WO2009140970A1 - Procédé et système de purification et de désodorisation de gaz de refoulement provenant d'installations de production de déchets organiques - Google Patents

Procédé et système de purification et de désodorisation de gaz de refoulement provenant d'installations de production de déchets organiques Download PDF

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Publication number
WO2009140970A1
WO2009140970A1 PCT/DK2009/050113 DK2009050113W WO2009140970A1 WO 2009140970 A1 WO2009140970 A1 WO 2009140970A1 DK 2009050113 W DK2009050113 W DK 2009050113W WO 2009140970 A1 WO2009140970 A1 WO 2009140970A1
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WIPO (PCT)
Prior art keywords
absorption
absorbing agent
column
gas
liquid
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PCT/DK2009/050113
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English (en)
Inventor
Jan Johnsen
Steffen G. Christensen
Peter Ravn
Preben Jensen Dahl
Hisamitsu Takai
Hitoshi Ogawa
Original Assignee
Aarhus Universitet
Tamagawa University, College Of Agriculture
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Priority to JP2011511977A priority Critical patent/JP2011520610A/ja
Publication of WO2009140970A1 publication Critical patent/WO2009140970A1/fr

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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
    • B01D53/14—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 absorption
    • B01D53/1406—Multiple stage absorption
    • 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
    • B01D53/346—Controlling the process
    • 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
    • B01D53/54—Nitrogen compounds
    • B01D53/58—Ammonia
    • 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
    • B01D53/73—After-treatment of removed components
    • 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
    • B01D53/75—Multi-step processes
    • 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
    • B01D53/84—Biological processes
    • 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
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/104—Ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/406—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/804—UV light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/06—Aerobic processes using submerged filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the present invention relates to a method for purifying a gas comprising pollutants by an absorption process combined with biological purification processes, through which the pollutants absorbed in the aqueous absorbing agent will degrade to biomass, water and CO 2 . In cases where low molecular weight nitrogen containing compounds, such as ammonia, is present in the gas, said compounds will be reduced to N 2
  • the present invention also relates to a system adapted for performing the method according to the present invention, and uses of the method to purify gases as those which may be found in livestock buildings.
  • the odours and gasses emitted are by-products of the microbial decomposition of manure and other organic matter.
  • the amount and type of emission depends on the amount and type of microbial activity.
  • Over 160 compounds have been identified in odours from swine operations. The principal constituents are ammonia, amines, sulphur containing compounds, volatile fatty acids, indoles, skatoles, phenols, alcohols and carbonyls.
  • microorganisms utilize the odorous molecules as a source of nutrients and energy for growth, producing more biomass and carbon dioxide, water, and minerals, such as sulphates and nitrates. In this way the microorganisms convert organic and certain inorganic compounds to less toxic and odourless compounds.
  • odours compounds e.g. flow rate, volume, concentration, solubility, intensity, temperature, oxygen content
  • site characteristics e.g. operation, maintenance capabilities.
  • the physical and chemical methods have a high efficiency but are expensive due to their consumption of a large amount of chemicals, demand labour control and maintenance of equipment.
  • Biological methods are cost efficient, has general high reduction efficiency and are environmentally acceptable. They are able to effectively remove a wide range of biodegradable pollutants at low concentration in the gas flow and can be used under ambient pressure and temperature and therefore the energy consumption and maintenance requirements are relatively low. Biological systems are often easy to operate and have a relatively low consumption of chemicals.
  • Bioscrubbers have been successfully used in many industrial and agricultural applications, and their use is growing.
  • a bioscrubber consists of two units: an absorption column (air wet scrubber) and a bioreactor (water purification unit). The principle is based on physical separation or absorption of gaseous compounds in the aqueous washing phase in an absorption column followed by microbiological purification treatment in a second stage in the bioreactor. Subsequently, the purified liquid phase effluent is recirculated to the absorption column.
  • wet scrubbers include packed towers, wet cyclone, spray tower and venture scrubber.
  • bioscrubbers make it possible to dimension each part separately. If the inlet volume or concentration of polluted gas are increasing or the effluent emission standards are decreased and the wet scrubber capacity is sufficient, then additional bioreactor modules can be added to the water purification unit, and thereby increasing the bioreactor volume and hence the biodegradation capacity separately from the absorption column.
  • the absorption column In the livestock building, the absorption column is typically placed inside the ventilation chimney, whereas the bioreactor is placed for example at floor level.
  • odour substances odorants
  • ammonia and dust particles are absorbed by water droplets. Water droplets are provided to the absorption column through water nozzles, who receive water recycled from the bioreactor.
  • the bioreactor can receive and supply purified water for several absorption columns.
