CN106268179B - A kind of energy saving technique and system of synthetical recovery sulfuric acid purification spent acid - Google Patents
A kind of energy saving technique and system of synthetical recovery sulfuric acid purification spent acid Download PDFInfo
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- CN106268179B CN106268179B CN201610723207.0A CN201610723207A CN106268179B CN 106268179 B CN106268179 B CN 106268179B CN 201610723207 A CN201610723207 A CN 201610723207A CN 106268179 B CN106268179 B CN 106268179B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/14—Separation 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 by absorption
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/14—Separation 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 by absorption
- B01D53/1406—Multiple stage absorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/14—Separation 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 by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/005—Oxides; Hydroxides; Oxyacids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/50—Inorganic acids
- B01D2251/506—Sulfuric acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/10—Inorganic absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention discloses a kind of energy saving techniques of synthetical recovery sulfuric acid purification spent acid：High-temperature flue gas is passed through first grade scrubber；Go out sour nozzle inside the acid pump of bottom of tower to first grade scrubber admission line, acid solution inversely contacts the SO absorbed in flue gas with high-temperature flue gas3；Continue to cool down into follow-up conventional purge flow after the flue gas cool-down of acid solution washing, the condensation diluted acid that follow-up cooling procedure generates returns to the SO maintained in first grade scrubber in tower3And water balance；Heavy metal dirt and arsenic element in flue gas form sulfate and arsenious acid after acid solution is washed；Arsenious acid in acid solution is oxidized to arsenic acid by compressed air aerator；It is sent into cooling densifying tower containing the acid solution of arsenic acid and heavy metal hydrochlorate；The concentrated acid that cooling densifying tower comes out filters out heavy metal sulfate slag through slag filter, and filtrate enters SO2Reductive jar is passed through highly concentrated SO into tank2The arsenious acid that gas is reduced to arsenic acid to be slightly soluble in sulfuric acid precipitates；Acid solution containing arsenious acid precipitation obtains arsenious acid filter cake after being separated by solid-liquid separation.
Description
Technical field
The present invention relates to a kind of energy saving techniques and system of synthetical recovery sulfuric acid purification spent acid.
Background technology
The spent acid of purification system is to it using vulcanization alkaline agent or alkaline agent except the weight such as As, Cu in flue gas acid preparing technique at present
Again into full factory's sewage disposal system after metal ion and neutralization.Although having neutralized spent acid, being extracted As, Cu plasma, production
The largely gypsum containing heavy metal is given birth to, it is virtually impossible to be used again, long-term stack causes serious secondary pollution again, handles
Come abnormal intractable.
Titanium dioxide industry is it has been proposed that the mode for carrying out multiple-effect evaporation to system spent acid carries out enrichment recycling, but operates item
Part is extremely harsh.Because by 10% or so Waste Sulfuric Acid concentrate to 80% or more, the boiling point of sulfuric acid will be raised to 200 DEG C or more, right
Equipment selection harshness is that on the one hand, heating steam is necessary for middle pressure steam, and surprising consumption is also the weight that the technique can not be promoted
Want reason.
It has been proposed that the concentrate spent acid by the way of MVR engine driven superchargings.But due to sulfuric acid boiling point with the dense promotion of acid and
It dramatically increases.MVR systems can only handle the solution that 20 DEG C of boiling points of highest rise or so, sulfuric acid concentration can only concentrate to 48%, recycling
The value utilized is little.The power grid electric energy expense of another aspect MVR consumption is not low, unless private station is had, otherwise, economy
There are also problems for upper feasibility.
Invention content
The present invention is directed to overcome the deficiencies of the prior art and provide a kind of energy saving technique of synthetical recovery sulfuric acid purification spent acid and
System.
