WO2015161672A1 - 一种净化含有粉尘的烟气的方法及装置 - Google Patents

一种净化含有粉尘的烟气的方法及装置 Download PDF

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WO2015161672A1
WO2015161672A1 PCT/CN2015/000268 CN2015000268W WO2015161672A1 WO 2015161672 A1 WO2015161672 A1 WO 2015161672A1 CN 2015000268 W CN2015000268 W CN 2015000268W WO 2015161672 A1 WO2015161672 A1 WO 2015161672A1
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light energy
pretreatment
bin
flue gas
liquid
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PCT/CN2015/000268
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English (en)
French (fr)
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傅国琳
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林小晓
车道岚
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Publication of WO2015161672A1 publication Critical patent/WO2015161672A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
    • 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
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • 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
    • 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
    • B01D53/86—Catalytic processes

Definitions

  • the invention relates to a purification method and device, in particular to a method and a device for purifying dust containing dust.
  • PM2.5 particulate matter 2.5
  • Particulate compositions can cause significant visual effects, such as soot, which consists of sulfur dioxide, nitrogen oxides, carbon monoxide, mineral dust, organic matter, and elemental carbon, also known as black carbon or soot. Due to the presence of sulfur, the particles are hygroscopic, and SO 2 is converted to sulfuric acid at low temperature and high humidity. This will result in reduced visibility, yellow air, ozone and stinging inhalation.
  • soot consists of sulfur dioxide, nitrogen oxides, carbon monoxide, mineral dust, organic matter, and elemental carbon, also known as black carbon or soot. Due to the presence of sulfur, the particles are hygroscopic, and SO 2 is converted to sulfuric acid at low temperature and high humidity. This will result in reduced visibility, yellow air, ozone and stinging inhalation.
  • the effects of inhaled particulate matter by humans and animals have been extensively studied; health problems caused by PM2.5 include asthma, lung cancer, cardiovascular problems, respiratory diseases, birth defects and
  • the comparison resistance is less than 104-105 ohms per centimeter or more than 1010 ⁇ 1011 ohms per centimeter of dust. If no measures are taken, the dust removal efficiency will be affected. (3) It does not have the offline maintenance function. Once the equipment fails, or it is running with disease, it can only be shut down for maintenance. All in all, the cost of building and maintaining any equipment other than PM is very high.
  • the pretreatment chamber has the ability to eliminate PM10, and the light energy bin is a PM2.5 removal device.
  • High intensity UV lamps and Fenton reactions can react with any organic and inorganic molecules and decompose.
  • the invention can eliminate the dust generated in the coal-fired exhaust gas, and is a physical compounding chemical method. The dust is washed with water, oxidized/catalyzed, and decomposed into carbon dioxide and water.
  • the technical solution of the present invention is a method for treating dust containing dust, which comprises the following steps:
  • the solution is configured with a mass percentage of hydrogen peroxide and water of 3% to 5%;
  • the molar ratio of hydrogen peroxide to metal system is greater than or equal to 10:1;
  • step (1') is added to adjust the pH to 3 or less with nitric acid, and then an oxidizing agent is added to oxidize the carbon particles to carbon monoxide, and the oxidizing agents are hydrogen peroxide, molybdenum oxide and tungsten oxide.
  • a mixture, a mixture of magnesium oxide and magnesium hydroxide or ferric oxide wherein the diameters of the solid particles of molybdenum oxide, tungsten oxide, magnesium oxide, magnesium hydroxide and ferric oxide are less than 20 nm, the volume of hydrogen peroxide and water
  • the ratio is 1:18-22, the molar ratio of molybdenum oxide to tungsten oxide is 1:1, magnesium oxide and hydroxide
  • the molar ratio of magnesium is 1:1, the ratio of molybdenum oxide to water is 10 mol/L, the ratio of tungsten oxide to water is 10 mol/L, and the ratio of magnesium oxide to water is 10 mol/L or more.
  • the ratio of magnesium to water is 10 mol/L or more, and the ratio of ferric oxide to water is 20 mol/L or more.
  • the concentration of the oxidizing agent in the above step (1') needs to be monitored periodically and the oxidizing agent is supplemented as needed to stabilize the concentration of the oxidizing agent in the solution.
  • the metal system in the above step (2) is a Fe(II)/F(III) system or a Cu(I)/Cu(II) system; when the metal system is a Fe(II)/F(III) system, The illumination is ultraviolet light having a wavelength of 200 nm to 400 nm; when the metal system is a Cu(I)/Cu(II) system, the illumination is visible light having a wavelength of 600 nm to 800 nm.
  • the Fe(II)/F(III) system described above consists of FeSO 4 and Fe 3 O 4 particles having a diameter of less than 20 nm.
  • the Cu(I)/Cu(II) system described above consists of Cu 2 O and CuSO 4 particles having a diameter of less than 20 nm.
  • the manner of sufficient contact in the above step (4) is to spray the liquid through the spray device to the gas to increase the area and time of contact of the exhaust gas with the liquid.
  • the liquid from which the pretreatment vessel is derived is removed from the pretreatment vessel by a water pump after removing the particulate matter larger than 10 ⁇ m.
  • the hydrogen peroxide described above is produced by reacting magnesium peroxide, sodium peroxide or calcium peroxide having a diameter of less than 50 nm in the solution.
  • the above ⁇ -hydroxy acid is glycolic acid, pyruvic acid or lactic acid.
  • the manner of sufficient contact in the above step (7) is at least one of directly introducing a gas into the liquid or spraying the liquid through the shower device to the gas.
  • An apparatus for realizing the method described above comprising: a pretreatment chamber and a light energy storage bin; the pretreatment bin comprising a pretreatment bin body, a pretreatment bin sprinkler device, a pretreatment bin air inlet, a pretreatment bin pump, and a storage a liquid reservoir, a pre-treatment tank outlet, a pre-treatment tank inlet, and a pre-treatment tank outlet, the bottom of the pre-treatment chamber is a reservoir, and the pre-chamber outlet is disposed at the reservoir.
  • the pretreatment bin inlet, the pretreatment bin inlet and the pretreatment bin outlet are disposed on the pretreatment bin above the reservoir, and the pretreatment bin outlet is above the pretreatment bin inlet,
  • the pretreatment chamber sprinkling device is disposed in the pretreatment chamber, and the pretreatment tank pump is connected to the output end of the accumulator and the input end of the pretreatment chamber sprinkling device through a pipeline;
  • the light energy chamber Including light energy bin body, light energy bin air inlet, light energy bin air outlet, light energy bin inlet, gas-liquid mixing channel, light energy bin pump, light energy bin outlet, light energy bin shower device
  • an illumination device, the light energy storage port and the light energy storage port are disposed at an upper portion of the light energy storage body, and the light energy storage port is disposed in a middle portion of the light energy storage body, and the light energy storage is discharged
  • the mouth is disposed at the bottom of the light energy storage body, the gas-liquid mixing channel, the light energy storage device and the illumination device are located in the
  • a pretreatment chamber inspection cover is arranged on the top of the pretreatment chamber body, a pretreatment chamber inspection door is arranged on the side wall of the pretreatment chamber body, a funnel-shaped collecting plate is arranged on the top of the liquid storage device, and a pretreatment is arranged on the side wall of the liquid storage device.
  • Warehouse level and sampling port is arranged on the top of the pretreatment chamber body, a pretreatment chamber inspection door is arranged on the side wall of the pretreatment chamber body, a funnel-shaped collecting plate is arranged on the top of the liquid storage device, and a pretreatment is arranged on the side wall of the liquid storage device.
  • the pretreatment chamber spray device is a pressure spray device disposed on the top of the pretreatment chamber, or a pressure spray device disposed on the top of the pretreatment chamber and a spray disposed on the inner wall of the pretreatment chamber Sprinkler system.
  • the spray droplets of the above-mentioned pressure sprinkler device are uniform wires; the diameter of each drop is 2 to 3 mm, and the interval between each drop is 6 to 10 mm.
  • the pretreatment cartridge body described above is made of a stainless steel metal plate.
  • the pretreatment tank pump described above is an acid-resistant water pump.
  • the light energy storage body is made of stainless steel metal plate, and the inner wall of the light energy storage compartment is coated with an anti-corrosion coating.
