CN110713299B - Passivation agglomeration complexing agent, preparation method and boiler flue gas treatment method - Google Patents

Passivation agglomeration complexing agent, preparation method and boiler flue gas treatment method Download PDF

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CN110713299B
CN110713299B CN201911007337.4A CN201911007337A CN110713299B CN 110713299 B CN110713299 B CN 110713299B CN 201911007337 A CN201911007337 A CN 201911007337A CN 110713299 B CN110713299 B CN 110713299B
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passivation
flue gas
complexing agent
agglomeration
flue
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CN110713299A (en
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李湧
张涛
何敏
张润伟
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Wuhan Tiankonglan Environmental Protection Technology Co ltd
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Wuhan Tiankonglan Environmental Protection Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
    • B01D47/06—Spray cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/01—Pretreatment of the gases prior to electrostatic precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/01—Pretreatment of the gases prior to electrostatic precipitation
    • B03C3/013—Conditioning by chemical additives, e.g. with SO3
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/10—Treatment of water, waste water, or sewage by heating by distillation or evaporation by direct contact with a particulate solid or with a fluid, as a heat transfer medium
    • C02F1/12—Spray evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/16—Treatment of water, waste water, or sewage by heating by distillation or evaporation using waste heat from other processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention provides a passivation agglomeration complexing agent, which comprises the following components in percentage by mass: 0.001 to 0.2% of amine, 0.0001 to 0.01% of fat, 0.0002 to 0.001% of alcohol, 0.0008 to 0.01% of surfactant and the balance of water; the amine is polyacrylamide and/or alkenamine; the grease is a binary copolymer of acrylic acid and acrylate, or a ternary copolymer of acrylic acid, AMPS and maleic anhydride, or oleate; the alcohol is aromatic alcohol or aliphatic alcohol; the surfactant is Triton X100 or sodium dodecyl benzene sulfonate; also provides a preparation method of the passivation agglomeration complexing agent; also provides a boiler flue gas treatment method, which adopts the passivation agglomeration complexing agent. In the invention, the complexing agent is sprayed into the front flue and the rear flue of the air preheater, SO that secondary pollution can not be generated, and SO in boiler flue gas is realized while desulfurization wastewater is absorbed3And PM2.5 fine particles and other pollutants, and the passivation effect ensures that the system cannot be corroded, the operation is reliable, and the agglomeration effect reduces the emission concentration of a rear dust remover.

Description

Passivation agglomeration complexing agent, preparation method and boiler flue gas treatment method
Technical Field
The invention relates to the technical field of flue gas environmental protection, in particular to a passivation agglomeration complexing agent, a preparation method and a boiler flue gas treatment method.
Background
Pollutants generated by coal-fired boiler flue gas in China are of a composite type, except for SO required to be treated by China2、NOxAnd in addition to particulates, SO will be appreciated in the future3And (4) pollution discharge. Because of SO3The toxicity of the sulfur dioxide is more than ten times higher than that of sulfur dioxide, and the sulfur dioxide has strong corrosivity, not only is an important reason for reducing visibility and aggravating haze, but also is the chief culprit of colored smoke plume of a power plant, and is dischargedAcid rain can also form when entering the atmosphere. Secondly, SO is increased in the SCR denitration process2Formation of SO3Conversion of (2), SO in flue gas3The concentration is increased to enable the ammonia gas to react with escaped ammonia gas in the denitration process to produce NH4HSO4The solid is adhered to the air preheater, so that the running resistance of the air preheater is increased, and even the air preheater is blocked. Therefore, the research on the cooperative treatment of the multi-stage pollutants in the coal-fired gas is very important.
At present SO2The limestone-gypsum wet desulphurization technology is mostly adopted for removal, but the desulphurization wastewater with high salt content, high suspended matter concentration, high hardness and high chloride ion concentration, which is one of the most difficult-to-treat wastewater of coal-fired power plants, is generated in the operation process, particularly, the high-concentration chloride ions have extremely strong corrosivity on a flue, seriously affect the stable operation of a system and the service life of equipment, and become a technical obstacle for implementing desulphurization wastewater treatment. The existing desulfurization waste water treatment method mainly adopts an evaporative crystallization method, and is divided into a main flue evaporative crystallization method and a bypass flue evaporative crystallization method from an evaporative type. The bypass evaporative crystallization is limited because a bypass flue needs to be newly built, the system is complex, the engineering cost is high, and some power plants even have no vacant positions; the main flue evaporation is because chlorine ion corrodes the flue of power plant, and the particle concentration of flue gas has been increased to the crystallization salt that produces simultaneously, causes the load increase of former dust remover, makes the emission concentration of particulate matter exceed standard and not generally promoted.
At present SO3The removal is mainly through a low-temperature electric dust remover and a wet-type electric dust remover. More than 90% of SO in the flue gas can be removed by a low-temperature electric dust remover3However, the low-temperature electric dust collector has an application range for coal quality, and the technical index of the ash-sulfur ratio is mainly adopted for judgment, so that the technology has certain limitation. The wet-type electric dust remover mainly removes ash by using a water film, can efficiently remove sulfuric acid mist adsorbed on the surface of particulate matters and is used for removing SO3The removal rate can reach 95 percent, but because the equipment of the method works in an acid and humid environment, the requirements on the materials of a polar plate, a polar line and a shell of the wet electric dust collector are higher, and an anode plate needs to be continuously sprayed to keep the polar plate clean,therefore, a set of circulating water and chemical treatment facilities needs to be additionally arranged, so that the waste water amount is large, and the problem of imbalance of the water balance of the whole desulfurization system is caused during operation.
Disclosure of Invention
The invention aims to provide a passivation agglomeration complexing agent, a preparation method and a boiler flue gas treatment method, and aims to solve the defects.
The invention is realized by the following steps:
the embodiment of the invention provides a passivation agglomeration complexing agent, which comprises the following components in percentage by mass: 0.001 to 0.2% of amine, 0.0001 to 0.01% of fat, 0.0002 to 0.001% of alcohol, 0.0008 to 0.01% of surfactant and the balance of water; the amine is polyacrylamide and/or alkenamine; the grease is a binary copolymer of acrylic acid and acrylate, or a ternary copolymer of acrylic acid, AMPS and maleic anhydride, or oleate; the alcohol is aromatic alcohol or aliphatic alcohol; the surfactant is Triton X100 or sodium dodecyl benzene sulfonate.
The modified polypropylene further comprises a salt of an organic acid, wherein the salt of the organic acid is sodium polyacrylate, and the mass percentage content of the salt of the organic acid is 0.002-0.01%.
Further, the amine is polyacrylamide and alkenylamine, and the mass percent content of the polyacrylamide and the mass percent content of the alkenylamine are both 0.0005-0.1%.
The embodiment of the invention also provides a preparation method of the passivation agglomeration complexing agent, which comprises the step of putting the amine, the ester, the alcohol, the surfactant and the water into a container for mixing and dissolving.
The embodiment of the invention also provides a boiler flue gas treatment method, wherein the passivation and agglomeration complexing agent as described in claim 1 is added into the desulfurization wastewater, and the mixed solution of the passivation and agglomeration complexing agent and the desulfurization wastewater is sprayed into the high-temperature flue to perform passivation and agglomeration reaction with the high-temperature flue gas in the high-temperature flue.
Further, the flue gas in the high-temperature flue sequentially passes through an air preheater, a dust remover and a desulfurizing tower, and the passivation and agglomeration complexing agent is sprayed into the flue gas flow paths in front of and behind the air preheater.
Further, outlet powder is monitored at the outlet of the desulfurizing towerDust and SO3And the concentration and the monitoring result are fed back to the PLC, and the spraying amount of the passivation agglomeration complexing agent is automatically adjusted through the PLC.
Further, a smoke analyzer is adopted to perform constant-current sampling at an outlet at the rear part of the dust remover, and the emission concentration of particles is measured.
