CN109824022A - A kind of low temperature separating methods of nitric-sulfuric acid - Google Patents
A kind of low temperature separating methods of nitric-sulfuric acid Download PDFInfo
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- CN109824022A CN109824022A CN201910227313.3A CN201910227313A CN109824022A CN 109824022 A CN109824022 A CN 109824022A CN 201910227313 A CN201910227313 A CN 201910227313A CN 109824022 A CN109824022 A CN 109824022A
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 238000000605 extraction Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 22
- 238000010521 absorption reaction Methods 0.000 claims abstract description 6
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 87
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 77
- 239000003518 caustics Substances 0.000 claims description 32
- 239000003513 alkali Substances 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 11
- 239000003570 air Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002351 wastewater Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000013589 supplement Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- -1 stripping tower Substances 0.000 claims description 2
- 238000003809 water extraction Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 25
- 239000007788 liquid Substances 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 8
- 239000002699 waste material Substances 0.000 description 6
- 230000035611 feeding Effects 0.000 description 5
- 239000007792 gaseous phase Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
The present invention provides a kind of cryogenic treatment process of nitric-sulfuric acid, and nitric-sulfuric acid produces isolated sulfuric acid product with 40~100 DEG C of feeding stripping tower tops, gas stripping gas with 50~150 DEG C of feeding stripping tower lower parts, gas phase of the stripping tower overhead extraction containing nitric acid, stripping tower tower bottom；Gas phase of the stripping tower overhead extraction containing nitric acid enters water scrubber lower part, production water to wash tower bottom extraction absorbs the nitric acid entered in the gas phase of water scrubber lower part as cyclic absorption agent, after concentration of nitric acid reaches controlling value in production water, it is sent out as isolated nitric acid product, water scrubber overhead extraction gas phase tail gas.The present invention has the characteristics that technical process is simple, separation condition is mild, equipment selection is easy, energy conservation and environmental protection.
Description
Technical field
The present invention relates to environmental protection industry (epi) waste acid treatment fields, and in particular to a kind of low temperature separating methods of nitric-sulfuric acid are adopted
Nitric acid is separated with sulfuric acid with gas stripping process, and utilization is separately recovered.
Background technique
Nitric acid and sulfuric acid are all important industrial chemicals, are widely used in the industry such as manufacture chemical fertilizer, pesticide, explosive, dyestuff and produce
Product.Nitrating agent is important by the mixed acid solution that nitric acid and sulfuric acid form, during actual industrial production, to be used a large amount of
Sulfuric acid make catalyst and excessive nitric acid be added, catalyst total amount in chemical reaction process is constant, therefore terminates in reaction
After can generate a large amount of nitric-sulfuric acid waste liquid, main component is 50%~90% sulfuric acid and 5%~20% nitric acid, remaining is with water
Based on, 45% is accounted for hereinafter, wherein can be containing a small amount of other impurities such as nitrous acid, sulphite etc..If nitric-sulfuric acid waste liquid is straight
Run in and put and can cause seriously to pollute to ecological environment, while causing the biggish wasting of resources.
A kind of prior art is that nitric-sulfuric acid is emitted into neutralization pond, is discharged after being neutralized with lye, in this way to mixed bronsted lowry acids and bases bronsted lowry
Liquid is all biggish waste, while generating a large amount of nitrate and sulfate, is polluted the environment.Another prior art is
Nitric-sulfuric acid is sent to distillation still, the mode of distillation is used to produce nitric acid with gas phase by distillation kettle top, after condensation is cooling
Certain density nitric acid is formed, steaming excess is certain density sulfuric acid, nitric acid and sulfuric acid made full use of to realize, but
It will cause following adverse consequences using this technology: first, vapo(u)rizing temperature is high, and nitric acid, sulfate moieties decompose, and generates NOX、SO3Deng,
It pollutes the environment, and nitric acid, sulfuric acid yield is caused to reduce；Second, because of operation temperature height, separation equipment selection is difficult, only
Expensive metal material can be used, plant construction cost of investment is very high；Third, need for nitric-sulfuric acid to be heated to bubble point with
On, energy consumption is high.Therefore, there is an urgent need to one kind can reduce entreprise cost, energy-saving and environment-friendly nitric-sulfuric acid isolation technics.
Summary of the invention
The purpose of the present invention is to provide a kind of cryogenic treatment process of nitric-sulfuric acid, separation simple with technical process
Mild condition, equipment selection be easy, energy conservation and environmental protection the characteristics of.