  • the light energy storage tank liquid level device is arranged on the side wall of the light energy storage body, and the light energy storage room inspection cover is arranged on the top of the light energy storage body.
  • the illumination device described above is a quartz tube ultraviolet lamp or a visible light lamp.
  • the liquid in the pretreatment chamber is controlled by an acid-resistant water pump containing water and oxidizing reagents.
  • the water removes PM10 from the flue gas.
  • H 2 O 2 hydrogen peroxide
  • H 2 O 2 is equivalent to a strong oxidizing agent in an acidic reaction environment.
  • the velocity of the flue gas in the ventilation duct exceeds 6 m/s. At this rate, any material carried by the flue gas does not have much time to generate a chemical reaction unless the reaction is exothermic and spontaneous.
  • hydrogen peroxide is relatively inexpensive and safe compared to other strong oxidants, so that when the technology is applied to the industry on a large scale, the cost can be greatly reduced and the safety factor can be improved.
  • the peroxide is in a gaseous state, then although the gas reaction has a higher reaction kinetics and usually occurs very quickly, the reverse reaction can also occur immediately after equilibrium is reached. Since the oxides produced by peroxides are all in a transition state, they are not very stable. If there is no effective way to convert the transition state to other final products, the intermediate can be immediately converted back to the reactants thereby reducing the effectiveness of the oxidant. Therefore, the problem is solved successfully and effectively by placing the light energy chamber immediately behind the pretreatment chamber.
  • a sprinkler system is placed on the top and sides of the pretreatment chamber to ensure adequate long-term contact between the flue gas and the liquid.
  • the flue gas will enter the pretreatment chamber at an angle of 40-50 degrees, causing the flue gas to produce a spiral effect when moving upward.
  • Both the sprinkler system and the spiral effect increase the time that the flue gas stays inside the pretreatment chamber.
  • the even droplets of the shower at the top of the shower ensure maximum contact between the flue gas and the liquid without any back pressure on the exhaust system. Any droplets smaller than 2 mm can be easily carried into the light bin by the exhaust force. Cross-contamination reduces the efficiency of the equipment and therefore needs to be avoided.
  • the side shower system is sprayed to ensure adequate mixing of liquids and gases.
  • the dust is converted to carbon dioxide by using a photo-assisted Fenton reaction and a catalytic/oxidation reaction.
  • the Fenton reaction is a simple photoinduced oxidation/reduction catalytic reaction.
  • the main feature of the Fenton reaction is its production of reactive oxygen species (ROS), especially hydroxyl radicals. Hydroxyl radicals are the most effective reactive oxygen species, which oxidize any organic (including biomolecules) and inorganic matrices around them.
  • ROS reactive oxygen species
  • the original chemical reaction is the reaction of Fe(II) with H 2 O 2 to form Fe(III) and OH ⁇ (see Figure 4).
  • the reduction of Fe(III) to Fe(II) requires heat or light energy.
  • Fenton reaction efficiency of light depends on the concentration of H 2 O 2, Fe (II) / H 2 O 2 ratio, pH, reaction time and intensity of UV light.
  • concentration of H 2 O 2 Fe (II) / H 2 O 2 ratio
  • pH a pH of water
  • reaction time a pH of water
  • intensity of UV light The chemical, physical, initial, and temperature concentrations of the contaminants also have an important impact on the final efficiency.
  • the dust in the smoke (the main component of the smog) is actually the coal that is not completely burned.
  • the organic matter contained in the coal is decomposed by heat to produce a flammable gas, also known as "volatile matter” (VOC).
  • VOC volatile matter
  • a mixed gas of various compounds such as hydrocarbons, hydrogen, and carbon monoxide.
  • black smoke When the coal combustion conditions are not up to standard or the high volatile coal (low quality coal) is burned, it will easily produce unburned carbon particles, commonly known as “black smoke”; and produce more VOCs such as carbon monoxide, polycyclic aromatic hydrocarbons, Hydrocarbon contaminants such as aldehydes.
  • Any organic carbon-containing molecules present in the flue gas are oxidized to CO 2 as they pass through the light energy bin, and heavy metals and inorganic minerals are deposited in the fiber mercury removal filter in our exhaust duct.
  • the first reaction of hydroxyl radicals with hydrocarbons in flue gas in a light energy chamber is to remove one hydrogen atom from its molecular structure (R) and then form water and alkyl radicals (R ⁇ ) (see Figure 8).
  • the second reaction is that the alkyl radical (R ⁇ ) reacts rapidly with molecular oxygen to form a peroxy radical (see Figure 9), after which a number of steps are taken to ultimately produce carbon dioxide and water.
  • the advantages of the invention are: 1.
  • the advantage of the nano material is that the surface area is large, and the mutual transfer of the electron layers between the molecules is very rapid, and the chemical reaction rate can be exponentially accelerated; especially in the field of optics, the diameter of the nanometer is smaller. The greater the activity and momentum of energy. Therefore, in order to make any chemical reaction of the flue gas with such a fast flow rate, the advantages of nanotechnology are undeniable.
  • the self-oxidation-reduction reaction is spontaneous and has the characteristics of a catalyst, so it is not necessary to add it frequently, and the amount is small, which is very economical.
  • the present invention is based on the principle of photo-assisted Fenton reaction and has achieved great success in eliminating soot.
  • the present invention is the most economical and effective method of particulate removal today, which is a more economical and efficient way to control air pollution without any additional manufacturing and operating costs. It can be incorporated into existing dust removal systems for coal-fired boilers to increase their effectiveness and completely replace the old ones.
  • This filtration system can also be used in other industrial markets, including cement plants, steel plants, municipal waste combustion plants, medical waste combustion plants, chlorine gas plants, pulp and paper production plants.
  • Test report for purifying automobile exhaust gas according to the present invention:
  • Test report for purifying boiler exhaust gas according to the present invention (test site is a boiler room):
  • Figure 1 is a schematic view showing the structure of a pretreatment chamber having two types of shower devices in an apparatus for treating dust containing dust.
  • FIG. 2 is a schematic view showing the structure of a pretreatment chamber having a top pressure spray device in a device for treating dust containing dust according to the present invention.
  • FIG. 3 is a schematic view showing the structure of a light energy chamber in a device for treating dust containing dust according to the present invention.
  • FIG. 5 is a reaction equation for reducing the first Fe(III) to Fe(II) in the photo-assisted Fenton reaction in the method for treating dust containing dust according to the present invention.
  • Figure 7 is a reaction equation for the reduction of a third Fe(III) to Fe(II) in a photo-assisted Fenton reaction in a method for treating dust containing dust according to the present invention.
  • Figure 8 is a chemical reaction formula for reacting hydroxyl radicals with hydrocarbons to form water and alkyl radicals in a photo-assisted Fenton reaction in a method for treating dust containing flue gas according to the present invention.
  • Figure 9 is a chemical reaction formula for reacting alkyl radicals with molecular oxygen to form peroxy radicals in a photo-assisted Fenton reaction in a method for treating dust containing dust according to the present invention.
  • Figure 10 is a chemical reaction formula for decomposing C 2 H 6 into carbon dioxide and water in a method for treating dust containing dust according to the present invention.
  • 1-1 is the pre-treatment warehouse inspection cover
  • 1-2 is the pre-treatment tank sprinkler
  • 1-3 is the funnel-shaped collecting plate
  • 1-4 is the pre-treatment tank inlet
  • 1-5 is the sampling port
  • 1-6 is the pre-treatment tank pump
  • 1-7 is the accumulator
  • 1-8 is the pre-treatment tank outlet
  • 1-9 is the pre-treatment tank level
  • 1-10 is the pre-treatment tank inlet 1-11 is the pre-treatment warehouse inspection door
  • 1-12 is the pre-treatment tank outlet port
  • 1-13 is the pre-treatment tank body
  • 2-1 is the light energy bin outlet
  • 2-2 is the light energy bin air inlet.
  • 2-3 is the light energy inlet
  • 2-4 is the gas-liquid mixing channel
  • 2-5 is the light energy storage pump
  • 2-6 is the light energy storage port
  • 2-7 is the light energy storage liquid Positioner
  • 2-8 is the light energy tank shower device
  • 2-9 is the light energy warehouse inspection cover
  • 2-10 lighting equipment 2-11 is the light energy warehouse body.
