CN105424540A - Testing device for volatilization properties of ammonium bisulfate in coal-fired flue gas - Google Patents

Testing device for volatilization properties of ammonium bisulfate in coal-fired flue gas Download PDF

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Publication number
CN105424540A
CN105424540A CN201510860908.4A CN201510860908A CN105424540A CN 105424540 A CN105424540 A CN 105424540A CN 201510860908 A CN201510860908 A CN 201510860908A CN 105424540 A CN105424540 A CN 105424540A
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hydrogen sulfate
ammonium hydrogen
coal
constant temperature
volatilization
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吴文龙
马双忱
张小霓
张立男
郭阳
邓悦
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North China Electric Power University
Electric Power Research Institute of State Grid Henan Electric Power Co Ltd
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North China Electric Power University
Electric Power Research Institute of State Grid Henan Electric Power Co Ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N5/00Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
    • G01N5/04Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
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  • General Health & Medical Sciences (AREA)
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  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

The invention provides a testing device for volatilization properties of ammonium bisulfate in coal-fired flue gas. The device comprises a nitrogen supplying system, a volatilization system and a weighing system, wherein the volatilization system comprises a constant-temperature furnace, a glass cover and a crucible; one side of the constant-temperature furnace is connected with the nitrogen supplying system through a gas inlet pipe and a gas outlet pipe is arranged on the other side of the constant-temperature furnace; the glass cover is arranged in the constant-temperature furnace; the crucible is arranged in the glass cover and an ammonium bisulfate sample to be tested is stored in the crucible; and the weighing system is used for weighing the mass of the ammonium bisulfate sample. According to the testing device, the volatilization properties of the sample are obtained through monitoring change conditions of the ammonium bisulfate along temperatures and volatilization time; and a testing result can provide reliable theoretical foundation and data support to temperature regulation and control of the ammonium bisulfate of a coal-fired boiler, and the blocking problem of an air pre-heater, and the corrosion problem of subsequent equipment, caused by the ammonium bisulfate, are solved.