  • bioscrubbers possess many advantages as compared with other bioreactors, the main disadvantage of these systems is that they are only suitable for use in the treatment of gasses, which comprises compounds having a high solubility in water. Hence, there is a need to improve the method in order to increase the solubility of the pollutants in the absorbing agent, thereby making the method more efficient.
  • the present invention solves this problem by carefully controlling the pH of the aqueous absorbing agent throughout the absorption column and by controlling the size of the liquid droplets of absorbing agent in the absorption column.
  • the method does not produce chemical waste and it requires only limited amount of water to be added to compensate the loss of absorbing agent due to evaporation. Essentially all liquid absorbing agent is purified to such an extent that reuse of the absorbing agent is possible. Hence, the method provides a closed system, in which essentially all absorbing agent is recirculated to the absorption column and consequently no spent absorbing agent needs to be disposed of.
  • the present inventors have developed a new concept for a wet scrubber, which can treat a large volume of ventilation air with significantly less pressure drop as compared to known systems. It provides an environment friendly way to purify and deodorise the discharge gases from organic waste producing facilities.
  • This new type of wet scrubber will comprise one or more absorption columns preferably mounted in ventilation stacks and a central liquid purification unit.
  • absorption columns odorous components and ammonia in the ventilation air are absorbed in aqueous droplets, which also capture dust particles.
  • the absorption columns are supplied with purified aqueous absorbing agent from the central liquid purification unit.
  • the absorption column may be divided into at least two absorption zones. In each absorption zone the pH of the aqueous absorbing agent as well as the size of the droplets and spray rate of the absorbing agent is carefully controlled.
  • the liquid purification unit comprises a number of bioreactors and tanks with different functions such as for example degassing, sedimentation, sludge separation, flow adjustment and control.
  • the aqueous absorbing agent loaded with pollutants is collected at the bottom of the absorption column, from where the liquid is transferred to an adjustment tank.
  • a part of the liquid from the adjustment tank is recirculated to the first absorption zone located near the bottom of the absorption column, whereas another part of the liquid from the adjustment tank is transferred to a sequence of bioreactors.
  • the recirculated absorbing agent from the adjustment tank enters the absorption column by means of high-flow- rate spray nozzles, whereby relatively large droplets are formed.
  • the liquid is treated alternatively anaerobic and aerobic.
  • the organic compounds absorbed in the aqueous absorbing agent are degraded to biomass, water and carbon dioxide.
  • the low molecular weight nitrogen containing compounds, primarily ammonia, absorbed from the gas to be purified and the ammonia as an intermediate product of degradation process of nitrogen containing organic compounds are reduced to N 2 through the nitrogen cycle.
  • the ammonia absorbed from the feeding gas causes an increase in pH of the absorbing agent, while absorbed gaseous acids and the nitrification process causes a decrease in pH of the absorbing agent.
  • Degradation of the dusts and other compounds may cause either increasing or decreasing pH values and it may produce compounds providing liquid buffer effect.
  • the absorbing agent When reaching the last bioreactor in the sequence of bioreactors, the absorbing agent is recirculated to the second absorption zone located at the top of the absorption column, and enters the column as relatively small droplets by means of spray nozzles. Additionally, aqueous absorbing agent from one or more of the bioreactors or from the adjustment tank may be recirculated to absorption zones located between the first and second absorption zones, depending on pH of the aqueous absorbing agent and the pH wished for in a particular absorption zone of the column.
  • the absorption column may have a number of structured packing elements mounted at different heights.
  • the packing elements may be special designed concerning angle and height of the guide plate and distance between guide plates to improve absorption efficiency and at the same time to limit the pressure drop of the airflow.
  • the absorption column may be washed periodically preferably by using liquid supplied by the liquid purification unit to keep the column free of uncontrolled growth of biofilms, which may emit malodour.
  • an oxidising agent is injected into the aqueous absorbing agent and sprayed in the absorption column. In some cases an oxidising agent is injected directly in the absorption column by nozzle(s).
  • gas and absorbing agent may advantageously be further subjected to means of irradiation.
  • the new system is capable of providing absorbing agent with different pH values without using additives. This can be done by absorbing ammonia and nitrogen containing organic compounds from the feeding gas in the absorbing agent and by producing acids through the biological purification of the absorbing agent. If the feeding gas does not contain enough amounts of ammonia and nitrogen containing organic compounds, urea can be added in the bioreactors to enable generation of absorbing agent with different ph values.
  • the system does not produce chemical waste and it requires only limited amount of water to be added to compensate the loss of absorbing agent due to evaporation.
