CN113325133A - Method and device for detecting mercury in waste incineration flue gas - Google Patents
Method and device for detecting mercury in waste incineration flue gas Download PDFInfo
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Abstract
The invention relates to the technical field of environmental monitoring, in particular to a method for detecting mercury in waste incineration flue gas, which comprises the following steps: separating granular mercury and gaseous mercury in the flue gas by a filter membrane, and measuring the content of the granular mercury in the flue gas; introducing the flue gas into a clay mineral solid adsorbent soaked by deionized water, and collecting mercury oxide in the flue gas; introducing the flue gas into a solid acid adsorbent soaked by deionized water, and collecting elemental mercury in the flue gas; heating and resolving the clay mineral solid adsorbent and the solid acid adsorbent, and respectively measuring the contents of mercury oxide and elemental mercury. Still relate to collection system, including constant temperature sampling gun, constant temperature absorption bottle case, be provided with constant temperature filter in the constant temperature sampling gun, constant temperature absorption bottle incasement along the flue gas flow direction in proper order the intercommunication have the first bottle that is equipped with clay mineral class solid sorbent and the second bottle that is equipped with the solid acid sorbent. The invention is suitable for a high-temperature, high-humidity and high-corrosion flue gas detection environment, and the higher the temperature, the humidity and the acidity of the flue gas, the more beneficial the collection of the mercury by the clay mineral solid adsorbent and the solid acid adsorbent.
Description
Technical Field
The invention relates to the technical field of environmental monitoring, in particular to a method and a device for detecting mercury in waste incineration flue gas.
Background
Mercury, one of the most harmful heavy metals, is of increasing concern for pollution caused by it due to its difficult degradation and bioaccumulation. Waste incineration is another major source of mercury pollution. The dust, moisture, HCl, SOx and NOx content in the flue gas of the garbage incinerator are high, the flue gas is high in temperature, humidity and corrosion, and the working condition of flue gas detection is severe.
The mercury in flue gas exists in 3 forms, namely elemental mercury Hg0Hg, Hg oxide2+And particulate mercury Hgp。 Hg0And Hg2+Collectively known as gaseous mercury, is present in flue gas in gaseous form, Hg0Is insoluble in water and very volatile, but Hg0Can be catalytically oxidized to Hg2+。Hg2+The water-soluble organic fertilizer is soluble in water, is easy to be adsorbed by particles and is easy to capture and control; hg is a mercury vapor2+Can be reduced to Hg by heating to about 800 deg.C0。HgpMost of the water can be collected by the filter membrane filter.
The mercury sampling standard method accepted by the U.S. environmental protection agency is to collect mercury by using a solution absorption bottle method, and the method has high requirements on testing technology and personnel quality, strict requirements on collection and analysis of gas samples, high requirements on the purity of reagents, dilution effect caused by high-humidity flue gas, and gas flow easily influenced by dust in an adsorption solution; the reagent has various types, the collection and the preparation work in the early period are complicated, and the absorption liquid needs to be prepared as before and is not easy to carry and store; the collection time is long, at least 2 hours of collection are required, the analysis of the instrument is complicated, the analysis result is delayed, and the analysis result can be obtained in 3-5 days.
The method mainly adopts an activated carbon tube to collect mercury in China, but activated carbon is easy to adsorb other impurities and can only be used for purifying air; SO in flue gas2And NOx can inhibit the activated carbon from capturing mercury, and the mercury is easy to penetrate through, so that the detection repeatability of the device is poor.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method and the device for detecting the mercury in the waste incineration flue gas can be suitable for the flue gas with high temperature, high humidity and high corrosion, can accurately detect the mercury content of each form in the flue gas, and can be simply and repeatedly used.