In order to achieve the above object, technical solution provided by the invention is：
The energy saving technique process of the synthetical recovery sulfuric acid purification spent acid is as follows：
(1) 200 DEG C~300 DEG C of high-temperature flue gas is passed through first grade scrubber；The cleaning circulation pump of first grade scrubber is by level-one
The acid pump of scrubbing tower bottom of tower to the sour nozzle that goes out being arranged inside first grade scrubber admission line, acid solution spray after with high temperature cigarette
The circulation of vital energy in the wrong direction is to contact, the SO in flue gas3It is absorbed by acid solution；
(2) enter follow-up conventional purge after the flue-gas temperature of first grade scrubber acid solution washing is down to 70 DEG C~160 DEG C
Flow continues to cool down, and the condensation diluted acid that follow-up cooling procedure generates returns to the SO maintained in first grade scrubber in first grade scrubber3
And water balance；
(3) the heavy metal dirt in flue gas and arsenic element form sulfate and arsenous in first grade scrubber after acid solution is washed
Acid；Arsenious acid in acid solution is oxidized to arsenic acid by the compressed air aerator of first grade scrubber intracavity bottom setting；
(4) acid solution containing arsenic acid and heavy metal hydrochlorate is arranged by washing delivery pump and being sent into from first grade scrubber in sulfuric acid
Cooling densifying tower after drying and absorption process；The flue gas being discharged after first grade scrubber is washed carries out secondary suction through sulfuric acid drying and absorption process
Receive, sulfuric acid is dry inhale after partial fume be passed through cooling densifying tower to entering acid solution concentrate and the cooling of cooling densifying tower；
(5) flue gas that cooling densifying tower comes out is discharged into tail suction desulfurization；The concentrated acid that cooling densifying tower comes out is through acid sludge filter pump
Pump filters out heavy metal sulfate slag, filtrate enters SO to slag filter2Reductive jar, by being passed through highly concentrated SO into tank2Gas handle
Arsenic acid is reduced to be slightly soluble in the arsenious acid precipitation of sulfuric acid, and residual gas is incorporated to relieving haperacidity purifying smoke entrance；It is precipitated containing arsenious acid
Acid solution pumped into arsenic filter and be separated by solid-liquid separation by arsenic filter pump, obtain filtered clear acid and arsenious acid filter cake；It is sub-
Arsenic acid filter cake is collected after drying to get white arsenic product.
The energy conserving system of the synthetical recovery sulfuric acid purification spent acid includes first grade scrubber；The first grade scrubber side is set
There is vertically arranged admission line；The first grade scrubber lower part is exported equipped with recycle acid, and recycle acid outlet passes through wash cycle
It pumps and is connected to the sour nozzle that goes out being arranged inside admission line；Exhanst gas outlet, exhanst gas outlet are equipped at the top of the first grade scrubber
It is connected to conventional purge flow system；First grade scrubber intracavity bottom is equipped with compressed air aerator；The first grade scrubber
Lower part is additionally provided with acid solution outlet, and acid solution outlet is connected to by washing delivery pump with cooling densifying tower；The cooling densifying tower and sulphur
Sour drying and absorption process system connectivity；The cooling densifying tower lower part is exported equipped with acid sludge, and acid sludge outlet passes through acid sludge filter pump and slag
Filter is connected to；Slag filter and SO2Reductive jar is connected to；SO2Reductive jar is connected to by arsenic filter pump with arsenic filter.
Wherein, the first grade scrubber is equipped with multiple times sour entrances.The cooling densifying tower lower part acid outlet and enrichment
Pump entry is connected to, and enrichment circulating-pump outlet is connected to cooling densifying tower top.The arsenic filter connects with pneumatic conveyer dryer
It is logical；The pneumatic conveyer dryer is received arsenic device with cloth bag and is connected to.