  • the method provides a closed system, in which essentially all absorbing agent is re-circulated to the absorption column and consequently no spent absorbing agent needs to be disposed of.
  • a novel method based on the above described new concept is provided for purifying gases comprising pollutants.
  • a second aspect of the present invention provides a system especially adapted for performing the method of the present invention, whereas a third aspect relates to uses of the present method for the treatment of gases in order to obtain purified gases.
  • Figure 1 shows an absorption column (Version 1 ) comprising four spraying stages (A designates stage 1 , B designates stage 2, C designates stage 3 and D designates stage 4) and two absorption zones (E designates the first absorption zone and F designates the second absorption zone).
  • the absorption column further comprises a fan (G), a droplet separator (H), flow meters (I) and strainers (J).
  • the discharge air from a livestock building is entering the absorption column at point a, the cleaned air leaves the absorption column at point b, and the water to be purified in the purification unit leaves the absorption column at point c.
  • FIG. 2 shows a liquid purification unit (Version 1 ) comprising an adjustment tank/ sedimentation tank (0), an anaerobic tank (1 ) an aerobic tank (2), an anaerobic tank (3), an aerobic tank (4), an anaerobic tank (5), an aerobic tank (6), an ozone water generator (7), which comprises an injector (8) and a head-space (9), an ozone generator (10), a sedimentation tank (11 ), a sedimentation/degassing tank (12) and pumps (13).
  • Version 1 comprising an adjustment tank/ sedimentation tank (0), an anaerobic tank (1 ) an aerobic tank (2), an anaerobic tank (3), an aerobic tank (4), an anaerobic tank (5), an aerobic tank (6), an ozone water generator (7), which comprises an injector (8) and a head-space (9), an ozone generator (10), a sedimentation tank (11 ), a sedimentation/degassing tank (12) and pumps (13).
  • FIG. 3 is a sketch of structured packing element. The figure shows the absorption column wall (30), a guide plate (31 ), a guide plate holder (32), a guide plate angle (33), a guide plate height (34) and an installation angle (35).
  • Figure 4 shows an absorption column (version 2) comprising four spraying stages (A designates stage 1 , B designates stage 2, C designates stage 3 and D designates stage 4), a fan (G), a droplet separator (H), flow meters (I) and an ozone generator (K).
  • A designates stage 1
  • B designates stage 2
  • C designates stage 3
  • D designates stage 4
  • G fan
  • H droplet separator
  • I flow meters
  • K ozone generator
  • Figure 5 shows a liquid purification unit (Version 2) comprising an adjustment tank (20), a high-flow-rate biofiltration reactor (21 ), a blower (22), an anerobic/anoxic bioreactor (23), an aerobic bioreactor (24), a sedimentation/degassing tank (25), pumps (13) and pump & strainer (14).
  • Version 2 a liquid purification unit comprising an adjustment tank (20), a high-flow-rate biofiltration reactor (21 ), a blower (22), an anerobic/anoxic bioreactor (23), an aerobic bioreactor (24), a sedimentation/degassing tank (25), pumps (13) and pump & strainer (14).
  • the contaminated spray water from the absorption column enters the purification unit at point d, and leaves the purification unit after treatment at point e, f, g, or h, so that the water leaving the purification unit at point e is returned to the absorption column at stage 1 (A), the water leaving the purification unit at point f is returned to the absorption column at stage 2 (B), the water leaving the purification unit at point g is returned to the absorption column at stage 3 (C), and the water leaving the purification unit at point h is returned to the absorption column at stage 4 (D).
  • FIG. 1 shows an absorption column (Version 1 ) comprising four spraying stages is shown, whereas figure 2 shows a liquid purification unit (Version 1 ) comprising an adjustment/sedimentation tank (0), a sedimentation tank (1 1 ), a sedimentation/degassing tank (12) and three aerobic bioreactors (2, 4 and 6), three anaerobic bioreactors (1 , 3 and 5), an ozone water generator (7), and an ozone generator (10).
  • Figure 3 shows a sketch of the preferred structured packing elements
  • figure 4 and 5 show the at present most preferred embodiment of the invention.
  • FIG 4 an absorption column (Version 2) comprising four spraying stages is shown, and an ozone generator (K) is connected to the column.
  • Figure 5 shows a liquid purification unit (Version 2) comprising an adjustment tank (20), a high-flow-rate bio- filtration reactor (21 ), a blower (22), a sedimentation/degassing tank (25), an anaerobic/anoxic bioreactor (23) and an aerobic bioreactor (24).
  • the present invention provides a method for purifying and deodorising a gas comprising pollutants.
  • the gas to be purified is fed through an inlet near the bottom of an absorption column and then the gas is brought into contact with aqueous absorbing agent in a first absorption zone located near the bottom of the absorption column and in a second absorption zone located at the top of the absorption column.
