
wherein: 1-high voltage direct current power supply console; 2-high voltage conducting wire; 3-a high voltage electrode; 4-insulating rubber sleeve; 5-low voltage end; 6-a liquid level detector; 7-a fan; 8-gas collection and distribution port; 9-a reaction tank; 10-air outlet; 11-a liquid inlet; 12-a circulation pump; 13-a liquid storage tank; 14-a filtration system; 15-a solids tank; 16-epoxy resin insulation layer; 17-insulating pad.
[ detailed description ] embodiments
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover non-exclusive inclusions, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1 and 2, the integrated biogas desulfurization device comprises a reaction tank 9 for containing absorption liquid, wherein an air outlet 10 is arranged on the upper side of the reaction tank 9, an air collecting and distributing port 8 is arranged on the lower side of the reaction tank 9, the air collecting and distributing port 8 is connected with a fan 7 outside the reaction tank 9, a high-voltage electrode 3 and a low-voltage end 5 are arranged in the reaction tank 9, wherein one end, which is not immersed in the liquid level, of the high-voltage electrode 3 is connected with the positive pole of a high-voltage direct-current power supply console 1 through a high-voltage lead 2, and the other end, which is not inserted into the liquid. Wherein, the high-voltage electrode 3 is a needle-shaped high-voltage electrode, the outside of which is wrapped with an insulating rubber sleeve 4, and the low-voltage end 5 is a conductive copper bar. A liquid inlet 11 is arranged on the lower side of the reaction tank 9 opposite to the side surface of the gas collection and distribution port 8, and the outer side of the liquid inlet 11 is sequentially connected with a circulating pump 12 and a liquid storage tank 13. The bottom of the reaction tank 9 is provided with a filtering system 14 for solid-liquid separation, which is divided into two branches outside the reaction tank 9, one end of the filtering system is connected with a solid tank 15, and the other end of the filtering system is connected with a circulating pump 12. The surface of the reaction tank 9 is coated with an epoxy resin insulating layer, the bottom of the reaction tank is provided with an insulating pad 17, and the side surface of the inner wall of the reaction tank is provided with a liquid level detector 6. The high-voltage electrode 3 is immersed 3-5mm below the absorption liquid level, and the low-voltage end 5 extends below the liquid level.
The working principle and the process of the integrated methane desulfurization device are as follows:
the marsh gas enters a reaction tank 9 from a gas collecting and distributing port 8 through a fan 7, and the reaction tank contains Fe3+The absorption liquid can rapidly absorb the hydrogen sulfide in the methane; starting the high voltage DC power supply 1, the high voltage electrode 3 directly discharges to the liquid phase, the solution around the electrode is quickly vaporized to form a stable steam sheath, and OH and O are generated3Substances with strong oxidizability are subjected to further advanced treatment on the hydrogen sulfide gas, the treatment efficiency in the whole process is more than or equal to 98%, and the gas reaching the standard is discharged from an upper gas outlet 10; in the working process, hydrogen peroxide stored in a liquid storage tank 13 is blown into the reaction tank 9 from a liquid inlet 11 through a circulating pump 12 to supply water lost due to evaporation in discharging, and meanwhile, the absorption liquid inactivated due to reaction in the step 1 is activated, wherein a liquid level detector 6 judges the amount of the regenerated liquid needing to be supplemented; after the system operates for a period of time, the desulfurized absorption liquid flows out from the bottom of the reaction tank 9, the sulfur simple substance enters the solid tank 15 after solid-liquid separation by the filtering system 14, and the residual absorption liquid returns to the reaction tank 9 again for continuous use.
Example 1
The marsh gas enters a reaction tank 9 from a gas collecting and distributing port 8 through a fan 7, and the reaction tank contains Fe3+The absorption liquid can rapidly absorb the hydrogen sulfide in the methane; starting the high-voltage direct-current power supply 1, immersing the high-voltage electrode 3 into the liquid level of the absorption liquid for 3mm to directly discharge the liquid phase, and discharging the gas reaching the standard from a gas outlet 10 above; in the working process, hydrogen peroxide stored in a liquid storage tank 13 is blown into the reaction tank 9 from a liquid inlet 11 through a circulating pump 12, and the liquid level detector 6 judges the amount of the regeneration liquid required to be supplemented.
Example 2
The marsh gas enters a reaction tank 9 from a gas collecting and distributing port 8 through a fan 7, and the reaction tank contains Fe3+The absorption liquid can rapidly absorb the hydrogen sulfide in the methane; starting a high-voltage direct-current power supply 1, enabling a low-voltage end to extend into the liquid level of the absorption liquid, enabling a high-voltage electrode 3 to be immersed into the liquid level of the absorption liquid for 5mm to directly discharge a liquid phase, and discharging gas reaching the standard from a gas outlet 10 above; in the working process, hydrogen peroxide stored in a liquid storage tank 13 is blown into the reaction tank 9 from a liquid inlet 11 through a circulating pump 12, and the liquid level detector 6 judges the amount of the regeneration liquid required to be supplemented.
Example 3
The marsh gas enters a reaction tank 9 from a gas collecting and distributing port 8 through a fan 7, and the reaction tank contains Fe3+The absorption liquid can rapidly absorb the hydrogen sulfide in the methane; starting a high-voltage direct-current power supply 1, immersing a high-voltage electrode 3 into the liquid level of the absorption liquid for 4mm to directly discharge liquid phase, and discharging the gas reaching the standard from a gas outlet 10 above; in the working process, hydrogen peroxide stored in a liquid storage tank 13 is blown into the reaction tank 9 from a liquid inlet 11 through a circulating pump 12, the liquid level detector 6 judges the amount of the regenerated liquid to be supplemented, after the system runs for a period of time, the desulfurized absorption liquid flows out from the bottom of the reaction tank 9, the sulfur simple substance enters a solid tank 15 after solid-liquid separation of a filtering system 14, and the residual absorption liquid returns to the reaction tank 9 again for continuous use.