The cryogenic treatment process of nitric-sulfuric acid of the invention, includes the following steps:
(1) nitric-sulfuric acid is with 40~100 DEG C of feeding stripping tower tops, gas stripping gas with 50~150 DEG C of feeding stripping tower lower parts,
Gas phase of the stripping tower overhead extraction containing nitric acid, stripping tower tower bottom produce isolated sulfuric acid product；
(2) gas phase of the stripping tower overhead extraction containing nitric acid enters water scrubber lower part, to wash the production water of tower bottom extraction
The nitric acid entered in the gas phase of water scrubber lower part is absorbed as cyclic absorption agent, when concentration of nitric acid reaches control in production water
After value, sent out as isolated nitric acid product, water scrubber overhead extraction gas phase tail gas.
Further, above-mentioned cryogenic treatment process further includes step (3): water scrubber overhead extraction gas phase tail gas enters caustic wash tower
Lower part, the lye produced using alkali cleaning tower bottom is as cyclic absorption agent to the remaining acidic materials in the gas phase tail gas of caustic wash tower lower part
It is absorbed, after alkali cleaning tower bottom lye pH reaches controlling value, is sent out as waste water is neutralized, caustic wash tower overhead extraction gas phase reaches
Mark discharge.
Wherein, in the step (1), be sent into stripping tower nitric-sulfuric acid composition in mass, be sulfuric acid 50%~90%,
Nitric acid 5%~20%, remaining be water and other impurities；In nitric-sulfuric acid the molar flow of nitric acid and gas stripping gas ratio be 1:(70~
600)；Stripping tower empty tower gas velocity is controlled in 0.5~2m/s.
Wherein, in the step (1), the gas stripping gas be inert gas, preferably air, nitrogen, helium, neon one
Kind is a variety of；Stripping tower normal pressure or negative-pressure operation, full tower pressure drop are no more than 4KPaA, and operation temperature is 50~150 DEG C.
Wherein, in the step (2), the gas phase containing nitric acid enters water scrubber lower parts with 50~80 DEG C, produce water with 15~
40 DEG C of temperature is sent into water scrubber top；Water scrubber atmospheric operation, full tower pressure drop are no more than 2KPaA, and operation temperature is 15~40
℃。
Wherein, in the step (2), in the production water sent out as isolated nitric acid product nitric acid mass concentration be 10~
65%.
Wherein, in the step (3), caustic wash tower atmospheric operation, full tower pressure drop be no more than 2KPaA, operation temperature be 15~
40℃；The initial mass concentration of lye is 10~30%；As neutralize waste water send out alkali cleaning tower bottom lye pH be 7~
7.5；Lye is NaOH, Na2CO3, one of KOH or a variety of aqueous solutions.
The present invention also provides a kind of cryogenic process systems of nitric-sulfuric acid, including stripping tower, water scrubber and caustic wash tower；Institute
Stripping tower top is stated with feedstock pipeline, stripping tower lower part has gas stripping gas admission line, and air lift tower bottom has sulfuric acid
Product produces pipeline, and the gas phase extraction pipeline that stripper-overhead has is connected to the admission line that the water scrubber lower part has；
The production hydromining that the washing tower bottom has goes out pipeline and is connected to the production water feed pipe that water scrubber top has, and forms life
Water-flow circuit is produced, the production water-flow circuit is equipped with nitric acid product and produces branch, the gas having at the top of the water scrubber
Mutually extraction pipeline is connected to the admission line that the caustic wash tower lower part has；The lye that the alkali cleaning tower bottom has produces pipeline
It is connected to the lye feed pipe that caustic wash tower top has, lye circulation loop is formed, during the lye circulation loop is equipped with
Branch is produced with waste water, there is gas phase mouth at the top of the caustic wash tower.
Wherein, the feedstock pipeline on the stripping tower top is equipped with the first preheater；The gas stripping gas of stripping tower lower part
Admission line is equipped with the second preheater；The sulfuric acid product extraction pipeline of the air lift tower bottom is equipped with sulfuric acid delivery pump.
Wherein, it is successively arranged water-circulating pump and water scrubber recirculation cooler on the production water-flow circuit of the water scrubber,
Alkali circulating pump and caustic wash tower recirculation cooler are successively arranged on the lye circulation loop of the caustic wash tower.
Wherein, the water scrubber top is equipped with fresh production water and supplements pipeline, and the caustic wash tower top is equipped with fresh lye
Supplement pipeline.