Furthermore, the crystallized salt after evaporation and crystallization is collected and discharged by a dust remover along with the fly ash, and the water vapor is discharged into a desulfurizing tower along with the flue gas.
Further, the mixed liquid is sprayed in with a particle size of 10-25 μm by using a two-flow atomizing nozzle.
The invention has the following beneficial effects:
in the invention, the multiple pollutants used in front of the air preheater are synergistically treated to passivate and agglomerate the complexing agent, SO that the complexing agent is safe, nontoxic, obvious in effect, simple to operate and low in price, the complexing agent is sprayed into the front flue and the rear flue of the air preheater, secondary pollution is not generated to the complexing agent, and SO in boiler flue gas is realized while desulfurization wastewater is consumed3And PM2.5 fine particles and other pollutants, and the passivation effect ensures that the system cannot be corroded, the operation is reliable, and the agglomeration effect reduces the emission concentration of a rear dust remover.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the present invention will be described in detail with reference to the accompanying drawings and detailed embodiments, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts. Wherein:
FIG. 1 is a schematic structural diagram of a desulfurization wastewater concentration and flue evaporation integrated treatment process system provided by an embodiment of the invention;
FIG. 2 shows SO in flue gas according to an embodiment of the present invention3A schematic structural diagram of a removal system;
FIG. 3 is a schematic structural diagram of a first view angle of an atomizing spray gun for a flue according to an embodiment of the present invention;
FIG. 4 is a schematic structural diagram of an atomizing spray gun for a flue at a second viewing angle according to an embodiment of the present invention;
FIG. 5 is a front view of a lance flow and pressure regulation monitoring module provided in accordance with an embodiment of the present invention;
FIG. 6 is a schematic structural diagram of a main liquid spraying pipe and a branch liquid spraying pipe of a module for regulating and monitoring the flow and pressure of a spray gun according to an embodiment of the present invention;
FIG. 7 is a schematic structural diagram of an air main pipe and an air branch pipe of a module for regulating and monitoring the flow and pressure of a spray gun according to an embodiment of the present invention;
FIG. 8 is a side view of a lance flow and pressure regulation monitoring module provided in accordance with an embodiment of the present invention;
FIG. 9 is a schematic view of a mixing process of a passivation agglomeration complexing agent and desulfurization wastewater provided by an embodiment of the present invention;
FIG. 10 is a schematic structural diagram of a mixing and feeding system according to an embodiment of the present invention;
FIG. 11 is a schematic diagram of a mixing tank of a hybrid feed system according to an embodiment of the present invention;
FIG. 12 is a schematic structural diagram of a bin and a hopper of the hybrid feeding system according to an embodiment of the present invention;
FIG. 13 is a schematic view of a process for treating desulfurized wastewater according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1 and 2, an embodiment of the present invention provides a desulfurization wastewater concentration and flue evaporation integrated treatment process system, including a flue 5 and a passivation and agglomeration subsystem, wherein the passivation and agglomeration subsystem is adopted to spray a mixed solution of desulfurization wastewater and a passivation and agglomeration complexing agent into the flue 5.
Specifically, the passivation and agglomeration subsystem comprises a seed crystal method concentration evaporator, a filtering and precipitation device and a passivation and agglomeration preparation device, wherein the seed crystal method concentration evaporator is provided with a desulfurization wastewater inlet and a seed crystal liquid inlet, the seed crystal method concentration evaporator is of a system structure, the desulfurization wastewater inlet and the seed crystal liquid inlet are respectively used for adding desulfurization wastewater and seed crystal liquid into the seed crystal method concentration evaporator to realize the addition of the seed crystal liquid into the desulfurization wastewater, the seed crystal liquid can be calcium sulfate seed crystal solution to achieve the purpose of supplementing the seed crystal into the desulfurization wastewater, the calcium sulfate seed crystal solution is quantitatively conveyed into the seed crystal method evaporator by testing the conductivity of the solution in the evaporator and the display value of a densimeter (the CF value of the calcium sulfate concentration factor is 1.3-1.4), then the evaporation and the concentration of the desulfurization wastewater are realized by the evaporator, the evaporator adopts any form of MEE or MED or MVR + MED and the like, fresh steam provided from the outside is introduced into the seed crystal method concentration evaporator through the fresh steam pipe to exchange heat with the desulfurization wastewater through evaporation, so that the aim of concentrating the desulfurization wastewater is fulfilled. A concentrated solution (concentrated desulfurization wastewater) calandria of the seed crystal method concentration evaporator is communicated with a liquid inlet of the filtering and precipitating device, a liquid outlet of the filtering and precipitating device is communicated with a liquid inlet of the passivation and agglomeration preparation device, and the passivation and agglomeration preparation device is communicated with at least one atomization spray gun 4 positioned in a flue 5 through a passivation and agglomeration liquid outlet pipe. The liquid inlet of the filtering and precipitating device is positioned at the upper end, the liquid outlet of the filtering and precipitating device is positioned at the lower end, namely, the concentrated solution discharged by the seed crystal method concentrating evaporator enters from the liquid inlet at the upper end of the filtering and precipitating device, inorganic salt and solid insoluble substances in the concentrated solution are intercepted in a filtering and precipitating mode, and then the clarified concentrated solution can be guided into the passivation and agglomeration preparation device, the passivation and agglomeration preparation device is provided with a passivation and agglomeration complexing agent inlet, passivation and agglomeration complexing agent is added into the passivation and agglomeration preparation device from the inlet to form mixed solution of desulfurization wastewater and passivation and agglomeration complexing agent, and finally the mixed solution is sprayed into a flue 5 by an atomizing spray gun 4.
By the system, on one hand, SO in the agglomerated flue gas in the agglomeration complexing agent is passivated3、NH4HSO4Particulate matter (containing PM)2.5And heavy metal components in various types of flue gas), etc., into a mixture of large-particle inorganic salt particles, and on the other hand, canThe high temperature of the flue gas in the flue 5 is utilized to evaporate and crystallize the desulfurization waste water so as to eliminate the chloride ions in the desulfurization waste water. And the evaporator concentrated by adopting the crystal seed method has no scale formation, no blockage and no secondary pollution.
The system further comprises an adjusting tank, wherein a liquid outlet of the adjusting tank is communicated with a desulfurization wastewater inlet of the seed crystal method concentration evaporator through a delivery pump. The desulfurization waste water stock solution discharged from the desulfurization system of the coal-fired power plant enters an adjusting tank or a pot for temporarily storing the desulfurization waste water, the discharged amount of the desulfurization waste water per hour is high and low, the concentrated solution produced by the seed crystal method concentration evaporator does not exceed the maximum design amount of an evaporation and spraying system of a flue 5, namely, the concentration evaporator system is required to have a stable input amount, and the effect of stabilizing the input of the front end can be played through the adjusting tank or the pot.
Continuing to optimize the above embodiment, the system further comprises a condensate water tank/tank, wherein the condensate water outlet of the seed crystal method concentration evaporator is communicated with the inlet of the condensate water tank/tank, the outlet of the condensate water tank/tank is communicated with the back flush inlet of the filtering and precipitating device through the delivery pump, and the filtering and precipitating device is provided with a back flush outlet. The condensed water generated by the seed crystal method concentration evaporator is conveyed to a special condensed water tank/tank, can be used for supplementing water for a desulfurization system and can also be used for cleaning water for a subsequent system, wherein the cleaning is to clean the filtering and precipitating device in a back washing mode, specifically, a back washing inlet of the filtering and precipitating device is positioned at the lower end of the filtering and precipitating device and is lower than a liquid inlet of the filtering and precipitating device, and a back washing outlet of the filtering and precipitating device is positioned at the upper end of the filtering and precipitating device and is higher than a liquid outlet of the filtering and precipitating device, so that the flushing direction of the filtering and precipitating device is opposite to the precipitating and filtering direction, and inorganic salt and solid insoluble substances intercepted in the precipitating and filtering process can. Usually, the back washing outlet is communicated with a solid-liquid separator, flushed inorganic salt and solid insoluble substances can be used for preparing gypsum through the solid-liquid separator, and trace various precipitated inorganic salts contained in the gypsum can be ignored due to small mass ratio, so that the quality of the gypsum is not influenced.