In order to solve the technical problems, the invention adopts the technical scheme that:
the invention provides a method for detecting mercury in waste incineration flue gas, which comprises the following steps:
the method comprises the following steps: the method comprises the following steps of (1) enabling waste incineration flue gas to pass through a filter membrane, separating granular mercury and gaseous mercury in the waste incineration flue gas, and measuring the content of the granular mercury in the waste incineration flue gas;
step two: introducing the separated waste incineration flue gas into a clay mineral solid adsorbent soaked by deionized water, and collecting mercury oxide in the flue gas;
step three: then introducing the flue gas into a solid acid adsorbent soaked by deionized water for collecting elemental mercury in the flue gas;
step four: and D, performing thermal desorption on the clay mineral solid adsorbent and the solid acid adsorbent in the second step and the third step, and respectively measuring the contents of mercury oxide and elemental mercury released by the clay mineral solid adsorbent and the solid acid adsorbent, so as to obtain the content of gaseous mercury in the waste incineration flue gas.
The invention also provides a device for collecting mercury in waste incineration flue gas, which comprises a constant-temperature sampling gun, a constant-temperature adsorption bottle box, a sampling controller and a sampling air pump, wherein a sampling head of the constant-temperature sampling gun extends into a flue, a constant-temperature filter is arranged in the constant-temperature sampling gun, the tail end of the constant-temperature sampling gun is communicated with the constant-temperature adsorption bottle box, the tail end of the constant-temperature adsorption bottle box is communicated with the sampling controller, a first bottle body filled with a clay mineral solid adsorbent and a second bottle body filled with a solid acid adsorbent are sequentially communicated in the constant-temperature adsorption bottle box along the flow direction of the flue gas, and the sampling controller is communicated with and controls the sampling air pump.
The invention has the beneficial effects that: the content of the granular mercury is separately measured by separating the granular mercury from the gaseous mercury in the waste incineration flue gas; adsorbing mercury oxide by using a clay mineral solid adsorbent soaked by deionized water, and oxidizing element mercury in the flue gas into mercury oxide by using solid acid in the solid acid adsorbent soaked by the deionized water so as to be trapped in the solid acid adsorbent; and finally, respectively measuring the contents of mercury oxide and elemental mercury by heating and analyzing the clay mineral solid adsorbent and the solid acid adsorbent. The method is suitable for a high-temperature, high-humidity and high-corrosion flue gas detection environment, and the higher the flue gas temperature, humidity and acidity, the more beneficial the mercury collection of the clay mineral solid adsorbent and the solid acid adsorbent; the method can be used repeatedly for clay mineral solid adsorbents and solid acid adsorbents, and has the advantages of simple regeneration operation and detection cost reduction. The method comprises the following steps of separating granular mercury in flue gas by using a constant-temperature filter in a constant-temperature sampling gun, and then respectively carrying out adsorption of oxidized mercury and oxidation adsorption of element mercury through a first bottle body with a clay mineral solid adsorbent and a second bottle body with a solid acid adsorbent in a constant-temperature adsorption bottle box, so that simple and efficient collection operation is realized; the sampling controller controls the sampling pump to realize the monitoring of the flow rate of the flue gas.
Drawings
FIG. 1 is a schematic step diagram of a method for detecting mercury in waste incineration flue gas according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a device for collecting mercury in waste incineration flue gas according to an embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a sampling head of a device for collecting mercury in waste incineration flue gas according to an embodiment of the present invention;
fig. 4 is a schematic structural diagram of a first bottle body and a second bottle body of the collection device for mercury in waste incineration flue gas according to the embodiment of the invention.
Description of reference numerals:
1. a constant temperature sampling gun; 2. a constant temperature adsorption bottle box; 3. a sampling controller; 4. sampling an air pump; 5. a dehumidifying device; 6. a first bottle body; 7. a second bottle body; 8. a constant temperature filter; 9. a sampling head; 10. a communicating pipe; 11. sampling branch pipes; 12. an extension end; 13. a fixed end; 14. a first bracket; 15. a first moving member; 16. a second bracket; 17. a second moving member; 18. an adjusting ring; 19. a connecting member; 20. an air inlet pipe; 21. a placement chamber; 22. an air outlet pipe; 23. an upper chamber; 24. a retaining ring; 25. a lower cavity; 26. buckling; 27. A porous glass plate.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.