  • Embodiment 1 A method of treating dust containing dust, characterized by comprising the steps of:
  • the solution is configured to have a mass percentage of hydrogen peroxide to water of 5%;
  • the molar ratio of hydrogen peroxide to metal system is about 30:1;
  • the step (1') is added to adjust the pH to 3 or less with nitric acid, and then an oxidizing agent is added to oxidize the carbon particles to carbon monoxide, and the oxidizing agent is hydrogen peroxide, hydrogen peroxide and water.
  • the volume ratio is 1:20.
  • the concentration of the oxidizing agent in the above step (1') needs to be monitored every 10 hours and the oxidizing agent is supplemented as needed to stabilize the concentration of the oxidizing agent in the solution.
  • the metal system in the above step (2) is a Fe(II)/F(III) system; when the metal system is a Fe(II)/F(III) system, the illumination is ultraviolet light having a wavelength of 200 nm to 400 nm. .
  • the Fe(II)/F(III) system described above consists of FeSO 4 and Fe 3 O 4 particles having a diameter of less than 20 nm.
  • the manner of sufficient contact in the above step (4) is to spray the liquid through the spray device to the gas to increase the area and time of contact of the exhaust gas with the liquid.
  • the flue gas in step (4) described above enters from the lower portion of the pretreatment vessel and is oriented horizontally at an angle of 45 degrees to the vessel wall to increase the time of contact with the liquid.
  • the liquid from which the pretreatment vessel is derived is removed from the pretreatment vessel by a water pump after removing the particulate matter larger than 10 ⁇ m.
  • the above ⁇ -hydroxy acid is lactic acid.
  • the manner of sufficient contact in the above step (7) is to directly pass the gas into the liquid and spray the liquid through the spraying device to the gas.
  • An apparatus for implementing the method described above comprising a pretreatment bin and a light energy bin; the pretreatment bin comprising a pretreatment bin 1-13, a pretreatment bin sprinkler 1-2, a pretreatment bin inlet 1- 4.
  • the bottom of the processing cartridge body 1-13 is the accumulator 1-7, and the pre-chamber outlet port 1-8 is disposed at the accumulator 1-7, the pre-treatment bin inlet 1-4, the pre-treatment bin
  • the inlet port 1-10 and the pretreatment chamber outlet port 1-12 are disposed on the pretreatment cartridge body 713 above the reservoir 1-7, and the pretreatment cartridge outlet port 1-12 is in the pretreatment cartridge inlet port 1-4
  • the pretreatment chamber sprinkler device 1-2 is disposed in the pretreatment bin body 1-13, and the pretreatment bin pump 1-6 is connected to the output end of the accumulator 1-7
  • the pretreatment bin body 1-13 is provided with a pretreatment bin inspection cover 1-1 at the top, and the pretreatment bin body 1-13 is provided with a pretreatment bin inspection door 1-11 on the side wall of the pretreatment cartridge body 1-13, and the top of the reservoir 1-7 is set.
  • the funnel-shaped collecting plates 1-3, the side walls of the accumulators 1-7 are provided with pre-treatment tank levelers 1-9 and sampling ports 1-5.
  • the pretreatment chamber sprinkler device 1-2 described above is a pressure sprinkler device disposed at the top of the pretreatment cartridge body 1-13 and a spray sprinkler device disposed on the inner wall of the pretreatment cartridge body 1-13. (see picture 1)
  • the spray droplets of the above-mentioned pressurized shower device are uniform wires; each droplet has a diameter of 2 to 3 mm, and each droplet is spaced apart by 8 mm.
  • the pretreatment cartridge body 1-13 described above is made of a stainless steel metal plate.
  • the pretreatment bin pump 1-6 described above is an acid-resistant water pump.
  • the above-mentioned light energy storage body 2-11 is made of a stainless steel metal plate, and the inner wall of the light energy storage body 2-11 is coated with a 2-3 mm Teflon anticorrosive coating.
  • the light energy chamber liquid level device 2-7 is disposed on the side wall of the light energy storage body 2-11, and the light energy storage box inspection cover 2-9 is disposed at the top of the light energy storage body 2-11.
  • the illumination device 2-10 described above is a quartz tube ultraviolet lamp.
  • the diameter and height of the pretreated cartridge body 1-13 are 2.7 meters and 3 meters, respectively;
  • the diameter and height of the light energy bins 2-11 are 2.7 meters and 2.25 meters, respectively;
  • the flue gas discharged from the outlet port 1-12 of the pretreatment chamber is introduced into the light energy bin body 2-11 from the light source bin inlet 2-2, and is in contact with the liquid at the gas-liquid mixing channel 2-4. After the gas floats out of the liquid surface, it reacts with the droplets ejected by the light energy storage device 2-8 to decompose the hydrocarbons in the flue gas into carbon dioxide and water, and the carbon particles and carbon monoxide are oxidized to carbon dioxide.
  • Common hydrocarbons in the flue gas including C 2 H 6 , can be decomposed in the light energy bin (see Figure 10);
  • the purified gas is discharged from the light energy storage port 2-1 to the light energy storage body 2-11.
  • the method of the present invention has achieved a PM2.5 removal rate of 95.4% (from 105 ⁇ g/m 3 to 5 ⁇ g/m 3 ).
  • a method of treating dust containing dust characterized by comprising the steps of:
  • the solution is configured to have a mass percentage of hydrogen peroxide to water of 4%;
  • the molar ratio of hydrogen peroxide to metal system is 10:1;
  • the step (1') is added to adjust the pH to 3 or less with nitric acid, and then an oxidizing agent is added to oxidize the carbon particles to carbon monoxide.
  • the oxidizing agent is a mixture of molybdenum oxide and tungsten oxide, and is oxidized.
  • the diameter of the molybdenum and tungsten oxide solid particles is less than 20 nm, the molar ratio of molybdenum oxide to tungsten oxide is 1:1, the ratio of molybdenum oxide to water is 10 mol/L, and the ratio of tungsten oxide to water is 10 mol/L.
  • the concentration of the oxidizing agent in the above step (1') needs to be monitored periodically and the oxidizing agent is supplemented as needed to stabilize the concentration of the oxidizing agent in the solution.
  • the metal system in the above step (2) is a Cu(I)/Cu(II) system, and the light is visible light having a wavelength of 600 nm to 800 nm.
  • the Cu(I)/Cu(II) system described above consists of Cu 2 O and CuSO 4 particles having a diameter of less than 20 nm.
  • the manner of sufficient contact in the above step (4) is to spray the liquid through the spray device to the gas to increase the area and time of contact of the exhaust gas with the liquid.
  • the flue gas in step (4) described above enters from the lower portion of the pretreatment vessel and is oriented horizontally at an angle of 45 degrees to the vessel wall to increase the time of contact with the liquid.
  • the liquid from which the pretreatment vessel is derived is removed from the pretreatment vessel by a water pump after removing the particulate matter larger than 10 ⁇ m.
  • the hydrogen peroxide described above is produced after the reaction in the solution of magnesium peroxide having a diameter of less than 50 nm.
  • the above ⁇ -hydroxy acid is glycolic acid.
  • the manner of sufficient contact in the above step (7) is to directly pass the gas into the liquid and spray the liquid through the spraying device to the gas.
  • a dust removing device for realizing the above method comprises a pretreatment bin and a light energy bin;
  • the pretreatment bin comprises a pretreatment bin body 1-13, a pretreatment bin sprinkler device 1-2, a pretreatment bin air inlet 1 -4, pretreatment bin pump 1-6, accumulator 1-7, pretreatment bin outlet port 1-8, pretreatment bin inlet port 1-10 and pretreatment bin outlet port 1-12
  • the bottom of the pretreatment cartridge body 1-13 is the accumulator 1-7, and the pretreatment chamber outlet port 1-8 is disposed at the accumulator 1-7, the pretreatment chamber inlet 1-4, pretreatment Warehouse inlet 1-10 and pre-position
  • the silo outlets 1-12 are disposed on the pre-treatment tanks 1-13 above the accumulators 1-7, and the pre-chamber outlets 1-12 are above the pre-chamber inlets 1-4, said pre-
  • the treatment chamber spray device 1-2 is disposed in the pretreatment chamber body 1-13, and the pretreatment chamber pumping water pump 1-6 is connected to the output end of the liquid storage
  • the position of the bottom, the light energy bin pump 2-5 is connected to the output end of the bottom of the light energy bin body 2-11 and the input end of the light energy bin shower device 2-8 through a pipe; the pretreatment bin outlet port 1 - 12 Connect the light energy inlet 2-2.