The invention will be further described below：
Concrete technology flow process of the present invention is as follows：
200 DEG C~300 DEG C of high-temperature flue gas is introduced into purification first grade scrubber (the tower energy high temperature resistant peracid), purification one
Grade scrubbing tower is equipped with cleaning circulation pump, bottom of tower acid solution is squeezed into scrubbing tower nozzle, acid solution is inversely contacted with high-temperature flue gas fills
The mass-and heat-transfer divided.SO in flue gas3It is absorbed by recycle acid, the washing of purification two level, electric demisting condensation diluted acid all fill into level-one
It is dense according to the recycle acid in scrubbing tower that a regulating valve should be arranged to keep the dense stabilization of acid and the water balance in scrubbing tower in scrubbing tower
It spends to control the discharge rate of the cold diluted acid of Clean room, discharge diluted acid enters sewage workshop and is neutralized.Scrubbing tower recycle acid is dense
Can between 10%~80% (w%) arbitrary value, specifically by aforementioned regulating valve according to requiring to be controlled.Flue gas is washed by level-one
Tower height temperature acid elution, temperature are down to 70 DEG C~160 DEG C (concrete numerical value will provide in embodiment), enter back into follow-up conventional purge
Flow continues to cool down, and the condensation diluted acid that follow-up cooling procedure generates returns to the SO maintained in first grade scrubber in first grade scrubber3
And water balance.The elements such as heavy metal dirt and arsenic in flue gas enter solution in first grade scrubber through pickling, formed sulfate and
Arsenious acid.It is equipped with compressed air aerator in first grade scrubber bottom, the smaller arsenious acid of solubility in acid solution is oxidized to
The larger arsenic acid of solubility, is completely dissolved in sulfuric acid solution.High-temperature acid containing arsenic acid and heavy metal hydrochlorate is conveyed by washing
Pump from squeezed into first grade scrubber be arranged sulfuric acid is dry inhale after cooling densifying tower.By the flue gas extension after double absorption
It is passed through in cooling densifying tower to carrying out concentrate again and cooling (such as into the high-temperature acid of tower：It can by calculating required exhaust gas volumn
With in densifying tower acid it is dense carry to 93%, achieve the purpose that it is dry suction directly production string acid).Sour Wen Ze is reduced to close into tower cigarette
Temperature degree (65 DEG C~80 DEG C) is discharged into tail and inhales desulfurization.The concentrated acid that the relatively low temperature for reaching setting concentration contains crystal precipitation passes through acid
Slag filter pump squeezes into slag filter and filters out heavy metal sulfate slag, and filtrate enters SO2Reductive jar, by being passed through highly concentrated SO into tank2
The arsenious acid that gas is reduced to arsenic acid to be slightly soluble in sulfuric acid precipitates, and residual gas is incorporated to relieving haperacidity purifying smoke entrance.Contain arsenous
The wintercherry of acid precipitation is squeezed into arsenic filter by arsenic filter pump and is separated by solid-liquid separation.93% clear acid being obtained by filtration is sent to dry absorption section and follows
Naphthenic acid slot is as moisturizing and production acid.Then first be passed through hot-air in pneumatic conveyer dryer agitates drying to the arsenious acid filter cake of output.Weight
Particle falls into bottom of tower and is collected, and light particle enters cloth bag receipts arsenic device with dry gas and further removes down.The white arsenic collected is made
To be sold outside qualified products.Dry flue gas containing micro amount of arsenic is then incorporated to relieving haperacidity purifying smoke entrance circulation and stress.
Compared with prior art, the features of the present invention is：
1, this technique utilizes the 250 of smelting generation under the premise of not increasing any external evaporation energy consumption (steam, electricity etc.)
Evaporation heat source of~300 DEG C of high-temperature flue gas as spent acid concentrate.Pickling only by changing sulfuric acid purification process first grade scrubber
Pattern (will purification level-one Diluted Acid Washing temperature reduction technology make concentrated acid cleaning dust technique into), so that it may will purification acid-spending strength concentrate to connecing
Nearly 80%, then a densifying tower is set after sulfuric acid dry absorption section, using the low temperature dry flue gas after relieving haperacidity double absorption level-one
The high temperature spent acid of scrubbing tower discharge proposes a step concentrate and cooling.The high concentrated acid filtering heavy metal salt of low temperature, clear liquid are finally carried into arsenic, obtained
It can be sent into dry absorption section to 90% or so clear acid and replace part system moisturizing.Operating cost is at a fairly low, is particularly adapted to existing smelting
Refine the upgrading and transformation of flue gas acid preparing factory.
2, the design concentration of first grade scrubber recycle acid is preferable (still, if import flue gas to be no more than 80% in this technique
Water content is seldom, and the design concentration of recycle acid can also be promoted to 80% or more or even 90%).It need to be in first grade scrubber
Lower part solution area is equipped with compressed air aerator and (pays attention to：Compressed air must be the pressure 0.6MPa that is obtained with air compressor machine with
Upper compressed air.Unavailable Roots blower replaces, because water content is too high in its gas), by the smaller Asia of solubility in solution
Arsenic acid is oxidized to the larger arsenic acid of solubility.