Referring to fig. 1, a method for detecting mercury in waste incineration flue gas includes the following steps:
the method comprises the following steps: the method comprises the following steps of (1) enabling waste incineration flue gas to pass through a filter membrane, separating granular mercury and gaseous mercury in the waste incineration flue gas, and measuring the content of the granular mercury in the waste incineration flue gas;
step two: introducing the separated waste incineration flue gas into a clay mineral solid adsorbent soaked by deionized water, and collecting mercury oxide in the flue gas;
step three: then introducing the flue gas into a solid acid adsorbent soaked by deionized water for collecting elemental mercury in the flue gas;
step four: and D, performing thermal desorption on the clay mineral solid adsorbent and the solid acid adsorbent in the second step and the third step, and respectively measuring the contents of mercury oxide and elemental mercury released by the clay mineral solid adsorbent and the solid acid adsorbent, so as to obtain the content of gaseous mercury in the waste incineration flue gas.
From the above description, the beneficial effects of the present invention are: the content of the granular mercury is separately measured by separating the granular mercury from the gaseous mercury in the waste incineration flue gas; adsorbing oxidized mercury by using a clay mineral solid adsorbent soaked by deionized water, and oxidizing elemental mercury by using a solid acid adsorbent soaked by deionized water to enable the elemental mercury to become oxidized mercury and be trapped in the solid acid adsorbent; and finally, respectively measuring the contents of mercury oxide and elemental mercury by heating and resolving the clay mineral solid adsorbent and the solid acid adsorbent. The method is suitable for a high-temperature, high-humidity and high-corrosion flue gas detection environment, and the higher the flue gas temperature, humidity and acidity, the more beneficial the mercury collection of the clay mineral solid adsorbent and the solid acid adsorbent; the method can be used repeatedly for clay mineral solid adsorbents and solid acid adsorbents, and has the advantages of simple regeneration operation and detection cost reduction.
Further, the clay mineral solid adsorbent can be one of bentonite, attapulgite, hydrotalcite, kaolinite, montmorillonite, vermiculite and zeolite, and is treated by a microwave-enhanced acid leaching purification process.
The description shows that the clay mineral has abundant surface active groups, larger specific surface area and more micropores, can provide more adsorption sites for mercury, has stronger adsorption capacity, can greatly improve the collection efficiency of mercury oxide in flue gas, has abundant reserves and low price, and can effectively reduce the collection cost; the operation is convenient and fast in the field.
The clay mineral is treated by a microwave-enhanced acid leaching purification process, so that the content of oxide impurities in the clay mineral is reduced, the content of surface active groups is increased, and the specific surface area and the pore volume are increased, thereby improving the collection efficiency.
The specific steps of the microwave reinforced acid leaching purification process are as follows:
adding the clay mineral into a sulfuric acid solution with the concentration of 50% by mass according to the liquid-solid mass ratio of 3: 1, uniformly stirring, and then placing the mixture into a microwave oven for microwave impregnation for 4 hours, wherein the microwave output power is 300W. Then washing, filtering, drying and cooling with distilled water, and finally grinding to 180-220 meshes (0.177-0.125 mm).
Further, the solid acid of the solid acid adsorbent is prepared by taking a molecular sieve as a carrier and ammonium disulfate (NH)4)2S2O8The material is prepared by an immersion method; the molecular sieve can be USY (containing 0.05% of Na)2O), HY (the ratio of silicon to aluminum is 5), Hbeta (the ratio of silicon to aluminum is 50), HZSM-5 (the ratio of silicon to aluminum is 25) and MCM-41.
From the above description, it can be known that the molecular sieve has a large specific surface area, an open three-dimensional pore structure and excellent hydrothermal stability, and can withstand harsh regeneration conditions. S2O8 2-The molecular sieve type solid acid has higher sulfur content and more acid sites, and has high Hg content0The collection efficiency of (2) is higher.
Using molecular sieve as carrier, ammonium dithionate (NH)4)2S2O8The solid acid is developed by an impregnation method.
The specific process steps are as follows:
the preparation method of the solid acid comprises the following steps:
60g of the molecular sieve are placed in 200mL of ammonium disulfate solution (1mol/L) and stirred at room temperature for 1h at a stirring speed of 950 r/min. Then standing for a period of time, removing the supernatant, transferring to a crucible, and drying in an oven at 110 ℃. And roasting the dried solid acid in a muffle furnace at 550 ℃ for 3h in an air atmosphere, and finally grinding uniformly.