  • a purified and deodorised gas leaving the top of the column is obtained.
  • Aqueous absorbing agent is collected at the bottom of the absorption column and transferred to an adjustment tank in a liquid purification unit.
  • the liquid purification unit comprises a sequence of bioreactors, in which biological liquid purification take place.
  • Part of the absorbing agent from the adjustment tank is recirculated to the first absorption zone, whereas another part of the absorbing agent from the adjustment tank is transferred to the first bioreactor in the sequence of bioreactors.
  • the absorbing agent is purified by transferring the agent through the sequence of bioreactors, and finally absorbing agent from the last bioreactor in the sequence of bioreactors is transferred to the second absorption zone located at the top of the absorption column.
  • absorbing agent water, in which pollutants (such as for example ammonia) present in the gas to be purified is absorbed.
  • pollutants such as for example ammonia
  • the absorbing agent may or may not have been subjected to the biological purification processes taking place in the sequence of bioreactors of the liquid purification unit.
  • the biological purification processes due to the action of the biological purification processes and absorption of pollutants mainly ammonia, dusts and some gaseous acids in the absorbing agent, different pH levels of the absorbing agent can be obtained.
  • Absorption of ammonia causes increase in pH value of the absorbing agent, while absorbed gaseous acids and the nitrification process causes decrease in pH of the absorbing agent.
  • Degradation of the dusts and other compounds may cause either increasing or decreasing pH values.
  • the biological purification processes may also produce compounds providing the liquid buffer effect. Therefore, pH of absorbing agent transferred to the first absorption zone will always be higher than pH of the absorbing agent transferred to the second absorption zone in the absorption column.
  • the gas to be purified comprises ammonia.
  • Ammonia is a base and, consequently, the efficiency for aqueous absorbing agent to absorb ammonia increases as pH decreases. Therefore, pH of the absorbing agent in the top of the absorption column, where the very last residues of ammonia is removed from the gas, must be neutral or preferably weakly acidic in order to obtain a satisfactory degree of purification. In conventional absorption methods acids are added to the absorbing agent. However, this is not necessary in the present method as the purification unit is capable to supply absorbing agent with desired pH values.
  • the absorbing agent recirculated to the top of the absorbing column should be the absorbing agent, which has been purified for the longest period of time, in order to reach as low a pH value as possible. By this mode of operation pH is decreasing through out the column in such a way that pH in the lower part of the column is higher than pH in the top of the column.
  • the gas to be purified may also comprise odorants and dust. Depending on the chemical and physical property of the odorants present in the gas, these compounds may be absorbed in the absorption column at the location, where the chemical conditions are most suitable for absorption.
  • the dust is typically absorbed in the lowest part of the column, where pH typically is slightly alkaline. If the gas originates from a livestock building pathogens may also be present in the gas. Depending on the type of pathogen, these may be absorbed either at a specific pH value and hence at a specific location in the column or they may be absorbed through out the whole length of the column.
  • the gas to be purified in the method according to the present invention originates from a livestock building.
  • the absorbing agent enters the absorption column as liquid droplets.
  • the droplets are preferably smaller in the top of the absorption column, where only the very last traces of pollutants are to be removed, than in the lower part, where large amounts of pollutants are to be absorbed, and where the concentration of pollutants in the gas is only expected to be reduced to a certain level.
  • the absorbing agent enters the first absorption zone near the bottom of the absorption column as liquid droplets having a median diameter of 50 to 5000 ⁇ m, more preferred of 100 to 4000 ⁇ m, whereas the absorbing agent enters the second absorption zone at the top of the absorption column as liquid droplets having a median diameter of 10 to 500 ⁇ m, more preferred 100 to 300 ⁇ m.
  • the ratio between liquid and gas weight is an important parameter influencing gas purification efficiency.
  • the greater liquid to gas ratio the higher purification efficiency can be obtained.
  • the method of the present invention re-circulates a large part of the absorbing agent from the adjustment tank to the first absorption zone. By this way the system capacity for the biological purification, which is a relative slow process, is considerably reduced.
  • the liquid to gas weight ratio lies in the range of 1 to 10 when the total weight of the liquid sprayed is divided by the weight of the gas purified by the liquid.
  • the ratio lies in the range of 0.1 to 1 , when the weight of liquid that has passed through the biological purification process is divided by the weight of the gas purified. This is economically very beneficially as the less liquid to be treated in the biological purification process the smaller the liquid purification unit can be. Hence, the feasibility of the method is strongly influenced by this ratio.
