CN106007132B - The processing method and system of waste acid - Google Patents
The processing method and system of waste acid Download PDFInfo
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- CN106007132B CN106007132B CN201610360071.1A CN201610360071A CN106007132B CN 106007132 B CN106007132 B CN 106007132B CN 201610360071 A CN201610360071 A CN 201610360071A CN 106007132 B CN106007132 B CN 106007132B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/16—Treatment of water, waste water, or sewage by heating by distillation or evaporation using waste heat from other processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Abstract
The invention discloses a kind of processing method of waste acid and system, belong to chemical process technology field, wherein processing method comprises the following steps：Acid water progress separation of solid and liquid is obtained into supernatant；Supernatant is preheated to 50 DEG C~60 DEG C；Low-temperature flue gas is passed into haptoreaction in the supernatant after preheating, fluorine ion and chlorion in supernatant is changed into HF and HCL, and discharge is purged with low-temperature flue gas.Its system includes sour filter, heat exchanger, calcium chloride jar, purging reaction tower and tail gas absorber, the inlet of heat exchanger is connected with sour filter, liquid outlet is connected with the inlet of reaction tower, the gas outlet of heat exchanger is connected by calcium chloride jar with purging the air inlet of reaction tower, the air inlet for purging reaction tower is located at below the inlet of reaction tower, and the gas outlet of purging reaction tower is connected with tail gas absorber.The present invention can be realized using low-temperature flue gas removes fluorine removal, chlorion from waste acid, with advantages such as energy-saving and environmental protection, low-carbons.
Description
Technical field
The present invention relates to the processing method and system in chemical process technology field, more particularly to a kind of waste acid.
Background technology
In nonferrous smelting production process, sulfuric acid, acid manufacturing processes are generally prepared with the flue gas containing high-concentration sulfur dioxide
In the compositions such as dirt, acid mist contained in flue gas must be sprayed in cleansing phase using washing or pickling, realize dedusting, cooling and
The purpose of acid-mist-removing and remaining impurity, to meet the normal production of sulfuric acid.The smelting waste acid complicated component and concentration wherein produced
Height, the harmful substance such as F, Cl, As containing the beavy metal impurities such as Cu, Pb, Cd, Zn and high concentration, without processing directly discharge
Greatly harm can be caused to environment.
Corrosivity and high toxicity of the harm of fluorine, chlorion in waste acid mainly to equipment.In nonferrous smelting waste acid
Fluorine, chlorine ion concentration are generally in more than 10000mg/L, and fluorine, chlorion have very strong oxidisability under the conditions of acidic bodies of water, such as
Fluorine, chlorine ion concentration are too high in fruit water body, easily cause different degrees of corruption to part metals, glass and ceramic material in equipment
Erosion.
Problem present in traditional waste acid processing method is only to focus on a processing for heavy metal and arsenic in waste acid, except living together
Waste acid after reason contains F, Cl ion of high concentration, and direct reuse can cause the corrosion of equipment and pipeline, increase later maintenance into
This.Therefore, fluorine, the removal of chlorine study of increased attention in waste acid.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art there is provided a kind of processing method of waste acid, is had
There are the advantages such as energy-saving and environmental protection, low-carbon, can be achieved to remove Natural zeolite and chlorion from waste acid, and realize to a certain degree waste acid
Concentration, reclaim sulfuric acid and simultaneously recycled, it is high to the treatment effeciency of fluorine ion and chlorion.Present invention also offers one kind
For the system of waste acid processing, simple in construction, energy-conserving and environment-protective.
In order to solve the above technical problems, the invention provides a kind of processing method of waste acid, comprising the following steps：
（1）Acid water progress separation of solid and liquid is obtained into supernatant；
（2）The supernatant is preheated to 50 DEG C~60 DEG C；
（3）Low-temperature flue gas is passed into haptoreaction in the supernatant after the preheating, made in the supernatant
Fluorine ion and chlorion are changed into HF and HCL, and purge discharge with the low-temperature flue gas.