Further, the specific steps for determining the content of the granular mercury in the first step are as follows:
detecting the quality of the filter membrane before separation;
detecting the quality of the separated filter membrane;
and calculating the content of the granular mercury in the waste incineration flue gas according to the absolute value of the mass difference between the two.
From the above description, it can be known that, since the granular mercury is separated, the accurate content of the granular mercury in the flue gas can be simply obtained by comparing the mass of the filter membrane before and after the separation.
Further, the specific operation of the step four is as follows:
heating the clay mineral solid adsorbent and the solid acid adsorbent in the second step and the third step for desorption at the temperature of more than 600 ℃;
and introducing the quantitatively released mercury oxide and elemental mercury into a mercury detector to respectively determine the content of the mercury oxide and the content of the elemental mercury released by the clay mineral solid adsorbent and the solid acid adsorbent, so as to obtain the content of the gaseous mercury in the waste incineration flue gas.
From the above description, it can be known that the clay mineral solid adsorbent and the solid acid adsorbent are heated and resolved at a temperature of more than 600 ℃ by using a high-temperature catalytic thermal cracking atomic absorption method, so that the trapped mercury oxide and elemental mercury are fully released, and the mercury oxide and elemental mercury are introduced into a mercury detector for accurate determination.
Referring to fig. 2 to 4, a device for collecting mercury in waste incineration flue gas comprises a constant temperature sampling gun 1, a constant temperature adsorption bottle box 2, a sampling controller 3 and a sampling air pump 4, wherein a sampling head 9 of the constant temperature sampling gun 1 extends into a flue, a constant temperature filter 8 is arranged in the constant temperature sampling gun 1, the tail end of the constant temperature sampling gun 1 is communicated with the constant temperature adsorption bottle box 2, the tail end of the constant temperature adsorption bottle box 2 is communicated with the sampling controller 3, a first bottle 6 filled with a clay mineral solid adsorbent and a second bottle 7 filled with a solid acid adsorbent are sequentially communicated in the constant temperature adsorption bottle box along the flow direction of flue gas, and the sampling controller 3 is communicated with and controls the sampling air pump 4.
As can be seen from the above description, the constant temperature filter 8 in the constant temperature sampling gun 1 is used to separate the particulate mercury in the flue gas, and then the first bottle 6 with the clay mineral solid adsorbent in the constant temperature adsorption bottle box and the second bottle 7 with the solid acid adsorbent are used to respectively perform mercury oxide adsorption and elemental mercury oxidation adsorption, so as to implement simple and efficient collection operation; the sampling controller 3 controls the sampling pump to realize the monitoring of the flow rate of the flue gas.
Further, the sampling head 9 includes communicating pipe 10 and sample branch pipe 11, communicating pipe 10 and 1 front end intercommunication of constant temperature sampling rifle, communicating pipe 10 includes three extension end 12, extension end 12 is connected with a plurality of sample branch pipes 11, and is a plurality of the front end of sample branch pipe 11 is provided with the sample connection.
It can be known from the above description that the communicating pipe 10 with three extending ends 12 and the plurality of sampling branch pipes 11 are arranged, the flue is divided into a plurality of detection areas through the plurality of sampling ports, the flue gas of each sampling port is collected and mixed for detection, the detection result fully represents the gas components at each position in the flue, the result is real and reliable, the sampling amount is increased, and the sampling time is saved.
Further, three extension ends 12 of the communication pipe 10 extend to form a triangular cone structure, and the sampling branch pipe 11 has an inclined included angle greater than 30 degrees with the extension end 12 as a horizontal plane.
From the above description, the triangular cone-shaped spatial structure enables the communicating tube 10 to cover more flue space, so that the subsequent sampling is more reliable. The more than 30 degree inclined included angle of the sampling branch pipe 11 further enlarges the covered flue space.
Further, the heating temperature of the constant-temperature sampling gun 1, the constant-temperature filter 8 and the constant-temperature adsorption bottle box 2 is not lower than the temperature of the flue gas.
