CN105833695A - Device and technology for wet desulfurization and denitrification of flue gas of coal-fired boiler and treatment of wastewater - Google Patents

Device and technology for wet desulfurization and denitrification of flue gas of coal-fired boiler and treatment of wastewater Download PDF

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CN105833695A
CN105833695A CN201610290678.7A CN201610290678A CN105833695A CN 105833695 A CN105833695 A CN 105833695A CN 201610290678 A CN201610290678 A CN 201610290678A CN 105833695 A CN105833695 A CN 105833695A
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waste water
flue gas
flue
oxidation
wastewater
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CN201610290678.7A
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Chinese (zh)
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CN105833695B (en
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王岳军
寿冬金
吴忠标
冯斌
莫建松
毛明春
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浙江天蓝环保技术股份有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/60Simultaneously removing sulfur oxides and nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/73After-treatment of removed components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/76Gas phase processes, e.g. by using aerosols
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/78Liquid phase processes with gas-liquid contact
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/10Oxidants
    • B01D2251/104Ozone
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • Y02A50/2344

Abstract

The invention discloses a device and technology for wet desulfurization and denitrification of flue gas of a coal-fired boiler and treatment of wastewater .The technological process includes the steps that the flue gas enters a wastewater evaporative cooling stage through a draught fan outlet to be cooled and then enters an ozonation stage, the flue gas is fully mixed with ozone to be oxidized and then enters a supergravity device through a supergravity desulfurization and denitrification device inlet, the flue gas is subjected to forcible absorption with desulfurization and denitrification absorption liquid in a packed bed on a rotor, and finally the flue gas is demisted by a demister and then discharged through a flue gas outlet of the supergravity device .Replacement absorbent slurry is subjected to oxidation and denitrification treatment in sequence and then returned to the evaporative cooling stage to perform spraying cooling on the flue gas .By means of the device and the technology, desulfurization and denitrification efficiency is improved, and meanwhile water consumption is low; wastewater generated in desulfurization and denitrification is subjected to innocent treatment, sulfate is collected, and thus the coal-fired flue gas can meet stricter discharge standards.

Description

A kind of fire coal boiler fume wet desulphurization denitration and wastewater treatment equipment and technique

Technical field

The present invention relates to technical field of air pollution control, be specifically related to a kind of fire coal boiler fume wet method The technique that desulphurization denitration and waste water process.

Background technology

China is coal production state maximum in the world and country of consumption, and coal is in the energy resource structure of China In still account for significant proportion.For many years, in China's primary energy total quantity consumed coal account for 75% with On, it is contemplated that in coming 10 years, coal will account for about the 70% of total energy consumption, in phase from now on When, in long period, the energy supply based on coal will not change with consuming general layout.Based on coal Energy consumption structure be to cause China to pollute the most important reason that is on the rise.

In Industrial Boiler coal-fired flue-gas pollution control technology, desulphurization and denitration is often at multiple independent systems Being respectively completed in system, it is big that classification processes not only floor space, system complex, and equipment investment with Operating cost is higher.Therefore, by integrated for desulphurization and denitration subsystem, form combined desulfurization and denitration skill Art is increasingly becoming domestic and international study hotspot.There is manufacturer's many employings catalytic reduction method associating of rich strength Nitrogen oxides and form waste gas of sulfur dioxide are administered in wet desulphurization, and account for the most middle and small scale of China Enterprise is more by the mode of wet desulphurization denitration.And along with up-to-date waste gas emission standard Putting into effect, the disposal ability of the existing denitration device of a lot of enterprises can not meet the requirement of GB, It is badly in need of newly-built denitration device or interpolation secondary denitration device.

Control to pollutants various in flue gas, the wet method combined desulphurization denitration skill used both at home and abroad Art, is oxidized to the NO of high-valence state by the NO in flue gas2Or N2O5Taken off by corresponding desulfurization again Nitre absorbs SO2、NO2、N2O5Generate corresponding sulfate and nitrite or nitrate.Nitrous acid Salt is a kind of noxious material, is widely present in natural water body, soil and food, is that organic nitrogen divides The important intermediate solved.After human body takes in nitrite, can be with secondary amine, tertiary amine and amino chemical combination Thing reaction forms strong carcinogen nitrosamine compound, thus induces digestive system canceration.Internal excess Nitrite oxidation of divalent iron ion in blood also can be made to be ferric ion, make normal blood red egg It is changed into ferrihemoglobin in vain, loses oxygen carrying capacity, cause histanoxia, nitrite occurs Poisoning.To this end, the nitrite maximum residue limit of food and drinking water is had clearly by countries in the world Regulation.In recent years, along with Consciousness of food security and the enhancing of environmental consciousness, the nitrite of people It is one of the important mensuration project of food, water quality and environmental monitoring, therefore to its desulphurization denitration waste water The research that nitrite controls has very important significance.

Conventional wet desulphurization FGD has the highest desulfuration efficiency, but China is that water provides in the world One of country of source famine, particularly many coal-burning power plants are in the west of water resource famine Rich coal resources area, portion, power plant is difficult to use the conventional wet lay combined desulfurization nitre skill of a large amount of water consumption Art.Publication number CN1768902A ozone oxidation and denitration method of boiler flue gas in temperature range is The boiler flue low-temperature zone of 110~150 DEG C sprays into ozone O3, the nitric oxide NO in boiler is aoxidized Become high-valence state nitrogen oxides soluble in water.Wet denitration is all to spray into Strong oxdiative after air-introduced machine Agent ozone, makes the NO in flue gas be oxidized to the nitrogen oxides of high-valence state.Ozone is at the flue gas of 130 DEG C Temperature is readily decomposed to the reduction that oxygen causes the utilization rate of ozone, easily ignites in flue simultaneously Glass flake anticorrosive coat, therefore need spray cooling or change flue material.The nitrogen of high-valence state Oxide enters in desulphurization system and is absorbed into corresponding nitrate anion and nitrite, by gypsum Quality affects, and is not further processed NO3-N and NO2-N.