The present invention uses the process and system of air lift, reduces the gaseous phase partial pressure of system component, i.e., by volatile components
It is gas phase by liquid phase and difficult volatile component still maintains the mode of liquid phase, achievees the purpose that nitric acid is separated with sulfuric acid.The present invention
By the way of the feeding temperature of control gas stripping gas intake air temperature and mixed acid waste liquor, obtain nitric-sulfuric acid under lower temperature conditions
With separation.In conventional isolation techniques, the operation temperature of (generally -0.095MPaG) is 210 DEG C or so under condition of negative pressure, often
The operation temperature of pressure is 320 DEG C or so, and the operation temperature of this case is down to 50-150 DEG C.Because separation condition is mild, separation temperature
It is cheap and easy to get to spend the materials such as equipment, pipeline, valve lower, for nitric-sulfuric acid separation；Point of nitric acid, sulfuric acid is not will cause
It solves and secondary pollution is formed to environment；Separating energy consumption is low, and the rate of recovery of nitric acid is up to 95% or more, and retrieval of sulfuric acid rate is up to 99%
More than.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is system and flow diagram of the invention.
Wherein, the first preheater of 1-；The second preheater of 2-；3- stripping tower；4- sulfuric acid delivery pump；5- water scrubber；6- water follows
Ring pump；7- water scrubber recirculation cooler；8- caustic wash tower；9- alkali circulating pump；10- caustic wash tower recirculation cooler.
Specific embodiment
In order to better understand the present invention, present invention will now be described in detail with reference to the accompanying drawings..
The low temperature separating methods of nitric-sulfuric acid of the invention, by the way of being passed through inert gas to nitric-sulfuric acid system,
The gaseous phase partial pressure of volatile components nitric acid in reduction system so that liquid phase nitric acid is changed into gas phase and difficult volatile component sulfuric acid will not
It is gas phase by liquid phase, to achieve the purpose that separate nitric acid and sulfuric acid.
Nitric-sulfuric acid is first fed to stripping tower 3, and it is sulfuric acid 50%~90%, nitric acid that nitric-sulfuric acid, which forms in mass,
5%~20%, remaining is water and other impurities.Nitric-sulfuric acid is sent into stripping tower after the first preheater 1 is heated to 40~100 DEG C
3 tops, gas stripping gas are sent into 3 lower part of stripping tower after the second preheater is heated to 50~150 DEG C, and gas-liquid two-phase is in stripping tower 3
Counter current contacting, carries out mass transfer and heat transfer, the gas phase nitric acid being vaporized are produced by stripper-overhead and is sent into water scrubber
5, the sulfuric acid after separating nitric acid is produced by 3 bottom of stripping tower, is sent into corresponding storage tank through sulfuric acid delivery pump 4.Gas gas is generally lazy
Property gas, can be one or more for air, nitrogen, helium, neon etc..3 normal pressure of stripping tower or negative-pressure operation, full tower pressure drop is not
It is advisable more than 4KPaA, operation temperature is preferably at 50~150 DEG C.For the gas stripping efficiency for improving nitric acid in nitration mixture, need in operation temperature
Degree is horizontal lower to maintain lower nitric acid gaseous phase partial pressure, in nitric-sulfuric acid the molar flow of nitric acid and gas stripping gas ratio with 1:(70~
600) it is preferred, further gas velocity control can be improved reactivity and efficiency, therefore can be further by stripping tower void tower gas
Speed control is in 0.5~2m/s.
Gas phase nitric acid from 3 top of stripping tower enters 5 lower part of water scrubber with 50~80 DEG C, produces water from 5 bottom of water scrubber
Portion's extraction is simultaneously sent into 5 top of water scrubber by water-circulating pump 6, production water enter before water scrubber 5 by water scrubber recirculation cooler 7 into
Row heat exchange, is then sent into 5 top of water scrubber with 15~40 DEG C of temperature.Gas-liquid two-phase counter current contacting in water scrubber 5 produces water
Most nitric acid in gas stripping gas are absorbed, gas phase is produced at the top of water scrubber 5, the liquid phase of formation is adopted as production water from tower bottom
It moves in circles out and by the conveying of water-circulating pump 6, when concentration of nitric acid reaches controlling value, generally nitric acid in tower bottom liquid phase (production water)
When mass concentration reaches 10~65%, nitric acid storage tank is emitted into as separation product.It is supplemented in real time into tower as needed fresh
Water is produced, fresh production water specially can be arranged pipeline from tower top as shown in the figure and fill into, can also be with the pipe of circulation production water
It is filled into after road cocurrent, arbitrary way is easy to accomplish to be not particularly limited.5 atmospheric operation of water scrubber, full tower pressure drop are no more than
2KPaA is advisable, and operation temperature is preferably at 15~40 DEG C.