As can be seen from the above description, the heating temperature maintained by the constant temperature sampling gun 1 and the constant temperature filter 8 is to prevent the condensation of water vapor and mercury; the heating temperature kept by the constant temperature adsorption bottle box 2 is used for accelerating the collection of mercury by the clay mineral solid adsorbent and the solid acid adsorbent.
Further, the first bottle 6 and the second bottle 7 are both of a U-shaped porous glass plate 27 structure.
Through the structure of the U-shaped porous glass plate 27, the flue gas can be fully contacted with the clay mineral solid adsorbent and the solid acid adsorbent in the first bottle body 6 and the second bottle body 7, and the detection efficiency is ensured.
The first embodiment of the invention is as follows:
referring to fig. 1, a method for detecting mercury in waste incineration flue gas includes the following steps:
the method comprises the following steps: separating granular mercury and gaseous mercury from the collected quantitative waste incineration flue gas through a filter membrane under the condition that the environmental temperature is not lower than the temperature of the collected waste incineration flue gas;
detecting the quality of the filter membrane before separation;
detecting the quality of the separated filter membrane;
and calculating the content of the granular mercury in the waste incineration flue gas according to the absolute value of the mass difference between the two.
Step two: introducing the separated waste incineration flue gas into a clay mineral solid adsorbent soaked by deionized water under the condition that the environmental temperature is not lower than the temperature of the waste incineration flue gas during collection, and collecting mercury oxide in the flue gas;
step three: then introducing the flue gas into a solid acid adsorbent soaked by deionized water under the condition that the environmental temperature is not lower than the temperature of the waste incineration flue gas during collection, and collecting element mercury in the flue gas;
step four: heating the clay mineral solid adsorbent and the solid acid adsorbent in the second and third steps to be analyzed at the temperature of more than 600 ℃;
and introducing the quantitatively released mercury oxide and elemental mercury into a mercury detector to respectively determine the content of the mercury oxide and the content of the elemental mercury released by the clay mineral solid adsorbent and the solid acid adsorbent, so as to obtain the content of the gaseous mercury in the waste incineration flue gas.
The second embodiment of the invention is as follows:
referring to fig. 2 to 4, a device for collecting mercury in waste incineration flue gas comprises a constant-temperature sampling gun 1, a constant-temperature adsorption bottle box 2, a sampling controller 3 and a sampling air pump 4, wherein a sampling head 9 of the constant-temperature sampling gun 1 extends into a flue, the constant-temperature sampling gun 1 is coated with polytetrafluoroethylene, and the polytetrafluoroethylene is high-temperature resistant, moisture resistant, high corrosion resistant, high wear resistant and surface non-sticky, and is suitable for high-temperature, high-humidity and high-corrosion flue gas detection environments.
A constant temperature filter 8 is arranged in the constant temperature sampling gun 1, the constant temperature filter 8 comprises a filter membrane, the filter membrane is a Teflon filter membrane, and the Teflon filter membrane has chemical stability and inertia and is suitable for environments with strong chemical corrosivity, strong acid and strong base; meanwhile, the water-repellent gas filter also has a water-repellent characteristic, can filter water in gas, and is suitable for detecting waste incineration flue gas.
The end of constant temperature sampling gun 1 communicates constant temperature adsorption bottle case 2, the end of constant temperature adsorption bottle case 2 communicates dehydrating unit 5, constant temperature adsorption bottle incasement along the flue gas flow direction in proper order the intercommunication have the first bottle 6 that is equipped with clay mineral class solid sorbent and the second bottle 7 that is equipped with solid acid sorbent, dehydrating unit 5 communicates sampling controller 3, sampling controller 3 communicates and controls sampling aspiration pump 4.
The three extending ends 12 of the communicating pipe 10 extend to form a triangular cone structure.
The sampling branch pipe 11 has an inclined included angle of more than 30 degrees with the extending end 12 as a horizontal plane.