  • the pretreatment bin body 1-13 is provided with a pretreatment bin inspection cover 1-1 at the top, and the pretreatment bin body 1-13 is provided with a pretreatment bin inspection door 1-11 on the side wall of the pretreatment cartridge body 1-13, and the top of the reservoir 1-7 is set.
  • the funnel-shaped collecting plates 1-3, the side walls of the accumulators 1-7 are provided with pre-treatment tank levelers 1-9 and sampling ports 1-5.
  • the pretreatment chamber shower device 1-2 described above is a pressure shower device disposed at the top of the pretreatment cartridge body 1-13. (See Figure 2)
  • the spray droplets of the above-mentioned pressurized shower device are uniform wires; each droplet has a diameter of 2 to 3 mm, and each droplet is spaced apart by 8 mm.
  • the pretreatment cartridge body 1-13 described above is made of a stainless steel metal plate.
  • the pretreatment bin pump 1-6 described above is an acid-resistant water pump.
  • the above-mentioned light energy storage body 2-11 is made of a stainless steel metal plate, and the inner wall of the light energy storage body 2-11 is coated with a 2-3 mm Teflon anticorrosive coating.
  • the light energy chamber liquid level device 2-7 is disposed on the side wall of the light energy storage body 2-11, and the light energy storage box inspection cover 2-9 is disposed at the top of the light energy storage body 2-11.
  • the illumination device 2-10 described above is a visible light lamp.
  • one of the advantages of using the Cu(I)/Cu(II) system is that the light absorption peak of Cu 2 O is 600 nm, and the light absorption peak of CuSO 4 is 700 nm, which is in the visible light region which is very harmful. (600-800nm, near-infrared).

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Abstract

一种净化含有粉尘的烟气的方法及装置，该方法包括水洗和氧化/催化反应过程，该装置包括预处理仓和光能仓。预处理仓具有消除PM10的能力，光能仓为PM2.5的去除装置。采用芬顿试剂和UV灯有效地去除了烟气中的颗粒物、碳氢化合物等有害物质。

Description

一种净化含有粉尘的烟气的方法及装置 (一)技术领域：
本发明涉及一种净化方法及装置，特别是一种净化含有粉尘的烟气的方法及装置。
(二)背景技术：
PM2.5对健康的影响已经在时下引起了广泛的关注。什么是颗粒物2.5(PM2.5)？他们是指结合在地球大气中直径小于2.5微米的小片固体或液体物质。颗粒物组合物可引起明显的视觉效果，如烟尘，它由二氧化硫、氮氧化物、一氧化碳、矿物粉尘、有机物质和元素碳组成，也被称为黑色碳或煤烟。由于硫的存在，颗粒是吸湿的，并且SO2会在高湿度及低温下转化为硫酸。这将导致能见度降低、黄色空气、臭氧与刺痛的吸入感。人类与动物吸入微粒物质的影响已经被广泛地研究；PM2.5导致的的健康问题包括哮喘、肺癌、心血管问题、呼吸系统疾病、先天缺陷和过早死亡。
颗粒物排放在大多数工业化国家都受到严格监管。由于环境问题，大多数行业都需要进行某种粉尘收集系统的操作，以控制颗粒物排放。这些系统包括离心除尘器(旋流除尘器)、纤维过滤除尘器(袋式除尘器)、湿式除尘器和静电除尘器。然而，便宜的除尘设备效率很低，通常达不到80％；好的设备譬如静电除尘，虽然效率可高达99％，但也有其致命缺点：(1)设备庞大，耗钢多，需高压变电和整流设备，故投资高。(2)除尘效率受粉尘比电阻的制约，一般对比电阻小于104～105欧姆每公分或大于1010～1011欧姆每公分的粉尘，若不采取一定措施，除尘效率将受到影响。(3)不具备离线检修功能，一旦设备出现故障，或者带病运行，或者只能停炉检修。总而言之，任何有效率除PM的设备建造与维护费用都是非常高的。
中国也已提出了对空气中颗粒物排放的限制(见下表)，各个工厂企业也都按规定裝了除尘设备。然而庞大的维护费的确使中小企业入不敷出。因此发展一个价廉而有效的除尘裝置是当务之急。
  PM10 PM2.5
年均 70微克/立方米 35微克/立方米
日均(24小时) 150微克/立方米 75微克/立方米
(三)发明内容：
本发明的目的在于提供一种净化含有粉尘的烟气的方法及装置，该系统的一项最佳功能是在没有任何额外费用的情况下解决了PM10与PM2.5的去除问题。预处理仓具有消除PM10的能力，光能仓为PM2.5的去除装置。高强度UV灯和芬顿反应可以与任何有机和无机分子发生反应并分解。本发明可以排除燃煤废气中产生的粉尘，是一种物理配合化学的方法，粉尘经过水洗，氧化/催化的反应与分解之后成为二氧化碳与水。
本发明的技术方案：一种处理含有粉尘的烟气的方法，其特征在于包括以下步骤：
(1)在预处理容器中加入水；
(2)在反应容器中加入含有芬顿试剂且使用α-羟基酸调节pH值至小于等于3的溶液，所述芬顿试剂包含能发生光助芬顿反应的金属系统和过氧化氢；
所述溶液配置过氧化氢与水的质量百分比为3％～5％；
过氧化氢与金属系统摩尔比大于等于10∶1；
(3)根据金属系统的光吸收峰，在反应容器中设置光照系统；
(4)将废气通入预处理容器，与液体充分接触，使直径大于10微米的固体颗粒留在液体中；
(5)将含有直径大于10微米的固体颗粒的液体导出预处理容器；