  • the method provides a closed system, in which essentially all absorbing agent is recirculated to the absorption column and consequently no spent absorbing agent needs to be disposed of. Therefore, only limited amount of water is needed to be added to the system to compensate the loss of absorbing agent due to evaporation. Evaporation of the absorbing agent occurs in the absorption column and in the liquid purification unit. The rate of evaporation depends on temperature and relative humidity of the air to which the liquid is exposed.
  • pH of the absorbing agent is carefully controlled throughout the absorption column and the purification unit.
  • pH of the absorbing agent transferred to the adjustment tank of the purification unit lies in the range of 5 - 11
  • pH of the absorbing agent recirculated to the first absorption zone lies in the range of 4 - 10
  • pH of the absorbing agent recirculated to the second absorption zone lies in the range of 3 - 9.
  • urea can be added in the bioreactors to enable generation of absorbing agent with different pH values. Using urea as additive in stead of acids is preferred due to lower price compared with acids. The process mentioned herein does not produce chemical waste.
  • the oxidising agent may be added to and mixed with absorbing agent from one or a number of the bioreactors of the liquid purification unit. In addition to the deodorising effect, oxidation is an effective disinfection method and it can be used to eliminate possible pathogens in the absorption columns.
  • the oxidising agent may be any chemical oxidising agent known in the art.
  • the oxidising agent is ozone.
  • the gas and absorbing agent may advantageously be further subjected to means of irradiation in order to prevent undesired growth of biofilms on the surfaces inside the absorption column and to promote the elimination of pathogens.
  • means of irradiation may be used, but ultraviolet (UV) radiation is preferred.
  • microorganism may grow and form a biofilm on said packing elements.
  • These microorganisms are either added to the column on purpose, or they may enter the column together with the gas to be purified or as suspended material in the absorbing agent and then settle and grow on the packing element. A skilled person would know how to generate such a biofilm.
  • the absorption column is therefore washed regularly by using the absorbing agent from the liquid purification unit to keep the absorption column free of biofilm.
  • This strategy makes the present method easier for a non-specialist, e.g. a farmer, to operate.
  • the absorption column is washed regularly as used herein is meant that the column is washed as often as necessary in order to keep the growth of the biofilm at the desired low level. It lies within the skills of an ordinary practitioner to evaluate when the column should be washed.
  • the amount of pollutant removed from the gas stream may depend on the type and amount of pollutants in the feeding gas as well as the exact chemical and physical composition of the feeding gas. Preferably, however, the amount of ammonia in the gas to be purified may be reduced by at least 80%. Furthermore, if odorants and dust are also present the amount of those compounds is preferably reduced by at least 40% and 80%, respectively.
  • the method may comprise one or more additional steps. More particularly, the method of the present invention may comprise a further step, in which the gas to be purified is also brought in contact with absorbing agent in one or more absorption zones located between the first absorption zone and the second absorption zone in the absorption column. In such cases, the method also comprises the further step of transferring absorbing agent from the adjustment tank or from one or more of the bioreactors in the purification unit to said one or more absorption zones located between the first and the second absorption zone in the absorption column. Preferably, the absorbing agent is transferred from one or more bioreactors located between the first and the last bioreactors to said one or more absorption zones located between the first and the second absorption zones in the column.
  • the absorbing agent enters the absorption column as liquid droplets having a median diameter lying in the range of 10 - 5000 ⁇ m.
  • the pH of said absorbing agent is equal to pH of the absorbing agent entering the first absorption zone or more preferred pH lies in the range between pH of the absorbing agent entering the first absorption zone and pH of the absorbing agent entering the second absorption zone.
  • a system for purifying a gas comprising pollutants is also provided by the present invention.
  • This system comprises an absorption column having a first absorption zone located near the bottom of the absorption column and a second absorption zone located above the first absorption zone at the top of the absorption column.
  • Each of said absorption zones is provided with means for inlet of absorbing agent into the absorption column.
  • the system further comprises a liquid purification unit, in which the absorbed pollutants are removed from the absorbing agent by biochemical degradation due to the action of microorganisms.
  • liquid outlet and the liquid inlets of the absorption column are fluidly connected to the liquid purification unit.
  • the liquid purification unit comprises a sequence of bioreactors. These bioreactors are fluidly connected. Preferably, the bioreactors are connected in series. By this configuration, the absorbing agent flows from one reactor to the next reactor. As the degree of purification increases from bioreactor to bioreactor, the pH of the absorbing agent changes from bioreactor to bioreactor due to the biological degradation processes as discussed above.
  • the liquid purification unit comprises an adjustment tank for receiving absorption agent collected at the bottom of the column and for controlling the liquid flow and a last bioreactor for providing absorbing agent to the second absorption zone of the column.