The communicating pipe 10 is of a closable structure, and is convenient to carry and store when going out. Specifically, the extension end 12 has elasticity, and can be laterally offset by a certain angle relative to the communication pipe 10; the sampling head 9 further comprises a fixed end 13, a first support 14, a first moving part 15, a second support 16 and a second moving part 17, wherein the fixed end 13 is arranged between the three extending ends 12 and extends along the length direction of the sampling head 9, the number of the first supports 14 is three, the three supports correspond to the three extending ends 12 respectively, one end of the first support 14 is hinged to the fixed end 13, the other end of the first support is hinged to the first moving part 15, a first moving groove along the length direction of the first moving part is formed in one side, facing the fixed end 13, of each extending end 12, and the first moving part 15 is movably arranged in the first moving groove; the number of the second supports 16 is three, the second supports correspond to the first supports 14 respectively, one end of each second support 16 is hinged to the first support 14, the other end of each second support is hinged to a second moving part 17, a second moving groove is formed in the fixed end 13 along the length direction of the fixed end, and the second moving parts 17 are movably arranged in the second moving grooves.
The tail end of the sampling head 9 is sleeved with an adjusting ring 18 which can move along the length direction of the sampling head 9, and a connecting piece 19 is connected between the adjusting ring 18 and the second moving piece 17.
The connecting piece 19 can move along the inner wall of the adjusting ring 18 relative to the adjusting ring 18, one side of the sampling head 9 is provided with tooth sockets along the length direction, and the inner wall of one side of the adjusting ring 18 is provided with teeth corresponding to the tooth sockets. When the adjusting ring 18 moves to a proper position along the length direction of the sampling head 9, the adjusting ring 18 is rotated to enable the tooth side to be embedded into the tooth socket, the fixing of the adjusting ring 18 is completed, and then the three extending ends 12 are unfolded; conversely, when the adjusting ring 18 is moved to a proper position along the length direction of the sampling head 9, the three extending ends 12 will be pulled back by the first support 14 to be close to the fixed end 13, so as to realize contraction.
In fig. 3, in order to visually represent the closed structure of the communicating tube 10, two second brackets 16 are simultaneously hinged to one second moving member 17; in fact, the whole second moving member 17 may be a ring structure sleeved on the fixed end 13, three second brackets 16 are respectively connected between the three extending ends 12 forming the triangular cone and the peripheral surface of the second moving member 17, and the corresponding connecting members 19 may be respectively connected with the second moving member 17 from the intervals between the three extending ends 12.
During operation, the heating temperature of the constant-temperature sampling gun 1, the constant-temperature filter 8 and the constant-temperature adsorption bottle box 2 is not lower than the smoke temperature.
Two first bottles 6 and two second bottles 7 are arranged in the constant-temperature adsorption bottle box 2, and each first bottle 6 and each second bottle 7 are connected in series to form a group of samples, and two groups of samples are simultaneously sampled in parallel.
The placing cavity 21 comprises an upper cavity 23 and a lower cavity 25, a buckle 24 is sleeved at the lower end of the upper cavity 23, a circle of buckle 26 is sleeved at the upper end of the lower cavity 25, the buckle 26 and the buckle 24 are mutually clamped, and the upper cavity 23 and the lower cavity 25 are fixedly matched to form the complete placing cavity 21. Such a quick-connect arrangement can be convenient and fast when the contents of the placing cavity 21 are taken and placed.
The clay mineral solid adsorbent in the first bottle body 6 can be one of bentonite, attapulgite, hydrotalcite, kaolinite, montmorillonite, vermiculite and zeolite. The clay mineral has abundant surface active groups, can provide more adsorption sites for heavy metals, has larger specific surface area, more micropores, strong adsorption capacity, abundant reserves and low price, can greatly improve the acquisition efficiency of mercury oxide in flue gas, reduces the acquisition cost, and is convenient to operate on site.
The clay mineral solid adsorbent in the second embodiment is zeolite.
The solid acid of the solid acid adsorbent in the second bottle body 7 takes a molecular sieve as a carrier, and ammonium dithionate (NH)4)2S2O8Prepared by an immersion method. The molecular sieve can be USY (containing 0.05% of Na)2O), HY (the ratio of silicon to aluminum is 5), Hbeta (the ratio of silicon to aluminum is 50), HZSM-5 (the ratio of silicon to aluminum is 25) and MCM-41. The molecular sieve has larger specific surface area, open three-dimensional pore structure and excellent hydrothermal stability, and can be subjected to harsh regeneration conditions. S2O8 2-The molecular sieve type solid acid has higher sulfur content and more acid sites, and has high Hg content0The collection efficiency of (2) is higher.