(6)将净化后的烟气排出预处理容器；
(7)将步骤(6)排出的烟气通入反应容器，与芬顿试剂充分接触反应，使烟气中的碳氢化合物分解为二氧化碳和水，碳颗粒和一氧化碳氧化为二氧化碳；
(8)将反应后溶液导出，并定时监测导出溶液中芬顿试剂的浓度，根据监测的情况，添加新的含有芬顿试剂的溶液使溶液成分保持稳定；
(9)将净化后的气体排出反应容器。
上述所述步骤(1)后加入步骤(1’)为使用硝酸调整pH值至3以下，然后加入氧化试剂，使碳颗粒氧化为一氧化碳，所述氧化试剂为过氧化氢、氧化钼和氧化钨的混合物、氧化镁和氢氧化镁的混合物或三氧化二铁，其中，氧化钼、氧化钨、氧化镁、氢氧化镁和三氧化二铁固体颗粒的直径小于20nm，过氧化氢与水的体积比为1∶18～22，氧化钼和氧化钨的摩尔比为1∶1，氧化镁和氢氧化 镁的摩尔比为1∶1，氧化钼与水的用量比大于等于10mol/L，氧化钨与水的用量比大于等于10mol/L，氧化镁与水的用量比大于等于10mol/L，氢氧化镁与水的用量比大于等于10mol/L，三氧化二铁与水的用量比大于等于20mol/L。
上述所述步骤(1’)中的氧化试剂的浓度需要定时监测并根据需要补充氧化试剂使溶液中氧化试剂浓度稳定。
上述所述步骤(2)中的金属系统为Fe(II)/F(III)系统或Cu(I)/Cu(II)系统；当金属系统为Fe(II)/F(III)系统时，则光照为波长为200nm～400nm的紫外光；当金属系统为Cu(I)/Cu(II)系统时，光照为波长为600nm～800nm的可见光。
上述所述Fe(II)/F(III)系统由直径小于20纳米的FeSO4和Fe3O4颗粒构成。
上述所述Cu(I)/Cu(II)系统由直径小于20纳米的Cu2O和CuSO4颗粒构成。
上述所述步骤(4)中充分接触的方式为将液体通过喷淋装置向气体喷淋，以增加废气与液体接触的面积和时间。
上述所述步骤(4)中的烟气从预处理容器下部进入，方向水平并与容器壁呈40～50度角，以增加与液体接触的时间。
上述所述步骤(5)中，导出预处理容器的液体在除去大于10微米的颗粒物后，由抽水泵通过管道输回到预处理容器内。
上述所述过氧化氢为直径小于50纳米的过氧化镁、过氧化钠或过氧化钙在所述溶液中反应后产生的。
上述所述过氧化氢的消耗量通过定期收集样品被密切的监测，并且使用碘/高锰酸钾(I/KMnO4)滴定法观察过氧化物的消耗率。
上述所述α-羟基酸为乙醇酸、丙酮酸或乳酸。
上述所述步骤(7)中充分接触的方式为将气体直接通入液体或将液体通过喷淋装置向气体喷淋中的至少一种。
一种实现上述所述方法的装置，包括预处理仓和光能仓；所述预处理仓包括预处理仓体、预处理仓喷淋装置、预处理仓进气口、预处理仓抽水泵、储液器、预处理仓出液口、预处理仓进液口和预处理仓出气口，所述预处理仓体的底部是储液器，预处理仓出液口设置在储液器处，所述预处理仓进气口、预处理仓进液口和预处理仓出气口设置在储液器上方的预处理仓体上，预处理仓出气口在预处理仓进气口的上方，所述预处理仓喷淋装置设置在预处理仓体内，所述预处理仓抽水泵通过管道连接储液器的输出端和预处理仓喷淋装置的输入端；所述光能仓 包括光能仓体、光能仓进气口、光能仓出气口、光能仓进液口、气液混合通道、光能仓抽水泵、光能仓出液口、光能仓喷淋装置和光照设备，所述光能仓进气口和光能仓出气口设置在光能仓体的上部，所述光能仓进液口设置在光能仓体的中部，所述光能仓出液口设置在光能仓体的底部，所述气液混合通道、光能仓喷淋装置和光照设备位于光能仓体内，气液混合通道的输入端连接光能仓进气口，气液混合通道的输出端位于光能仓体下部接近仓底的位置，所述光能仓抽水泵通过管道连接光能仓体底部的输出端和光能仓喷淋装置的输入端；所述预处理仓出气口连接光能仓进气口。
上述所述预处理仓体顶部设置预处理仓检修盖，预处理仓体的侧壁上设置预处理仓检修门，储液器顶部设置漏斗形收集板，储液器的侧壁上设置预处理仓液位器和采样口。
上述所述预处理仓喷淋装置为设置在预处理仓体内顶部的加压喷淋装置，或者为设置在预处理仓体内顶部的加压喷淋装置和设置在预处理仓体内壁上的喷雾式喷淋装置。
上述所述加压喷淋装置的喷淋液滴为均匀的连线；每滴液滴的直径为2～3毫米，每滴之间间隔6～10毫米。
上述所述预处理仓体由不锈钢金属板制成。
上述所述预处理仓抽水泵为耐酸水泵。
上述所述光能仓体由不锈钢金属板制成，光能仓体内壁上涂有防腐涂层。
上述所述光能仓体的侧壁上设置光能仓液位器，光能仓体顶部设置光能仓检修盖。
上述所述光照设备为石英管紫外灯或可见光灯。
本发明的工作原理：
1、预处理仓的工作原理：
预处理仓内的液体由一个耐酸水泵来控制循环，液体内含有水和氧化试剂，水可以去除烟气内的PM10。氧化试剂采用过氧化氢(H2O2)时，H2O2在酸性的反应环境下相当于强氧化剂。烟气在通风管道的速度超过6米/秒，以此种速度，烟气所携带的任何物质没有太多的时间去产生化学反应，除非该反应是放热的与自发的。此外，相对于其他强氧化剂，过氧化氢比较便宜与安全，从而在此技术大规模的应用于工业时可以大大的降低了成本并且提高了安全防范系数。
如果过氧化物是处于气体状态，那么虽然气体反应具有较高的反应动力并通常发生非常快，但在达到平衡后其逆反应也可立即产生。由于过氧化物所产生的氧化物都属于过渡态，它们不是非常稳定。如果没有有效的办法将过渡态转化成其它最终产物，该中间体可马上转换回成反应物而因此减少了氧化剂的功效。因此，将光能仓紧接在预处理仓的后面，成功和有效的解决了这个问题。
预处理仓的顶部和侧面放置了喷淋系统以确保烟气和液体之间有充分长时间的接触。烟气将以40-50度角进入预处理仓，造成烟气在向上移动时产生螺旋效应。喷淋系统与螺旋效应均能提升烟气停留在预处理仓内部的时间。顶部淋浴的液滴均匀的连线，确保在不对排气系统产生任何反压的情况下，烟气与液体之间的最大接触。任何小于2毫米的液滴会很容易被排气力量带入光能仓。交叉污染会降低设备的效率，因此需要避免。侧面淋浴系统均为喷雾式以确保液体与气体的充分混合。
2、光能仓的工作原理：
在光能仓中，通过使用光助芬顿反应以及催化/氧化反应将粉尘转化成二氧化碳。芬顿反应是一个简单的光诱导氧化/还原催化反应，芬顿反应的主要特点是其产生活性氧(ROS)，特别是羟基自由基。羟基自由基是最有效的活性氧，它可以氧化在其周边的任何有机(包括生物分子)及无机基质。其原始的化学反应为Fe(II)与H2O2反应生成Fe(III)和OH·(见图4)，还原Fe(III)至Fe(II)需要热或光的能量。在没有基质与底物以及有光能的情况下，有三个主要机理(见图5-7)。光助芬顿反应的效率主要取决于H2O2的浓度、Fe(II)/H2O2的比例、pH值、反应时间与UV光的强度。污染物的化学特性、物理特性、初始浓度以及温度，也对最终的效率具有重要的影响。
烟气中的粉尘(霧霾的主要成分)其实就是燃烧未完全的煤，煤中含的有机物质在受热分解后产生可燃性气体，亦被称为“挥发分”(VOC)，它是由各种碳氢化合物、氢气、一氧化碳等化合物组成的混合气体。当煤燃烧条件不達标時或挥发分高的煤(劣质煤)燃烧时易产生未燃尽極小的碳粒，俗称“黑烟”；并产生更多的VOC如一氧化碳、多环芳烃类、醛类等碳氢化合污染物。
任何存在于烟气中的有机含碳分子会在其穿过光能仓时被氧化成CO2，重金属和无机矿物则会沉积在我们的排气管道中的纤维除汞过滤器中。在光能仓中羟基自由基与烟气中的碳氢化合物第一个反应是除去其分子结构(R)中的一个氢原子，然后形成水和烷基自由基(R·)(见图8)，第二个反应是烷基自由基(R·) 再与分子氧迅速反应形成过氧自由基(见图9)，在这之后再经过许多步骤，最终生成二氧化碳和水。
