CN108373159A - The retracting device and recovery method of ammonia during a kind of ammonium paratungstate production - Google Patents
The retracting device and recovery method of ammonia during a kind of ammonium paratungstate production Download PDFInfo
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- CN108373159A CN108373159A CN201810444896.0A CN201810444896A CN108373159A CN 108373159 A CN108373159 A CN 108373159A CN 201810444896 A CN201810444896 A CN 201810444896A CN 108373159 A CN108373159 A CN 108373159A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/12—Separation of ammonia from gases and vapours
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Abstract
The invention discloses the retracting device and recovery method of ammonia during a kind of ammonium paratungstate production, device includes distillation system, pretreatment system, blow-removing system and hydrochloric acid spray system.Distillation system includes mainly rectifying column, helical-lobe compressor, condenser, condensate liquid storage tank, reboiler and temperature indicating device.Pretreatment system includes mainly activation pot, and filter plate is equipped in activation pot.Blow-removing system includes mainly stripping tower, inlet tube, discharge pipe, gas vent and wastewater outlet, and stripping tower is equipped with sampling window.Hydrochloric acid spray system includes mainly spray column, air inlet, spray head, and spray column is equipped with liquid form.The ammonia recovery unit of the present invention is easy to operate, easy to control, includes using the ammonia in distillation system recycling flue gas using the method that it carries out recovery ammonia, pretreatment system, blow-removing system and hydrochloric acid spray system collective effect recycle the ammonia in waste water.Using device of the present invention carry out recovery ammonia method is simple, the rate of recovery is high.
Description
Technical field
The invention belongs to technical field of wet metallurgy, are related to the recycling of ammonia, specially a kind of ammonium paratungstate production
The retracting device and recovery method of ammonia in the process.
Background technology
Ammonium paratungstate (APT) is the important intermediate products of wet method smelting tungsten process, and ion exchange, crystallization processes are Tungsten smeltings
Main flow technique, and will produce a large amount of exhaust gas and waste water in the production process.Ammonia nitrogen exhaust gas occurs mainly with APT crystallizations and steams
Vapour and partial tail gas, ammonia nitrogen waste water occur mainly with ion exchange and APT Crystallization Procedures in APT production processes.
Publication No. CN101439865 applications for a patent for invention provide a kind of in production ammine in ammonium paratungstate recycling profit
Method.During producing the solution evaporative crystallization of ammonium paratungstate, what free ammonia and crystallization process in solution discharged
Ammonia gaseous form can volatilize, collect gaseous ammonia by closed container, then ammonia is recycled by way of condensation separation, the ammonia of recycling
It returns to production main flow and prepares parsing agent, the rate of recovery of ammonia is 90% or more.Publication No. CN102910648A patents of invention Shen
The method that please provide the recycling of one step tungsten and ammonia from the ammonium para-tungstate crystal mother solution of Tungsten smelting.In ammonium paratungstate APT evaporation knots
After the completion of crystalline substance, mother liquor is pumped into stripping reaction kettle, and the calcium hydroxide of calcium oxide or 95% of 90% or more content or more is added, and is led to
It crosses normal pressure stripping to recycle ammonia, after ammonia concentrates gas-liquid separation by condenser, is prepared into ammonium chloride with hydrochloric acid spray and returns
Main flow, ammonia nitrogen concentration is down to 30mg/L in water.
The existing method about recovery ammonia is normally only directed to ammonia nitrogen tail gas, or is recycled only for the ammonia nitrogen in waste water,
Use value is not high, while to increase additional cost.For the rare report of ammonia recovery method during production APT, needle
Ammonia recovery unit during production APT is had not been reported.
Invention content
The purpose of the present invention is to provide a kind of retracting device for ammonia during ammonium paratungstate production and utilize the dress
The method for carrying out recovery ammonia is set, on the basis of control cost, the exhaust gas containing ammonia nitrogen and waste water that generated to APT production processes carry out
Recovery ammonia ensures that the ammonia nitrogen discharge capacity in APT production processes is up to standard, environmentally protective.