Referring to fig. 2, the embodiment of the invention also provides a flue 5 knotThe structure is generally a boiler/kiln tail flue 5, an air preheater 51 is arranged in the flue 5, and a first nozzle of an atomizing spray gun 4 is arranged in front of the air preheater 51 along the flow direction of flue gas in the flue 5. In this embodiment, the air preheater 51 is an air preheater, and exchanges heat with the high-temperature flue gas in the flue 5, and the first nozzle of the atomizing spray gun 4 is arranged in front of the air preheater 51, that is, the flue gas firstly flows through the area where the first nozzle is located, and then passes through the air preheater 51. When the liquid sprayed out from the first nozzle enters the flue 5, the liquid can be agglomerated to adsorb SO in the flue gas, assuming that the liquid is an agglomerating agent or the passivation agglomeration complexing agent3、NH4HSO4Particulate matter (containing PM)2.5And heavy metal components in various types of flue gas), etc., into a mixture of large-particle inorganic salt particles, so that the scaling of the air preheater 51 can be effectively reduced. Generally speaking, along the flue gas flow direction, a denitration device is arranged in front of the air preheater 51, a dust remover 52 is arranged behind the air preheater 51, that is, the flue gas sequentially passes through the denitration device, the air preheater 51 and the dust remover 52, the flue gas is subjected to denitration treatment and then enters the air preheater 51 for heat exchange, and then is subjected to dust removal through the dust remover 52, the first nozzle of the atomizing spray gun 4 is a flow channel between the denitration device and the air preheater 51, the flue gas temperature of the flow channel is 200-400 ℃, and the flow channel can be used for eliminating SO in the flue gas after denitration treatment3、NH4HSO4And particulate matter, and the like. A second nozzle of the atomizing spray gun 4 is arranged at the part of the flue 5 corresponding to the space between the air preheater 51 and the dust remover 52, the temperature of the flue gas in the space is 100-200 ℃, and if liquid sprayed by the second nozzle is an aggregating agent, the liquid is used for continuously aggregating and adsorbing SO in the flue gas3、NH4HSO4And particles, etc., when the liquid sprayed out of the second nozzle is assumed to be the mixed liquid of the passivator and the desulfurization wastewater, the desulfurization wastewater can be evaporated and crystallized by utilizing the high temperature of the flue gas in the flue 5 to eliminate the chloride ions in the desulfurization wastewater, and certainly, when the liquid sprayed out of the second nozzle is the mixed liquid of the desulfurization wastewater and the passivation agglomeration complexing agent, the SO in the flue gas can be continuously agglomerated and adsorbed on the one hand3、NH4HSO4And particles, on the other hand, evaporating and crystallizing the desulfurization waste water. The generated particles can be collected with the fly ash by the dust collector 52, and the dust collector 52 is an electric dust collector. A single-layer or multi-layer atomizing spray gun 4 can be arranged in front of and behind the air preheater 51 corresponding to the flue 5, and the distance between every two layers of atomizing spray guns 4 is 3-8 m.
In a preferable scheme, the spraying direction of the atomizing spray gun 4 at the part extending into the flue 5, specifically, the spraying position (the first spraying opening or the second spraying opening) is the forward direction of the flue gas, that is, the spraying direction of the liquid of the atomizing spray gun 4 is the same as the flowing direction of the flue gas at the corresponding position, the spraying angle is 30-90 degrees, the particle size of the sprayed droplets is 10-150 μm, and the retention time of the droplets in the flue 5 is 0.2-2 s. Continuing to optimize the embodiment, a guide plate 53 is further arranged in the flue 5, the guide plate 53 is over against the part of the atomizing spray gun 4 extending into the flue 5, the flue gas sequentially flows through the guide plate 53 and the area where the atomizing spray gun 4 is located, specifically, the guide plate 53 is arranged right in front of the first nozzle and the second nozzle, and the flue gas firstly passes through the guide plate 53, SO that the SO subjected to agglomeration and adsorption is enabled to be obtained3And the dust particles uniformly pass through the nozzle atomization layer, so that the uniform mixing of the crystal particles in the sprayed liquid and the flue gas is ensured. The guide plate 53 adopts a V-shaped structure, is arranged in the range that the front end of the nozzle of the atomizing spray gun 4 is more than 1m, the design of the guide plate 53 is obtained by fluid simulation, the nozzle of the atomizing spray gun 4 is uniformly covered on the section of the flue 5 according to the flow field simulation result, the sufficient mixing of fog drops and flue gas is ensured, and SO in the flue gas is adsorbed3To achieve the removal of SO3The purpose of (1).
Referring to fig. 2 to 4, an atomizing spray gun 4 for a flue 5 is further provided in an embodiment of the present invention, and the atomizing spray gun 4 can be used in cooperation with the above-mentioned flue 5 structure, and further can be applied to SO in flue gas3And a desulfurization waste water treatment system, although the two systems can also adopt other atomizing spray guns 4. Specifically, the atomizing spray gun 4 includes a spray gun tube 41 and an air injection tube 42, wherein one end of the spray gun tube 41 is provided with an inlet 411 and a compressed air inlet 412, the other end is provided with an atomizing nozzle 43, the air injection tube 42 is arranged along the length direction of the spray gun tube 41, and the air injection tube 42 is close to one end of the inlet 411 is provided with an air inlet 421, the other end is provided with an air outlet 43An air outlet 422 is provided and the air outlet 422 is disposed adjacent to and toward the atomizing nozzle 43, thereby forming a two-fluid spray gun structure. In the present embodiment, the first nozzle opening and the second nozzle opening correspond to the atomizing nozzle 43, and the nozzle openings are embodied in the form of the atomizing nozzle 43. The spray gun pipe 41 is the main work part of the atomizing spray gun 4, and the air injection pipe 42 is the auxiliary work part, and the above-mentioned liquid passes through the inlet 411 and gets into in the spray gun pipe 41, and the compressed air that the air compressor machine 54 produced simultaneously passes through the compressed air import 412 and gets into in the spray gun pipe 41, and then can make liquid can be by the blowout of atomizing nozzle 43 department, in addition because the gas outlet 422 of air injection pipe 42 is close to atomizing nozzle 43, can effectually spout the smoke and dust of gathering around the atomizing nozzle 43, prevent that atomizing nozzle 43 from blockking up the scale deposit. Atomizing spray gun 4 sprays in flue 5, atomizing nozzle 43 is the fog export, be the cold junction in flue 5, high temperature smoke and dust can be to low temperature atomizing nozzle 43 gathering in flue 5, though spun desulfurization waste water is the high salt solution, have high viscidity and easy evaporation crystallization in high temperature, adhere to around the nozzle, but adopt the air jet tube 42 of this kind of structure regularly to spout atomizing nozzle 43 all around, prevent atomizing nozzle 43 scale deposit all around, through experimental verification, the frequency of spouting is every 8 minutes 10 seconds of jetting (when jetting air supply pressure 0.3~0.4 MPa) or every 20 minutes 8 seconds of jetting (when jetting air supply pressure 0.5~0.7 MPa), can avoid atomizing nozzle 43 scale deposit. Certainly, in order to prevent the crystallization and scaling inside the atomizing nozzle 43, the atomizing spray gun 4 needs to be cleaned with clean water before being started and stopped every time, so that no desulfurization wastewater is left in the pipeline of the atomizing spray gun 4.