Therefore need to develop a kind of wet method combined desulphurization denitration technology preferably, cigarette can be removed efficiently SO in gas2Innoxious with the waste water consuming less water consumption and desulphurization denitration generation while NOx Process, make coal-fired flue-gas can reach tightened up discharge standard.

Summary of the invention

The present invention provides a kind of fire coal boiler fume wet desulphurization denitration and wastewater treatment equipment and technique, Improving denitrification efficiency, can consume less water consumption simultaneously, the waste water that desulphurization denitration produces is innoxious Process, make coal-fired flue-gas can reach tightened up discharge standard.

A kind of fire coal boiler fume wet desulphurization denitration and waste water treatment process, comprise the steps:

Flue gas, in air-introduced machine enters flue, carries out spraying cooling and ozone oxidation in flue successively, Flue gas after ozone oxidation enters in supergravity reactor, flue gas and absorption in supergravity reactor Liquid carries out strengthening and absorbs, and is then discharged by the exhanst gas outlet of supergravity reactor after demister is except mist;

The slurries produced in supergravity reactor fall to absorb in flow container, and stirring is simultaneously to absorbing flow container In supplement absorbent, and by fresh water (FW) maintain absorbing liquid water evaporation balance, the absorbing liquid after allotment is entered Enter in supergravity reactor and smoke reaction;The absorbing liquid changed during allotment is delivered to wastewater oxidation tank, In wastewater oxidation tank, it is passed through air carry out forcing oxidation, forces the waste water after oxidation to send into denitrogenation of waste water In tank, adding denitrifier in denitrogenation of waste water tank in waste water, the waste water after denitrogenation processing is delivered to For flue gas is carried out spraying cooling in described flue, with flue gas generation heat exchange after evaporation section water steam Gas, remaining atomized drop is sent into outside flue after being caught by the demister being arranged in described flue In crystallizer, isolating crystal, magma is recycled to described cigarette together with the waste water after described denitrogenation processing For flue gas is carried out spraying cooling in road.

The present invention also provides for a kind of fire coal boiler fume wet desulphurization denitration and wastewater treatment equipment, this Bright method is preferably realized by this device, including booster fan, exports, with booster fan, the cigarette being connected Road, also includes that the waste water evaporative cooling system being sequentially arranged, ozone oxidation system, hypergravity absorb system System and wastewater oxidation desulphurization system;

Described waste water evaporative cooling system includes:

First demister, is arranged in described flue, and the walling of flue below this first demister is arranged Liquid outlet;

Crystallizer, the charging aperture of this crystallizer is connected with described liquid outlet, discharging opening is connected crystal and divides From device;

Evaporation spray thrower, is arranged in described flue and is positioned at the first demister upstream, and this evaporation sprays The magma outlet of the external described crystallizer of device;

Described ozone oxidation system includes ozone generator and is arranged in described flue and is positioned at first The ozone barrier of demister downstream external ozone generator;

Described hypergravity absorption system includes:

Supergravity reactor, this supergravity reactor has liquid passage inlet, exhanst gas outlet, fluid path import And serum outlet, wherein liquid passage inlet connects the outlet of described flue;

Absorbing flow container, the fluid path import of described supergravity reactor and serum outlet are connected to this absorption Flow container;

Described wastewater oxidation denitrification system includes:

The discharging opening of the external described absorption flow container of wastewater oxidation tank, built-in oxidation air and its charging aperture;

Denitrogenation of waste water tank, charging aperture connects the discharging opening of described wastewater oxidation pipe, discharging opening connects described Evaporation spray thrower.

Preferably, described supergravity reactor includes:

Hypergravity shell, described liquid passage inlet, fluid path import, serum outlet and exhanst gas outlet are all offered On this hypergravity shell;

The rotor of built-in filler, this rotor passes through the external driving means of rotating shaft;

Being positioned at the shower at described rotor center, this shower is fed by the external fluid path of fluid path import Pipe.

It is further preferred that the external exhaust pass of described exhanst gas outlet, in exhaust pass, place arranges second Demister.

It is further preferred that the filler of hypergravity bed be silk screen, Raschig ring, Pall ring, cascade ring, Arc saddle, square saddle, metal saddle ring, Dixon ring, ripple packing any one.Material can by pottery, The material manufactures such as metal, plastics and graphite.

Outside serum outlet is positioned at housing bottom, liquid passage inlet is positioned in housing sidewall, exhanst gas outlet is positioned at Roof portion, fluid path import is positioned at case top.

Described driving means is preferably motor, and motor drives hypergravity bed to rotate by rotating shaft.

Described shower includes:

The house steward of external described fluid path feed pipe,

Some arms vertically running through filler center, all arms all access described house steward and each arm On offer some spouts.

Preferably, the described built-in agitator of absorption flow container, described absorption flow container configuration absorbent tank and work Skill water supplements pipe, arranges measuring pump between absorbent tank and absorption flow container, and described absorption flow container is with overweight Connected by described fluid path feed pipe between the fluid path import of power reactor, this fluid path feed pipe is arranged Circulating pump.

Agitator in described absorption flow container preferably employs side stirring;The serum outlet absorbing flow container is positioned at Bottom, connects wastewater oxidation tank by drainage conduit.

Described crystallizer built-in wastewater heat exchange pipe, further, the entrance of described wastewater heat exchange pipe is external Described denitrogenation of waste water tank, export external described evaporation spray thrower.

Described crystallizer is back taper, connects central authorities' sedimentation pipe bottom back taper, and central authorities' sedimentation pipe is external Described crystal separator, the magma outlet of crystal separator accesses evaporation spray thrower by pipeline, connects On pipeline between evaporation spray thrower and crystal separator and wastewater heat exchange pipe, circulating pump is set.