The gas phase produced at the top of water scrubber 5 enters 8 lower part of caustic wash tower, and caustic wash tower 8 is used for not absorbing and isolated tail gas
Handled, existing conventional vent gas treatment mode can be used, can also preferred this case following processing mode, due to nitre sulphur
Main component nitric acid and sulfuric acid have been efficiently separated in nitration mixture, and remaining unabsorbed tail gas amount is less, make neutralisation treatment mode
The post-processing operation of progress greatly simplifies, and 8 load of caustic wash tower is small, medicament investment is small, and equipment can minimize optimization etc..Lye is certainly
The extraction of 8 bottom of caustic wash tower is simultaneously sent into 8 top of caustic wash tower by alkali circulating pump 9, lye enter before caustic wash tower 8 recycled by caustic wash tower it is cold
But device 10 exchanges heat, and is then sent into 5 top of water scrubber with tower operation temperature.Gas-liquid two-phase counter current contacting, alkali in caustic wash tower 8
Water scrubber 5 is produced remaining acidic materials (mostly nitric acid) in gas phase and absorbed by liquid, and gas phase row up to standard is produced at the top of caustic wash tower 8
It puts, the liquid phase of formation is produced from tower bottom as lye and moved in circles by the conveying of alkali circulating pump 9, when tower bottom liquid phase pH reaches control
Value, when generally 7~7.5, as neutralizing outside discharge of wastewater to system.Fresh lye is supplemented into tower in real time as needed, newly
Fresh lye specially can be arranged pipeline from tower top as shown in the figure and fill into, can also with filled into after the pipeline cocurrent of circulation alkali liquor,
Arbitrary way is easy to accomplish to be not particularly limited.8 atmospheric operation of caustic wash tower, full tower pressure drop are advisable no more than 2KPaA, operation
Temperature is preferably at 15~40 DEG C.Lye can use NaOH, Na2CO3, the alkaline solutions such as KOH, initial lye or fresh lye
Mass concentration is generally advisable with 10~30%, but is not necessary restriction.
The specific implementation method of this case is introduced so that nitric-sulfuric acid discharges in certain explosive production enterprise as an example below.
Sulfur acid 85% in nitric-sulfuric acid waste liquid contains nitric acid 8%, aqueous 7%, inlet amount 500Kg/h, through the first preheater
It is heated to 70 DEG C of feeding stripping towers；Gas stripping gas uses nitrogen, flow 2200Nm3/ h is heated to 90 DEG C of feedings through the second preheater
Stripping tower.Air lift tower bottom obtains 98% concentrated sulfuric acid product, and 88 DEG C of temperature, 62 DEG C of stripping tower top gaseous phase nitric acid is sent into washing
Tower.
To produce water as the gas phase nitric acid in absorbent cyclic absorption gas stripping gas, periodic detection tower bottom liquid concentration of nitric acid,
After concentration of nitric acid reaches 45%, the valve for leading to nitric acid storage tank is opened, after nitric acid product is delivered to nitric acid storage tank, into tower
Supplement fresh production water.It is cooling to production water using water scrubber recirculation cooler to guarantee assimilation effect, keep tower operation temperature
At 25 DEG C.
Water scrubber top gaseous phase is sent into caustic wash tower, using 30%NaOH aqueous solution as absorbent cyclic absorption gas stripping gas in it is surplus
Residual air phase nitric acid, periodic detection tower bottom liquid pH value, when pH reaches 7.2, wastewater treatment process valve is led in unlatching, by tower bottom waste water
After being delivered to wastewater treatment process, 30%NaOH is supplemented into tower.For the heat for removing neutralization reaction releasing in time, alkali cleaning is utilized
Tower recirculation cooler cools down to lye, keeps tower operation temperature at 25 DEG C.Tower top tail gas qualified discharge.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of cryogenic treatment process of nitric-sulfuric acid, includes the following steps:
(1) nitric-sulfuric acid is with 40~100 DEG C of feeding stripping tower tops, and gas stripping gas is with 50~150 DEG C of feeding stripping tower lower parts, air lift
Column overhead produces the gas phase containing nitric acid, and stripping tower tower bottom produces isolated sulfuric acid product；
(2) gas phase of the stripping tower overhead extraction containing nitric acid enters water scrubber lower part, using wash tower bottom extraction production water as
Cyclic absorption agent absorbs the nitric acid entered in the gas phase of water scrubber lower part, when concentration of nitric acid reaches controlling value in production water
Afterwards, it is sent out as isolated nitric acid product, water scrubber overhead extraction gas phase tail gas.