In a preferred embodiment, the atomizing spray gun 4 further comprises a mounting seat 44, and the gun tube 41 and the gas lance 42 are mounted on the mounting seat 44. The mounting seat 44 is of a flange structure, and the atomizing spray gun 4 is positioned and mounted on the flue 5 through the mounting seat 44, so that one side of the atomizing spray gun 4 with the atomizing nozzle 43 is positioned in the flue 5 and the other side is positioned outside the flue 5 with the mounting seat 44 as a boundary. The central axis of the atomizing nozzle 43 is perpendicular to the length extension direction of the lance tube 41, so that when the lance tube 41 is extended into the flue 5 along the radial direction of the flue 5, the ejection direction of the atomizing nozzle 43 can be adjusted to be the forward direction of the flue gas.
Continuing to optimize the structure of atomizing spray gun 4, jet-propelled pipe 42 includes trunk 423 and two spinal branch pipes 424 that set up side by side, and two spinal branch pipes 424 communicate with trunk 423 through adapter 45, and air inlet 421 are located the one end that branch pipe 424 was kept away from to trunk 423, all are provided with in the one end that trunk pipe 423 was kept away from to each branch pipe 424 the gas outlet 422. In this embodiment, the gas injection pipe 42 has one gas inlet 421 and two gas outlets 422, so that the action area of the gas injection pipe 42 on the atomizing nozzle 43 is relatively large. In actual installation, two branch pipes 424 pass through the mounting seat 44, namely the adapter 45 and the main pipe 423 are located outside the flue 5, most of the structures of the two branch pipes 424 are located inside the flue 5, and the other parts are located outside the flue 5. A reinforcing rib 46 is usually interposed between the two branch pipes 424, and the two branch pipes 424 are welded to the reinforcing rib 46, whereby the strength (deformation and bending prevention) of the atomizing spray gun 4 in the flue 5 can be enhanced, and the position of the gas lance 42 can be fixed. The structure of the trunk 423 is detailed, the trunk 423 comprises a hose section 425 and a hard pipe section 426, the hose section 425 and the hard pipe section 426 are communicated through a solenoid valve 427, the air inlet 421 is located in the hose section 425, the hard pipe section 426 is communicated with the adapter 45, wherein the solenoid valve 427 can be provided with a delay switch control, the hose section 425 is convenient to be switched, and the hard pipe section 426 is used for ensuring the strength requirement. The lance pipe 41 windward side has welded angle iron 4740 mm 3mm, and length is from 200mm department to the atomizing nozzle 43 farthest end apart from connecting mount pad 44 terminal surface, wraps whole lance pipe 41 windward side, and the lance pipe 41 supports on the medial surface of angle iron 47 at least partially promptly, and the material of angle iron 47 can be adopted ordinary carbon steel, and the lance pipe 41 can adopt the stainless steel.
Referring to fig. 2, 5-8, for the atomizing spray gun 4, of course, the atomizing spray gun 4 may be of the above-mentioned two-fluid structure, or may adopt another structural form, and the embodiment of the present invention further provides a spray gun flow and pressure adjusting and monitoring module 6, which can ensure that the compressed air pressure of each atomizing spray gun 4 is consistent and the flow of the aggregation liquid is consistent, and ensure that the atomizing effect is optimal. The monitoring module 6 comprises a frame 61, a liquid spraying main pipe 62 and an air main pipe 63, wherein a plurality of liquid spraying branch pipes 64 with one ends capable of being communicated to the atomizing spray gun 4 and a plurality of air branch pipes 65 which are in one-to-one correspondence with the liquid spraying branch pipes 64 and with one ends capable of being communicated with the atomizing spray gun 4 are further arranged on the frame 61, the other ends of the liquid spraying branch pipes 64 are communicated to the liquid spraying main pipe 62, the other ends of the air branch pipes 65 are communicated to the air main pipe 63, a flow meter 641 is arranged on each liquid spraying branch pipe 64, a pressure regulating valve 651 and a pressure meter 652 are arranged on each air branch pipe 65, and each pressure regulating valve 651 and each flow meter. The monitoring module 6 of this embodiment corresponds to a plurality of sets of atomizing spray guns 4, wherein the number of atomizing spray guns 4 is the same as the number of spray branch pipes 64 and air branch pipes 65, and is in a one-to-one correspondence relationship. The liquid (the mixed liquid of the desulfurization wastewater and the passivating agent, or the mixed liquid of the desulfurization wastewater and the passivation and agglomeration complexing agent, or the agglomeration agent) firstly enters the main liquid spraying pipe 62, then is shunted to each branch liquid spraying pipe 64 through the main liquid spraying pipe 62, and finally enters each corresponding atomization spray gun 4, the compressed air generated by the air compressor 54 firstly enters the main air pipe 63, then is shunted to each branch air pipe 65 through the main air pipe 63, and finally enters each corresponding atomization spray gun 4, and specifically, the branch liquid spraying pipes 64 and the branch air pipes 65 are connected with the corresponding atomization spray guns 4 through hoses 68.
Respective metering valves are provided in each spray manifold 64 and each air manifold 65 for monitoring and controlling fluid flow therein. Specifically, a manual ball valve 642 (which closes the liquid spray branch pipe 64 and further closes the liquid pipeline of the corresponding single atomizing spray gun 4), a check valve 643 (which prevents liquid from flowing backwards), a needle valve 644 (which is used for adjusting the liquid flow rate of the liquid spray branch pipe 64 entering the corresponding atomizing spray gun 4), a flow meter 641 (which is used for monitoring the liquid flow rate entering the atomizing spray gun 4), and a pressure gauge 645 (which is used for monitoring the liquid pressure in the liquid spray branch pipe 64 and the corresponding atomizing spray gun 4) are arranged on each liquid spray branch pipe 64; each air branch pipe 65 is provided with a manual ball valve 653 (which closes the air branch pipe 65 and thus closes the compressed air line of the corresponding single atomizing spray gun 4), a check valve 654 (which prevents the compressed air from flowing backwards), a pressure regulating valve 651 (which regulates the pressure of the compressed air entering the corresponding atomizing spray gun 4 from the air branch pipe 65), and a pressure gauge 652 (which monitors the pressure of the compressed air in the air branch pipe 65 and the corresponding atomizing spray gun 4). The instrument valves are all centralized in one frame 61, so that the liquid flow and the compressed air pressure of the atomizing spray gun 4 on the same layer can be conveniently and uniformly regulated and monitored.
Therefore, the compressed air pressure of all the atomizing spray guns 4 is adjusted to be consistent through the manual pressure adjusting valve 651, the compressed air pressure of each atomizing spray gun 4 is monitored through the local pressure gauge 652, and when the compressed air pressure of one atomizing spray gun 4 is lower than that of other atomizing spray guns 4 on the same layer, whether the branch pipe of the atomizing spray gun 4 leaks air or not needs to be focused; when the pressure of the compressed air in one of the atomizing spray guns 4 is higher than that of the other atomizing spray guns 4 in the same layer, the important concern is whether the branch pipes of the atomizing spray gun 4 are blocked.
In addition, the flow meter 641 monitors the liquid flow of each atomizing spray gun 4, and when the liquid flow of one atomizing spray gun 4 is lower than that of other atomizing spray guns 4 in the same layer, whether the atomizing spray gun 4 is blocked needs to be focused; when the liquid flow rate of one of the atomizing spray guns 4 is higher than that of the other atomizing spray guns 4 in the same layer, attention needs to be paid to whether the atomizing spray gun 4 leaks liquid. The flowmeter 641 can be a rotameter, and the float of the rotameter is made of teflon and coated on the surface, so that the friction coefficient of the float can be reduced, and the rotameter can be ensured to be normally used in viscous liquid.
In the preferred embodiment, each branch spray pipe 64 is connected to the corresponding air branch pipe 65 through a purge pipe 66, and a connecting valve 661 is disposed on the purge pipe 66. In normal operation, connecting valve 661 is closed, and when it is open, spray manifold 64 can be purged with compressed air from air manifold 65.