Above-mentioned processing method, it is preferred that also including tail gas absorption step, is specially to enter the HF and HCL purgings
In the tail gas absorber, the filler of the tail gas absorber is NaOH, Ca (OH)2, one or more in CaO.
Above-mentioned processing method, it is preferred that the acid water includes the sulfuric acid that mass concentration is 5%~15%, concentration is
2000mg/L~3665mg/L fluorine ion, concentration is 2000mg/L~2644mg/L chlorion.It is further preferred that also wrapping
The heavy metal ion such as Pb, Cu, As are included, in now common handling process, the removal of heavy metal contaminants can be realized, but locate
Water after reason still contains substantial amounts of fluorine, chlorion, and result in can not realize circulating and recovering.
Above-mentioned processing method, it is preferred that the step（3）Containing 0%~4% SO in the low-temperature flue gas2Gas.
Above-mentioned processing method, it is preferred that the temperature of the low-temperature flue gas is 100 DEG C~200 DEG C, water content≤20mg/
Nm3.The saturated water adsorptive value of low-temperature flue gas described in per unit is 1092g/kg~1552g/ under 150 DEG C~200 DEG C temperature conditionss
kg.Above-mentioned processing method, it is preferred that the step（1）Described in separation of solid and liquid using membrane filtration separate or inorganic porous material
Material is separated by filtration.It is preferred that, the porous material is preferably polyamide or polyacrylamide；The aperture of porous material is preferably
50 μm~100 μm.The filter sizes that the membrane filtration separation is used are preferably 50 μm~100 μm.
Above-mentioned method, it is preferred that the step（2）Described in preheating be specially by low-temperature flue gas or steam and supernatant
Carry out heat exchange.It is further preferred that the temperature of the low-temperature flue gas is 150 DEG C~200 DEG C, or using steam pressure 0.2Mpa
More than.
Above-mentioned method, it is preferred that the step（3）In be passed through speed≤5m/s of the low-temperature flue gas.
Above-mentioned processing method, it is preferred that the step（3）In, the supernatant formation thickness is 0.5 μm~1 μm
After liquid film, then with the low-temperature flue gas haptoreaction.
Above-mentioned processing method, it is preferred that the step（3）In, the Su Shuai that the low-temperature flue gas enters from reaction tower≤
5m/s。
Above-mentioned processing method, it is preferred that the filler in the tail gas absorber is NaOH, Ca（OH）2, in CaO one
Plant or a variety of.
As a total technical concept, present invention also offers a kind of system for above-mentioned processing method, including acid
Filter, heat exchanger, calcium chloride jar, purging reaction tower and tail gas absorber, the inlet of the heat exchanger and the sour mistake
Filter is connected, and liquid outlet is connected with the inlet of reaction tower, and the gas outlet of the heat exchanger passes through the calcium chloride jar and institute
The air inlet connection of purging reaction tower is stated, the air inlet of the purging reaction tower is located at below the inlet of reaction tower, described to blow
The gas outlet for sweeping reaction tower is connected with the tail gas absorber.
Above-mentioned system, it is preferred that if the purging reaction tower includes tower body and the dry reaction in the tower body
Pipe and some heat exchanger tubes, the tower body sidewall are provided with steam inlet and condensation-water drain, one end of each heat exchanger tube and institute
Steam inlet connection is stated, the other end is connected with the condensation-water drain；One end of each reaction tube connects with the inlet
Logical, the other end is connected with the air inlet；The top of the tower body is provided with gas outlet, and bottom is provided with liquid outlet.
Above-mentioned system, it is preferred that some heat exchanger tubes are horizontally placed in tower body, is spaced between adjacent heat exchange tubes
Arrangement, some reaction tubes are vertically arranged in tower body, arranged for interval between adjacent reaction pipe, the reaction tube with it is described
Cross-contact between heat exchanger tube.
Above-mentioned system, it is preferred that reaction tube described in the purging reaction tower is graphite reaction tube；The purging reaction
The tower body of tower is graphite tower body；The heat exchanger tube of the purging reaction tower is Graphtic heat exchanging pipe.