Evaporation spray thrower place flue section is connected by reducing with the first demister place flue section.

The external oxidation fan of oxidation air in wastewater oxidation tank.

Described denitrogenation of waste water tank is configured with denitrifier tank and pH regulates tank, all by the pipe of band measuring pump Road connects;The described built-in agitator of denitrogenation of waste water tank, this agitator preferably employs overhead stirrer.

Flue gas enters back into ozone after the flue gas that air-introduced machine exports is introduced into the cooling of waste water evaporative cooling section In oxidation panel, after flue gas and ozone are sufficiently mixed oxidation, flue gas is entered by high gravity desulfurization denitrification apparatus Mouth enters in super-gravity device, and flue gas carries out strengthening in hypergravity bed and inhales with desulphurization denitration absorbing liquid Receive, after discharged by the exhanst gas outlet of super-gravity device after demister is except mist;

The slurries that hypergravity produces fall in absorbing liquid circulating tank, add and inhale in absorbing liquid circulating tank Receive agent and maintain stablizing of absorption flow container, and maintain absorbing liquid volume by fresh water (FW);The absorbing liquid changed It is delivered to wastewater oxidation denitrogenation tank, after carrying out forcing oxidation, then by adding denitrifier in waste water, Nitrite anions in removing waste water, the pH value of regulation waste water.

Waste water, will be useless by waste water circulation pump and waste water atomizer after wastewater oxidation denitrogenation processing Spray into after water atomization in flue gas, with flue gas generation heat exchange after evaporation section steam, remaining atomization Drop is caught by demister and falls into crystallizer, isolates crystal, and magma is recycled to useless together with waste water Water atomizing nozzle.

Arranging evaporation spray thrower in evaporative cooling section, evaporation spray thrower may select Conventional waste water spraying layer, Preferably spraying layer is covered with whole flue, and the spacing between each nozzle of spraying layer is identical, it is ensured that atomization Waste water energy uniformly mix with flue gas, improve flue gas cool-down effect and drop evaporation effect, waste water nozzle Direction, with Gas phase Smoke is equidirectional sprays in flue gas, is reduced flue gas through the resistance of waste water spraying layer.

The preferably particle diameter D of waste water spray atomizing50=10~300 μm;Waste water spray flow and exhaust gas volumn Liquid-gas ratio=0~0.05L/m3, more preferably 0.01~0.02L/m3, most preferably 0.02L/m3; Flue gas cool-down 20~50 DEG C.

Waste water spraying layer rear is provided with the first demister, between flue and the first demister by reducing even Connecing, the control gas speed by the flue gas of demister, preferred gas speed is 1~10m/s.First demister Preferably flap demister, further preferably, the flap of described flap demister is provided with rapping apparatus. Further preferably, rapping apparatus includes vibration hammer and connecting rod, and rapping apparatus carries out rapping to flap, really Guarantor delivers droplets on, the little particle of crystal shakes off from flap, drops down onto in crystallizer.Preferably demister rapping Cycle is 30~300s.

Flap demister can use conventional flap demister, it is preferable that by polylith metal except mist flap edge Vertically to composition side by side, the bearing of trend of flap is identical with flue gas direction.The bending shape of described bending plate Formula can use the rule multiple bending form such as bending, irregular bending.As preferably, described bending plate A length of 2~8m, the distance between two folding lines is 300mm~800mm, and the angle of bending part is 140 °~170 °.

Further preferably, the spacing between adjacent two bending plates is 100mm~400mm.

Crystallizer has certain taper, i.e. bigger sectional area is arranged at top, the saturated solution that demister falls Can preferably be crystallized device to collect, the waste water after wastewater oxidation denitrogenation passes through crystallization with the form of coil pipe Device, the waste water of lower temperature carries out heat exchange with the saturated solution of higher temperature in crystallizer, the mistake of cooling Journey makes the solution in crystallizer produce supersaturation, make crystal produce in a large number, grow up.Supersaturated solution Isolating crystal by central downtake and reduce its degree of supersaturation, mother liquor is incorporated in waste pipe be delivered to give up Water spray layer.

The waste water water temperature preferably entering crystallizer heat exchange is 5~25 DEG C, more preferably 10~20 DEG C, Most preferably 15 DEG C, the temperature being supersaturated liquid in central authorities' sedimentation pipe is 20~30 DEG C.

Ozone oxidation section uses ozone to be the NO in oxidizing flue gas, the overall reaction equation of oxidation Formula is: NO+O3→NO2+O2;Ozone grid is set after being positioned at waste water evaporative cooling section, the most smelly Oxygen grid is covered with whole flue, and the spacing between each nozzle of ozone grid is identical, it is ensured that atomization Waste water energy uniformly mixes with flue gas, it is ensured that ozone can preferably carry out aoxidizing more entering with the NO in flue gas Preferably, the spout of all nozzles sprays in flue gas with Gas phase Smoke is equidirectional one step, reduces to enter flue gas Cross the resistance of ozone grid, reduce flue gas turbulence level.

Preferably, the ozone sprayed into nitrogen oxides in effluent mol ratio is: nO3: nNO=0.5~2.5; More preferably 1.5~2.5, most preferably 2.5.

Hypergravity conversion zone is positioned at ozone oxidation section downstream, and the absorbing liquid absorbed in flow container passes through absorbing liquid Absorbing liquid is delivered to the hypergravity bed that fluid path import shower nozzle sprays to rotate by circulating pump, absorbs also by super Gravity bed returns absorption flow container through fluid path outlet after throwing away.