3, this technique varies without the conventional purge flow after first grade scrubber.According to the difference of flue gas condition, it should be noted that two
The problem of aspect：One, as SO in the flue gas into before purification system2With H2The volume ratio V of OSO2：VH2O≥
When, illustrate in flue gas that moisture is not only able to meet follow-up 98% acid production, and can while purification system concentrate highly concentrated waste acid
Any acid waste water is not discharged.Two, work as VSO2：VH2O＜When, illustrate aqueous mistake in flue gas
More, in addition to maintaining the dry water for inhaling 98% acid balance of production, purification system need to be removed more than VSO2The vapor of volume.This is again
In two kinds of situation：(1) if exceeding VSO2V in the steam vapour amount and purifying smoke of volumeSO3Volume is suitable, then purification system
Any acid waste water can not be discharged；(2) if SO in flue gas3It is not enough to and exceeds VSO2The vapor of volume makes setting
First grade scrubber recycle acid it is dense (such as 80% acid), then whole condensation diluted acids of purification section can not be filled into first grade scrubber
Interior, gesture necessary loss, the cold diluted acid decontaminated water processing section of discharge part Clean room neutralize.Nevertheless, SO in flue gas3Maximum
Loss amount is not more than the 30% of total amount.
4, the high-temperature acid of first grade scrubber by the delivery pump of high silicon iron (or high silicon stainless steel) material be sent to densifying tower into
Row cooling concentrate.Densifying tower should be arranged after the final double absorption of sulfuric acid.It is that 80% (quality is dense when the acid into densifying tower is dense
Degree) when, water vapor pressure ＜ 1Pa, 80% acid saturated vapor pressure~500Pa after being inhaled due to two in 70 DEG C of flue gases, with 80% acid and
Two inhale after smoke contacts can make 80% acid concentration continue to improve, temperature continues to reduce.By taking concentrate to 93% acid as an example, because two suctions follow
Naphthenic acid is 98% acid, and the saturated vapor pressure corresponded in exiting flue gas is less than 93% sour water vapour pressure, Gu it is to follow with 93% acid
Naphthenic acid can also then continue growing the moisture content in gas phase, so that its water vapor pressure is reached the saturated vapor pressure of 93% acid, to reach handle
Acid is further concentrated into 93% purpose from 80%.The exhaust gas volumn size of required cooling should be by the dense corresponding gas-liquid of recycle acid in tower
Balance and system heat balance are calculated.In general, required exhaust gas volumn can be less than whole exhaust gas volumns that double absorption comes out, institute
To take after the double absorption of part flue gas into the concentration tower.
5, the solubility of various heavy metal sulfates is all very low under concentrated acid, can all crystallize precipitation substantially, therefore, increases from cooling
The concentrated acid of dense tower output can be directly separated by filtration.Containing a small amount of concentrated acid (93%) to cast iron corruption in the heavy metal sulfate filtered out
Corrosion is smaller, can usual manner transport.
6, it filters in the sulfuric acid after acid sludge and contains arsenic acid, be passed through SO2Gas carries out reaction reduction, and it is micro- to regenerate arsenious acid
Insoluble precipitate.Then it is separated by filtration again, filtration cakes torrefaction is obtained into white arsenic product, the clear acid of filtering gained fills into the dry suction production of sulfuric acid
String acid.
Description of the drawings
Fig. 1 is the energy conserving system structural schematic diagram of synthetical recovery sulfuric acid purification spent acid of the present invention.
In figure：1, first grade scrubber；2, admission line；3, go out sour nozzle；4, compressed air aerator；5, washing conveying
Pump；6, cooling densifying tower；7, acid sludge filter pump；8, slag filter；9、SO2Reductive jar；10, arsenic filter pump；11, arsenic filter；
12, sour entrance is returned；13, enrichment circulating pump；14, pneumatic conveyer dryer；15, cloth bag receives arsenic device.