Compared with prior art, the advantage of the invention is that：
（1）The invention provides a kind of processing method of waste acid, low-temperature flue gas is inversely contacted with liquid film, the temperature of low-temperature flue gas
Degree can reach 100~200 DEG C, and low-temperature flue gas is that a kind of difficulty of enterprise utilizes waste heat, and with certain calorific value and moisture pick-up properties,
The calorific value of low-temperature flue gas can realize concentrating certainly for waste acid, further reduce energy consumption；And Cryogenic air has moisture-absorption characteristics, it can promote
Enter F, Cl ion in waste water and be converted into gaseous state to be removed, compared to hot-air, its reaction efficiency is higher, more energy-saving ring
Protect.Using the processing method of the present invention, i.e., suitable for high concentration acid water, the acid waste water of low fluorine chlorine condition is also applied for,
Accommodation is wider.
（2）The invention provides a kind of processing method of waste acid, it is preferred that uses dried low-temperature flue gas, controls low
Water content≤20mg/Nm of warm flue gas3, further increase fluorine in waste acid, the conversion of chlorion form.
（3）The invention provides a kind of processing method of waste acid, it is preferred that after waste acid filtering, flows down, is formed from top to bottom
The liquid film of micron level, the liquid film of formation adds gas liquid interfacial area so that the gas-liquid of reaction is more uniformly spread, reaction effect
Rate is higher.
（4）The invention provides a kind of processing method of waste acid, it is preferred that define Su Shuai that low-temperature flue gas is passed through≤
5m/s, preventing and treating air-flow velocity is too high, causes to cause disturbance to the liquid film of waste acid formation, liquid flooding is formed in reactor so that dirty
Acid solution is carried over together with air-flow, influences treatment effect.
（5）The invention provides a kind of waste acid processing system, including sour filter, heat exchanger, calcium chloride jar, purging are anti-
Tower and tail gas absorber are answered, it is simple in construction, realized using the low-temperature flue gas produced in nonferrous smelting production process to acid water
Heating, and realize to F, Cl ion in waste water, the waste water after processing also can be as smelt productions such as electrolysis or ore dressings
Supplemental acid, with advantages such as energy-saving and environmental protection.
（6）The invention provides a kind of waste acid processing system, wherein the reaction tube in purging reaction tower intersects with heat exchanger tube
It is arranged inside tower body, whole gas-liquid contact reaction distribution is more reasonable, using the reaction channel and heat exchanger channels of intersection, bilateral
The design in road is more easily controlled reaction condition, heat utilization it is more efficient.
（7）The invention provides a kind of system handled for waste acid, wherein purging reaction tower is made of graphite material,
Strong acid, the corrosion of hot environment, and hot mass transfer efficiency high can be resistant to.
Brief description of the drawings
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, clear, complete description is carried out to the technical scheme in the embodiment of the present invention.
Fig. 1 is system structure diagram of the invention.
Fig. 2 is the structural representation for purging reaction tower of the invention.
Marginal data：
In the accompanying drawings, 1, sour filter；2nd, heat exchanger；3rd, calcium chloride jar；4th, reaction tower is purged；5th, tail gas absorber；
6th, absorbing liquid circulating pump；41st, tower body；42nd, reaction tube；43rd, heat exchanger tube；411, air inlet；412nd, inlet；413rd, steam enters
Mouthful；414th, condensation-water drain；415th, gas outlet；416th, liquid outlet；Ith, waste acid stoste；IIth, low-temperature flue gas；IIIth, the waste acid of retention
Impurity；IVth, the acid after purification concentration；Vth, absorbing liquid；VIth, tail gas；TI, thermometer；FI, pressure gauge；PI, pressure gauge.
Embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Embodiment
Material and instrument employed in following examples are commercially available.
During the waste acid of use is nonferrous smelting production process, it is produced to prepare sulfuric acid with the flue gas of high-concentration sulfur dioxide
Waste acid, in actual application, waste acid can be the mixed acid produced by any industrial production being related to, and main body is sulphur
Acid, contains fluorine and chlorion.