本发明的优越性：1、纳米材料的优点为其表面积大，分子之间电子层的互相传送非常迅速，可使化学反应速度指数般地加快；尤其在光学领域中，纳米的直径越小光能的活性与动量越大。所以想使流速如此快的烟气产生任何化学反应，纳米技术的优点是不可否定的。自身的氧化还原反应为自发性，具有催化剂的特性，所以无需经常加添，用量少，非常的经济。2、本发明建立在光助芬顿反应的原理上，并在消除烟尘上取得了巨大成功。本发明是现今最经济、有效的去除颗粒物的方法，这是一个更经济、更高效的方式来控制空气污染，无需任何额外的制造与运行成本。它可以被纳入到燃煤锅炉现有的除尘系统用来提高其有效性，也可以完全取代原来的旧系统。此过滤系统也可适用在其它的工业市场，包括水泥厂、钢铁厂、市政府废物燃烧厂、医疗废物燃烧厂、氯气制造厂、纸浆和纸张生产厂等。
本装置除尘效果检测试验报告如下：
1、本发明用于净化汽车尾气的试验报告：
检测标准(方法)及使用仪器
[根据细则26改正25.05.2015]　
Figure WO-DOC-FIGURE-1
检测结果
                                      单位：毫克/立方米
[根据细则26改正25.05.2015]　
Figure WO-DOC-FIGURE-2
2、本发明用于净化锅炉废气的试验报告(试验地点为某锅炉房)：
检测标准(方法)及使用仪器
[根据细则26改正25.05.2015]　
Figure WO-DOC-FIGURE-3
检测结果          单位：毫克/立方米
[根据细则26改正25.05.2015]　
Figure WO-DOC-FIGURE-4
备注：标准值依据《火电场大气污染物排放标准》(GB13223-2011)
(四)附图说明：
图1为本发明所涉一种处理含有粉尘的烟气的装置中有两种喷淋装置的预处理仓的结构示意图。
图2为本发明所涉一种处理含有粉尘的烟气的装置中有顶部的加压喷淋装置的预处理仓的结构示意图。
图3为本发明所涉一种处理含有粉尘的烟气的装置中光能仓的结构示意图。
图4为本发明所涉一种处理含有粉尘的烟气的方法中光助芬顿反应中Fe(II)氧化为Fe(III)的反应方程式。
图5为本发明所涉一种处理含有粉尘的烟气的方法中光助芬顿反应中第一种Fe(III)还原为Fe(II)的反应方程式。
图6为本发明所涉一种处理含有粉尘的烟气的方法中光助芬顿反应中第二种Fe(III)还原为Fe(II)的反应方程式。
图7为本发明所涉一种处理含有粉尘的烟气的方法中光助芬顿反应中第三种Fe(III)还原为Fe(II)的反应方程式。
图8为本发明所涉一种处理含有粉尘的烟气的方法中光助芬顿反应中羟基自由基与碳氢化合物反应形成水和烷基自由基的化学反应式。
图9为本发明所涉一种处理含有粉尘的烟气的方法中光助芬顿反应中烷基自由基与分子氧反应形成过氧自由基的化学反应式。
图10为本发明所涉一种处理含有粉尘的烟气的方法中C2H6被分解成二氧化碳和水的化学反应式。
其中，1-1为预处理仓检修盖，1-2为预处理仓喷淋装置，1-3为漏斗形收集板，1-4为预处理仓进气口，1-5为采样口，1-6为预处理仓抽水泵，1-7为储液器，1-8为预处理仓出液口，1-9为预处理仓液位器，1-10为预处理仓进液口，1-11为预处理仓检修门，1-12为预处理仓出气口，1-13为预处理仓体，2-1为光能仓出气口，2-2为光能仓进气口，2-3为光能仓进液口，2-4为气液混合通道，2-5为光能仓抽水泵，2-6为光能仓出液口，2-7为光能仓液位器，2-8为光能仓喷淋装置，2-9为光能仓检修盖，2-10光照设备，2-11为光能仓体。
(五)具体实施方式：
实施例1：一种处理含有粉尘的烟气的方法，其特征在于包括以下步骤：
(1)在预处理容器中加入水；
(2)在反应容器中加入含有芬顿试剂且使用α-羟基酸调节pH值至小于等于3的溶液，所述芬顿试剂包含能发生光助芬顿反应的金属系统和过氧化氢；
所述溶液配置过氧化氢与水的质量百分比为5％；
过氧化氢与金属系统摩尔比约为30∶1；
(3)根据金属系统的光吸收峰，在反应容器中设置光照系统；
(4)将废气通入预处理容器，与液体充分接触，使直径大于10微米的固体颗粒留在液体中；
(5)将含有直径大于10微米的固体颗粒的液体导出预处理容器；
(6)将净化后的烟气排出预处理容器；
(7)将步骤(6)排出的烟气通入反应容器，与芬顿试剂充分接触反应，使烟气中的碳氢化合物分解为二氧化碳和水，碳颗粒和一氧化碳氧化为二氧化碳；
(8)将反应后溶液导出，并定时监测导出溶液中芬顿试剂的浓度，根据监测的情况，添加新的含有芬顿试剂的溶液使溶液成分保持稳定；
(9)将净化后的气体排出反应容器。
上述所述步骤(1)后加入步骤(1’)为使用硝酸调整pH值至3以下，然后加入氧化试剂，使碳颗粒氧化为一氧化碳，所述氧化试剂为过氧化氢，过氧化氢与水的体积比为1∶20。
上述所述步骤(1’)中的氧化试剂的浓度需要每10小时监测并根据需要补充氧化试剂使溶液中氧化试剂浓度稳定。
上述所述步骤(2)中的金属系统为Fe(II)/F(III)系统；当金属系统为Fe(II)/F(III)系统时，则光照为波长为200nm～400nm的紫外光。
上述所述Fe(II)/F(III)系统由直径小于20纳米的FeSO4和Fe3O4颗粒构成。
上述所述步骤(4)中充分接触的方式为将液体通过喷淋装置向气体喷淋，以增加废气与液体接触的面积和时间。
上述所述步骤(4)中的烟气从预处理容器下部进入，方向水平并与容器壁呈45度角，以增加与液体接触的时间。
上述所述步骤(5)中，导出预处理容器的液体在除去大于10微米的颗粒物后，由抽水泵通过管道输回到预处理容器内。
上述所述过氧化氢的消耗量通过每10小时收集样品被密切的监测，并且使用碘/高锰酸钾(I/KMnO4)滴定法观察过氧化物的消耗率。
上述所述α-羟基酸为乳酸。
上述所述步骤(7)中充分接触的方式为将气体直接通入液体并将液体通过喷淋装置向气体喷淋。
一种实现上述所述方法的装置，包括预处理仓和光能仓；所述预处理仓包括预处理仓体1-13、预处理仓喷淋装置1-2、预处理仓进气口1-4、预处理仓抽水泵1-6、储液器1-7、预处理仓出液口1-8、预处理仓进液口1-10和预处理仓出气口1-12，所述预处理仓体1-13的底部是储液器1-7，预处理仓出液口1-8设置在储液器1-7处，所述预处理仓进气口1-4、预处理仓进液口1-10和预处理仓出气口1-12设置在储液器1-7上方的预处理仓体713上，预处理仓出气口1-12在预处理仓进气口1-4的上方，所述预处理仓喷淋装置1-2设置在预处理仓体1-13内，所述预处理仓抽水泵1-6通过管道连接储液器1-7的输出端和预处理仓喷淋装置1-2的输入端；所述光能仓包括光能仓体2-11、光能仓进气口2-2、光能仓出气口2-1、光能仓进液口2-3、气液混合通道2-4、光能仓抽水泵2-5、光能仓出液口2-6、光能仓喷淋装置2-8和光照设备2-10，所述光能仓进气口2-2和光能仓出气口2-1设置在光能仓体2-11的上部，所述光能仓进液口2-3设置在光能仓体2-11的中部，所述光能仓出液口2-6设置在光能仓体2-11的底部，所述气液混合通道2-4、光能仓喷淋装置2-8和光照设备2-10位于光能仓体2-11内，气液混合通道2-4的输入端连接光能仓进气口2-2，气液混合 通道2-4的输出端位于光能仓体2-11下部接近仓底的位置，所述光能仓抽水泵2-5通过管道连接光能仓体2-11底部的输出端和光能仓喷淋装置2-8的输入端；所述预处理仓出气口1-12连接光能仓进气口2-2。
上述所述预处理仓体1-13顶部设置预处理仓检修盖1-1，预处理仓体1-13的侧壁上设置预处理仓检修门1-11，储液器1-7顶部设置漏斗形收集板1-3，储液器1-7的侧壁上设置预处理仓液位器1-9和采样口1-5。