Specifically, in view of the deficiencies of the prior art, the present invention provides following technical solutions：
The retracting device of ammonia during a kind of ammonium paratungstate production, including：Distillation system, pretreatment system, blow-removing system,
And hydrochloric acid spray system；
The distillation system includes rectifying column 1, is connect by pipeline with the top of rectifying column 1 helical-lobe compressor 10, with
Condenser 11 that helical-lobe compressor 10 is connected by pipeline, the condensate liquid storage tank 12 being connected by pipeline with condenser 11, wherein
Condensate liquid storage tank 12 is also connected by pipeline with rectifying column 1, which is equipped with valve 121；The bottom of rectifying column 1 passes through two
Pipeline is connected with reboiler 13, wherein a pipeline is the input channel that material enters reboiler 13 in tower, another is to boil again
Boiling steam enters the output channel of rectifying column 1 in device 13, which is equipped with valve 131；The middle part of the rectifying column 1
Equipped with smoke inlet 14, bottom tower reactor is equipped with discharge port 15；
The pretreatment system includes activation pot 2 and elevator pump 21, and the activation pot 2 passes through pipeline and tower reactor discharge port 15
It is connected, which is equipped with valve 51；Entrance 22, the discharge port being connected with elevator pump 21 23 and and wind are additionally provided on activation pot 2
The connected gas outlet 24 of machine 8；
The blow-removing system includes stripping tower 3, and the top of the stripping tower 3 is equipped with that inlet tube 31, lower part is equipped with and air blast
The connected discharge pipe 32 of machine 6, top go out equipped with gas vent 33, bottom after the stripping being connected with wind turbine 8 equipped with waste water after stripping
Mouth 34, wherein inlet tube 31 is connected by elevator pump 21 with the discharge port 23 of activation pot 2, and spray is additionally provided on the inlet tube 31
Shower device 35；
The hydrochloric acid spray system includes spray column 4, and the middle part of the spray column 4 is equipped with air inlet 41, top is equipped with spray
Drench the spray head 42 of hydrochloric acid, bottom is equipped with recovered liquid and exports 43, wherein air inlet 41 is connected with wind turbine 8.
Preferably, it is equipped with temperature indicating device 17 positioned at the top of smoke inlet 14 on rectifying column 1, the wastewater outlet 34 passes through pipe
Road is connected with elevator pump 21, which is equipped with branch pipe 38.Temperature indicating device can monitor the temperature in rectifying column in real time, improve the cigarette that gives up
Separating effect of the gas in rectifying column.
Preferably, the lower part of the activation pot 2 is equipped with filter plate 25, and the air outlet of the discharge pipe 32 is at least 2.It crosses
Filter plate can filter out the insoluble substance that original in waste water or activation generates, and multiple air outlets can improve stripping efficiency.
Preferably, the lower section of the spray equipment 35 is equipped with packing layer 36, and the lower part of the stripping tower 3 is higher than wastewater outlet
34 position is equipped with sampling window 37.By the ammonia-nitrogen content in sampling window sampling analysis waste water, stripping number is determined, ensure discharge
Waste water in ammonia-nitrogen content meet discharge standard.
Preferably, the lower part of the spray column 4 is equipped with liquid form 46, the wind turbine higher than the position of recovered liquid outlet 43
Heat exchanger 9 is equipped between 8 and air inlet 41.Heat exchanger is lowered into the ammonia temperature in hydrochloric acid spray column, improves hydrochloric acid
Absorb the efficiency of ammonia.
The present invention also provides a kind of recovery method of ammonia during ammonium paratungstate production, which uses aforementioned
Ammonia recovery unit, including following procedure：
S1. distillation system is utilized to handle flue gas：The flue gas that ammonium paratungstate generates will be produced to fill by smoke inlet 14
Enter in rectifying column 1, open valve 121 and valve 131, biphase gas and liquid flow is formed in rectifying column 1, ammonia, ammonia are obtained in top of tower
Gas liquefies after helical-lobe compressor 10 and condenser 11 becomes liquefied ammonia；After rectifying stops, valve 51 is opened by the tower of rectifying column 1
Kettle raffinate flows into activation pot 2 from discharge port 15 through piping；
S2. the bottom product for utilizing pretreatment system Ammonia-Containing Wastewater Treatment and rectifying column, then uses hydrochloric acid spray system
Absorb the ammonia that pretreatment generates：The ammonia-containing water that ammonium paratungstate generates will be produced to be input in activation pot 2 by entrance 22, with
After bottom product mixing, alkali is added to activate；The ammonia that activation generates flows to wind turbine 8 by gas outlet 24, enters back into spray column 4, ammonia
Gas is contacted with the hydrochloric acid that spray head 42 sprays, is reacted, and generates ammonium chloride；Waste water is in elevator pump 21 after activation in activation pot 2
The lower inlet tube 31 into blow-removing system of effect；
S3. the ammonia in the waste water after the activation of blow-removing system stripping is utilized, then hydrochloric acid spray system is used to absorb stripping
Ammonia out：Liquid in inlet tube 31 is sprayed by spray equipment 35, and the liquid sprayed out comes out with discharge pipe 32
Gas contacts, and stripping obtains ammonia；Ammonia flows to wind turbine 8 by gas vent 33, enters back into spray column 4, ammonia and spray head
42 hydrochloric acid contact, the reactions sprayed, generate ammonium chloride；Ammonia-nitrogen content after stripping in sample detection stripping tower 3 in waste water.
Preferably, the process S1 further includes by the temperature in 17 monitoring tower of temperature indicating device, and temperature is controlled at 92-94 DEG C,
The working pressure range of helical-lobe compressor 10 described in process S1 is 7-8 atmospheric pressure.
Preferably, add the alkali being added in alkali activation to be sodium hydroxide or calcium hydroxide described in process S2, activated adding alkali
It is also added into vulcanized sodium later.