Specific implementation mode
Embodiment 1
The energy conserving system includes first grade scrubber 1；1 side of the first grade scrubber is equipped with vertically arranged admission line
2；1 lower part of the first grade scrubber is exported equipped with recycle acid, and recycle acid outlet is by cleaning circulation pump with setting in admission line 2
Internal goes out the connection of sour nozzle 3；1 top of the first grade scrubber is equipped with exhanst gas outlet, exhanst gas outlet and conventional purge flow system
System connection；1 intracavity bottom of first grade scrubber is equipped with compressed air aerator 4；1 lower part of the first grade scrubber is additionally provided with acid solution
Outlet, acid solution outlet are connected to by washing delivery pump 5 with cooling densifying tower 6；The cooling densifying tower 6 and sulfuric acid drying and absorption process system
System connection；6 lower part of cooling densifying tower is exported equipped with acid sludge, and acid sludge outlet is connected by acid sludge filter pump 7 and slag filter 8
It is logical；Slag filter 8 and SO2Reductive jar 9 is connected to；SO2Reductive jar 9 is connected to by arsenic filter pump 10 with arsenic filter 11.
Wherein, the first grade scrubber 1 is equipped with multiple times sour entrances 12.6 lower part acid outlet of the cooling densifying tower with
13 entrance of enrichment circulating pump is connected to, and the outlet of enrichment circulating pump 13 is connected to 6 top of cooling densifying tower.The arsenic filter 11 and gas
Flash dryer 14 is connected to；The pneumatic conveyer dryer 14 is received arsenic device 15 with cloth bag and is connected to.
Case history：
1, contain H2O is 5%, SO2Concentration ＞ 5%, SO3A concentration of 0.2%, temperature is that 300 DEG C of flue gas during smelting enters level-one
Scrubbing tower, and from the wash cycle acid acid solution counter current contacting squeezed into of pump and occurs mass-and heat-transfer.Recycle acid temperature is 147 DEG C, and acid is dense
Degree is 80%.30% SO in flue gas3It is directly entered in wash cycle acid solution, remaining 70%SO3Enter follow-up tradition with flue gas
Cleaning equipment, and all returned in first grade scrubber in the form of condensing diluted acid, whole SO in recovered flue gas3Ingredient does not have at this time
Have and is arranged outside any diluted acid.According to the water balance in scrubbing tower, a small amount of new water should be supplemented into scrubbing tower for maintaining 80% in tower
The concentration of acid.Flue gas passes through first grade scrubber high temperature acid elution, and temperature is down to 149 DEG C, enter back into follow-up conventional purge flow after
Continuous cooling.The elements such as heavy metal dirt and arsenic in flue gas enter solution in first grade scrubber through pickling, form sulfate and Asia
Arsenic acid.It is equipped with compressed air aerator in first grade scrubber bottom, the smaller arsenious acid of solubility in acid solution is oxidized to molten
Arsenic acid larger Xie Du.High-temperature sulfuric acid containing arsenic acid and heavy metal hydrochlorate squeezes into setting in the dry suction of sulfuric acid by washing delivery pump
Cooling densifying tower later.Flue gas extension after double absorption is passed through in cooling densifying tower to the high-temperature acid into tower again
Concentrate is to 90% and is cooled to 73 DEG C, and the flue gas that densifying tower comes out is discharged into tail and inhales desulfurization.The wintercherry of cooling densifying tower passes through slag mistake
Filter pump squeezes into slag filter and filters out heavy metal sulfate slag, and filtrate enters SO2Reductive jar.By being passed through highly concentrated SO into tank2Gas
Arsenic acid is reduced to be slightly soluble in the arsenious acid precipitation of sulfuric acid, residual gas is incorporated to relieving haperacidity purifying smoke entrance.It is heavy containing arsenious acid
The wintercherry in shallow lake is squeezed into arsenic filter by arsenic filter pump and is separated by solid-liquid separation.90% clear acid being obtained by filtration is sent to dry absorption section cycle
Acid tank is as moisturizing and production acid.Then first be passed through hot-air in pneumatic conveyer dryer agitates drying to the arsenious acid filter cake of output.Weight
Grain falls into bottom of tower and is collected, and light particle enters cloth bag receipts arsenic device with dry gas and further removes down.The white arsenic collected is made
To be sold outside qualified products.