In addition, the voltage, Fe, during system operation3+Amount of addition H2O2The parameters such as the supply speed and the like can be adjusted according to the methane volume and the hydrogen sulfide content to be processed. When the gas flow is low and the concentration is low, the device is operated under low load, when the gas flow is large and the concentration is high, the power supply voltage is increased, and simultaneously more Fe is added3+And H2O2High load operation is realized. The method is widely applicable to biogas desulfurization projects of different scales and different categories.
Claims (9)
1. An integrated biogas desulfurization device is characterized by comprising a reaction tank (9) for containing absorption liquid, wherein an air outlet (10) is formed in the upper side of the reaction tank, an air collecting and distributing port (8) is formed in the lower side of the reaction tank, the air collecting and distributing port (8) is connected with a fan (7) outside the reaction tank (9), a high-voltage electrode (3) and a low-voltage end (5) are arranged in the reaction tank (9), one end, which is not immersed in the liquid level, of the high-voltage electrode (3) is connected with the positive electrode of a high-voltage direct-current power supply console (1) through a high-voltage lead (2), and the other end, which is not immersed in the liquid level, of the low-voltage end (; the high-voltage electrode (3) is immersed below the absorption liquid level and does not exceed 3mm, and the low-voltage end (5) extends below the liquid level.
2. An integrated biogas desulfurization device according to claim 1, wherein the high voltage electrode (3) is a needle-shaped high voltage electrode, the exterior of which is wrapped with an insulating rubber sleeve (4), and the low voltage end (5) is a conductive copper rod.
3. The integrated biogas desulfurization device according to claim 1, wherein a liquid inlet (11) is provided at the lower side of the reaction tank (9) relative to the side of the gas collection and distribution port (8), and a circulating pump (12) and a liquid storage tank (13) are sequentially connected to the outer side of the liquid inlet (11).
4. An integrated biogas desulfurization device according to claim 3, characterized in that the bottom of the reaction tank (9) is provided with a filtering system (14) for solid-liquid separation, which is divided into two branches outside the reaction tank (9), one end of which is connected with the solid tank (15) and the other end of which is connected with the circulating pump (12).
5. The integrated biogas desulfurization device according to claim 1, wherein the surface of the reaction tank (9) is coated with an epoxy resin insulation layer, the bottom is provided with an insulation pad (17), and the side surface of the inner wall is provided with a liquid level detector (6).
6. An integrated biogas desulfurization method according to any one of claims 1 to 5, characterized by comprising the steps of,
step 1, methane enters a reaction tank (9) from a gas collection and distribution port (8) through a fan (7), and hydrogen sulfide in the methane is rapidly absorbed by absorption liquid;
and 2, starting the high-voltage direct-current power supply, directly discharging the high-voltage electrode (3) to the liquid phase, generating strong oxidizing substances around the electrode, further deeply treating hydrogen sulfide, and discharging the treated methane from the gas outlet (10).
7. The integrated biogas desulfurization method according to claim 6, wherein the regeneration liquid stored in the liquid storage tank (13) is blown into the reaction tank (9) from the liquid inlet (11) through the circulating pump (12) to replenish the water lost by the discharge evaporation in the step 2 and simultaneously activate the absorption liquid inactivated by the reaction in the step 1; wherein the liquid level detector (6) judges the amount of the regeneration liquid needing to be supplemented.
8. The integrated biogas desulfurization method according to claim 6, wherein the desulfurized absorption liquid flows out from the bottom of the reaction tank (9), the solid and liquid are separated by the filtration system (14), the elemental sulfur enters the solid tank (15), and the residual absorption liquid returns to the reaction tank (9).
9. The integrated biogas desulfurization method of claim 6, wherein the absorption liquid is an oxidizing liquid containing ferric ions, and the regeneration liquid is a hydrogen peroxide liquid.
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| CN101239278A (en) * | 2008-03-07 | 2008-08-13 | 黄立维 | Device for cleaning treatment harmful gas and technique thereof |
| CN106398790A (en) * | 2016-06-23 | 2017-02-15 | 西南石油大学 | A hydrogen sulfide removing device and method for natural gas |
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| CN2535115Y (en) * | 2002-04-01 | 2003-02-12 | 广东杰特科技发展有限公司 | Vertical streamer-discharge flue gas desulfurizing wet reactor |
| CN102512926B (en) * | 2011-12-27 | 2014-03-12 | 浙江工业大学 | Method for removing sulfuryl fluoride by coupling plasma and chemical absorbing |
| JP2014188497A (en) * | 2013-03-28 | 2014-10-06 | Taiyo Nippon Sanso Corp | Detoxification treatment apparatus and detoxification treatment method |
| CN203610027U (en) * | 2013-09-30 | 2014-05-28 | 浙江大学 | Integrated purification device for gaseous pollutants |
| CN103864185B (en) * | 2014-02-20 | 2015-09-30 | 中国石油大学(华东) | The efficient Quick Oxidation of glow discharge is utilized to fix method and the device thereof of arsenic in waste water |
| CN108130147A (en) * | 2017-12-27 | 2018-06-08 | 山东明硕新能源科技有限公司 | A kind of biogas desulfurization purifier |
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| CN101239278A (en) * | 2008-03-07 | 2008-08-13 | 黄立维 | Device for cleaning treatment harmful gas and technique thereof |
| CN106398790A (en) * | 2016-06-23 | 2017-02-15 | 西南石油大学 | A hydrogen sulfide removing device and method for natural gas |
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