  • the adjustment tank is fluidly connected to a high-flow-rate bio-filtration reactor.
  • the adjustment tank is an adjustment/sedimentation tank.
  • the absorption column may further comprise one or more absorption zones located between the first and the second absorption zone in the absorption column, and each of said one or more absorption zones are fluidly connected to the adjustment tank or to one or more of the bioreactors in the liquid purification unit.
  • This configuration has the advantage of providing more than two absorption zones in the column.
  • Each absorption zone is characterised by having a specific pH level in order to optimise the absorption process as described above.
  • the aqueous liquid is supplied to the absorption column as liquid droplets.
  • the means for inlet of absorbing agent is provided with nozzles.
  • the means for inlet of absorbing agent in the first absorption zone is provided with high-spray-rate nozzles, because such nozzles provide droplets of the preferred size and spray rate at this location.
  • the high-spray-rate nozzles are spiral spray nozzles.
  • the means for inlet of absorbing agent in the second absorption zone is provided with nozzles, which are capable of forming droplets with median diameters lying in the range of 10 - 500 ⁇ m.
  • Most preferred nozzles are hollow cone spray nozzles. More than one nozzle may be present at each absorption zone. When more than one nozzle is present, said nozzles are preferably arranged in a grid.
  • the absorption column may be packed with structured packing elements mounted between the first and the second absorbing zones in the absorption column in order to improve the absorption efficiency of pollutants in the absorbing agent. This is achieved by changing the direction of the gasflow passing through the packing elements resulting in increased velocity and flow direction differences between gas and droplets and thereby increased absorption efficiency.
  • the packing elements also contribute to improvement of absorption efficiency by adsorbing the liquid on their surfaces.
  • the absorbing agent adsorbed on the surfaces of the packing elements absorbs pollutants. And, the liquid flows downward on the surfaces and forms relatively large droplets when it drops down from down side edge of the packing elements, which results in increased droplet surface and velocity and flow direction differences between gas and droplets.
  • the structured packing elements developed for the present invention has guide plate angles ranging from 5 to 20 degree, which are meant to change the gasflow direction of the gas passing through the packing elements and at the same time to limit the pressure drop of the gasflow.
  • the guide plate heights and the distances between the guide plates range from 5 to 200 mm, depending on the desired surface area, number of droplet generation edges, frequency of the flow direction changes and cleaning/washing convenience.
  • the installation angle can be differed from one packing element to other to optimize the gasflow.
  • a biofilm may be growing on the surface of the packing material.
  • This biofilm may be formed as a result of microorganisms originating from the purification unit, which have entered the absorption column together with recirculated absorbing agent, the microorganism may have entered the column together with the feeding gas, or the microorganisms may have been added to the column on purpose in order to form the biofilm. If a biofilm is present, the degradation of the pollutant in the gas may already commence when the gas passes through the column. In this way the rate and efficiency of purification in the system is increased.
  • the absorption column free of biofilms is preferred.
  • a number of nozzles can be installed inside the absorption column to enable automated spray washing by using water supplied by the liquid purification unit.
  • the absorption column can be washed several times during a day so that the sediments on the surfaces are washed out regularly and transferred to the liquid purification unit.
  • the system may additionally comprise an oxidation unit, which may be connected with the absorption column and/or one or more of the bioreactor(s) in the liquid purification unit.
  • the oxidation unit preferably continuously generates an oxidising agent, which is then added to the absorbing agent.
  • This oxidation unit is preferably included in the system in cases where the gas comprises pollutants, which are difficult to degrade by the microorganisms in the purification unit. In such cases pollutants may be fully degraded by the oxidising agent, or the pollutants may be degraded to intermediate products, which subsequently may be absorbed and degraded by the microorganisms in the purification unit.
  • the oxidising agent is injected directly in the absorption column by nozzles in cases where the gas comprises pollutants, which are difficult to absorb in absorbing agent.
  • oxidisation is an effective disinfection method and it can be used to eliminate possible pathogens in the absorption columns.
  • the oxidising unit is an ozone generator.
  • the system may in addition to the oxidation unit further comprise means for providing irradiation in the absorption column as inhibitor for undesired growth of biofilms on the surfaces inside the absorption column and to promote the elimination of pathogens.
  • means for providing irradiation is means for providing ultraviolet (UV) radiation.
  • the system according to the present invention may further comprise a sedimentation tank for collection of sediments and/or a degassing tank for removal of gas bubbles from the liquid before pumping the liquid.
  • the method according to the present invention may be used to purify gases comprising more than 1 ppm ammonia. Most preferred, the method according to the present invention is used for purifying gases originating from livestock buildings.