Preferably, the ammonia-nitrogen content after the stripping in the sample detection stripping tower 3 described in process S3 in waste water is by taking
Sample window 37 samples, and when the ammonia-nitrogen content of waste water is less than 15mg/L after stripping, is discharged by branch pipe 38, otherwise in the work of elevator pump 21
Inlet tube 31 is come back under, carries out stripping again.
Preferably, the ammonia described in process S2 and S3 by also passing through heat exchange before after wind turbine 8, into spray column 4
Device 9 carries out cooling processing, and temperature is reduced to 35 DEG C or less.
Compared with prior art, it effect of the invention and has an advantage that：
The present invention provides a set of ammonia recovery unit in APT production processes, the recovery ammonia for realizing system is sharp again
It is easy to operate, easy to control, at low cost with, the device, there is very high practical value.Specifically, ammonia of the present invention returns
Receiving apparatus has following advantage：
(1) ammonia for using helical-lobe compressor to come out rectifying tower top compresses, and enables ammonia total condensation, recycles
To liquefied ammonia, the economic value that liquefied ammonia recycles is high.
(2) filter plate is equipped in the activation pot in ammonia recovery unit, after adding alkali activation plus sulfide in tank in waste water
Molybdenum is transformed into insoluble molybdenum slag, is filtered out through filter plate.
(3) stripping tower of ammonia recovery unit is equipped with sampling window, can accurately detect the ammonia-nitrogen content in waste water after stripping
And W content, determine that waste water is expelled directly out or stripping is handled again according to sampling analysis result, stringent control is discharged useless
Ammonia-nitrogen content in water.
(4) ammonia that activation or stripping generate is introduced into heat exchanger after wind turbine, and hydrochloric acid spray is entered back into after cooling
Tower is drenched, the absorption efficiency of hydrochloric acid is improved.
Using device of the present invention carry out recovery ammonia method is simple, the rate of recovery is high, the recycling form of ammonia is mainly chlorine
Change ammonium and liquefied ammonia.Ammonium chloride can be used for preparing strippant and return to ion-exchange process, and liquefied ammonia can be not only used for preparing strippant,
Other purposes can also be made.In addition, after recovery method of the present invention handles flue gas and waste water in APT productions, final
There is discharge of wastewater after stripping or further carry out sewage disposal, is discharged without exhaust gas.
Below in conjunction with the accompanying drawings with various specific implementation modes, the invention will be described further.
Description of the drawings
Fig. 1 is ammonia recovery unit schematic diagram of the present invention；
Wherein, 1- rectifying columns, 10- helical-lobe compressors, 11- condensers, 12- condensate liquids storage tank, 13- reboilers, 14- flue gases
Entrance, 15- discharge ports, 16- accumulator tanks, 17- temperature indicatings device, 121- valves, 131- valves, 2- activation pots, 21- elevator pumps, 22- enter
Mouth, 23- discharge ports, the gas outlets 24-, 25- filter plates, 3- stripping towers, 31- inlet tubes, 32- discharge pipes, 33- gas vents, 34-
Wastewater outlet, 35- spray equipments, 36- packing layers, 37- sampling windows, 38- branch pipes, 4- spray columns, 41- air inlets, 42- sprays
Head, the outlet of 43- recovered liquids, 44- elevator pumps, 45- packing layers, 46- liquid forms, 51- valves, 52- valves, 6- air blowers, 7-
Hydrochloric acid tank, 8- wind turbines, 9- heat exchangers.
Specific implementation mode
Ammonia recovery unit of the present invention includes：Distillation system, pretreatment system, blow-removing system and hydrochloric acid spray system
System.Distillation system mainly enters including rectifying column 1, helical-lobe compressor 10, condenser 11, condensate liquid storage tank 12, reboiler 13, flue gas
Mouth 14 and temperature indicating device 17.Wherein, the main function of helical-lobe compressor 10 is by ammonia compression, the liquid from 1 top of rectifying column out
Change, a liquefied ammonia part returns in rectifying column, and tower bottoms also returns to after entering reboiler boiling in rectifying column, maintains in rectifying column
Biphase gas and liquid flow.Pretreatment system includes mainly that the ammonia-containing water for being generated in bottom product and APT production processes alkalizes
Activation pot 2, the filter plate 25 being arranged in activation pot 2 can filter out in waste water original insoluble substance or add sodium hydroxide and
The molybdenum slag generated after vulcanized sodium.Blow-removing system includes mainly stripping tower 3, inlet tube 31, spray equipment 35 and is connected with air blower 6
The discharge pipe 32 containing multiple air outlets, flow speed controller and temperature controller, the liquid for spraying out are equipped in spray equipment
After body and the gas come out from discharge pipe come into full contact with, the volatile component ammonia stripping in liquid is come out, sampling window is passed through
37 take the waste water after stripping to carry out ammonia-nitrogen content analysis, and only ammonia-nitrogen content meets discharge standard (ammonia-nitrogen content is less than 15mg/L)
It could be discharged from branch pipe 38, being otherwise again introduced into inlet tube 31 by elevator pump 21 carries out spray stripping.Hydrochloric acid spray system master
To include spray column 4, spray head 42 and air inlet 41, the ammonia entered in spray column 4 from air inlet 41 first passes through heat exchange in advance
Device 9 is cooled to 35 DEG C hereinafter, can be come into full contact with the hydrochloric acid sprayed out from spray head 42, and reaction generates ammonium chloride.