2, contain H2O is 10%, SO2Concentration ＜ 10%, SO3A concentration of 0.2%, the flue gas during smelting that temperature is 300 DEG C enters one
Grade scrubbing tower, and from the wash cycle acid acid solution counter current contacting squeezed into of pump and occurs mass-and heat-transfer.30% SO in flue gas3Into
In wash cycle acid solution, remaining 70%SO3Enter follow-up conventional purification apparatus with flue gas, it, can not since system contains dilutional hyponatremia
Subsequent condensation diluted acid is all filled into first grade scrubber, therefore a regulating valve is set according to acid concentration is recycled in scrubbing tower to control
The discharge rate of the cold diluted acid of Clean room.Discharge diluted acid enters sewage workshop neutralisation treatment, to keep recycle acid in first grade scrubber dense
It is 80%, acid temperature is 155 DEG C.Flue gas passes through first grade scrubber high temperature acid elution, and temperature is down to 157 DEG C, net into follow-up tradition
Change flow to continue to cool down.The elements such as heavy metal dirt and arsenic in flue gas enter solution in first grade scrubber through pickling, form sulphur
Hydrochlorate and arsenious acid.It is equipped with compressed air aerator in first grade scrubber bottom, by the smaller arsenious acid of solubility in acid solution
It is oxidized to the larger arsenic acid of solubility.High-temperature sulfuric acid containing arsenic acid and heavy metal hydrochlorate is existed by washing delivery pump and squeezing into be arranged
Cooling densifying tower after the dry suction of sulfuric acid.Flue gas extension after double absorption is passed through in cooling densifying tower into tower height temperature
Concentrate to 90% and is cooled to 73 DEG C to acid again, and the flue gas that densifying tower comes out is discharged into tail and inhales desulfurization.The wintercherry of cooling densifying tower is logical
It crosses slag filter pump and squeezes into slag filter and filter out heavy metal sulfate slag, filtrate enters SO2Reductive jar.It is highly concentrated by being passed through into tank
SO2The arsenious acid that gas is reduced to arsenic acid to be slightly soluble in sulfuric acid precipitates, and residual gas is incorporated to relieving haperacidity purifying smoke entrance.Contain Asia
The wintercherry of arsenic acid precipitation, which is squeezed by arsenic filter pump in arsenic filter, to be separated by solid-liquid separation.90% clear acid being obtained by filtration is sent to dry suction work
Duan Xunhuan acid tanks are as moisturizing and production acid.The arsenious acid filter cake of output then first be passed through in pneumatic conveyer dryer hot-air agitate it is dry
It is dry.Weight particle falls into bottom of tower and is collected, and light particle enters cloth bag receipts arsenic device with dry gas and further removes down.That collects is white
Arsenic is sold as qualified products outside.
3, it is not lose completeness, the embodiment data of this technique first grade scrubber and cooling densifying tower can also be following a variety of
Situation, but it is not limited to following situations (table 1).
Table 1
Claims (5)
1. a kind of energy saving technique of synthetical recovery sulfuric acid purification spent acid, which is characterized in that the technical process is as follows：
(1) 200 DEG C~300 DEG C of high-temperature flue gas is passed through first grade scrubber；The cleaning circulation pump of first grade scrubber washs level-one
For the acid pump of tower bottom of tower to the sour nozzle that goes out being arranged inside first grade scrubber admission line, acid solution is inverse with high-temperature flue gas after spraying
To contact, the SO in flue gas3It is absorbed by acid solution；
(2) enter follow-up conventional purge flow after the flue-gas temperature of first grade scrubber acid solution washing is down to 70 DEG C~160 DEG C
Continue to cool down, the condensation diluted acid that follow-up cooling procedure generates returns to the SO maintained in first grade scrubber in first grade scrubber3And water
Balance；
(3) the heavy metal dirt in flue gas and arsenic element form sulfate and arsenious acid in first grade scrubber after acid solution is washed；
Arsenious acid in acid solution is oxidized to arsenic acid by the compressed air aerator of first grade scrubber intracavity bottom setting；
(4) acid solution containing arsenic acid and heavy metal hydrochlorate is sent into setting in the dry suction of sulfuric acid by washing delivery pump from first grade scrubber
Cooling densifying tower after flow；The flue gas being discharged after first grade scrubber is washed carries out double absorption through sulfuric acid drying and absorption process,
Partial fume after the dry suction of sulfuric acid is passed through acid solution concentrate and cooling of the cooling densifying tower to the cooling densifying tower of entrance；
(5) flue gas that cooling densifying tower comes out is discharged into tail suction desulfurization；The concentrated acid that cooling densifying tower comes out through acid sludge filter pump pump to
Slag filter, filters out heavy metal sulfate slag, and filtrate enters SO2Reductive jar, by being passed through highly concentrated SO into tank2Gas is arsenic acid
It is reduced to be slightly soluble in the arsenious acid precipitation of sulfuric acid, residual gas is incorporated to relieving haperacidity purifying smoke entrance；Acid containing arsenious acid precipitation
Liquid is pumped into arsenic filter by arsenic filter pump and is separated by solid-liquid separation, and filtered clear acid and arsenious acid filter cake are obtained；Arsenious acid
Filter cake is collected after drying to get white arsenic product.