  • the absorption column (Version 2) and the liquid purification unit (Version 2), which are used for the (at present) most preferred system for performing the purification method according to the present invention is shown in figure 4 and 5, respectively.
  • the absorption column has four spraying stages each comprising nozzles to be used as means for inlet of absorbing agent.
  • the first and the second spraying stages located at the lower part of the absorption column are provided each with one spiral spray nozzle having a spray rate of about 30 l/min at 4 atm.
  • spraying stages 3 and 4 are located at the upper part of the absorption column.
  • Each of the spray stages 3 and 4 is provided with 4 hollow cone spray nozzles arranged in a grid.
  • the spray rate of one hollow cone spray nozzle is about 0.5 l/min at 4 atm.
  • Three piles each composed of four structured packing elements are placed above the spraying stage 2, beneath the spraying stage 3 and 4, respectively.
  • a droplet separator is installed at the top of the absorption column. Ozone gas is directly injected in the absorption column at a point between spraying stage 2 and 3 by a nozzle.
  • the gas to be purified is fed to the absorption column by a ventilator installed in the horizontal duct, and is pressed through the absorption column.
  • the gas leaves the column through the top.
  • Absorbing agent is entering the absorption column at four different heights (stage 1 , 2, 3 and 4), as indicated in the figure, and leaves the column at the bottom, and is then transferred to the adjustment tank in the liquid purification unit.
  • the pH value of the absorbing agent in the adjustment tank lies above 7.
  • the liquid purification unit consists of an adjustment tank, a high-flow-rate biofiltration reactor, an anaerobic/anoxic bioreactor, an aerobic bioreactor and a sedimentation/degassing tank.
  • the absorbing agent collected at the bottom of the absorption column flows to the adjustment tank, from which the absorbing agent is pumped up to the top of a high-flow-rate bio-filtration reactor.
  • the major part of the absorbing agent returns to spraying stage 1 and 2.
  • a minor part of the filtered absorbing agent from the bio-filtration reactor is treated further by flowing through the anaerobic/anoxic bioreactor, the aerobic bioreactor and the sedimentation/degassing tank.
  • the purified absorbing agent is transferred to the spraying stages 3 and 4.
  • the rest of the absorbing agent from the bio-filtration reactor returns to the adjustment tank.
  • biomass is produced. At a point said bacteria will die and then sediment in the bioreactors. If not removed from the bioreactors, eventual the biomass will take up all space in the bioreactor. Therefore, sediment is continuously recirculated to anaerobic/anoxic bioreactor, wherein the dead biomass is used as nutritients for the further growing of bacteria.
  • the gas entering the absorption column was a gas having an ammonia concentration of 22 ppm and an odour concentration of 1200 European odour unit (ou E/m 3 ).
  • the liquid to gas weight ratio was 6.5 when the liquid sprayed at all four spraying stages was taken in account and the ratio was 0.55 when only the liquid sprayed at spraying stages 3 and 4 was taken in account, i.e. when the weight of the liquid that has passed through the biological purification process was divided by the weight of the gas purified by the liquid.
  • the reaction time for absorbing pollutants in the absorbing agent was estimated to 1.9 seconds. No ozone was supplied in this specific experiment.
  • the concentration of ammonia in the gas at the outlet was 1 ppm, whereas the concentration of odorants was 700 ou E/m 3 . This mounts to a reduction of ammonia of 95% and a reduction of odorants of 42%.
  • the gas entering the absorption column was a gas having an ammonia concentration of 20 ppm and an odour concentration of 1200 ou E/m 3 .
  • the liquid to gas weight ratio was 6.2 when the liquid sprayed at all four spraying stages was taken in account and the ratio was 0.53 when only the liquid sprayed at spraying stages 3 and 4 was taken in account, i.e. when the weight of the liquid that has passed through the biological purification process was divided by the weight of the gas purified by the liquid.
  • the reaction time for absorbing pollutants in the absorbing agent was estimated to 1.8 seconds.
  • Ozone was injected directly in the absorption column at a point between spraying stages 2 and 3.
  • the concentration of ammonia in the gas at the outlet was 1 ppm, whereas the concentration of odorants was 160 ou E/m 3 . This mounts to a reduction of ammonia of 90% and a reduction of odorants of 87%.

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  • Gas Separation By Absorption (AREA)
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Abstract

La présente invention concerne un procédé de purification d’un gaz comprenant des polluants par un procédé d’absorption combiné à des procédés de purification biologique. Les polluants absorbés dans l’agent d’absorption aqueux vont être dégradés en biomasse, en eau et en CO2. La présente invention concerne également un système conçu pour mettre en oeuvre le procédé de la présente invention et les utilisations du procédé pour purifier des gaz tels que ceux que l’on peut trouver dans les bâtiments d’élevage.