" useless ammonia " in APT production processes refers to the ammonia in ammonia and waste water in production process in flue gas；Wherein, give up cigarette
Gas refers to a large amount of ammonia tail gas and water vapour that APT crystallization process generates, as shown in chemical equation (5)；Ammonia-containing water refers to APT
The friendship extraction raffinate of crystalline mother solution and ion-exchange process, ammonia mainly exist in the form of ammonium hydroxide and ammonium ion etc..
Include mainly following procedure using the method that ammonia recovery unit of the present invention recycles ammonia in APT production processes：
S1. distillation system is utilized to handle flue gas：The nitrogenous flue gas of APT generations is produced by high pressure stainless steel centrifugal blower
Then extraction enters via smoke inlet 14 in rectifying column 1, it (can be regulating valve, V-shaped valve, angle to open valve 121 and 131
Valve or butterfly valve etc.), rectifying column 1 is interior to form biphase gas and liquid flow, and by repeatedly part vaporization, with after partial condensation, tower top obtains
Ammonia after concentration compresses, is condensed into liquefied ammonia (under room temperature, the working pressure range of helical-lobe compressor is 7-8 atmospheric pressure), liquid
The ion exchange main flow that ammonia can return to APT production processes utilizes, and realizes recycling.Pass through control valve 121 and valve
131 control reflux ratios, make temperature in rectifying column maintain 92-94 DEG C.Rectifying tower reactor raffinate flows into activation pot 2 through piping, waits for
It is further processed.
S2. the bottom product for utilizing pretreatment system Ammonia-Containing Wastewater Treatment and rectifying column, then utilizes hydrochloric acid spray system
Absorb the ammonia generated：The ammonia-containing water of APT production processes is input to by entrance in activation pot 2 and is mixed with bottom product,
Add sodium hydroxide to activate, vulcanized sodium is then added.Occur in activation pot chemical reaction (chemical equation (1) that sees below, (2),
(3) and (4)) ammonia that generates via wind turbine 8, elutes to obtain into hydrochloric acid spray column after into heat exchanger 9 cooling down by hydrochloric acid
Ammonium chloride can be used for preparing strippant, realize recycling.Contain sodium molybdate in activation pot in waste water, after vulcanized sodium is added,
Molybdenum slag is generated, is filtered out through filter plate 25.Waste water after activation process is flowed out from discharge port 23, is passed through under the action of elevator pump 21
Inlet tube 31 enters stripping tower 3.
S3. the ammonia in the waste water after the activation of blow-removing system stripping is utilized, absorbing stripping using hydrochloric acid spray system comes out
Ammonia：Contain temperature and speed control in spray equipment 35 on inlet tube, control the temperature and speed of the liquid of sprinkling,
The liquid sprayed out comes into full contact with the air come out from discharge pipe 32, volatile ammonia stripping is come out, in stripping tower
Temperature be 50-85 DEG C.Sampling window 37 is used to obtain the waste water progress ammonia-nitrogen content analysis after stripping, is determined according to analysis result
The number of stripping, general stripping 2-4 times.The ammonia that stripping obtains repeatedly is exported from gas vent 33, via wind turbine 8 and heat exchange
Device 9 enters hydrochloric acid spray column, generates ammonium chloride (chemical equation (6) seen below) with hydrochloric acid haptoreaction, ammonium chloride can return
It returns ion-exchange process and prepares strippant.Heat exchanger make enter hydrochloric acid spray column in gas temperature be reduced to 35 DEG C hereinafter,
Improve the efficiency of absorption by Hydrochloric Acid ammonia.
Liquid form 46 on hydrochloric acid spray column 4 is to be set for the liquid level in observing tower when the liquid level in tower reaches
When definite value, stop hydrochloric acid and reacted with the spray of ammonia, recovered liquid (ammonium chloride solution) is collected by recovered liquid outlet 43.
It is equipped with packing layer in the tower of stripping tower and hydrochloric acid spray column, its object is to：The liquid of packing layer uppermost spray
It flows downward in film-form along filler surface, and the gas below packing layer is continuously from bottom to top contacted with liquid countercurrent, is increased
The big contact area of gas and liquid, stripping efficiency improve, and the efficiency of absorption by Hydrochloric Acid ammonia also improves.
Following chemical equation is shown in the chemical reaction that ammonia recovering process is related to：
(NH4)2WO4+2NaOH→Na2WO4+2NH3·H20 (1)
(NH4)2MoO4+2NaOH→Na2MoO4+2NH3·H20 (2)
MoO4 2-+3S2-+4H20→MoS3↓+80H- (4)
NH3+HCl(aq)→NH4Cl (6)
Below by way of specific embodiment, the invention will be described further.