Description

The proving installation of ammonium hydrogen sulfate boiling characteristics in a kind of coal-fired flue-gas
Technical field
The present invention relates to a kind of device for testing coal-fired power plant sulfureous in flue gas acid hydrogen ammonium boiling characteristics, belonging to field of combustion technology.
Background technology
In order to the discharge of control NOx, " fossil-fuel power plant atmospheric pollutant emission standard " specifies, NO in coal-burning power plant xdischarge capacity control at 100mg/m 3.SCR and SNCR denitration technology are with NH 3or urea is that reductive agent is to NO xcarrying out selective reduction, is that coal-burning power plant reduces NO xthe effective technology of discharge.
In SCR and SNCR denitrating flue gas process, under certain condition, SO 3with escape ammonia (NH unreacted in exiting flue gas 3) and water vapor can generate ammonium hydrogen sulfate (NH 4hSO 4, be called for short ABS) and ammonium sulfate ((NH 4) 2sO 4, be called for short AS), the generation of the two depends on NH 3and SO 3ratio.Theoretically, NH is worked as 3/ SO 3when mol ratio is greater than 2, tend to generate AS; Work as NH 3/ SO 3when mol ratio is less than 1, tend to generate ABS.
Its reaction that may exist is as follows:
The boiling point of ammonium hydrogen sulfate is 350 DEG C, and fusing point is 140 DEG C, has hydroscopicity, viscosity, corrosivity, presents gaseous state, liquid state, graininess respectively at different temperature.Gaseous state or granular ammonium hydrogen sulfate can with flow of flue gas, and the ammonium hydrogen sulfate viscosity of liquid state is extremely strong, the a large amount of flying dusts in flue gas can be adsorbed, finally be deposited on metal wall or be stuck in interlayer, air preheater is caused to block, and then cause air preheater running resistance to increase, and ammonium hydrogen sulfate has stronger corrosivity, can bring the etching problem of follow-up equipment.
For preventing the formation of ammonium hydrogen sulfate from resulting in blockage to air preheater, there is following research direction at present: control SO 3generation, control the escaping of ammonia, air preheater transformation and temperature adjusting.
Temperature adjusting refers to by controlling the running temperature of corresponding boiler plant or facilities and equipments transformation, ammonium hydrogen sulfate is volatilized smoothly, thus eliminates its harmful effect.Therefore need to test the boiling characteristics of ammonium hydrogen sulfate, to determine the temperature adjusting method of ammonium hydrogen sulfate and to carry out the selection of temperature.
For coal unit, when in flue gas, fly ash content is higher, ammonium hydrogen sulfate is liquid at 146 DEG C-207 DEG C, is gaseous state at relatively high temperatures, can decomposes and generate ammonia, sulfuric anhydride and water during higher temperature.Have the resolution characteristic of scholar to ammonium hydrogen sulfate to be studied, find that the decomposition of ammonium hydrogen sulfate is the reaction of one dimension phase boundray, its reaction mechanism is
This scholar finds that the decomposition temperature of pure ammonium hydrogen sulfate is more than 345 DEG C, reaches maximal value at 490 DEG C of decomposition rates, but there is no research to the boiling characteristics of different ammonium hydrogen sulfate sample.
The patent No. is the proving installation that the Chinese patent of CN104374667A discloses material boiling characteristics under a kind of ultrahigh vacuum thermal environment, comprises test container, vacuum-pumping system, heated for controlling temperature test platform, water-cooled temperature control collecting platform and TT&C system.This device can determine the volatilization temperature of material under ultravacuum thermal environment and volatility product, but can not test the rate of volatilization of ammonium hydrogen sulfate, therefore cannot provide theoretical foundation and Data support for the temperature adjusting of coal-burning boiler ammonium hydrogen sulfate.
Summary of the invention
The object of the invention is to the drawback for prior art, provide the proving installation of ammonium hydrogen sulfate boiling characteristics in a kind of coal-fired flue-gas, the temperature adjusting for ammonium hydrogen sulfate provides reliable theoretical foundation and Data support.
Problem of the present invention realizes with following technical proposals:
The proving installation of ammonium hydrogen sulfate boiling characteristics in a kind of coal-fired flue-gas, formation comprises nitrogen supply system, volatilization system and Weighing system, described volatilization system comprises constant temperature oven, cloche and crucible, and the side of described constant temperature oven is connected with nitrogen supply system by draft tube, and opposite side is provided with escape pipe; Described cloche is placed in constant temperature oven; Described crucible is placed in cloche, and its inside holds tested ammonium hydrogen sulfate sample; Described Weighing system is electronic balance, and weigh the quality of ammonium hydrogen sulfate sample in crucible, the testing procedure of described proving installation is as follows:
A. ammonium hydrogen sulfate sample is put into crucible, utilize nitrogen supply system to input nitrogen in constant temperature oven, cloche, crucible and ammonium hydrogen sulfate sample are all in nitrogen atmosphere;
B. with constant temperature oven, heated at constant temperature is carried out to the ammonium hydrogen sulfate sample held in the crucible of cloche inside;
C. timing electronic balance weighing crucible quality record data, utilizes following formula to calculate the rate of volatilization of ammonium hydrogen sulfate sample under design temperature:
ν=Δm/Δt
Wherein, ν represents the rate of volatilization of ammonium hydrogen sulfate sample; Δ t represents the adjacent time interval weighing ammonium hydrogen sulfate sample quality for twice; Δ m represents the mass change amount of ammonium hydrogen sulfate sample in time interval Δ t;
D. with the design temperature of the step-size change constant temperature oven of setting, repeat step a ~ step c, obtain the ammonium hydrogen sulfate sample rate of volatilization data at multiple temperature;
E. according to rate of volatilization-time curve under the different temperatures of the Plotting data ammonium hydrogen sulfate sample of record.
The proving installation of ammonium hydrogen sulfate boiling characteristics in above-mentioned coal-fired flue-gas, condenser system and extract system is also comprised in formation, described condenser system comprises serpentine condenser, water bath with thermostatic control system and the water circulating pump be arranged in water bath with thermostatic control system and Meng Shi wash bottle, the escape pipe of one termination constant temperature oven of described serpentine condenser, the other end is connected with extract system through Meng Shi wash bottle; The water inlet of described water circulating pump and water delivering orifice connect the two ends of serpentine condenser outer sleeve respectively, and the composition of the condensed product in serpentine condenser and content adopt the chromatography of ions to measure.
The proving installation of ammonium hydrogen sulfate boiling characteristics in above-mentioned coal-fired flue-gas, described nitrogen supply system comprises Nitrogen source gases, flowmeter and electric heater unit, the exhausr port of described Nitrogen source gases is connected with the draft tube of constant temperature oven by flowmeter, and described electric heater unit is arranged in the draft tube of constant temperature oven.
The proving installation of ammonium hydrogen sulfate boiling characteristics in above-mentioned coal-fired flue-gas, described Nitrogen source gases is nitrogen cylinder or nitrogen making machine.
The proving installation of ammonium hydrogen sulfate boiling characteristics in above-mentioned coal-fired flue-gas, the top of described cloche or sidepiece are provided with cover door.
The proving installation of ammonium hydrogen sulfate boiling characteristics in above-mentioned coal-fired flue-gas, described Weighing system adopts electronic balance.
The proving installation of ammonium hydrogen sulfate boiling characteristics in above-mentioned coal-fired flue-gas, described extract system adopts vacuum pump.
The proving installation of ammonium hydrogen sulfate boiling characteristics in above-mentioned coal-fired flue-gas, described constant temperature oven carries out heated at constant temperature to ammonium hydrogen sulfate sample at different set temperature, the adjacent time interval Δ t weighing ammonium hydrogen sulfate sample quality for twice.
The present invention obtains the boiling characteristics of sample with the situation of change of temperature and volatilizes by monitoring ammonium hydrogen sulfate sample, the temperature adjusting that its test result can be coal-burning boiler ammonium hydrogen sulfate provides reliable theoretical foundation and Data support, is conducive to solving air preheater blocking and the etching problem of follow-up equipment that ammonium hydrogen sulfate causes.
Accompanying drawing explanation
Fig. 1 is the structural representation of the proving installation of ammonium hydrogen sulfate boiling characteristics in this coal-fired flue-gas.
In figure, each label is expressed as: 1-Nitrogen source gases; 2-flowmeter; 3-electric heater unit; 4-constant temperature oven; 5-cloche; 6-crucible; 7-electronic balance; 8-serpentine condenser; 9-water circulating pump; 10-Meng Shi wash bottle; 11-vacuum pump; 12-water bath with thermostatic control system.
Embodiment
Referring to Fig. 1, this device comprises nitrogen supply system, volatilization system, condenser system, extract system and Weighing system.The function and structure of each system is as follows:
Nitrogen supply system: for providing nitrogen atmosphere and certain gas flow rate for test process, comprise Nitrogen source gases 1(nitrogen cylinder or nitrogen making machine), flowmeter 2 and electric heater unit 3;
Volatilization system: the heating for ammonium hydrogen sulfate is volatilized, comprises constant temperature oven 4, cloche 5 and crucible 6.Wherein, constant temperature oven 4 internal temperature can be heated to 200 DEG C ~ 500 DEG C (comprising other temperature ranges), and this constant temperature oven opens the door in front side, and establishes air inlet and outlet pipe in both sides.Cloche 5 establishes side to open the door, the resistance to 500 DEG C of high temperature (comprising higher temperature) of crucible 6;
Condenser system: for the condensation of ammonium hydrogen sulfate volatility product, comprises water bath with thermostatic control system 12, serpentine condenser 8, water circulating pump 9 and Meng Shi wash bottle 10;
Extract system: for control system air pressure inside, prevents air pressure excessive, mainly comprises vacuum pump 11;
Weighing system, for weighing the mass change of ammonium hydrogen sulfate in volatilization process, to obtain the rate of volatilization of ammonium hydrogen sulfate, comprise precision electronic balance 7, precision is that 0.1mg(comprises more accurate electronic balance), can precise ammonium hydrogen sulfate quality at various temperatures over time.
The method of testing of ammonium hydrogen sulfate boiling characteristics: in nitrogen atmosphere, by the ammonium hydrogen sulfate sample heated at constant temperature in the crucible 6 in constant temperature oven 4 pairs of cloches 5, timing precision electronic balance 7 weighs the quality of crucible 6 and records data, the condensed product after ammonium hydrogen sulfate volatilization is obtained in serpentine condenser 8, the absorption of tail gas is carried out with Meng Shi wash bottle 10, and bleeding with vacuum pump 11 thereafter, in case locking system internal gas pressure is excessive.
Tested ammonium hydrogen sulfate sample can be pure ammonium hydrogen sulfate, the flying dust of different ammonium hydrogen sulfate content, the on-the-spot ammonium hydrogen sulfate sample in coal-burning power plant.
The heating-up temperature of constant temperature oven can select several heating-up temperature points within the scope of reasonable temperature.In the test of each heating-up temperature point, every certain time period, the registration of recorded electronic balance, to obtain the rate of volatilization of ammonium hydrogen sulfate under certain probe temperature over time.
Ammonium hydrogen sulfate rate of volatilization is defined as the variable quantity of ammonium hydrogen sulfate quality in the unit interval, is expressed as:
ν=Δm/Δt
Wherein, ν represents the rate of volatilization of ammonium hydrogen sulfate sample; Δ t represents the time interval of twice weighing ammonium hydrogen sulfate sample quality; Δ m represents the mass change amount of ammonium hydrogen sulfate sample in time interval Δ t.
Finally, rate of volatilization-time curve under different temperatures can be gone out according to Plotting data.
Below by specific embodiment, the present invention is further illustrated.
Nitrogen supply system selects the nitrogen cylinder of nitrogen gas purity >99.99%, and measurement range is the flowmeter 2 of 0-1L/min, and electric heater unit 3 can by air preheat to 200 DEG C.In volatilization system, the temperature of constant temperature oven 4 can be heated to 500 DEG C, and volume is 50cm*50cm*20cm; Open the door in cloche 5 side, its volume is 20cm*20cm*10cm; Ceramic crucible 6 can be high temperature resistant 500 DEG C, is highly 10cm.In condenser system, the temperature of water bath with thermostatic control system 12 can reach 100 DEG C, bleeds with the vacuum pump 11 that flow is 2.5L/min.Weighing system choice accuracy is the precision electronic balance 7 of 0.1mg.
Operation steps is: open nitrogen cylinder, adjust flux is 1L/min, electric heater unit 3 temperature is adjusted to 150 DEG C, constant temperature oven 4 temperature is adjusted to 340 DEG C, 350 DEG C, 360 DEG C, 370 DEG C, 380 DEG C respectively, heated at constant temperature is carried out to the ammonium hydrogen sulfate sample of certain coal-burning boiler equal in quality, in the test of each temperature spot, weigh the quality of crucible 6 and record every 10min electronic balance 7.In serpentine condenser 8, observe the condensed form of ammonium hydrogen sulfate volatility product, the condensation product in serpentine condenser 8 and Meng Shi wash bottle 10 is characterized.Calculate rate of volatilization, rate of volatilization-time curve under drafting different temperatures.
Although give detailed description and explanation to the embodiment of patent of the present invention above; but should be noted that; anyone changes and amendment, all within the protection domain of patent of the present invention the various equivalences that above-mentioned embodiment carries out in the conception according to patent of the present invention.