PCT/DK2009/050113 2008-05-20 2009-05-19 Procédé et système de purification et de désodorisation de gaz de refoulement provenant d'installations de production de déchets organiques WO2009140970A1 (fr)

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CN102161914A (zh) * 2011-03-14 2011-08-24 徐州市佳谷环保科技有限公司 生物质制气一体化燃气净化装置
JP2012148217A (ja) * 2011-01-17 2012-08-09 Toshiba Corp 廃水の生物学的処理方法及び廃水処理装置
CN103599684A (zh) * 2013-11-14 2014-02-26 深圳市利源水务设计咨询有限公司 一种光催化氧化与生物降解除臭装置及除臭工艺
CN105435626A (zh) * 2015-12-31 2016-03-30 佛山市南海区晶鼎泰机械设备有限公司 一种智能除臭装置
CN105536463A (zh) * 2015-12-31 2016-05-04 佛山市南海区晶鼎泰机械设备有限公司 一种臭气的除臭净化方法及臭气的除臭净化系统
FR3073747A1 (fr) * 2017-11-20 2019-05-24 Sources Biolaveur bi-etage a regulation externe
CN110180350A (zh) * 2019-04-23 2019-08-30 湘潭大学 废气废水一体化处理设备及废气废水处理方法
CN111318161A (zh) * 2018-12-13 2020-06-23 中国石油化工股份有限公司 污水二级生化处理装置产生废气的处理方法
WO2021262002A1 (fr) * 2020-06-23 2021-12-30 Joz B.V. Système et procédé pour réduire l'émission d'azote à partir de fumier animal contenant de l'ammonium
NL2025894B1 (nl) * 2020-06-23 2022-02-21 Joz B V Inrichting en systeem voor het verminderen van uitstoot van stikstof uit ammonium-houdende dierlijke mest
NL2025895B1 (nl) * 2020-06-23 2022-02-21 Joz B V Werkwijze voor het verminderen van uitstoot van stikstof uit ammonium-houdende dierlijke mest

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KR102186319B1 (ko) * 2020-06-09 2020-12-03 삼성엔지니어링 주식회사 습식 배기가스 정화 장치 및 습식 배기가스 정화 방법
CN112844039B (zh) * 2021-01-20 2023-06-27 衡阳市嘉信环保科技有限公司 一种自维护式甲醛处理设备
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Publication number Priority date Publication date Assignee Title
JP2012148217A (ja) * 2011-01-17 2012-08-09 Toshiba Corp 廃水の生物学的処理方法及び廃水処理装置
CN102161914A (zh) * 2011-03-14 2011-08-24 徐州市佳谷环保科技有限公司 生物质制气一体化燃气净化装置
CN102161914B (zh) * 2011-03-14 2013-02-20 徐州市佳谷环保科技有限公司 生物质制气一体化燃气净化装置
CN103599684A (zh) * 2013-11-14 2014-02-26 深圳市利源水务设计咨询有限公司 一种光催化氧化与生物降解除臭装置及除臭工艺
CN105435626A (zh) * 2015-12-31 2016-03-30 佛山市南海区晶鼎泰机械设备有限公司 一种智能除臭装置
CN105536463A (zh) * 2015-12-31 2016-05-04 佛山市南海区晶鼎泰机械设备有限公司 一种臭气的除臭净化方法及臭气的除臭净化系统
FR3073747A1 (fr) * 2017-11-20 2019-05-24 Sources Biolaveur bi-etage a regulation externe
CN111318161A (zh) * 2018-12-13 2020-06-23 中国石油化工股份有限公司 污水二级生化处理装置产生废气的处理方法
CN110180350A (zh) * 2019-04-23 2019-08-30 湘潭大学 废气废水一体化处理设备及废气废水处理方法
CN110180350B (zh) * 2019-04-23 2022-01-25 湘潭大学 废气废水一体化处理设备及废气废水处理方法
WO2021262002A1 (fr) * 2020-06-23 2021-12-30 Joz B.V. Système et procédé pour réduire l'émission d'azote à partir de fumier animal contenant de l'ammonium
NL2025894B1 (nl) * 2020-06-23 2022-02-21 Joz B V Inrichting en systeem voor het verminderen van uitstoot van stikstof uit ammonium-houdende dierlijke mest
NL2025895B1 (nl) * 2020-06-23 2022-02-21 Joz B V Werkwijze voor het verminderen van uitstoot van stikstof uit ammonium-houdende dierlijke mest

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