It should be noted that the material that the present invention uses is commercially available.
Embodiment 1
Ammonia recovery unit of the present invention refers to Fig. 1, and the device mainly includes 4 main parts：Distillation system, pre- place
Reason system, blow-removing system and hydrochloric acid spray system.
Distillation system includes mainly rectifying column 1, is connect by pipeline with the top of rectifying column 1 helical-lobe compressor 10 and
Condenser 11 that helical-lobe compressor 10 is connected by pipeline, the condensate liquid storage tank 12 being connected by pipeline with condenser 11, meanwhile,
Condensate liquid storage tank 12 is also connected by pipeline with rectifying column 1, which is equipped with regulating valve 121.The bottom of rectifying column 1 passes through two
Root pipeline is connected with reboiler 13, wherein a pipeline is the input channel that material enters reboiler 13 in tower, another is again
Boiling steam enters the output channel of rectifying column 1 in boiling device 13, which is equipped with regulating valve 131.
The middle part of rectifying column 1 is equipped with smoke inlet 14, and bottom tower reactor is provided with discharge port 15, and 14 top of smoke inlet is also set
There is the temperature indicating device 17 of temperature in monitoring rectifying column.
The flue gas that ammonium paratungstate production process generates enters rectifying column 1 by smoke inlet 14, and the top of tower is rectifying
Section, lower part is stripping section, and the reflux ratio in rectifying column, the temperature in control tower can be adjusted by control valve 121 and 131.
Temperature indicating device 17 can monitor the temperature in rectifying column in real time.The ammonia that tower top comes out quilt after helical-lobe compressor 10 and condenser 11
It compresses, be condensed into liquefied ammonia and be stored in condensate liquid storage tank 12.When the liquefied ammonia in condensate liquid storage tank 12 reaches a certain amount of, valve is opened
Door 52, is input to accumulator tank 16, liquefied ammonia can be reused for the production of APT, can also make other purposes, realize flue gas by liquefied ammonia
In recovery ammonia recycle.
Pretreatment system includes mainly the activation pot 2 being connected with tower reactor discharge port 15 by pipeline, which is equipped with valve
Door 51 opens valve 51 and tower bottom of rectifying tower raffinate is put into activation pot 2.Activation pot 2 is equipped with entrance 22, bottom is equipped with and carries
The connected discharge port 23 of pump 21 is risen, top is equipped with the gas outlet 24 being connected with wind turbine 8；By entrance 22 by APT production processes
Ammonia-containing water is filled in activation pot 2, is mixed with bottom product, and alkali activation is then added, and the ammonia of generation is flowed by gas outlet 24
To wind turbine 8.Liquid is flowed out from discharge port 23 after activation in activation pot 2, and blow-removing system is entered under the action of elevator pump 21.
Blow-removing system includes stripping tower 3, and the top of stripping tower 3 is equipped with the inlet tube 31, the lower part that are equipped with spray equipment 35
Gas vent 33 after the stripping that is connected with wind turbine 8, bottom are equipped with equipped with blowing equipped with the discharge pipe 32 that is connected with air blower 6, top
Wastewater outlet 34 after de-.Liquid in inlet tube 31 is that waste water is pumped by elevator pump 21 after the activation in activation pot 2, outlet air
The air outlet of pipe 32 is 2.
Hydrochloric acid spray system includes spray column 4, and the middle part of the spray column is equipped with the air inlet 41 being connected with wind turbine 8, top
Spray head 42, bottom equipped with 1 spray hydrochloric acid are equipped with recovered liquid and export 43.Wind turbine 8 collect gas by air inlet 41 into
Enter in spray column 4, is contacted with the hydrochloric acid that spray head 42 sprays, reacts generation ammonium chloride, realize the recycling of ammonia.Spray head 42 passes through
Pipeline is connected with one end of elevator pump 44, and the other end of elevator pump 44 is connected by pipeline with hydrochloric acid tank 7；The work of elevator pump 44
With being that hydrochloric acid is pumped into spray head.
Embodiment 2
On the basis of embodiment 1, described device that the present invention is further explained.
Ammonia recovery unit described in the present embodiment and 1 described device of embodiment difference lies in：The lower part of activation pot 2 was equipped with
Filter plate 25 can filter out the insoluble substance that original in waste water or activation generates.The air outlet of discharge pipe 32 has 4, spray
The quantity for drenching head 42 is 2.Wastewater outlet 34 is connected by pipeline with elevator pump 21, and branch pipe 38 is additionally provided on the pipeline；When blowing
When waste water needs stripping again after de-, waste water after stripping is re-entered by inlet tube 31 by elevator pump 21, again stripping；
When the ammonia-nitrogen content of waste water meets discharge standard after stripping, discharged by branch pipe 38.
The lower section of spray equipment 35 is equipped with packing layer 36, and the lower section of spray head 42 also is provided with packing layer 45.Above packing layer
The liquid of sprinkling flows downward along filler surface in film-form, and the gas below packing layer is continuously from bottom to top inverse with liquid
Stream contact increases the contact area of gas and liquid, and stripping efficiency improves, and the efficiency of absorption by Hydrochloric Acid ammonia also improves.