Low-temperature flue gas come from nonferrous smelting electrolysis stage waste heat carry out air heat exchange, the hot-air formed by,
Containing 0%~4% SO in the low-temperature flue gas2Gas, remaining composition is similar with composition of air, and temperature is in 150 DEG C~200 DEG C scopes.
Embodiment 1
A kind of processing method of waste acid, comprises the following steps：
（1）It is 10% to take sulfuric acid mass fraction in acid water, detection waste water, and chlorine ion concentration 2000mg/L, fluorine ion is dense
Spend 2000mg/L.
（2）Waste acid is passed through into polypropylene（pp）The fibre bundle of material（50 μm of aperture）Progress is filtrated to get supernatant.
（3）Take the low-temperature flue gas of a part of non-ferrous metal metallurgy electrolysis stage（Temperature is about 115 DEG C, composition and air class
Seemingly）Exchanged heat with supernatant in heat exchanger（Low-temperature flue gas does not contact with each other with supernatant）, supernatant is preheated to 60 DEG C.
（4）Low-temperature flue gas after preheating is using calcium chloride jar drying to water content ＜ 20mg/Nm3.It is dried
Low-temperature flue gas temperature is about 105 DEG C；The saturated water adsorptive value of low-temperature flue gas is about 952g/ described in per unit under the temperature conditionss
kg。
（5）Supernatant after preheating is pumped into by acid-proof pump at the top of reaction tower, and thickness is formed in reaction tower and is
About 0.5 μm of liquid film, step（4）In low-temperature flue gas after drying（It is 5 m to dry hot air flowrate3/min）, with about
1.4m/s speed is passed through from reaction tower bottom, with supernatant haptoreaction.Fluorine ion and chlorion and low temperature in supernatant
After smoke contacts, it is changed into HF and HCL, and be discharged into the exhaust outlet at the top of low-temperature flue gas purging in tail gas absorber, tail gas
Filler Ca in absorption tower（OH）2HF and HCL is absorbed.Supernatant after reacted is pumped into reaction tower in bottom collection
Top is flowed down, and forms the circulation of liquid stream.
After above-mentioned circular response time 30min, sulfuric acid mass fraction is 28.6% in the acid solution after processing, and is determined
Fluorine ion is reduced to 20mg/L and 50mg/L respectively with chlorine ion concentration in gelled acid.
Embodiment 2
Referring to Fig. 1 and Fig. 2, a kind of acid water processing system of the invention, including sour filter 1, heat exchanger 2, gas
Drying tower 3, purging reaction tower 4 and tail gas absorber 5, the inlet of heat exchanger 2 are connected with sour filter 1, liquid outlet and purging
The inlet 412 of reaction tower 4 is connected, and the gas outlet of heat exchanger 2 passes through calcium chloride jar 3 with purging the air inlet 411 of reaction tower 4
Connection, the air inlet 411 of purging reaction tower 4 is located at the lower section of inlet 412 of purging reaction tower 4, purges the gas outlet of reaction tower 4
415 connect with tail gas absorber 5.Wherein heat exchanger 2, calcium chloride jar 3, purging reaction tower 4, the gas flow tube of tail gas absorber 5
Road is sequentially communicated to form gas channel；Sour filter 1, heat exchanger 2, the fluid pipe of purging reaction tower 4 are sequentially communicated to form liquid
Circulation road.