2. a kind of energy conserving system of synthetical recovery sulfuric acid purification spent acid, the energy conserving system includes first grade scrubber (1)；Its feature
It is, first grade scrubber (1) side is equipped with vertically arranged admission line (2)；First grade scrubber (1) lower part is equipped with
Recycle acid exports, and recycle acid outlet is connected to setting in the internal sour nozzle (3) that goes out of admission line (2) by cleaning circulation pump；
Exhanst gas outlet is equipped at the top of the first grade scrubber (1), exhanst gas outlet is connected to conventional purge flow system；First grade scrubber
(1) intracavity bottom is equipped with compressed air aerator (4)；First grade scrubber (1) lower part is additionally provided with acid solution outlet, and acid solution goes out
Mouth is connected to by washing delivery pump (5) with cooling densifying tower (6)；The cooling densifying tower (6) connects with sulfuric acid drying and absorption process system
It is logical；Cooling densifying tower (6) lower part is exported equipped with acid sludge, and acid sludge outlet is connected by acid sludge filter pump (7) and slag filter (8)
It is logical；Slag filter (8) and SO2Reductive jar (9) is connected to；SO2Reductive jar (9) is connected by arsenic filter pump (10) and arsenic filter (11)
It is logical.
3. energy conserving system as claimed in claim 2, which is characterized in that the first grade scrubber (1) enters equipped with multiple times acid
Mouth (12).
4. energy conserving system as claimed in claim 2, which is characterized in that cooling densifying tower (6) the lower part acid outlet and enrichment
Circulating pump (13) entrance is connected to, and enrichment circulating pump (13) outlet is connected to cooling densifying tower (6) top.
5. energy conserving system as claimed in claim 2, which is characterized in that the arsenic filter (11) connects with pneumatic conveyer dryer (14)
It is logical；The pneumatic conveyer dryer (14) is received arsenic device (15) with cloth bag and is connected to.
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| CN107265410A (en) * | 2017-07-03 | 2017-10-20 | 成都世远科技有限公司 | The high temperature purification technique of containing sulfate Waste Sulfuric Acid in Waste Sulfuric Acid recycled product sulfuric acid process |
| CN107162305A (en) * | 2017-07-07 | 2017-09-15 | 金川集团股份有限公司 | A kind of acid waste water processing unit and its application method |
| CN111747382B (en) * | 2020-05-25 | 2022-04-15 | 惠州宇新化工有限责任公司 | Method and system for concentrating and recycling dilute acid by using alkylation waste acid recycling device |
| CN112387096A (en) * | 2020-10-16 | 2021-02-23 | 楚雄滇中有色金属有限责任公司 | Novel method for purifying and recycling arsenic-containing flue gas by using acidic liquid medium |
| CN113289473B (en) * | 2021-06-11 | 2022-11-29 | 封云 | Method for treating heavy metal before smelting flue gas desulfurization |
| CN113893671B (en) * | 2021-10-09 | 2024-01-23 | 长沙有色冶金设计研究院有限公司 | Wet denitration method for high-sulfur flue gas |
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