Embodiment 3
On the basis of embodiment 2, described device that the present invention is further explained.
Ammonia recovery unit described in the present embodiment and 2 described device of embodiment difference lies in：The quantity of spray head 42 is 4
It is a, it is equipped with liquid form 46 higher than the position of recovered liquid outlet 43 in spray column lower part, for observing the recovered liquid in spray column
Liquid level.Meanwhile it being equipped with sampling window 37 higher than the position of wastewater outlet 34 in the lower part of stripping tower 3, it is used for sampling analysis stripping
Ammonia-nitrogen content in waste water afterwards, it is ensured that ammonia-nitrogen content is up to standard in the waste water of discharge.The ammonia recovery unit of the present embodiment is also in wind turbine 8
It is provided with heat exchanger 9 between air inlet 41, is lowered into the gas temperature of spray column, improves the effect of absorption by Hydrochloric Acid ammonia
Rate.
Embodiment 4
The ammonia in APT production processes is recycled using ammonia recovery unit of the present invention often to tie for producing 1 ton of APT
Crystalline substance 1 ton of APT of production generates 128.65kg flue gas, and wherein ammonia level is 84.11kg；Ammonia-nitrogen (NH in waste water3- N) contain
Amount is 68.4kg.
Process S1 recycles the ammonia in flue gas using distillation system, and concrete operations are as follows：
It produces the flue gas containing ammonia nitrogen that APT is generated to be extracted out by high pressure stainless steel centrifugal blower, then via smoke inlet 14
Into in rectifying column 1, valve 121 and 131 is opened, biphase gas and liquid flow is formed in rectifying column 1, by repeatedly part vaporization and part
After condensation, tower top obtains the ammonia of high-purity.Under the action of helical-lobe compressor 10 and condenser 11, ammonia is compressed, is liquefied
As liquefied ammonia, the operating pressure of helical-lobe compressor 10 is 7 atmospheric pressure.A part of liquefied ammonia returns in rectifying column, most of to store
In condensate liquid storage tank 12, finally liquefied ammonia is stored into accumulator tank 16.By in 131 control tower of control valve 121 and valve
Reflux ratio makes temperature in rectifying column maintain 92 DEG C, passes through temperature in 17 monitoring tower of temperature indicating device.After rectifying, recycling obtains
Liquefied ammonia 125L.The economic value of liquefied ammonia is high, and the ion exchange main flow that can return to APT production processes utilizes, and can also be used as other
On the way.
After rectifying stops, valve 51 is opened, tower bottom of rectifying tower raffinate flows into activation pot 2 through piping.
Process S2 recycles hydrochloric acid spray system using the bottom product of pretreatment system Ammonia-Containing Wastewater Treatment and rectifying column
System absorbs the ammonia that activation generates, and process is as follows：
The ammonia nitrogen waste water of APT production processes is input to by entrance 22 in activation pot 2, it is mixed with the bottom product of rectifying column
It closes, sodium hydroxide 200kg is added, reaction equation (1), (2) and (3) is shown in the chemical reaction of generation.React generate ammonia from
Gas outlet 24 flows to wind turbine 8, then enters spray column 4 by air inlet 41 after heat exchanger 9 is cooled to 30 DEG C, with spray head
Ammonium chloride is obtained by the reaction in the hydrochloric acid contact of 42 sprinklings, is stored in the lower part of spray column.After sodium hydroxide activation is added, also
The sodium sulfide solution of a concentration of 80g/L of 15L need to be added, the molybdenum in waste water is transformed into molybdenum slag (see chemical equation (4)), through filtering
Plate 25 filters out.Waste water is flowed out from discharge port 23 after filtered activation process, passes through inlet tube 31 under the action of elevator pump 21
Into stripping tower 3.
Process S3, the ammonia in waste water after being activated using blow-removing system stripping absorb stripping using hydrochloric acid spray system
Ammonia out, it is specific as follows：
The liquid sprayed out from spray equipment 35 comes into full contact with the air come out from discharge pipe 32, by volatile ammonia
Air-blowing takes off.The ammonia that stripping obtains from gas vent 33 export, via wind turbine 8 and heat exchanger 9 be cooled to 30 DEG C it is laggard
Enter hydrochloric acid spray column, ammonium chloride is generated with hydrochloric acid haptoreaction.Stripping temperature in stripping tower 3 is 70 DEG C, is sprayed by adjusting
The speed of shower device sprinkling liquid and temperature and discharge pipe go out wind velocity and temperature realizes.Sampling window 37 is for obtaining
Waste water after stripping carries out ammonia-nitrogen content analysis, and repeatedly after stripping 3 times, the ammonia-nitrogen content in waste water is 8mg/L, passes through branch pipe 38
Waste water is discharged, but also needs to ensure that other harmful substances such as the heavy metal in waste water meet wastewater discharge standard and could discharge.This
After inventing flue gas and the waste water in the recovery method processing APT productions, is discharged without exhaust gas, reduce pollution.