Preferably, absorbing liquid is NaOH, magnesium hydroxide, ammoniacal liquor, sodium carbonate, sodium acid carbonate etc. Other sodium salts or ammonium salt solution, liquid-gas ratio is 1~10L/m3, more preferably 4~8L/m3, Most preferably 5L/m3

Flue gas is entered in super-gravity device by hypergravity gas approach, enters the hypergravity bed of high-speed rotation And there is strengthening mass transport process in the filling surface within hypergravity bed or the absorbing liquid between filler, makes cigarette Gas reaches the effect of desulphurization denitration.

Preferably, the hypergravity level of super-gravity device is 50~500, more preferably 300~500, Most preferably 500, hypergravity level is defined as centripetal acceleration and weight when hypergravity reaction unit runs The ratio of power acceleration.

The wet method combined desulphurization denitration of hypergravity absorbs overall reaction equation:

The little water droplet that flue gas is carried secretly after hypergravity bed in flue gas removed by demister, then through super Gravity exhanst gas outlet discharges flue gas.Controlled by absorbent tank and absorbent measuring pump and maintain absorbing liquid The pH stable of absorbing liquid in tank.

Preferably, the pH value of absorbing liquid is 4~10, more preferably 4~8, most preferably 8, The serum density of absorbing liquid is 1.0~1.3 × 103Kg/m3

Fresh water (FW) maintains and absorbs the liquid level of absorbing liquid in flow container, and side stirring makes absorbing liquid in absorption flow container equal One is stable.Absorbing liquid after the wet method combined desulphurization denitration of hypergravity absorbs enters wastewater oxidation denitrogenation Section, aoxidizes through pressure, stirs, adds denitrifier, be delivered to waste water and steam after regulation pH value of waste water Sending out temperature descending section, key reaction equation is:

Technological parameter in wastewater oxidation denitrogenation section is preferably as follows:

Preferably, the SO in oxidative absorption flue gas is forced2Quality with oxidized input air be 0.1~2.5Kg/m3, wherein said oxidation wind is air.The denitrifier added is sulfamic acid, nAmino Sulfonic acid: nNitrite anions=0.1~2.0, further preferred nSulfamic acid: nNitrite anions=1.5~2.0, most preferably 2.0, Regulation pH value of waste water is 6~9.

Compared with prior art, there is advantages that

(1) waste water evaporative cooling section effect, in hypergravity absorber portion change absorbing liquid through peroxidating, Waste water evaporative cooling section is entered, by the waste water of atomization and higher temperature after denitrogenation, regulation pH value Flue gas mixes, and waste water has evaporated more moisture simultaneously, reduces the temperature of flue gas, improves cigarette The humidity of gas, the drop in flue gas is concentrated and is even evaporated crystallization, caught by the demister in this section, Being separated with the form of crystal by sulfate in waste water, the processing for subsequent sulphuric acid salt crystal provides bar Part.The flue gas of demister outlet be low temperature, the flue gas of high humidity be that subsequent oxidation section, absorber portion are created Favourable atmosphere.

(2) ozone oxidation section flue gas is after waste water evaporative cooling section, and cigarette temperature drop is low, therefore this section The degree that the ozone sprayed into causes ozone self to decompose because of flue-gas temperature is substantially reduced, simultaneously through except mist Flue gas flow rate after device is more uniform and stable, is more beneficial for ozone and is evenly mixed in flue gas, therefore will Greatly enhance the utilization rate of ozone, be more beneficial for ozone and the NO in flue gas is oxidized to NO2

(3) hypergravity absorber portion uses hypergravity absorption plant to carry out removing the SO in flue gas2With NOx, uses the SO absorbed in flue gas2Intermediate product inferior sulfate radical or bisulfite absorb warp NO after oxidation2, the most only it is stripped of two kinds of pollutants the most efficiently by a kind of absorbing liquid, saves Resource, reduces operating cost.This device can be by the different hypergravity level of regulation, liquid simultaneously Gas ratio, the pH value of absorbent adapt to the load fluctuation of various coal-burning boiler.Flue gas steams through waste water After sending out temperature descending section, the cigarette temperature of flue gas declines and containing substantial amounts of steam, improves absorbing liquid to SO2's Absorption efficiency, reduces the evaporation of the moisture of absorbent simultaneously, decreases what absorbent caused because of evaporation Fresh water (FW) supplements.

(4) in wastewater oxidation denitrogenation section, waste water adds a certain proportion of denitrifier after forcing oxidation Make the harmful components nitrite anions in waste water generate harmless nitrogen, solve waste water Nitrite pair The harm of environment.

The more conventional wet method combined process for desulfurization and denitration of present invention process is in efficient removing flue gas SO2With greatly save water consumption while NOx, solve after denitration absorbs nitrous in absorbing liquid The impact on desulfurization of acid group, nitrate anion, the waste water of generation has carried out innoxious process and has reclaimed Sulfate, solves the nitrite anions harm to environment water, and waste water reaches low emission even without discharge Degree.

Accompanying drawing explanation

Fig. 1 is the present invention a kind of fire coal boiler fume wet desulphurization denitration and the structural representation of waste water process Figure.

Fig. 2 is the schematic diagram of ozone grid of the present invention.

Fig. 3 is the schematic diagram of waste water atomizing spray of the present invention.

Fig. 4 is the present invention the first demister top view.

Fig. 5 is the present invention the first demister side view.