上述所述预处理仓喷淋装置1-2为设置在预处理仓体1-13内顶部的加压喷淋装置和设置在预处理仓体1-13内壁上的喷雾式喷淋装置。(见图1)
上述所述加压喷淋装置的喷淋液滴为均匀的连线；每滴液滴的直径为2～3毫米，每滴之间间隔8毫米。
上述所述预处理仓体1-13由不锈钢金属板制成。
上述所述预处理仓抽水泵1-6为耐酸水泵。
上述所述光能仓体2-11由不锈钢金属板制成，光能仓体2-11内壁上涂有2-3mm铁氟龙(Teflon)防腐涂层。
上述所述光能仓体2-11的侧壁上设置光能仓液位器2-7，光能仓体2-11顶部设置光能仓检修盖2-9。
上述所述光照设备2-10为石英管紫外灯。
本实施例中除尘装置的工作方法：
以用于每日燃烧约30吨煤的15吨燃煤锅炉为例：
预处理仓的工作方法：
(1)预处理仓体1-13的直径和高度分别为2.7米和3米；
(2)注入40厘米水位的水，构成2289升水，使用硝酸调整pH值至3以下，然后加入327升的35％过氧化氢；
(3)开启预处理仓抽水泵1-6，预处理仓喷淋装置1-2开始工作；
(4)烟气从预处理仓进气口1-4与预处理仓体1-13内壁夹角四十五度的方向进入预处理仓体1-13内，使烟气在向上移动时产生螺旋效应；
(5)烟气中直径大于10微米的固体颗粒留在液体中；
(6)将含有直径大于10微米的固体颗粒的液体从预处理仓出液口1-8导出；
(7)将净化后的烟气从预处理仓出气口1-12排出；
(8)过氧化氢(H2O2)的消耗量通过每10小时的样品收集被密切的监测，并且使用碘/高锰酸钾(I/KMnO4)滴定法观察过氧化物的消耗率。
光能仓的工作方法：
(1)光能仓体2-11的直径和高度分别为2.7米与2.25米；
(2)向光能仓体2-11注入5725升的水，加入817升的35％H2O2和64公斤的FeSO4(FeSO4∶H2O2＝1∶5w/w)；
(3)在光能仓体2-11内设置4个1000W宽频、波长为200nm至400nm、光吸收峰值等于365nm的UV光(FeSO4在365nm具有最高的吸收系数)；
(4)开启光能仓喷淋装置2-8；
(5)将预处理仓出气口1-12排出的烟气从光能仓进气口2-2通入光能仓体2-11，在气液混合通道2-4处与液体接触反应，气体浮出液面后，又与光能仓喷淋装置2-8喷出的液滴接触反应，使烟气中的碳氢化合物分解为二氧化碳和水，碳颗粒和一氧化碳氧化为二氧化碳，其中，烟气中常见的碳氢化合物包括C2H6能够在光能仓中被分解(见图10)；
(6)将反应后溶液从光能仓出液口2-6导出，过氧化氢(H2O2)的消耗量通过每10小时的样品收集被密切的监测，并且使用碘/高锰酸钾(I/KMnO4)滴定法观察过氧化物的消耗率，根据烟气中的CO2含量，计量泵将从贮液罐中补充过氧化氢至光能仓体2-11；
(7)将净化后的气体从光能仓出气口2-1排出光能仓体2-11。
根据本实施例所述15吨燃煤锅炉的工业测试数据来看，本发明所述方法已经达到了95.4％的PM2.5去除率(从105微克/立方米至5微克/立方米)。
实施例2：
一种处理含有粉尘的烟气的方法，其特征在于包括以下步骤：
(1)在预处理容器中加入水；
(2)在反应容器中加入含有芬顿试剂且使用α-羟基酸调节pH值至小于等于3的溶液，所述芬顿试剂包含能发生光助芬顿反应的金属系统和过氧化氢；
所述溶液配置过氧化氢与水的质量百分比为4％；
过氧化氢与金属系统摩尔比为10∶1；
(3)根据金属系统的光吸收峰，在反应容器中设置光照系统；
(4)将废气通入预处理容器，与液体充分接触，使直径大于10微米的固体颗粒留在液体中；
(5)将含有直径大于10微米的固体颗粒的液体导出预处理容器；
(6)将净化后的烟气排出预处理容器；
(7)将步骤(6)排出的烟气通入反应容器，与芬顿试剂充分接触反应，使烟气中的碳氢化合物分解为二氧化碳和水，碳颗粒和一氧化碳氧化为二氧化碳；
(8)将反应后溶液导出，并定时监测导出溶液中芬顿试剂的浓度，根据监测的情况，添加新的含有芬顿试剂的溶液使溶液成分保持稳定；
(9)将净化后的气体排出反应容器。
上述所述步骤(1)后加入步骤(1’)为使用硝酸调整pH值至3以下，然后加入氧化试剂，使碳颗粒氧化为一氧化碳，所述氧化试剂为氧化钼和氧化钨的混合物，氧化钼和氧化钨固体颗粒的直径小于20nm，氧化钼和氧化钨的摩尔比为1∶1，氧化钼与水的用量比为10mol/L，氧化钨与水的用量比为10mol/L。
上述所述步骤(1’)中的氧化试剂的浓度需要定时监测并根据需要补充氧化试剂使溶液中氧化试剂浓度稳定。
上述所述步骤(2)中的金属系统为Cu(I)/Cu(II)系统，光照为波长为600nm～800nm的可见光。
上述所述Cu(I)/Cu(II)系统由直径小于20纳米的Cu2O和CuSO4颗粒构成。
上述所述步骤(4)中充分接触的方式为将液体通过喷淋装置向气体喷淋，以增加废气与液体接触的面积和时间。
上述所述步骤(4)中的烟气从预处理容器下部进入，方向水平并与容器壁呈45度角，以增加与液体接触的时间。
上述所述步骤(5)中，导出预处理容器的液体在除去大于10微米的颗粒物后，由抽水泵通过管道输回到预处理容器内。
上述所述过氧化氢为直径小于50纳米的过氧化镁所述溶液中反应后产生的。
上述所述过氧化氢的消耗量通过每8小时收集样品被密切的监测，并且使用碘/高锰酸钾(I/KMnO4)滴定法观察过氧化物的消耗率。
上述所述α-羟基酸为乙醇酸。
上述所述步骤(7)中充分接触的方式为将气体直接通入液体并将液体通过喷淋装置向气体喷淋。
一种实现上述所述方法的除尘装置，包括预处理仓和光能仓；所述预处理仓包括预处理仓体1-13、预处理仓喷淋装置1-2、预处理仓进气口1-4、预处理仓抽水泵1-6、储液器1-7、预处理仓出液口1-8、预处理仓进液口1-10和预处理仓出气口1-12，所述预处理仓体1-13的底部是储液器1-7，预处理仓出液口1-8设置在储液器1-7处，所述预处理仓进气口1-4、预处理仓进液口1-10和预处 理仓出气口1-12设置在储液器1-7上方的预处理仓体1-13上，预处理仓出气口1-12在预处理仓进气口1-4的上方，所述预处理仓喷淋装置1-2设置在预处理仓体1-13内，所述预处理仓抽水泵1-6通过管道连接储液器1-7的输出端和预处理仓喷淋装置1-2的输入端；所述光能仓包括光能仓体2-11、光能仓进气口2-2、光能仓出气口2-1、光能仓进液口2-3、气液混合通道2-4、光能仓抽水泵2-5、光能仓出液口2-6、光能仓喷淋装置2-8和光照设备2-10，所述光能仓进气口2-2和光能仓出气口2-1设置在光能仓体2-11的上部，所述光能仓进液口2-3设置在光能仓体2-11的中部，所述光能仓出液口2-6设置在光能仓体2-11的底部，所述气液混合通道2-4、光能仓喷淋装置2-8和光照设备2-10位于光能仓体2-11内，气液混合通道2-4的输入端连接光能仓进气口2-2，气液混合通道2-4的输出端位于光能仓体2-11下部接近仓底的位置，所述光能仓抽水泵2-5通过管道连接光能仓体2-11底部的输出端和光能仓喷淋装置2-8的输入端；所述预处理仓出气口1-12连接光能仓进气口2-2。
上述所述预处理仓体1-13顶部设置预处理仓检修盖1-1，预处理仓体1-13的侧壁上设置预处理仓检修门1-11，储液器1-7顶部设置漏斗形收集板1-3，储液器1-7的侧壁上设置预处理仓液位器1-9和采样口1-5。
上述所述预处理仓喷淋装置1-2为设置在预处理仓体1-13内顶部的加压喷淋装置。(见图2)
上述所述加压喷淋装置的喷淋液滴为均匀的连线；每滴液滴的直径为2～3毫米，每滴之间间隔8毫米。