Process S2 and S3 are directed to absorb ammonia with hydrochloric acid spray system, and the hydrochloric acid in spray head 42 is in hydrochloric acid tank 7
Hydrochloric acid be pumped under the action of elevator pump 44, the hydrochloric acid of sprinkling flows downward along the surface of packing layer 45 in film-form,
It is come into full contact with upstream ammonia, chemical reaction occurs and generates ammonium chloride drop, is finally accumulated as in the bottom of spray column 4
Ammonium chloride solution.By the liquid level in 46 observing tower of liquid form, when the liquid level in tower reaches setting value, stop hydrochloric acid
It is reacted with the spray of ammonia, recovered liquid, i.e. ammonium chloride solution is collected by recovered liquid outlet 43, recycling is amounted to and obtains ammonium chloride
250kg。
Embodiment 5
The present embodiment includes altogether a, b and c, and totally 3 groups of experiments, operating process is same as Example 4, but in ammonia recovery unit
Each system operating condition it is different, be specifically shown in Table 1.Wherein, overall recovery is to recycle in obtained liquefied ammonia and ammonium chloride
Nitrogen total mole number/flue gas be calculated with the total nitrogen molal quantity in waste water.
Table 1. tests the operating condition comparison of a, b, c and embodiment 4
| Test a | Test b | Test c | Embodiment 4 | |
| Temperature (DEG C) in rectifying column | 92 | 93 | 94 | 92 |
| The operating pressure of helical-lobe compressor | 7 atmospheric pressure | 8 atmospheric pressure | 8 atmospheric pressure | 7 atmospheric pressure |
| Stripping temperature (DEG C) | 85 | 50 | 70 | 70 |
| Stripping number | 3 | 4 | 2 | 3 |
| Ammonia-nitrogen content (mg/L) in waste water after stripping | 7 | 15 | 10 | 8 |
| Into the gas temperature (DEG C) of hydrochloric acid spray column | 30 | 35 | 34 | 30 |
| Recycling obtains liquefied ammonia volume (L) | 120 | 130 | 130 | 125 |
| Recycling obtains ammonium chloride (kg) | 260 | 250 | 245 | 250 |
| Overall recovery (%) | 93.79 | 95.51 | 94.60 | 93.62 |
Can see from the data of upper table, using recovery method of the present invention to the ammonia that is generated in APT production processes into
Row recycling, the rate of recovery is high, and the ammonia-nitrogen content after stripping in waste water meets discharge standard, environmentally protective.The recovery method recycles
The ammonia arrived is liquefied ammonia and ammonium chloride, and ammonium chloride can return to the ion-exchange process prepared in APT technological processes, for preparing solution
Vapor；Liquefied ammonia can be not only used for preparing strippant, can also make other purposes, and economic value is high.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in,
It should be covered by the protection scope of the present invention.
Claims (10)
1. the retracting device of ammonia during a kind of ammonium paratungstate production, which is characterized in that the ammonia recovery unit includes：Rectifying system
System, pretreatment system, blow-removing system and hydrochloric acid spray system；
The distillation system includes rectifying column (1), is connect by pipeline with the top of rectifying column (1) helical-lobe compressor (10),
The condenser (11) being connect by pipeline with helical-lobe compressor (10), the condensate liquid storage tank being connected by pipeline with condenser (11)
(12), wherein condensate liquid storage tank (12) is also connected by pipeline with rectifying column (1), which is equipped with valve (121)；Rectifying
The bottom of tower (1) is connected by two pipelines with reboiler (13), wherein a pipeline is that material enters reboiler (13) in tower
Input channel, another enters the output channel of rectifying column (1) for reboiler (13) interior boiling steam, is set on the output channel
There is valve (131)；The middle part of the rectifying column (1) is equipped with smoke inlet (14), and bottom tower reactor is equipped with discharge port (15)；
The pretreatment system includes activation pot (2) and elevator pump (21), and the activation pot (2) passes through pipeline and tower reactor discharge port
(15) it is connected, which is equipped with valve (51)；It is additionally provided with entrance (22) on activation pot (2), goes out with what elevator pump (21) was connected
Material mouth (23) and the gas outlet (24) being connected with wind turbine (8)；
The blow-removing system includes stripping tower (3), and the top of the stripping tower (3) is equipped with inlet tube (31), lower part is equipped with and drum
The connected discharge pipe (32) of wind turbine (6), top are equipped with equipped with gas vent (33), bottom after the stripping being connected with wind turbine (8) blows
Wastewater outlet (34) after de-, wherein inlet tube (31) is connected by elevator pump (21) with the discharge port (23) of activation pot (2), institute
It states and is additionally provided with spray equipment (35) on inlet tube (31)；
The hydrochloric acid spray system includes spray column (4), and the middle part of the spray column (4) is equipped with air inlet (41), top is equipped with
Spray the spray head (42) of hydrochloric acid, bottom is equipped with recovered liquid and exports (43), wherein air inlet (41) is connected with wind turbine (8).