Shown in figure, reference is as follows:

1-fan inlet 2-booster fan 3-fan outlet

4-ozone grid 5-ozone generator 6-source of the gas

7-evaporates spray thrower 8-the first circulating pump 9-crystallizer

10-wastewater heat exchange pipe 11-crystal separator 12-central authorities sedimentation pipe

13 first demister 14-liquid passage inlet 15-rotors

16-shower 17-hypergravity shell 18-rotating shaft

19-motor 20-slurries efferent duct 21-the second demister

22-exhanst gas outlet 23-absorbent tank 24-absorbent measuring pump

25-fresh water (FW) supplements pipe 26-agitator 27-the second circulating pump

28-absorbs flow container 29-denitrogenation circulating pump 30-oxidation fan

31-wastewater oxidation tank 32-denitrogenation of waste water tank 33-agitating device

34-denitrifier tank 35-denitrifier measuring pump 36-measuring pump

37-pH value regulation tank 401-ozone nozzle 402-ozone grid

403-flue 701-waste water atomizer 702-waste water shower

703-flue 1301-metal removes mist flap 1302-flue

1303-vibration hammer 1304-drive link 1305-vibrator

Detailed description of the invention

As shown in Fig. 1~Fig. 5, a kind of row fire coal boiler fume wet desulphurization denitration and waste water process dress Put, after being arranged on deduster, export the flue being connected, flue including booster fan 2 with booster fan Interior being followed successively by waste water evaporative cooling section and ozone oxidation section along flue gas flow direction, flue outlet downstream sets successively Put hypergravity absorber portion and wastewater oxidation denitrogenation section.

Waste water evaporative cooling section arranges waste water evaporative cooling system, and waste water evaporative cooling system is by evaporating spray Drench device the 7, first circulating pump 8, crystallizer 9, wastewater heat exchange pipe 10, crystal separator 11, central authorities Sedimentation pipe the 12, first demister 13 forms.Crystallizer 9 is sedimentation crystallizing pond, and bottom is with necessarily Tapering, arranges wastewater heat exchange pipe 10 in sedimentation crystallizing pond, and bottom connects central authorities' sedimentation pipe 12, waste water The outlet of heat exchanger tube accesses the first circulating pump, accesses evaporation spray thrower by the first circulating pump, and central authorities are heavy Fall pipe 12 accesses crystal separator 11, and the magma outlet of crystal separator accesses the first circulating pump, logical Cross the first circulating pump and access evaporation spray thrower.

The optional conventional waste water shower 702 of evaporation spray thrower 7, waste water shower is at flue 703 If being inside set to dried layer, every layer arranges some showers, is preferably covered with whole flue, every waste water Uniformly offering waste water atomizer 701 on shower, all of waste water shower is aggregated into a house steward, By external first circulating pump of this house steward.

As shown in Figure 4 and Figure 5, the first demister is the most flat by polylith for the structure of the first demister 13 The metal of row forms except mist flap 1301, and the bearing of trend of flap is consistent with flue gas flow direction, adjacent folding Space between plate is exhaust gases passes, and each flap all configures some rapping apparatus, rapping apparatus bag The vibrator 1305 include the vibration hammer 1303 being arranged on flap, being arranged on outside flue 1302 and connection The drive link 1304 of vibration hammer and vibrator.

Waste water in crystallizer is atomized into little liquid in evaporative crystallization circulating pump enters evaporation spray thrower 7 Spray into after Diing in flue and be evaporated cooling, crystallization that evaporation produces and not evaporate droplet completely logical Crossing waste water evaporation demister (the first demister) to catch, droplet and crystal fall to crystallizer 9, Isolate the magma after crystal to continue cycling through with waste water.Rapping apparatus carries out rapping to flap, by little liquid Drip, the little particle of crystal shakes off from flap, drops down onto in crystallizer 9.

Ozone oxidation section arranges ozone oxidation system, as in figure 2 it is shown, carry out flue gas mixed oxidization, smelly Oxygen oxidative system is made up of ozone grid 4, ozone generator 5, source of the gas 6, ozone grid 4 structure As in figure 2 it is shown, ozone grid 402 is perpendicular to flue gas direction and is installed in flue 403 in Fig. 2, smelly Oxygen nozzle 401 injection direction is identical with flue gas direction.

Wherein flue 403, flue 703 and flue 1302 refer both to same flue.

Hypergravity absorber portion installs hypergravity system, and hypergravity system is by supergravity reactor, absorbing liquid Tank 28, absorbent tank the 23, second circulating pump 27 and absorbent measuring pump 24 form.

Supergravity reactor by hypergravity shell 17, the rotor 15 that is placed in hypergravity shell 17, if Put the shower 16 with rotor center, motor 19 and be connected the rotating shaft 18 of motor and rotor and form.Super Liquid passage inlet 14, fluid path import, serum outlet and exhanst gas outlet 22 is offered, slurry on gravity shell Liquid outlet is positioned at housing bottom and is positioned at by slurries efferent duct 20 external absorption flow container, liquid passage inlet The outlet of in housing sidewall and external booster fan rear flue, exhanst gas outlet are positioned at cover top portion, liquid Road import is positioned at case top, the external exhaust pass of exhanst gas outlet, arranges second and remove in this exhaust pass Day with fog 21.

Filling filler in rotor, filler is silk screen, Raschig ring, Pall ring, cascade ring, arc saddle, square Saddle, metal saddle ring, Dixon ring, ripple packing any one.Material can by pottery, metal, mould The material manufactures such as material and graphite.

Shower 16 in supergravity reactor is by the house steward of external described fluid path feed pipe and some perpendicular Directly run through filler center arm composition, all arms all access offer on house steward and each arm some Spout, house steward runs through fluid path import external absorbing liquid supply line.

Absorbing the built-in agitator of flow container 28 26, agitator 26 uses side to stir, and absorbs flow container configuration and inhales Receive agent tank 23 and fresh water (FW) supplements pipe 25, absorbent metering is set between absorbent tank and absorption flow container Pump, is absorbed and is connected by fluid path feed pipe between flow container and the fluid path import of supergravity reactor, this liquid Second circulating pump 27 is set on the feed pipe of road;The serum outlet absorbing flow container is positioned at bottom, passes through discharge Pipe connects wastewater oxidation tank 31.