上述所述预处理仓体1-13由不锈钢金属板制成。
上述所述预处理仓抽水泵1-6为耐酸水泵。
上述所述光能仓体2-11由不锈钢金属板制成，光能仓体2-11内壁上涂有2-3mm铁氟龙(Teflon)防腐涂层。
上述所述光能仓体2-11的侧壁上设置光能仓液位器2-7，光能仓体2-11顶部设置光能仓检修盖2-9。
上述所述光照设备2-10为可见光灯。
在本实施例中，使用Cu(I)/Cu(II)系统的优点之一是Cu2O的光吸收峰值在600nm，CuSO4的光吸收峰值在700nm，都是在危害非常小的可见光区(600-800nm，近红外)。

Claims (22)

  1. 一种净化含有粉尘的烟气的方法，其特征在于包括以下步骤：
    (1)在预处理容器中加入水；
    (2)在反应容器中加入含有芬顿试剂且使用α-羟基酸调节pH值至小于等于3的溶液，所述芬顿试剂包含能发生光助芬顿反应的金属系统和过氧化氢；
    所述溶液配置过氧化氢与水的质量百分比为3％～5％；
    过氧化氢与金属系统摩尔比大于等于10∶1；
    (3)根据金属系统的光吸收峰，在反应容器中设置光照系统；
    (4)将废气通入预处理容器，与液体充分接触，使直径大于10微米的固体颗粒留在液体中；
    (5)将含有直径大于10微米的固体颗粒的液体导出预处理容器；
    (6)将净化后的烟气排出预处理容器；
    (7)将步骤(6)排出的烟气通入反应容器，与芬顿试剂充分接触反应，使烟气中的碳氢化合物分解为二氧化碳和水，碳颗粒和一氧化碳氧化为二氧化碳；
    (8)将反应后溶液导出，并定时监测导出溶液中芬顿试剂的浓度，根据监测的情况，添加新的含有芬顿试剂的溶液使溶液成分保持稳定；
    (9)将净化后的气体排出反应容器。
  2. 根据权利要求1所述一种净化含有粉尘的烟气的方法，其特征在于所述步骤(1)后加入步骤(1’)为使用硝酸调整pH值至3以下，然后加入氧化试剂，使碳颗粒氧化为一氧化碳，所述氧化试剂为过氧化氢、氧化钼和氧化钨的混合物、氧化镁和氢氧化镁的混合物或三氧化二铁，其中，氧化钼、氧化钨、氧化镁、氢氧化镁和三氧化二铁固体颗粒的直径小于20nm，过氧化氢与水的体积比为1∶18～22，氧化钼和氧化钨的摩尔比为1∶1，氧化镁和氢氧化镁的摩尔比为1∶1，氧化钼与水的用量比大于等于10mol/L，氧化钨与水的用量比大于等于10mol/L，氧化镁与水的用量比大于等于10mol/L，氢氧化镁与水的用量比大于等于10mol/L，三氧化二铁与水的用量比大于等于 20mol/L。
  3. 根据权利要求2所述一种净化含有粉尘的烟气的方法，其特征在于所述步骤(1’)中的氧化试剂的浓度需要定时监测并根据需要补充氧化试剂使溶液中氧化试剂浓度稳定。
  4. 根据权利要求1所述一种净化含有粉尘的烟气的方法，其特征在于所述步骤(2)中的金属系统为Fe(II)/F(III)系统或Cu(I)/Cu(II)系统；当金属系统为Fe(II)/F(III)系统时，则光照为波长为200nm～400nm的紫外光；当金属系统为Cu(I)/Cu(II)系统时，光照为波长为600nm～800nm的可见光。
  5. 根据权利要求4所述一种净化含有粉尘的烟气的方法，其特征在于所述Fe(II)/F(III)系统由直径小于20纳米的FeSO4和Fe3O4颗粒构成。
  6. 根据权利要求4所述一种净化含有粉尘的烟气的方法，其特征在于所述Cu(I)/Cu(II)系统由直径小于20纳米的Cu2O和CuSO4颗粒构成。
  7. 根据权利要求1所述一种净化含有粉尘的烟气的方法，其特征在于所述步骤(4)中充分接触的方式为将液体通过喷淋装置向气体喷淋，以增加废气与液体接触的面积和时间。
  8. 根据权利要求1所述一种净化含有粉尘的烟气的方法，其特征在于所述步骤(4)中的烟气从预处理容器下部进入，方向水平并与容器壁呈40～50度角，以增加与液体接触的时间。
  9. 根据权利要求1所述一种净化含有粉尘的烟气的方法，其特征在于所述步骤(5)中，导出预处理容器的液体在除去大于10微米的颗粒物后，由抽水泵通过管道输回到预处理容器内。
  10. 根据权利要求1或2所述一种净化含有粉尘的烟气的方法，其特征在于所述过氧化氢为直径小于50纳米的过氧化镁、过氧化钠或过氧化钙在所述溶液中反应后产生的。
  11. 根据权利要求1或3所述一种净化含有粉尘的烟气的方法，其特征在于所述过氧化氢的消耗量通过定期收集样品被密切的监测，并且使用碘/高锰酸钾(I/KMnO4)滴定法观察过氧化物的消耗率。
  12. 根据权利要求1所述一种净化含有粉尘的烟气的方法，其特 征在于所述α-羟基酸为乙醇酸、丙酮酸或乳酸。
  13. 根据权利要求1所述一种净化含有粉尘的烟气的方法，其特征在于所述步骤(7)中充分接触的方式为将气体直接通入液体或将液体通过喷淋装置向气体喷淋中的至少一种。
  14. 一种实现权利要求1所述方法的装置，包括预处理仓和光能仓；所述预处理仓包括预处理仓体、预处理仓喷淋装置、预处理仓进气口、预处理仓抽水泵、储液器、预处理仓出液口、预处理仓进液口和预处理仓出气口，所述预处理仓体的底部是储液器，预处理仓出液口设置在储液器处，所述预处理仓进气口、预处理仓进液口和预处理仓出气口设置在储液器上方的预处理仓体上，预处理仓出气口在预处理仓进气口的上方，所述预处理仓喷淋装置设置在预处理仓体内，所述预处理仓抽水泵通过管道连接储液器的输出端和预处理仓喷淋装置的输入端；所述光能仓包括光能仓体、光能仓进气口、光能仓出气口、光能仓进液口、气液混合通道、光能仓抽水泵、光能仓出液口、光能仓喷淋装置和光照设备，所述光能仓进气口和光能仓出气口设置在光能仓体的上部，所述光能仓进液口设置在光能仓体的中部，所述光能仓出液口设置在光能仓体的底部，所述气液混合通道、光能仓喷淋装置和光照设备位于光能仓体内，气液混合通道的输入端连接光能仓进气口，气液混合通道的输出端位于光能仓体下部接近仓底的位置，所述光能仓抽水泵通过管道连接光能仓体底部的输出端和光能仓喷淋装置的输入端；所述预处理仓出气口连接光能仓进气口。
  15. 根据权利要求14所述的一种净化含有粉尘的烟气的装置，其特征在于所述预处理仓体顶部设置预处理仓检修盖，预处理仓体的侧壁上设置预处理仓检修门，储液器顶部设置漏斗形收集板，储液器的侧壁上设置预处理仓液位器和采样口。
  16. 根据权利要求14所述的一种净化含有粉尘的烟气的装置，其特征在于所述预处理仓喷淋装置为设置在预处理仓体内顶部的加压喷淋装置，或者为设置在预处理仓体内顶部的加压喷淋装置和设置在预处理仓体内壁上的喷雾式喷淋装置。
  17. 根据权利要求16所述的一种净化含有粉尘的烟气的装置，其特征在于所述加压喷淋装置的喷淋液滴为均匀的连线；每滴液滴的直径为2～3毫米，每滴之间间隔6～10毫米。
  18. 根据权利要求14所述的一种净化含有粉尘的烟气的装置，其特征在于所述预处理仓体由不锈钢金属板制成。
  19. 根据权利要求14所述的一种净化含有粉尘的烟气的装置，其特征在于所述预处理仓抽水泵为耐酸水泵。
  20. 根据权利要求14所述的一种净化含有粉尘的烟气的装置，其特征在于所述光能仓体由不锈钢金属板制成，光能仓体内壁上涂有防腐涂层。
  21. 根据权利要求14所述的一种净化含有粉尘的烟气的装置，其特征在于所述光能仓体的侧壁上设置光能仓液位器，光能仓体顶部设置光能仓检修盖。
  22. 根据权利要求14所述的一种净化含有粉尘的烟气的装置，其特征在于所述光照设备为石英管紫外灯或可见光灯。
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