Further, the monitoring module 6 further includes a branch section 67, wherein a part of the liquid spraying branch pipes 64 is communicated with the liquid spraying main pipe 62 through the branch section 67, in addition, each part of the liquid spraying branch pipes 64 is directly connected with the liquid spraying main pipe 62, and an electric cut-off valve 671 is arranged on the branch section 67, so that the electric cut-off valve 671 can be remotely closed when the liquid is operated at a low flow rate, so as to close the liquid spraying branch pipes 64 corresponding to the branch section 67, and only the liquid spraying branch pipes 64 directly connected with the liquid spraying main pipe 62 are kept. For the structure, the branch section 67, the main spray pipe 62 and the main air pipe 63 are all provided with a blowdown valve 69, which can be used for realizing blowdown of corresponding pipelines.
Referring to fig. 2 and 9, the embodiment of the invention also provides a passivation agglomeration complexing agent, which can be applied to a desulfurization wastewater concentration and flue 5 evaporation integrated treatment process system and SO in flue gas3In the removal system, when the desulfurization waste water is mixed and sprayed into the flue 5, various functions of passivation and agglomeration can be realized. The composition of said compound agent is water-base organic mixed agent formed from amine and ester, fatty alcohol or aromatic alcohol, surfactant and water-soluble high-molecular compound, the above-mentioned amine is polyacrylamide and alkamine or organic acid salt; the ester is a binary copolymer of acrylic acid and acrylate, or a ternary copolymer of acrylic acid, AMPS and maleic anhydride, or oleate; the alcohol substance is isopropanol; the surfactant is any one of Triton X100, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate, and the components in percentage by mass are as follows: 0.001 to 0.2% of amine, 0.0001 to 0.01% of fat, 0.0002 to 0.001% of alcohol, 0.0008 to 0.01% of surfactant and the balance of water.
The passivation is mainly based on a physical and chemical mechanism, and certain functional groups in the amine and the ester can react with substances in the electrolyte or can play a role in inhibiting the ion diffusion speed in the solution, so that the corrosion speed of the metal is slowed down. Aliphatic alcohol or aromatic alcohol and SO in flue gas3The sulfonation reaction is carried out, and SO in the flue gas is removed3Meanwhile, the organic product generated after the reaction has water solubility, particularly has various surface activities such as emulsification, wetting and the like, and further promotes the agglomeration effect of fine particles. The agglomeration is mainly characterized in that the surfactant promotes the wetting of superfine particles by reducing the surface tension of the solution and accelerates the superfine particles to enter the inside of the liquid drops of the passivation agglomeration complexing agent, thereby improving the capture speed and the capture amount of the superfine particles. After the sodium-based surfactant is adsorbed by the particles, the conductivity of the particles can be enhanced, and the specific resistance of the particles is reduced. After the water-soluble high molecular compound is dissolved in water, the formed charged groups can generate electric neutralization with ultrafine particles; the long polymer chains adsorbed on the surface of one particle may be adsorbed on another particle at the same timeOn the surface of the particles, two or more particles are agglomerated together in a bridging mode, and the particles can be agglomerated due to the electric neutralization and adsorption bridging effects, so that the fly ash removal efficiency of the electrostatic dust collector 52 is improved.
Specifically, in the first embodiment of passivating the agglomeration complexing agent: 0.001-0.2% of polyacrylamide and alkenyl amine, 0.0001-0.01% of binary copolymer of acrylic acid and acrylate, 0.0002-0.001% of fatty alcohol, 0.0008-0.01% of Triton X100 and the balance of water, wherein the percentage content of polyacrylamide and alkenyl amine is 0.0005-0.1%, the percentages are mass percentages, and the following component percentages are mass percentages. In this embodiment, coal used in a power plant has a sulfur content of 0.75% (low-sulfur coal), and a 30-ten-thousand-watt coal-fired unit is sprayed into a passivation agglomeration complexing agent (0.0005% polyacrylamide, 0.0005% alkenylamine, 0.0001% acrylic acid-acrylate copolymer, 0.0002% fatty alcohol, 0.0008% Triton X100, and the balance water) prepared by desulfurization wastewater in front of and behind an air preheater 51 and 3m through a flue 5, respectively, and the passivation agglomeration complexing agent is atomized into droplets with an average particle size of about 10 to 20 μm and sprayed into the flue 5 under the action of pressurized air, and the droplets interact in the flue 5 for a residence time of about 1s to promote agglomeration and growth of ultrafine particles, and are captured by a subsequent dust catcher 52. And a flue gas analyzer is adopted to perform constant-current sampling at the rear outlet of the dust remover 52, and the emission concentration of the particles is measured. The result shows that the passivation agglomeration complexing agent of the formula generates obvious agglomeration of fly ash particles, and the dust concentration after the dust remover 52 is 80mg/m of that when the passivation agglomeration accelerating agent is not sprayed3Respectively reduced to 40mg/m3The reduction ratio reaches 50 percent, and SO3The concentration is 10 mg/m from the beginning3Reduced to 4 mg/m3The reduction ratio reaches 60%, and after continuous three-month operation, the operation is stopped, the maintenance is carried out, the flue 5 is checked, no obvious corrosion phenomenon is found, and the corrosion level of chloride ions in the desulfurization wastewater is reduced by 70%. The passivation agglomeration complexing agent comprises the following components in percentage by mass: 0.1% polyacrylamide and 0.1% alkenylamine, 0.01% acrylic acid and acrylate copolymer, 0.001% fatty alcohol, 0.01% Triton X100, and waterThe dust concentration is reduced by 55%, SO3The reduction ratio of (2) can be up to 64%, and the corrosion level of chloride ions in the desulfurization wastewater is reduced by 75%.
In example two, the passivating agglomeration complexing agent: 0.001-0.2% of salt of enamine and organic acid, 0.0001-0.01% of terpolymer of acrylic acid, AMPS and maleic anhydride, 0.0005-0.05% of aromatic alcohol, 0.0008-0.01% of sodium dodecyl benzene sulfonate and the balance of water, wherein the AMPS is 2-acrylamide-2-methyl propanesulfonic acid, and the balance of water, the salt of the organic acid is sodium polyacrylate, and the mass percentage content of the salt of the organic acid is 0.002-0.01%. In this embodiment, the sulfur content of coal used in a power plant is 1.78% (sulfur coal), a passivation agglomeration complexing agent (0.001% enamine, 0.002% sodium polyacrylate, 0.0001% terpolymer of acrylic acid, AMPS and maleic anhydride, 0.0005% aromatic alcohol, 0.0008% sodium dodecylbenzenesulfonate, and the balance water) prepared from desulfurization wastewater is sprayed into the front of 60 ten thousand kilowatt unit electrostatic precipitator 52 of a coal-fired power plant through a liquid dispensing pump, compressed air, and atomizing nozzle 43, and is sprayed into the front of air preheater 51 and the rear flue 5 by 1m and 4m frames, respectively, and is sprayed into the vertical flue 5 by a particle size of about 10-25 μm, and the emission concentration of smoke dust is 68mg/Nm from the original emission concentration3Down to 30 mg/Nm3Reduction of about 56%, SO3The concentration is 15 mg/m from the beginning3Reduced to 4 mg/m3The reduction is about 73 percent, and the running pressure difference of the air preheater 51 is kept in a normal range all the time after the continuous running for half a year, and the phenomenon of crystal blockage does not occur. When the device is stopped and overhauled, the flue 5 is checked, obvious corrosion and flue 5 caking phenomena are not found, and the corrosion level of chloride ions in the desulfurization wastewater is reduced by 75 percent. The passivation agglomeration complexing agent comprises the following components in percentage by mass: 0.2% of enamine, 0.01% of sodium polyacrylate, 0.01% of terpolymer of acrylic acid, AMPS and maleic anhydride, 0.05% of aromatic alcohol, 0.01% of sodium dodecyl benzene sulfonate and the balance of water, the dust concentration reduction ratio is up to 60%, and the SO concentration is reduced by 60% by weight3The reduction ratio of (2) can be up to 75%, and the corrosion level of chloride ions in the desulfurization wastewater is reduced by 80%.