In the present embodiment, heat exchanger 2 includes inlet, liquid outlet, air inlet, gas outlet.The inlet of heat exchanger 2 and acid
Filter 1 is connected, and pressure gauge FI is provided with connecting pipe of the inlet of heat exchanger 2 with sour filter 1；Heat exchanger 2 goes out liquid
Mouthful connected with the inlet 412 positioned at purging reaction tower 4 top, in inlet of the liquid outlet with purging reaction tower 4 of heat exchanger 2
412 connecting pipe is provided with thermometer TI；Liquid passes through the fluid flow tube of heat exchanger 2 after the inlet of heat exchanger 2 enters
Road, and discharged from liquid outlet.The gas outlet of heat exchanger 2 is connected by calcium chloride jar 3 with purging the air inlet 411 of reaction tower 4,
Gas, by the airflow line of heat exchanger 2, is discharged after the air inlet of heat exchanger 2 enters from the gas outlet of heat exchanger 2.Enter one
Walk preferably, airflow line and the fluid pipe of heat exchanger 2 contact with each other, and do not interconnect.
In the present embodiment, calcium chloride jar 3 includes air inlet, gas drier and gas outlet.Calcium chloride jar 3 enters
Gas port is connected with the gas outlet of heat exchanger 2, and the gas outlet of calcium chloride jar 3 is connected with purging the air inlet 411 of reaction tower 4；
The gas outlet of calcium chloride jar 3 and the connecting pipe of the air inlet 411 of purging reaction tower 4 are provided with thermometer TI, pressure gauge FI
With pressure gauge PI.
In the present embodiment, purging reaction tower 4 includes tower body 41 and some reaction tubes 42 in tower body 41 and some
Heat exchanger tube 43, the side wall of tower body 41 is provided with steam inlet 413 and condensation-water drain 414, and one end of each heat exchanger tube 43 is entered with steam
Mouth 413 is connected, and the other end is connected with condensation-water drain 414；Inlet 412 and air inlet 411 are divided into the two ends of reaction tube 42,
One end of each reaction tube 42 is connected with inlet 412, and the other end is connected with air inlet 411.The bottom of tower body 41 is provided with out liquid
Mouth 416, the top of tower body 41 is provided with gas outlet 415.It is preferred that, liquid outlet 416 is connected with inlet 412 by liquid pump.
In the present embodiment, some heat exchanger tubes 43 are horizontally placed in tower body 41, arranged for interval between adjacent heat exchange tubes 43,
Some reaction tubes 42 are vertically arranged in tower body 41, arranged for interval between adjacent reaction pipe 42, reaction tube 42 and heat exchanger tube 43
Between cross-contact, but do not interconnect.
In the present embodiment, tower body 41 is graphite tower body；Reaction tube 42 is graphite reaction tube；Heat exchanger tube 43 exchanges heat for graphite
Pipe.
In the present embodiment, tail gas absorber 5 includes gas inlet, tower body, offgas outlet, absorbing liquid entrance, absorbing liquid and followed
Ring pump 6 and absorbing liquid outlet.Gas inlet is connected with purging the gas outlet 415 of reaction tower 4, when tail gas enters tail gas absorber 5
Afterwards, tail gas reacts with the absorbing liquid inside tower body, it is impossible to discharged from offgas outlet the part being absorbed by liquid absorption；And tail gas
In the composition that can be absorbed by liquid absorption with absorbing liquid, export and discharge from absorbing liquid, and suction is pumped into by absorbing liquid circulating pump 6
Liquid entrance is received, the circulation of liquid stream is formed；Pressure gauge FI and pressure are provided with the pipeline of absorbing liquid entrance and absorbing liquid outlet
Table PI.It is further preferred that absorbing liquid is alkali lye, specially Ca（OH）2Or NaOH.
A kind of application of acid water processing system of the invention in processing acid water, specifically includes following steps：
（1）Take sulphur in the acid water produced in smeltery's zinc concentrate boiling roaster flue gas acid preparing system, detection waste water
Sour mass fraction is 7.6%, chlorine ion concentration 2644mg/L, fluorinion concentration 3665mg/L.
（2）By acid water by sour filter 1, sour filter 1 is retained by surface filter（It is 500 to retain precision
Mesh）Impurity in acid water, the acid water by sour filter 1 is supernatant.