2. ammonia recovery unit according to claim 1, which is characterized in that positioned at smoke inlet (14) on rectifying column (1)
Top is equipped with temperature indicating device (17), and the wastewater outlet (34) is connected by pipeline with elevator pump (21), which is equipped with branch pipe
(38)。
3. ammonia recovery unit according to claim 2, which is characterized in that the lower part of the activation pot (2) is equipped with filter plate
(25), the air outlet of the discharge pipe (32) is at least 2.
4. according to claim 1-3 any one of them ammonia recovery units, which is characterized in that the lower section of the spray equipment (35)
Equipped with packing layer (36), the lower part of the stripping tower (3) is equipped with sampling window (37) higher than the position of wastewater outlet (34).
5. according to claim 1-4 any one of them ammonia recovery units, which is characterized in that the lower part of the spray column (4) is high
The position that (43) are exported in recovered liquid is equipped with liquid form (46), and heat exchange is equipped between the wind turbine (8) and air inlet (41)
Device (9).
6. the recovery method of ammonia during a kind of ammonium paratungstate production, which uses any one of claim 1-5 institutes
The ammonia recovery unit stated, which is characterized in that the recovery method includes following procedure：
S1. distillation system is utilized to handle flue gas：The flue gas that ammonium paratungstate generates will be produced to be filled with by smoke inlet (14)
In rectifying column (1), valve (121) and valve (131) are opened, biphase gas and liquid flow is formed in rectifying column (1), ammonia is obtained in top of tower
Gas, ammonia liquefies after helical-lobe compressor (10) and condenser (11) becomes liquefied ammonia；After rectifying stops, opening valve (51) will
The bottom product of rectifying column (1) flows into activation pot (2) from discharge port (15) through piping；
S2. the bottom product for utilizing pretreatment system Ammonia-Containing Wastewater Treatment and rectifying column, then uses hydrochloric acid spray system to absorb
Pre-process the ammonia generated：The ammonia-containing water that ammonium paratungstate generates will be produced to be input in activation pot (2) by entrance (22), with
After bottom product mixing, alkali is added to activate；The ammonia that activation generates flows to wind turbine (8) by gas outlet (24), enters back into spray column
(4), ammonia is contacted with the hydrochloric acid that spray head (42) sprays, is reacted, and generates ammonium chloride；Waste water exists after activation in activation pot (2)
Enter the inlet tube (31) of blow-removing system under the action of elevator pump (21)；
S3. the ammonia in the waste water after the activation of blow-removing system stripping is utilized, then uses hydrochloric acid spray system to absorb stripping and comes out
Ammonia：Liquid in inlet tube (31) is sprayed by spray equipment (35), and the liquid sprayed out comes out with discharge pipe (32)
Gas contact, stripping obtains ammonia；Ammonia flows to wind turbine (8) by gas vent (33), enters back into spray column (4), ammonia
It contacts, react with the hydrochloric acid that spray head (42) sprays, generate ammonium chloride；After stripping in sample detection stripping tower (3) in waste water
Ammonia-nitrogen content.
7. the recovery method of ammonia according to claim 6, which is characterized in that the process S1 further includes by temperature indicating device
(17) temperature in monitoring tower, at 92-94 DEG C, the working pressure range of helical-lobe compressor (10) described in process S1 is for temperature control
7-8 atmospheric pressure.
8. the recovery method of ammonia according to claim 7, which is characterized in that be added in the activation of described in process S2 plus alkali
Alkali is sodium hydroxide or calcium hydroxide, and vulcanized sodium is also added into after adding alkali activation.
9. according to the recovery method of claim 6-8 any one of them ammonia, which is characterized in that the sample detection described in process S3
Ammonia-nitrogen content after stripping in stripping tower (3) in waste water is sampled by sampling window (37), the ammonia-nitrogen content of waste water after stripping
When less than 15mg/L, it is discharged by branch pipe (38), otherwise comes back to inlet tube (31) under the action of elevator pump (21), again
Carry out stripping.
10. according to the recovery method of claim 6-9 any one of them ammonia, which is characterized in that the ammonia described in process S2 and S3
For gas by also carrying out cooling processing through over-heat-exchanger (9) before after wind turbine (8), into spray column (4), temperature is reduced to 35
DEG C or less.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414741A (en) * | 2022-07-27 | 2022-12-02 | 中材锂膜(宁乡)有限公司 | Waste gas recovery system and method |
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| CN207246095U (en) * | 2017-09-06 | 2018-04-17 | 江西铜鼓有色冶金化工有限责任公司 | A kind of recovery ammonia is sealed with stainless steel wind turbine |
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| GB958054A (en) * | 1960-04-01 | 1964-05-13 | United States Steel Corp | Method of recovering ammonia from coke-oven gases |
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| CN115414741A (en) * | 2022-07-27 | 2022-12-02 | 中材锂膜(宁乡)有限公司 | Waste gas recovery system and method |
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