In example three of the passivating agglomeration complexing agent: 0.001-0.2% of polyacrylamide and organic acid salt, 0.0001-0.01% of oleic acid ester0.001-0.1% of aromatic alcohol, 0.0008-0.01% of sodium dodecyl sulfate and the balance of water, wherein the salt of the organic acid is sodium polyacrylate, and the mass percentage content of the salt of the organic acid is 0.002-0.01%. In this embodiment, the sulfur content of coal used in a power plant is 4.23% (high sulfur coal), and before the electrostatic precipitator 52 of 30 ten thousand kilowatt units in a coal-fired power plant, passivation agglomeration complexing agent (0.001% polyacrylamide, 0.002% sodium polyacrylate, 0.0001% oleic acid, 0.001% aromatic alcohol, 0.0008% sodium dodecylbenzene sulfonate, and the balance water) prepared by using desulfurization wastewater is sprayed into 1m and 3m frames respectively before the air preheater 51 and the rear flue 5, and sprayed into the vertical flue 5 with a particle size of about 10-20 μm, and the emission concentration of smoke dust is 80mg/Nm from the original one3Reduced to 26 mg/Nm3Reduction of about 68%, SO3The concentration is 60mg/m from the beginning3Reduced to 12 mg/m3And the reduction is about 80%, and after the air preheater 51 continuously runs for one quarter, the running pressure difference is always kept in a normal range, and the crystal blockage phenomenon does not occur. When the device is stopped and overhauled, the condition of the flue 5 is found to be good through inspection, and the corrosion level of chloride ions in the desulfurization wastewater is reduced by 75 percent. The passivation agglomeration complexing agent comprises the following components in percentage by mass: 0.2 percent of polyacrylamide, 0.01 percent of sodium polyacrylate, 0.01 percent of oleic acid ester, 0.1 percent of aromatic alcohol, 0.01 percent of sodium dodecyl benzene sulfonate and the balance of water, the dust concentration reduction ratio is up to 70 percent, and SO3The reduction ratio of (2) can be up to 84%, and the corrosion level of chloride ions in the desulfurization wastewater is reduced by 85%.
The embodiment of the invention also provides a preparation method of the passivation agglomeration complexing agent, and the amine, the ester, the alcohol, the surfactant and the water are put into a container to be mixed and dissolved. Mixing the prepared passivation and agglomeration complexing agent with desulfurization wastewater, spraying the mixture into a high-temperature flue 5 to perform passivation and agglomeration reaction with high-temperature flue gas in the high-temperature flue 5, and mixing powder of the passivation and agglomeration complexing agent with the desulfurization wastewater in a two-step mixing mode, namely mixing pretreated (such as filtration) desulfurization wastewater and powder of the passivation and agglomeration complexing agent in an emulsifying tank 1 to form emulsion, introducing the emulsion into a mixing tank 2, and then mixing pretreated desulfurization wastewater againMix once more with the emulsion in the blending tank 2 and form mixed liquid, mixed liquid in the blending tank 2 can directly leading-in atomizing spray gun 4, also can add a buffer memory jar, and earlier mixed liquid stores in buffer memory jar, and leading-in atomizing spray gun 4 of mixed liquid in the buffer memory jar, and of course should measure at the in-process of leading-in atomizing spray gun 4. The flue 5 is communicated to the desulfurization tower, specifically, the flue gas sequentially passes through the denitration device, the air preheater 51, the dust remover 52 and the desulfurization tower, the crystallized salt and the agglomerated solid particles after the desulfurization wastewater is evaporated and crystallized are collected and discharged by the dust remover 52 along with the fly ash, and the water vapor is discharged into the desulfurization tower along with the flue gas. A flue gas analyzer is adopted to perform constant-current sampling at the rear outlet of the dust remover 52, the particle emission concentration is measured, and the outlet dust and SO are monitored at the outlet of the desulfurizing tower through a CEMS (flue gas on-line monitoring system)3The monitoring result is fed back to the PLC, and the spraying amount of the passivation agglomeration complexing agent is automatically adjusted through the PLC.
When only the removal of SO from flue gases in the flue 5 is considered3Meanwhile, the embodiment of the invention also provides SO in the flue gas3The removing system is different from the desulfurization wastewater concentration and flue 5 evaporation integrated treatment process system, and liquid sprayed by the atomizing spray gun 4 is an aggregating agent. The main components of the agglomerant are macromolecular compound, inorganic salt, surfactant and pH regulator. The special coating comprises, by mass, 0.001% -0.01% of polyethyleneimine, 0.001% -0.1% of tween 80, and the like. The agglomeration agent is sprayed into the flue 5 by the atomizing spray gun 4, SO that SO in the flue gas can be eliminated3、NH4HSO4And particles and the like, wherein the mass percentage of the formula is polyethyleneimine: 0.005%, tween 80: 0.01%, potassium chloride: 0.05 percent of agglomerating agent, and the flow of the atomizing spray gun 4 is reasonably adjusted to ensure that SO in the flue gas3The removal rate of the catalyst reaches more than 90 percent. The system of this embodiment includes flue 5, emulsification tank 1, blending tank 2 and atomizing spray gun 4, and wherein emulsification tank 1 is used for once diluting, and blending tank 2 is then used for the secondary to dilute, specifically is that emulsification tank 1's discharge gate passes through the feed inlet intercommunication of emulsification pump with blending tank 2, and the discharge gate of blending tank 2 passes through the positive displacement pump223 communicating with the atomizing spray gun 4.
The specific operation steps are as follows: injecting dilution water into an emulsification tank 1, adding an agglomerant powder into the emulsification tank 1, mixing and diluting with water, wherein the particle size of the agglomerant powder is 200-300 meshes, mixing a mixed solution through a rotor pump and an emulsification pump, shearing and stirring through the emulsification pump, homogenizing, and then refluxing into the emulsification tank 1, the concentration of the solution in the emulsification tank 1 is 0.3-1%, a densimeter 15 can be arranged in the emulsification tank 1 and used for monitoring the concentration of the solution in the emulsification tank 1, then adding the dilution water into a mixing tank 2, injecting the solution in the emulsification tank 1 into the mixing tank 2 for further dilution, uniformly mixing through a stirrer, the concentration of the solution in the mixing tank 2 is 0.3-1 ‰, certainly, a densimeter 25 is also arranged in the mixing tank 2 and used for monitoring the concentration of the solution in the mixing tank, finally inputting compressed air and the mixed solution in the mixing tank 2 into an atomization spray gun 4 through a pipeline, spraying the mixed solution into a front flue 5 and a rear flue 5 of, according to SO in the flue gas3The concentration and the flue gas temperature of the flue gas, the flow rate of the agglomeration agent mixed liquid and the pressure of compressed air are regulated, certain atomized liquid drops are formed in the flue 5 and are uniformly mixed with the flue gas to adsorb SO in the flue gas3And fine particulate dust particles pass through the dust separator 52 and are captured and discharged with the ash. In the process, densimeters are arranged in the emulsifying tank 1 and the mixing tank 2 respectively and used for monitoring the concentration of the solution in the emulsifying tank and the mixing tank.
Referring to fig. 2 and 10-12, in practice when considering the disposition of the agglomeration agent, passivating agent and passivating agglomeration complexing agent, a mixing and feeding system can be adopted, which comprises a hopper 3, a mixing tank 2, an emulsifying tank 1, a mixing barrel 12 and a controller, wherein the emulsifying tank 1 is provided with a first liquid level meter 14, the hopper 3 is connected with the mixing barrel 12 through a blanking machine 32, the emulsifying tank 1 is communicated with the mixing barrel 12 through a pipeline, the mixing barrel 12 is connected with the mixing tank 2 through the pump set 11, a first flow meter 13 is arranged on a flow path between the mixing barrel and the mixing tank 2, the mixing tank 2 is further provided with a liquid supply pipe 23, a liquid discharge pipe 22 and a second liquid level meter 24, the liquid supply pipe 23 is provided with a second flow meter 231 and an air-operated valve 232, the liquid discharge pipe 22 is provided with a liquid discharge pump 223, and the first liquid level meter 14, the blanking machine 32, the first flow meter 13, the second liquid level meter 24 and the second flow meter 231 are all electrically connected to the controller.