（3）Take the low-temperature flue gas of a part of non-ferrous metal metallurgy electrolysis stage（Temperature is about 220 DEG C, is contained in low-temperature flue gas
There is ＜ 0.5% SO2）It is passed through and is flowed out along airflow line from the gas outlet of heat exchanger 2, same time step from the air inlet of heat exchanger 2
Suddenly（2）In the obtained inlet of supernatant from heat exchanger 2 be passed through and flowed out along fluid pipe from the liquid outlet of heat exchanger 2,
In heat exchanger 2, low-temperature flue gas, to supernatant, makes supernatant be preheated to more than 65 DEG C by heat transfer.
（4）Low-temperature flue gas flows to calcium chloride jar 3, in the work of gas drier after the gas outlet discharge of heat exchanger 2
Under, by low-temperature flue gas drying to water content ＜ 20mg/Nm3.The temperature of low-temperature flue gas after heat exchange is about 110 DEG C.
（5）By the supernatant after preheating after the liquid outlet outflow of heat exchanger 2, pushed up by acid-proof pump from purging reaction tower 4
It is pumped into the inlet 412 in portion.Supernatant flows to each reaction tube 42 respectively, forms the liquid film that thickness is about 0.5 μm.Meanwhile,
Step（4）In Cryogenic air after drying（Air mass flow is 4 m3/ min to 5 m3Between/min）, with the m/s of ＜ 2 speed
It is passed through from the air inlet 411 of purging reaction tower 4 bottom, and each leads into each reaction tube 42, and supernatant haptoreaction, then
Discharged from the gas outlet 415 of purging reaction tower 4.
（6）In step（5）While progress, the low-temperature flue gas of another part is from positioned at the steaming for purging the side wall of reaction tower 4
Vapor inlet 413 enters, and each leads into each heat exchanger tube 43.Because the temperature of low-temperature flue gas is about 220 DEG C, when low-temperature flue gas is logical
Cross after heat exchanger tube 43, transfer heat in the reaction tube 42 contacted with heat exchanger tube 43, make the supernatant being located in reaction tube 42
Temperature reach more than 80 DEG C, after now the fluorine ion and chlorion in supernatant are contacted with low-temperature flue gas, be changed into HF and HCL,
And purged with low-temperature flue gas, it is discharged into along the gas outlet 415 at the top of purging reaction tower 4 in tail gas absorber 5, tail gas absorber 5
In filler Ca（OH）2HF and HCL is absorbed.Simultaneously；Low-temperature flue gas is changed into condensed water to the cold in heat exchanger tube 43, from condensation
Flowed out in water out 414.Supernatant after reacted is pumped into and is located in bottom collection, and from the liquid outlet 416 of purging reaction tower 4
The top inlet 412 of tower body 41, forms the circulation of liquid stream.
（7）After above-mentioned circular response time 30min, sulfuric acid mass fraction is 34.6% in the acid solution after processing, and is surveyed
Determine fluorine ion in gelled acid and be reduced to 86.4mg/L and 62.2mg/L respectively with chlorine ion concentration.
Acid water after Examples 1 and 2 are handled, can replace the dry suction supplement water of acid making system, or conduct
Finished acid., also can be as electrolysis or the supplemental acid of the smelt production such as ore dressing due to passing through above-mentioned technical finesse.
The above described is only a preferred embodiment of the present invention, not making any formal limitation to the present invention.Though
So the present invention is disclosed as above with preferred embodiment, but is not limited to the present invention.It is any to be familiar with those skilled in the art
Member, in the case where not departing from the Spirit Essence and technical scheme of the present invention, all using in the methods and techniques of the disclosure above
Appearance makes many possible variations and modification to technical solution of the present invention, or is revised as the equivalent embodiment of equivalent variations.Therefore,
Every content without departing from technical solution of the present invention, the technical spirit according to the present invention is to made for any of the above embodiments any simple
Modification, equivalent substitution, equivalence changes and modification, still fall within technical solution of the present invention protection in the range of.