2. the cryogenic treatment process of nitric-sulfuric acid according to claim 1, which is characterized in that in the step (1), be sent into
The nitric-sulfuric acid composition of stripping tower is sulfuric acid 50%~90%, nitric acid 5%~20%, remaining is water and other are miscellaneous in mass
Matter；The molar flow of nitric acid and gas stripping gas ratio is 1:(70~600 in nitric-sulfuric acid)；The control of stripping tower empty tower gas velocity 0.5~
2m/s。
3. the cryogenic treatment process of nitric-sulfuric acid according to claim 1, which is characterized in that described in the step (1)
Gas stripping gas is inert gas, preferably air, nitrogen, helium, neon it is one or more；Stripping tower normal pressure or negative-pressure operation,
Full tower pressure drop is no more than 4KPaA, and operation temperature is 50~150 DEG C.
4. the cryogenic treatment process of nitric-sulfuric acid according to claim 1, which is characterized in that in the step (2), contain nitre
The gas phase of acid enters water scrubber lower part with 50~80 DEG C, produces water with 15~40 DEG C of temperature and is sent into water scrubber top；Water scrubber
Atmospheric operation, full tower pressure drop are no more than 2KPaA, and operation temperature is 15~40 DEG C.
5. the cryogenic treatment process of nitric-sulfuric acid according to claim 1, which is characterized in that in the step (2), as
Nitric acid mass concentration is 10~65% in the production water that isolated nitric acid product is sent out.
6. the cryogenic treatment process of nitric-sulfuric acid according to claim 1, which is characterized in that the cryogenic treatment process is also
Including step (3): water scrubber overhead extraction gas phase tail gas enters caustic wash tower lower part, and the lye produced using alkali cleaning tower bottom is as following
Ring absorbent absorbs the remaining acidic materials in the gas phase tail gas of caustic wash tower lower part, when alkali cleaning tower bottom lye pH reaches control
After value processed, sent out as waste water is neutralized, caustic wash tower overhead extraction gas phase qualified discharge.
7. the cryogenic treatment process of nitric-sulfuric acid according to claim 6, which is characterized in that in the step (3), alkali cleaning
Tower atmospheric operation, full tower pressure drop are no more than 2KPaA, and operation temperature is 15~40 DEG C；The initial mass concentration of lye be 10~
30%；It is 7~7.5 as the pH for neutralizing the alkali cleaning tower bottom lye that waste water is sent out；Lye is NaOH, Na2CO3, in KOH one
Kind or a variety of aqueous solutions.
8. a kind of cryogenic process system of nitric-sulfuric acid, including stripping tower, water scrubber and caustic wash tower；The stripping tower top has
Feedstock pipeline, stripping tower lower part have gas stripping gas admission line, and there is air lift tower bottom sulfuric acid product to produce pipeline, air lift
The gas phase extraction pipeline that top of tower has is connected to the admission line that the water scrubber lower part has；The washing tower bottom has
Production hydromining go out pipeline and be connected to the production water feed pipe that water scrubber top has, form production water-flow circuit, it is described
It produces water-flow circuit and is equipped with nitric acid product extraction branch, the gas phase extraction pipeline and the alkali having at the top of the water scrubber
The admission line connection that the lower part Xi Ta has；What the lye extraction pipeline and caustic wash tower top that the alkali cleaning tower bottom has had
The connection of lye feed pipe forms lye circulation loop, and the lye circulation loop, which is equipped with, neutralizes waste water extraction branch, described
There is gas phase mouth at the top of caustic wash tower.
9. the cryogenic process system of nitric-sulfuric acid according to claim 8, which is characterized in that the original on the stripping tower top
Expect that feed pipe is equipped with the first preheater；The gas stripping gas admission line of stripping tower lower part is equipped with the second preheater；The gas
The sulfuric acid product extraction pipeline of stripper bottom is equipped with sulfuric acid delivery pump.
10. the cryogenic process system of nitric-sulfuric acid according to claim 8, which is characterized in that the production of the water scrubber
It is successively arranged water-circulating pump and water scrubber recirculation cooler on water-flow circuit, on the lye circulation loop of the caustic wash tower successively
Equipped with alkali circulating pump and caustic wash tower recirculation cooler；The water scrubber top is equipped with fresh production water and supplements pipeline, the alkali cleaning
Tower top is equipped with fresh lye and supplements pipeline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910227313.3A CN109824022A (en) | 2019-03-25 | 2019-03-25 | A kind of low temperature separating methods of nitric-sulfuric acid |
Applications Claiming Priority (1)
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| CN115806275A (en) * | 2022-11-21 | 2023-03-17 | 山西北化关铝化工有限公司 | Method for treating nitric-sulfuric mixed acid generated by explosive synthesis |
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