The technical solution disclosed in this embodiment is similar to the above-mentioned solution for preparing an agglomerating agent, and a two-stage mixing and diluting method is also adopted, wherein the hopper 3 is used for providing powder, specifically, powder of each agent, into the mixing barrel 12, and the emulsifying tank 1 is used for providing liquid, which is different from the above-mentioned emulsifying tank 1, and has no mixing function, when the powder is an agglomerating agent, the liquid is water, and when the powder is a passivating agent or a passivating and agglomerating compound agent, the liquid is desulfurization wastewater, so that the first level meter 14 is arranged in the emulsifying tank 1, the liquid level in the emulsifying tank 1 is monitored by the first level meter 14, of course, a flow meter 16 and a pneumatic valve 17 are also arranged on a liquid supply pipe of the emulsifying tank 1, the liquid provided by the emulsifying tank 1 and the powder provided by the hopper 3 are mixed in the mixing barrel 12, wherein the mixing barrel 12 may be a vortex barrel, and may be used for realizing primary mixing between the powder and the liquid, wherein the emulsion tank 1 is higher than the mixing tank 12 as a whole, the liquid in the emulsion tank can enter the mixing tank 12 under the action of gravity, of course, a control valve, specifically two valves, one is a manual valve 121, the flow path on-off of which is controlled manually, the other is a pneumatic valve 122, the flow path on-off of which is controlled electrically, the two are connected in series, the hopper 3 and the mixing tank 12 are connected through a blanking machine 32, specifically a spiral blanking machine 32, the hopper 3 can be controlled accurately to feed the mixing tank 12 by controlling the rotation of the blanking machine 32, the emulsion is formed in the mixing tank 12, the emulsion is led into the mixing tank 2 through a pump set 11, the pump set 11 is an emulsion pump and a self-priming pump, a first flow meter 13 is arranged on the flow path between the pump set 11 and the mixing tank 2, and a pneumatic valve 131 is also connected in series, a second flow meter 231 and a pneumatic valve 232 are arranged on a liquid supply pipe 23 of the mixing tank 2, the mixing tank 2 is provided with a second liquid level meter 24 and a stirring motor 21, and the emulsion and the liquid are stirred and mixed in the mixing tank 2 through a liquid supply pipe 23 to obtain a solution meeting the requirement, and then the solution is discharged through a liquid discharge pipe 22, of course, an electric valve 221, a liquid discharge pump 223 and a third flow meter 222 are provided on the liquid discharge pipe 22, wherein the electric valve 221 and the third flow meter 222 are used for controlling an output flow path of the liquid discharge pump 223, namely, the on-off and the discharge flow rate between the liquid discharge pump 223 and the atomizing spray gun 4, and a manual valve 224 and an air-operated valve 225 are further provided on a flow path of the liquid discharge pipe 22 corresponding to the liquid discharge pump 223 and the mixing tank 2 to control the on-off of an input flow path of the liquid discharge pump 223.
A bin 31 is further provided, the bin 31 is connected with the hopper 3 through a spiral feeding machine 33, a first level indicator 35 is arranged in the bin 31, and the bin 31 is mainly used for storing materials and can supply materials into the mixing barrel 12 through the hopper 3. The caliber of the bin 31 is large, the dumping is convenient, and a first level indicator 35 and a vibration motor 34 are arranged on two side walls of the bin 31; the caliber of the hopper 3 is relatively small, a second material level meter 36 and a third material level meter 37 are respectively arranged at the high position and the low position of one side and are respectively used for monitoring the warning high position and the warning low position of the hopper 3, and a vibration motor 34 is arranged at the other side. The level meter is used for judging the material quantity, relevant signals are transmitted to the PLC, and the vibrating motor 34 has the function of reducing material hardening and is convenient to feed and discharge.
In the process, the controller is a PLC, the measurement and control element can transmit the equipment state to the PLC in time, the PLC and the industrial personal computer communicate through optical fiber remote transmission, the relevant state of the equipment is displayed in the software of the upper computer, and meanwhile, the software of the upper computer can also control the power element according to the relevant state.
The measurement and control elements generally comprise electrical measurement and control elements such as a level meter, a flowmeter, a liquid level meter, an electric valve, a pneumatic valve and the like. Level meters (a first level meter 35, a second level meter 36 and a third level meter 37) are arranged on the hopper 3 and the storage bin 31, and whether the level is proper or not is judged through the level meters so as to meet the process requirement; the flow meters (the first flow meter 111, the second flow meter 231 and the third flow meter 222) are arranged on the pipeline, display the liquid flow quantity and judge whether the pipeline is blocked or leaks water; the liquid level meters (the first liquid level meter 14 and the second liquid level meter 24) are arranged at the bottoms of the tanks (the emulsifying tank 1 and the mixing tank 2) to display the liquid level height in the tanks, so that the control of the ingredient concentration is facilitated; the electric valve and the pneumatic valve are arranged on the pipeline, and are indispensable in the batching process and the discharging process for cutting off or controlling the flow direction of liquid in the pipeline.
The power elements generally comprise a vibration motor 34, a spiral feeding machine 33, a spiral blanking machine 32, a stirring motor 21, a self-sucking pump, an emulsifying pump and a liquid discharging pump 223. The vibration motors 34 are arranged on the hopper 3 and the storage bin 31, so that material hardening can be reduced; the spiral feeder 33 is started when the bin 31 is used for conveying the material in the bin 31 to the hopper 3, and generally when the material level of the hopper 3 is low; the spiral blanking machine 32 is used for controlling blanking components; the stirring motor 21 is arranged above the mixing tank 2, and an impeller is arranged below the mixing tank and can uniformly stir the mixed solution; the self-sucking pump is arranged below the vortex barrel and is used for conveying the mixed solution into the mixing tank 2; the emulsification pump is arranged behind the self-sucking pump, so that the solution is mixed more uniformly; the drain pump 223 is installed at the rear of the mixing tank 2 and delivers the completely mixed solution.
The feeding, batching and discharging functions are complete, the working strength of workers is greatly reduced, and the control is convenient; the vibration motor 34 is added in the feeding process to reduce material hardening, the material level meter is added to supplement materials in time, the personnel is not required to monitor the materials constantly, the feeding is controlled by adopting the spiral feeding machine 33, the feeding component can be controlled by adopting the spiral blanking machine 32 through controlling the operation time, the stirring motor 21 is adopted to facilitate the uniform mixing of the materials, and the operation condition of the field equipment can be known in real time by adopting a flowmeter, a liquid level meter and the like; in addition, the measurement and control element and the power and signal cables related to the power element are connected with the electrical cabinet and the control cabinet through the field junction box, and the former part can be finished before leaving the factory, so that the field construction time and the construction difficulty are reduced, and the convenience in installation, debugging, overhauling and maintenance is greatly improved.
When the liquid discharge pump 223 is used as a spray pump, the liquid discharge pipe 22 is communicated with the atomizing spray gun 4, the liquid in the mixing tank 2 is sprayed into the flue 5 through the atomizing spray gun 4 via the liquid discharge pipe 22, and the whole mixing and feeding system is used for spraying the agglomeration agent, the passivating agent or the passivation agglomeration complexing agent and the like into the flue 5 so as to realize the treatment of the flue gas in the flue 5.