Motor 9 drives hypergravity bed to rotate by rotating shaft 18, and the absorbing liquid absorbed in flow container 28 is passed through Absorbing liquid is delivered to the hypergravity bed that fluid path import is sprayed to rotate by shower 16 by absorbing liquid circulating pump, Absorbing liquid returns absorption flow container 28 through slurries efferent duct 20 after being thrown away by hypergravity bed.Flue gas is by surpassing Gravity liquid passage inlet enters in super-gravity device, enters rotor 15 and the internal rotor of high-speed rotation There is strengthening mass transport process in the absorbing liquid between filling surface or filler, makes flue gas reach desulphurization denitration Effect.Flue gas removes, through the second demister 21, the droplet carried secretly in flue gas after hypergravity bed, Flue gas is discharged again through hypergravity exhanst gas outlet 22.By de-absorbent tank 23 and absorbent measuring pump 24 control and maintain to absorb the pH stable of absorbing liquid in flow container 28, and fresh water (FW) supplements pipe 25 and maintains Absorbing the liquid level of absorbing liquid in flow container 28, agitator 26 (side stirring) makes to absorb in absorption flow container 28 Liquid stable homogeneous.

Wastewater oxidation denitrogenation section arranges wastewater oxidation denitrification system, and wastewater oxidation denitrification system includes sequentially The wastewater oxidation tank 31 arranged and denitrogenation of waste water tank 32, the charging aperture of wastewater oxidation tank 31 connects absorption The discharging tube of flow container, the discharging opening of wastewater oxidation pipe connects denitrogenation of waste water tank 32 by circulating pump.

The built-in oxidation air of wastewater oxidation tank, the external oxidation fan of oxidation air 30, denitrogenation of waste water tank Configuration denitrifier tank 34, denitrifier measuring pump 35, pH value regulation tank 37, measuring pump 36 and stirring Device 33.Absorb in the absorbing liquid entrance wastewater oxidation tank 31 that flow container 28 is changed, through forcing oxidation After the inferior sulfate radical in waste water is completely oxidized to sulfate radical, then be delivered in denitrogenation of waste water tank 32 Under agitating device 33 stirring, from denitrifier tank 34 and denitrifier measuring pump 35 toward denitrogenation of waste water tank 32 After middle interpolation denitrifier denitrogenation, then regulate oxidation process denitrification by measuring pump 307, pH value regulation tank 37 In the pH value of rear waste water, then the wastewater heat exchange pipe of the crystallizer that waste water is delivered to evaporative cooling section.

Apparatus of the present invention carry out fire coal boiler fume wet desulphurization denitration and the technological process of waste water process As follows:

Flue gas is sent in technique by booster fan by flue gas, and flue gas evaporates in waste water evaporative cooling section successively Carry out ozone oxidation, hypergravity absorber portion carry out combined desulfurization and denitration in cooling, oxidation and denitration section, Discharged by the exhanst gas outlet at super-gravity device top after except mist after;

Ozone is produced by source of the gas and ozone generator, sprays into uniformly through ozone grid, and in flue gas NO carries out mixed oxidization.Technological parameter in oxidation and denitration section is preferably as follows:

The ozone sprayed into nitrogen oxides in effluent mol ratio is: nO3: nNO=0.5~2.5;Source of the gas is Air-source or source of oxygen.

In high gravity desulfurization denitration section, absorbing liquid is sprayed onto in hypergravity bed, through high gravity desulfurization denitration section Absorbing liquid after middle absorption absorbs in flow container in returning;By to absorbing supplementary absorbent maintenance in flow container The absorption efficiency of absorbing liquid, fresh water (FW) maintains the liquid level of absorbing liquid, makes absorbing liquid homogeneous by side stirring Stable.Technological parameter in high gravity desulfurization denitration section is preferably as follows:

Super-gravity device hypergravity level is 50~500, and liquid-gas ratio is 1~10L/m3, the stream of absorbing liquid Amount and the liquid-gas ratio 0.5~5.0L/m of exhaust gas volumn3.Absorbing liquid circulating tank pH value is 4~10, absorbing liquid For NaOH or magnesium hydroxide.The serum density of absorbing liquid is 1.0~1.3 × 103Kg/m3

The absorbing liquid changed in high gravity desulfurization denitration section enters in wastewater oxidation denitrogenation section, through peroxide Change, stir, add denitrifier, after regulation pH value of waste water, be delivered to waste water evaporative cooling section.Useless Technological parameter in water oxidation process denitrification section is preferably as follows:

Oxidizing process absorbs the SO in flue gas2Quality and oxidized input air be 0.1~2.5Kg/m3, its Described in oxidation wind be air.;The denitrifier added with the nitrite anions mol ratio in waste water is: nDenitrifier: nNitrite anions=0.1~2.0, regulation pH value of waste water is 6~9.

In waste water evaporative crystallization section, the waste water processed is delivered to waste water steams in wastewater oxidation denitrogenation section Send out spray, waste water atomization is uniformly sprayed in flue gas and is evaporated, caught by evaporative crystallization demister Droplet and crystal, drop down onto crystallizer after rapping demister, taken out out by crystal.At waste water evaporation knot Technological parameter in brilliant section is preferably as follows:

Being connected by reducing between flue with demister, the gas speed making the flue gas by demister is 1~10m/s, in waste water evaporative cooling section, the wastewater temperature in crystallizer is 5~25 DEG C, central authorities' sedimentation pipe The temperature of middle supersaturation liquid is 20~30 DEG C.The flow of waste water atomizing spray and the liquid-gas ratio of flue gas flow It is 0~0.02L/m3.The atomizing particle size of spray is 50~300 μm, and demister shaking cycle is 30~300s.