Claims (8)

1. the proving installation of ammonium hydrogen sulfate boiling characteristics in a coal-fired flue-gas, it is characterized in that, described device comprises nitrogen supply system, volatilization system and Weighing system, described volatilization system comprises constant temperature oven (4), cloche (5) and crucible (6), the side of described constant temperature oven (4) is connected with nitrogen supply system by draft tube, and opposite side is provided with escape pipe; Described cloche (5) is placed in constant temperature oven (4); Described crucible (6) is placed in cloche (5), and its inside holds tested ammonium hydrogen sulfate sample; Described Weighing system is electronic balance, and weigh the quality of ammonium hydrogen sulfate sample in crucible, the testing procedure of described proving installation is as follows:
A. ammonium hydrogen sulfate sample is put into crucible (6), utilize nitrogen supply system input nitrogen in constant temperature oven (4), cloche (5), crucible (6) and ammonium hydrogen sulfate sample are all in nitrogen atmosphere;
B. constant temperature oven (4) is used to carry out heated at constant temperature to the ammonium hydrogen sulfate sample held in the crucible (6) of cloche (5) inside;
C. timing electronic balance (7) weighs the quality of crucible (6) and records data, and the rate of volatilization of ammonium hydrogen sulfate sample under calculating design temperature;
D. with the design temperature of the step-size change constant temperature oven (4) of setting, repeat step a ~ step c, obtain the ammonium hydrogen sulfate sample rate of volatilization data at multiple temperature;
E. according to the rate of volatilization-time curve under the different temperatures of the Plotting data ammonium hydrogen sulfate sample of record.
2. the proving installation of ammonium hydrogen sulfate boiling characteristics in coal-fired flue-gas according to claim 1, it is characterized in that, condenser system and extract system is also comprised in formation, described condenser system comprises serpentine condenser (8), water bath with thermostatic control system (12) and the water circulating pump (9) be arranged in water bath with thermostatic control system (12) and Meng Shi wash bottle (10), the escape pipe of one termination constant temperature oven (4) of described serpentine condenser (8), the other end is connected with extract system through Meng Shi wash bottle (10); The water inlet of described water circulating pump (9) and water delivering orifice connect the two ends of serpentine condenser (8) outer sleeve respectively, and the composition of the condensed product in serpentine condenser (8) and content adopt the chromatography of ions to measure.
3. the proving installation of ammonium hydrogen sulfate boiling characteristics in coal-fired flue-gas according to claim 1 and 2, it is characterized in that, described nitrogen supply system comprises Nitrogen source gases (1), flowmeter (2) and electric heater unit (3), the exhausr port of described Nitrogen source gases (1) is connected with the draft tube of constant temperature oven (4) by flowmeter (2), and described electric heater unit (3) is arranged in the draft tube of constant temperature oven (4).
4. the proving installation of ammonium hydrogen sulfate boiling characteristics in coal-fired flue-gas according to claim 3, it is characterized in that, described Nitrogen source gases (1) is nitrogen cylinder or nitrogen making machine.
5. the proving installation of ammonium hydrogen sulfate boiling characteristics in coal-fired flue-gas according to claim 4, it is characterized in that, top or the sidepiece of described cloche (5) are provided with cover door.
6. the proving installation of ammonium hydrogen sulfate boiling characteristics in coal-fired flue-gas according to claim 5, is characterized in that, described Weighing system adopts electronic balance (7).
7. the proving installation of ammonium hydrogen sulfate boiling characteristics in coal-fired flue-gas according to claim 6, is characterized in that, described extract system adopts vacuum pump (11).
8. the proving installation of ammonium hydrogen sulfate boiling characteristics in coal-fired flue-gas according to claim 7, it is characterized in that, described constant temperature oven (4) carries out heated at constant temperature to ammonium hydrogen sulfate sample at different set temperature, and the adjacent time interval weighing ammonium hydrogen sulfate sample quality for twice is Δ t.
CN201510860908.4A 2015-11-30 2015-11-30 Testing device for volatilization properties of ammonium bisulfate in coal-fired flue gas Pending CN105424540A (en)

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CN109470594A (en) * 2018-10-29 2019-03-15 上海化工研究院有限公司 A kind of quantitative direct-evaporation-type toxicant exposure cabinet aerosol producer
CN115824876A (en) * 2022-11-07 2023-03-21 山东大学 Volatile substance volatilization rate testing device and method

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CN115824876A (en) * 2022-11-07 2023-03-21 山东大学 Volatile substance volatilization rate testing device and method
CN115824876B (en) * 2022-11-07 2024-05-31 山东大学 Volatile material volatilization rate testing device and method

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Application publication date: 20160323