The molecular sieve can be USY (containing 0.05% of Na)2O), HY (the ratio of silicon to aluminum is 5), Hbeta (the ratio of silicon to aluminum is 50), HZSM-5 (the ratio of silicon to aluminum is 25) and MCM-41.
The preparation method of the solid acid comprises the following steps:
60g of the molecular sieve are placed in 200mL of ammonium disulfate solution (1mol/L) and stirred at room temperature for 1h at a stirring speed of 950 r/min. Then standing for a period of time, removing the supernatant, transferring to a crucible, and drying in an oven at 110 ℃. And roasting the dried solid acid in a muffle furnace at 550 ℃ for 3h in an air atmosphere, and finally grinding uniformly.
The solid acid of the solid acid adsorbent of the second example was used as USY (containing 0.05% Na)2O) molecular sieve as carrier, ammonium disulfate (NH)4)2S2O8Prepared by an immersion method.
The method and apparatus of the present invention are compared to existing assay methods as follows:
the method simultaneously collects the mercury in the flue gas at the outlet of the dust remover of the garbage incinerator, and simultaneously performs a blank experiment on site under the condition that the boiler reaches full load under test conditions by adopting HJ 543-2009 cold atomic absorption spectrophotometry (temporary) for measuring mercury in waste gas of fixed pollution source, HJ 917-2017 active carbon adsorption/thermal cracking atomic absorption spectrophotometry for measuring mercury in waste gas of fixed pollution source and the method.
Three methods are used for collecting the detection result of the mercury content in the flue gas at the outlet of the dust remover of the garbage incinerator: the total mercury content collected by HJ 543-3The total mercury content in the gas state collected by HJ 917-2017 is 8.75 mu g/m3The method collects the granular mercury with the content of 0.08 mu g/m3The mercury oxide content is 3.05 mu g/m3The elemental mercury content was 6.11. mu.g/m3The total mercury content is 9.24 mu g/m3The total mercury content in the gas state is 9.16 mu g/m3. Experiments prove that the method and the device have higher mercury collection rate and more accurate detection results.
In summary, according to the detection method and the collection device for mercury in waste incineration flue gas provided by the invention, the content of granular mercury is separately measured by separating granular mercury from gaseous mercury in the flue gas; adsorbing oxidized mercury by using a clay mineral solid adsorbent wetted by deionized water, and oxidizing elemental mercury by using a solid acid adsorbent wetted by deionized water to convert the elemental mercury into oxidized mercury and trap the oxidized mercury in the solid acid adsorbent; and finally, respectively measuring the contents of mercury oxide and elementary mercury by heating and resolving the clay mineral solid adsorbent and the solid acid adsorbent. The method is suitable for a high-temperature, high-humidity and high-corrosion flue gas detection environment, and the higher the flue gas temperature, humidity and acidity, the more beneficial the mercury collection of the clay mineral solid adsorbent and the solid acid adsorbent; the method can be used repeatedly for clay mineral solid adsorbents and solid acid adsorbents, and has the advantages of simple regeneration operation and detection cost reduction. The method comprises the following steps of separating granular mercury in flue gas by using a constant-temperature filter in a constant-temperature sampling gun, and then respectively carrying out adsorption of oxidized mercury and oxidation adsorption of element mercury through a first bottle body with a clay mineral solid adsorbent and a second bottle body with a solid acid adsorbent in a constant-temperature adsorption bottle box, so that simple and efficient collection operation is realized; the sampling controller controls the sampling pump to realize the monitoring of the flow rate of the flue gas.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields are included in the scope of the present invention.