Embodiment 1

Certain fire coal boiler fume amount 59723m3/h, NOx349mg/Nm3、SO21501mg/Nm3's After initial flue gas enters wet desulphurization denitration and waste water treatment process, in waste water evaporative cooling section waste water with The liquid-gas ratio of flue gas is 0.02L/m3, demister shaking cycle is 30s, and atomizing particle size D50 is 60 μm;The ozone that in oxidation panel, flue gas sprays into and nitrogen oxides in effluent mol ratio are nO3: nNO=2.5; In hypergravity absorber portion, super-gravity device hypergravity level is 500, and liquid-gas ratio is 5L/m3, desulfurization takes off Nitre absorbent circulating tank pH value is 8;In wastewater oxidation denitrogenation section, the amount of inferior sulfate radical material and oxygen Wind transmission amount is 3mol/m3, the denitrifier n of interpolationSulfamic acid: nNitrite anions=2.0.Export after this technique NOx9mg/Nm3、SO24mg/Nm3, waste water nitrite 1.0mg/L.

Embodiment 2

Certain fire coal boiler fume amount 61723m3/h, NOx365mg/Nm3、SO21461mg/Nm3's After initial flue gas enters wet desulphurization denitration and waste water treatment process, in waste water evaporative cooling section waste water with The liquid-gas ratio of flue gas is 0.01L/m3, demister shaking cycle is 130s, and atomizing particle size D50 is 120 μm;The ozone that in oxidation panel, flue gas sprays into and nitrogen oxides in effluent mol ratio are nO3: nNO=1.5; In hypergravity absorber portion, super-gravity device hypergravity level is 300, and liquid-gas ratio is 4L/m3, desulfurization takes off Nitre absorbent circulating tank pH value is 7;In wastewater oxidation denitrogenation section, the amount of inferior sulfate radical material and oxygen Wind transmission amount is 6mol/m3, the denitrifier n of interpolationSulfamic acid: nNitrite anions=1.5.Export after this technique NOx12mg/Nm3、SO26mg/Nm3, waste water nitrite 2.7mg/L.

Embodiment 3

Certain fire coal boiler fume amount 57723m3/h, NOx333mg/Nm3、SO21601mg/Nm3's After initial flue gas enters wet desulphurization denitration and waste water treatment process, in waste water evaporative cooling section waste water with The liquid-gas ratio of flue gas is 0.015L/m3, demister shaking cycle is 200s, and atomizing particle size D50 is 300μm;The ozone that in oxidation panel, flue gas sprays into and nitrogen oxides in effluent mol ratio are nO3: nNO=1.0;In hypergravity absorber portion, super-gravity device hypergravity level is 100, and liquid-gas ratio is 8L/m3, Desulphurization denitration absorbent circulating tank pH value is 4;In wastewater oxidation denitrogenation section, inferior sulfate radical material Amount and oxidized input air are 3mol/m3, the denitrifier n of interpolationSulfamic acid: nNitrite anions=1.0.Through this technique Rear outlet NOx11mg/Nm3、SO29mg/Nm3, waste water nitrite 1.1mg/L.

Embodiment 4

Certain fire coal boiler fume amount 62723m3/h, NOx357mg/Nm3、SO21541mg/Nm3's After initial flue gas enters wet desulphurization denitration and waste water treatment process, in waste water evaporative cooling section waste water with The liquid-gas ratio of flue gas is 0.005L/m3, demister shaking cycle is 300s, and atomizing particle size D50 is 250μm;The ozone that in oxidation panel, flue gas sprays into and nitrogen oxides in effluent mol ratio are nO3: nNO=1.4;In hypergravity absorber portion, super-gravity device hypergravity level is 100, and liquid-gas ratio is 8L/m3, Desulphurization denitration absorbent circulating tank pH value is 4;In wastewater oxidation denitrogenation section, inferior sulfate radical material Amount and oxidized input air are 3mol/m3, the denitrifier n of interpolationSulfamic acid: nNitrite anions=0.5.Through this technique Rear outlet NOx11mg/Nm3、SO29mg/Nm3, waste water nitrite 17.7mg/L.

The foregoing is only the case that is embodied as of patent of the present invention, but the technical characteristic of patent of the present invention Be not limited thereto, any those skilled in the relevant art in the field of the invention, the change made Or modify all contain among the scope of the claims of the present invention.

Claims (10)