Claims (6)
1. a kind of processing method of waste acid, it is characterised in that comprise the following steps：
（1）Acid water progress separation of solid and liquid is obtained into supernatant；
（2）The supernatant is preheated to 50 DEG C~60 DEG C；
（3）Low-temperature flue gas is passed into haptoreaction in the supernatant after the preheating, make fluorine in the supernatant from
Son and chlorion are changed into HF and HCl, and purge discharge with the low-temperature flue gas；
The acid water includes the sulfuric acid that mass concentration is 5%~15%, and concentration is 2000mg/L~3665mg/L fluorine ion,
Concentration is 2000mg/L~2644mg/L chlorion；
The step（3）Containing 0%~4% SO in the low-temperature flue gas2Gas；The temperature of the low-temperature flue gas is 100 DEG C~110
DEG C, water content≤20mg/Nm3；
The step（3）Described in supernatant formation thickness contacted for after 0.5 μm~1 μm of liquid film, then with the low-temperature flue gas
Reaction；
The step（3）In, it is passed through speed≤5m/s of the low-temperature flue gas.
2. processing method according to claim 1, it is characterised in that also including tail gas absorption step, specially will be described
HF and HCl purgings enter in tail gas absorber, and the filler of the tail gas absorber is NaOH, Ca (OH)2, one kind in CaO or
It is a variety of.
3. processing method according to claim 1 or 2, it is characterised in that the step（1）Described in separation of solid and liquid use
Membrane filtration is separated or inorganic porous material is separated by filtration, and the aperture of the film or the inorganic porous material is 50 μm~100 μm；
The step（2）Described in preheating be specially that low-temperature flue gas and supernatant are subjected to heat exchange.
4. a kind of system for processing method any one of claims 1 to 3, it is characterised in that including sour filter
（1）, heat exchanger（2）, calcium chloride jar（3）, purging reaction tower（4）And tail gas absorber（5）, the heat exchanger（2）Feed liquor
Mouth and the sour filter（1）Connection, liquid outlet and reaction tower（4）Inlet（412）Connection, the heat exchanger（2）Go out
Gas port passes through the calcium chloride jar（3）With the purging reaction tower（4）Air inlet（411）Connection, the purging reaction tower
（4）Air inlet（411）Positioned at reaction tower（4）Inlet（412）Lower section, the purging reaction tower（4）Gas outlet（415）
With the tail gas absorber（5）Connection.
5. system according to claim 4, it is characterised in that the purging reaction tower（4）Including tower body（41）With located at
The tower body（41）Interior some reaction tubes（42）With some heat exchanger tubes（43）, the tower body（41）Side wall is provided with steam inlet
（413）And condensation-water drain（414）, each heat exchanger tube（43）One end and the steam inlet（413）Connection, the other end
With the condensation-water drain（414）Connection；Each reaction tube（42）One end and the inlet（412）Connection, it is another
End and the air inlet（411）Connection；The tower body（41）Top be provided with gas outlet（415）, bottom is provided with liquid outlet
（416）.
6. system according to claim 5, it is characterised in that some heat exchanger tubes（43）It is horizontally placed on tower body
（41）It is interior, adjacent heat exchange tubes（43）Between arranged for interval, some reaction tubes（42）It is vertically arranged at tower body（41）It is interior, phase
Adjacent reaction tube（42）Between arranged for interval, the reaction tube（42）With the heat exchanger tube（43）Between cross-contact；The tower body
（41）For graphite tower body, the reaction tube（42）For graphite reaction tube, the heat exchanger tube（43）For Graphtic heat exchanging pipe.
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Denomination of invention: Method and system for treating acidic wastewater Effective date of registration: 20190926 Granted publication date: 20170725 Pledgee: Bank of Changsha Limited by Share Ltd science and Technology Branch Pledgor: CHANGSHA HASKY ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT CO., LTD. Registration number: Y2019430000024 |
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Denomination of invention: Waste acid treatment system Effective date of registration: 20201202 Granted publication date: 20170725 Pledgee: Bank of Changsha Limited by Share Ltd. science and Technology Branch Pledgor: CHANGSHA HASKY ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT Co.,Ltd. Registration number: Y2020980008713 |