Claims (10)
1. A method for detecting mercury in waste incineration flue gas is characterized by comprising the following steps:
the method comprises the following steps: the method comprises the following steps of (1) enabling waste incineration flue gas to pass through a filter membrane, separating granular mercury and gaseous mercury in the waste incineration flue gas, and measuring the content of the granular mercury in the waste incineration flue gas;
step two: introducing the separated waste incineration flue gas into a clay mineral solid adsorbent soaked by deionized water, and collecting mercury oxide in the flue gas;
step three: introducing the flue gas into a solid acid adsorbent soaked by deionized water, and collecting elemental mercury in the flue gas;
step four: and D, heating and resolving the clay mineral solid adsorbent and the solid acid adsorbent in the second step and the third step, and respectively measuring the contents of mercury oxide and elemental mercury released by the clay mineral solid adsorbent and the solid acid adsorbent, so as to obtain the content of gaseous mercury in the waste incineration flue gas.
2. The method for detecting mercury in waste incineration flue gas according to claim 1, wherein the clay mineral solid adsorbent is one selected from bentonite, attapulgite, hydrotalcite, kaolinite, montmorillonite, vermiculite and zeolite, and is treated by a microwave-enhanced acid leaching purification process.
3. The method according to claim 1, wherein the solid acid of the solid acid adsorbent is a molecular sieve carrier, ammonium dithioate (NH)4)2S2O8The material is prepared by an immersion method; the molecular sieve can be USY (containing 0.05% of Na)2O), HY (the ratio of silicon to aluminum is 5), Hbeta (the ratio of silicon to aluminum is 50), HZSM-5 (the ratio of silicon to aluminum is 25) and MCM-41.
4. The method for detecting mercury in waste incineration flue gas according to claim 1, wherein the specific steps of determining the content of mercury in a granular state in the step one are as follows:
detecting the quality of the filter membrane before separation;
detecting the quality of the separated filter membrane;
and calculating the content of the granular mercury in the waste incineration flue gas according to the absolute value of the mass difference between the two.
5. The method for detecting mercury in waste incineration flue gas according to claim 1, wherein the specific operation of the fourth step is as follows:
heating the clay mineral solid adsorbent and the solid acid adsorbent in the second and third steps to be analyzed at the temperature of more than 600 ℃;
and introducing the quantitatively released mercury oxide and elemental mercury into a mercury detector to respectively determine the content of the mercury oxide and the content of the elemental mercury released by the clay mineral solid adsorbent and the solid acid adsorbent, so as to obtain the content of the gaseous mercury in the waste incineration flue gas.
6. The utility model provides a mercury's collection system in msw incineration flue gas, a serial communication port, including constant temperature sampling gun, constant temperature adsorption bottle case, sampling controller and sampling aspiration pump, the sampling head of constant temperature sampling gun stretches into in the flue, be provided with constant temperature filter in the constant temperature sampling gun, the terminal intercommunication constant temperature adsorption bottle case of constant temperature sampling gun, the terminal intercommunication sampling controller of constant temperature adsorption bottle case, constant temperature adsorption bottle incasement along the flue gas flow direction in proper order the intercommunication have the first bottle that is equipped with clay mineral class solid sorbent and the second bottle that is equipped with solid acid sorbent, sampling controller intercommunication and control sampling aspiration pump.
7. The device for collecting mercury in waste incineration flue gas as claimed in claim 6, wherein the sampling head comprises a communicating pipe and sampling branch pipes, the communicating pipe is communicated with the front end of the constant-temperature sampling gun, the communicating pipe comprises three extension ends, the extension ends are connected with a plurality of sampling branch pipes, and the front ends of the sampling branch pipes are provided with sampling ports.
8. The device for collecting mercury in waste incineration flue gas as claimed in claim 7, wherein three extending ends of the communicating pipe extend to form a triangular cone structure, and the extending ends of the sampling branch pipes are horizontal planes and have inclined included angles larger than 30 degrees.
9. The device for collecting mercury in waste incineration flue gas as claimed in claim 6, wherein the heating temperatures of the constant-temperature sampling gun, the constant-temperature filter and the constant-temperature adsorption bottle box are not lower than the flue gas temperature.
10. The device for collecting mercury in waste incineration flue gas as claimed in claim 6, wherein the first bottle body and the second bottle body are both of a U-shaped porous glass plate structure.
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