1. a fire coal boiler fume wet desulphurization denitration and waste water treatment process, it is characterised in that Comprise the steps:
Flue gas, in air-introduced machine enters flue, carries out spraying cooling and ozone oxidation in flue successively, Flue gas after ozone oxidation enters in supergravity reactor, flue gas and absorption in supergravity reactor Liquid carries out strengthening and absorbs, and is then discharged by the exhanst gas outlet of supergravity reactor after demister is except mist;
The slurries produced in supergravity reactor fall to absorb in flow container, and stirring is simultaneously to absorbing flow container In supplement absorbent, and by fresh water (FW) maintain absorbing liquid water evaporation balance, the absorbing liquid after allotment is entered Enter in supergravity reactor and smoke reaction;The absorbing liquid changed during allotment is delivered to wastewater oxidation tank, In wastewater oxidation tank, it is passed through air carry out forcing oxidation, forces the waste water after oxidation to send into denitrogenation of waste water In tank, adding denitrifier in denitrogenation of waste water tank in waste water, the waste water after denitrogenation processing is delivered to For flue gas is carried out spraying cooling in described flue, with flue gas generation heat exchange after evaporation section water steam Gas, remaining atomized drop is sent into outside flue after being caught by the demister being arranged in described flue In crystallizer, isolating crystal, magma is recycled to described cigarette together with the waste water after described denitrogenation processing For flue gas is carried out spraying cooling in road.
Fire coal boiler fume wet desulphurization denitration and waste water treatment process the most according to claim 1, It is characterized in that, during spraying cooling, after atomization, the particle diameter of droplet is D50=50~300 μm, waste water sprays Liquid-gas ratio=0 of flow and exhaust gas volumn~0.05L/m3, by the flue gas flow rate of demister in flue it is 1~10m/s.
Fire coal boiler fume wet desulphurization denitration and waste water treatment process the most according to claim 1, It is characterized in that, during ozone oxidation, ozone with nitrogen oxides in effluent mol ratio is: nO3: nNO=0.5~2.5.
Fire coal boiler fume wet desulphurization denitration and waste water treatment process the most according to claim 1, It is characterized in that, the hypergravity level of supergravity reactor is 50~500, and liquid-gas ratio is 1~10L/m3
Fire coal boiler fume wet desulphurization denitration and waste water treatment process the most according to claim 1, It is characterized in that, in absorption flow container, pH value is 4~10, and in absorption flow container, the serum density of absorbing liquid is 1.0~1.3 × 103Kg/m3
Fire coal boiler fume wet desulphurization denitration the most according to claim 1 And waste water treatment process, it is characterised in that absorb the SO in flue gas during wastewater oxidation2Quality It is 0.1~2.5Kg/m with oxidized input air3, wherein oxidation wind is air.
Fire coal boiler fume wet desulphurization denitration and waste water treatment process the most according to claim 1, It is characterized in that, denitrifier is sulfamic acid, and the addition of denitrifier presses nSulfamic acid: nNitrite anions=0.5~2.0 Meter, regulating pH value of waste water during denitrogenation is 6~9.
8. fire coal boiler fume wet desulphurization denitration and a wastewater treatment equipment, including booster fan, The flue being connected is exported, it is characterised in that also include the waste water evaporation fall being sequentially arranged with booster fan Temperature system, ozone oxidation system, hypergravity absorption system and wastewater oxidation desulphurization system;
Described waste water evaporative cooling system includes:
First demister, is arranged in described flue, and the walling of flue below this first demister is arranged Liquid outlet;
Crystallizer, the charging aperture of this crystallizer is connected with described liquid outlet, discharging opening is connected crystal and divides From device;
Evaporation spray thrower, is arranged in described flue and is positioned at the first demister upstream, and this evaporation sprays The magma outlet of the external described crystallizer of device;
Described ozone oxidation system includes ozone generator and is arranged in described flue and is positioned at first The ozone barrier of demister downstream external ozone generator;
Described hypergravity absorption system includes:
Supergravity reactor, this supergravity reactor has liquid passage inlet, exhanst gas outlet, fluid path import And serum outlet, wherein liquid passage inlet connects the outlet of described flue;
Absorbing flow container, the fluid path import of described supergravity reactor and serum outlet are connected to this absorption Flow container;
Described wastewater oxidation denitrification system includes:
The discharging opening of the external described absorption flow container of wastewater oxidation tank, built-in oxidation air and its charging aperture;
Denitrogenation of waste water tank, charging aperture connects the discharging opening of described wastewater oxidation pipe, discharging opening connects described Evaporation spray thrower.
Fire coal boiler fume wet desulphurization denitration and wastewater treatment equipment the most according to claim 8, It is characterized in that, described supergravity reactor includes:
Hypergravity shell, described liquid passage inlet, fluid path import, serum outlet and exhanst gas outlet are all offered On this hypergravity shell;
The rotor of built-in filler, this rotor passes through the external driving means of rotating shaft;
Being positioned at the shower at described rotor center, this shower is fed by the external fluid path of fluid path import Pipe.
Fire coal boiler fume wet desulphurization denitration and wastewater treatment equipment the most according to claim 8, It is characterized in that, the described built-in agitator of absorption flow container, described absorption flow container configuration absorbent tank and work Skill water supplements pipe, arranges measuring pump between absorbent tank and absorption flow container.
CN201610290678.7A 2016-05-03 2016-05-03 A kind of fire coal boiler fume wet desulphurization denitration and wastewater treatment equipment and technique CN105833695B (en)

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CN107875855A (en) * 2017-11-14 2018-04-06 大连海事大学 A kind of boat diesel engine exhaust emission integrated conduct method and device
CN108380017A (en) * 2018-02-11 2018-08-10 浙江天蓝环保工程有限公司 A kind of alkali kiln gas wet denitration technique that absorbent recycles and device
CN109173717A (en) * 2018-10-30 2019-01-11 华能国际电力股份有限公司 The method and system of nitrite is removed in calcium base-quaternary ammonium salt catalyst simultaneous SO_2 and NO removal slurries
CN109316931A (en) * 2018-10-15 2019-02-12 北京化工大学 Ship tail gas integrated purifying device and its application

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CN102974181A (en) * 2012-11-14 2013-03-20 江苏中显集团有限公司 Flue gas dedusting and desulfurization and denitrification craft and special device thereof
CN103394279A (en) * 2013-08-15 2013-11-20 北京化工大学 System device and method for deeply removing nitric oxide in industrial tail gas

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CN102974181A (en) * 2012-11-14 2013-03-20 江苏中显集团有限公司 Flue gas dedusting and desulfurization and denitrification craft and special device thereof
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Publication number Priority date Publication date Assignee Title
CN107875855A (en) * 2017-11-14 2018-04-06 大连海事大学 A kind of boat diesel engine exhaust emission integrated conduct method and device
CN108380017A (en) * 2018-02-11 2018-08-10 浙江天蓝环保工程有限公司 A kind of alkali kiln gas wet denitration technique that absorbent recycles and device
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CN109316931A (en) * 2018-10-15 2019-02-12 北京化工大学 Ship tail gas integrated purifying device and its application
CN109173717A (en) * 2018-10-30 2019-01-11 华能国际电力股份有限公司 The method and system of nitrite is removed in calcium base-quaternary ammonium salt catalyst simultaneous SO_2 and NO removal slurries

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