In addition, a concentration monitor 55 is arranged in the flue 5 for monitoring SO in the flue 53Concentration, and a temperature monitor 56 is also arranged in the flue 5 for monitoring the temperature of the flue gas in the flue 5, and both are arranged in front of the atomizing nozzle 43 of the atomizing spray gun 4 for monitoring the concentration before agglomerationFlue gas according to SO in flue 53The concentration of the agglomerating agent and the temperature of the flue 5 regulate the flow rate of the agglomerating agent solution.
Referring to fig. 2 and 13, when only the application of the chlorine ion passivating agent to treatment of desulfurization wastewater is considered, the embodiment of the invention provides a chlorine ion passivating agent, which can passivate desulfurization wastewater when being mixed with desulfurization wastewater and then sprayed into the flue 5, so that the chlorine ions in the desulfurization wastewater can lose activity and the corrosivity of the chlorine ions can be retarded. The components of the chloride ion passivator are water-based organic mixing agent consisting of amine and ester, wherein the amine is a salt of polyacrylamide and alkyleneamine or organic acid, the ester is a binary copolymer of acrylic acid and acrylate, or a ternary copolymer of acrylic acid, AMPS and maleic anhydride, and the components are as follows by mass percent: 0.001-0.2% of amine, 0.0001-0.01% of grease and the balance of water.
Specifically, in the first embodiment of the chloride ion passivating agent: 0.001-0.2% of polyacrylamide and alkenyl amine, 0.0001-0.01% of binary copolymer of acrylic acid and acrylate, and the balance of water, wherein the percentage content of polyacrylamide and alkenyl amine is 0.0005-0.1%, the percentages are mass percentages, and the following component percentages are mass percentages. After the chloride ion inactivating agent (0.0005% polyacrylamide and 0.0005% alkenylamine, 0.0001% acrylic acid and acrylate copolymer, which is water) in this example was mixed with the desulfurization waste water and sprayed into the flue 5, no significant corrosion was observed in the flue 5, so that the level of corrosion of chloride ions in the desulfurization waste water was reduced by 70%. The mass percentage of the chloride ion passivator is as follows: 0.1 percent of polyacrylamide and 0.1 percent of alkenylamine, 0.01 percent of binary copolymer of acrylic acid and acrylate, and the balance of water, the corrosion level of chloride ions in the desulfurization wastewater is reduced by 75 percent.
Specifically in example two of the chloride ion passivator: 0.001-0.2% of salt of enamine and organic acid, 0.0001-0.01% of terpolymer of acrylic acid, AMPS and maleic anhydride, and the balance of water, wherein AMPS is 2-acrylamide-2-methylpropanesulfonic acid, the salt of organic acid is sodium polyacrylate, and the mass percentage content of the salt of organic acid is 0.002-0.01%. After the chloride ion passivator (0.001% of enamine and 0.002% of sodium polyacrylate, 0.0001% of terpolymer of acrylic acid, AMPS and maleic anhydride, and the balance water) in this example was mixed with the desulfurization wastewater and sprayed into the flue 5, the flue 5 was inspected and no significant corrosion was found, so that the level of corrosion of chloride ions in the desulfurization wastewater was reduced by 75%. The mass percentage of the chloride ion passivator is as follows: 0.2% of enamine and 0.01% of sodium polyacrylate, 0.01% of terpolymer of acrylic acid, AMPS and maleic anhydride and the balance of water, and the corrosion level of chloride ions in the desulfurization wastewater is reduced by 80%.
The embodiment of the invention also provides a preparation method of the chloride ion passivator, and the amine, the grease and the water are put into an emulsifier to be mixed and dissolved, wherein the water is industrial water with the temperature of more than 10 ℃ to promote the dissolution of the industrial water, and the chloride ion passivator is prepared after the high molecular compound is completely and uniformly dissolved. The embodiment of the invention also provides a desulfurization wastewater treatment method, wherein the prepared chloride ion passivator and desulfurization wastewater are mixed to obtain a mixed solution, the mixed solution is sprayed into the high-temperature flue 5, and the mixed solution is evaporated and crystallized through high-temperature flue gas in the high-temperature flue 5. The high-temperature flue 5 is in the structure of the flue 5, the mixed liquid is sprayed into the area between the air preheater 51 and the dust remover 52 through the atomizing spray gun 4, and evaporative crystals generated by the desulfurization waste water can be collected to the dust remover 52 along with the fly ash without causing blockage of the air preheater 51. The atomization spray gun 4 sprays the mixed liquid into the flue 5 with the grain diameter of 30-60 mu m so as to ensure that the mixed liquid is evaporated and crystallized before entering the dust remover 52, the water vapor is discharged along with the flue gas, no by-product is generated, the zero emission treatment of the desulfurization wastewater is realized, and the water resource environment is protected. The chloride ion passivator can be prepared into high-concentration passivating solution for storage before use, and is diluted into mixed solution by using the desulfurization wastewater in proportion when in use, and the storage time of the mixed solution sprayed into the high-temperature flue 5 is no longer than one week. Of course, when the desulfurization waste water is diluted into the mixed solution in proportion, the amount of the desulfurization waste water and the concentration of chloride ions in the desulfurization waste water should be determined, then the amount of the high-concentration passivation solution should be calculated, and the flow rate of the mixed solution should be controlled when the high-concentration passivation solution enters the atomizing spray gun 4.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A passivation and agglomeration complexing agent is used for passivation and agglomeration of desulfurization wastewater in a high-temperature flue and is characterized in that: comprises the following components in percentage by mass: 0.001 to 0.2% of amine, 0.0001 to 0.01% of fat, 0.0002 to 0.001% of alcohol, 0.0008 to 0.01% of surfactant and the balance of water; the amine is polyacrylamide and/or alkenamine; the grease is a binary copolymer of acrylic acid and acrylate, or a ternary copolymer of acrylic acid, AMPS and maleic anhydride, or oleate; the alcohol is aromatic alcohol or aliphatic alcohol; the surfactant is Triton X100 or sodium dodecyl benzene sulfonate.
2. A passivating agglomerate complexing agent according to claim 1, characterized in that: the organic acid salt is sodium polyacrylate, and the mass percentage content of the organic acid salt is 0.002-0.01%.
3. A passivating agglomerate complexing agent according to claim 1, characterized in that: the amine is polyacrylamide and alkenylamine, and the mass percent content of the polyacrylamide and the mass percent content of the alkenylamine are both 0.0005-0.1%.
4. A preparation method of passivation agglomeration complexing agent is characterized in that: placing the amine, the ester, the alcohol, the surfactant and the water of claim 1 into a container, and mixing and dissolving.
5. A boiler flue gas treatment method is characterized in that: the passivation and agglomeration complexing agent as claimed in claim 1 is added into the desulfurization wastewater, and the mixed solution of the passivation and agglomeration complexing agent and the desulfurization wastewater is sprayed into the high-temperature flue to perform passivation and agglomeration reaction with high-temperature flue gas in the high-temperature flue.
6. The boiler flue gas treatment method according to claim 5, characterized in that: the flue gas in the high-temperature flue sequentially passes through an air preheater, a dust remover and a desulfurizing tower, and the passivation and agglomeration complexing agent is sprayed into the flue gas flow paths in front of and behind the air preheater.
7. The boiler flue gas treatment method according to claim 6, characterized in that: monitoring outlet dust and SO at the outlet of a desulfurization tower3And the concentration and the monitoring result are fed back to the PLC, and the spraying amount of the passivation agglomeration complexing agent is automatically adjusted through the PLC.
8. The boiler flue gas treatment method according to claim 6, characterized in that: and (3) adopting a flue gas analyzer to perform constant-current sampling at an outlet at the rear part of the dust remover, and measuring the particle emission concentration.
9. The boiler flue gas treatment method according to claim 6, characterized in that: the crystal salt after evaporation and crystallization is collected and discharged by a dust remover along with the fly ash, and the water vapor is discharged into a desulfurizing tower along with the flue gas.
10. The boiler flue gas treatment method according to claim 5, characterized in that: spraying the mixed solution with a dual-flow atomizing nozzle with the particle size of 10-25 μm.
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