CN107051155A - A kind of low-grade bittern containing alkali is used for the method for flue gas desulfurization oxidation nitre - Google Patents
A kind of low-grade bittern containing alkali is used for the method for flue gas desulfurization oxidation nitre Download PDFInfo
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- CN107051155A CN107051155A CN201710180085.XA CN201710180085A CN107051155A CN 107051155 A CN107051155 A CN 107051155A CN 201710180085 A CN201710180085 A CN 201710180085A CN 107051155 A CN107051155 A CN 107051155A
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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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- 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
- B01D53/18—Absorbing units; Liquid distributors therefor
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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
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/04—Preparation of sulfates with the aid of sulfurous acid or sulfites, e.g. Hargreaves process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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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
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Abstract
The invention discloses a kind of method that low-grade bittern containing alkali is used for flue gas desulfurization oxidation nitre, the low-grade bittern containing alkali that the present invention will be unable to be directly used in nitre processed is used for SO in boiler flue gas desulfurization, removing flue gas2So that while flue gas reaches discharge standard, generate NaHSO3、Na2SO3, by aoxidizing generation Na2SO4, Na in bittern2SO4Content increase, can be directly used as producing the raw material of glauber salt.The reasonable compositing characteristic using low grade brine of the invention, the sulfur content in boiler smoke is effectively reduced by desulfurization oxidation technology, qualified discharge is allowed to；Utilized for the bittern original place after desulfurization, the sulphur of removing is fixed into reproduction, effectively reduce energy consumption, the present invention also reduces the discharge of waste water and gas, with higher application value and environmental benefit while entreprise cost is reduced.
Description
Technical field
The invention belongs to nitre technology field processed, and in particular to one kind is in glauber salt production process by low-grade bittern containing alkali
For being used for the method for aoxidizing nitre processed after boiler flue gas desulfurization.
Background technology
Glauber salt, scientific name anhydrous sodium sulfate, inorganic compound, chemical formula Na2SO4, white crystal or powder, ten hydrates
Thing is also known as saltcake, and it is widely used in the industries such as printing and dyeing, papermaking, washing, metallurgy.The Hongchehu Lake area in Jiangsu has contained huge
Mirabilite resource, this area has successively built up multiple medium-and-large-sized glauber salt manufacturing enterprises such as white rose, Shanghai Pacific Ocean, south wind,
Form the glauber salt production base of Fia.
The existing main production process in this area is：The mirabilite resource of underground is produced with drilling solution method, passes through multiple-effect
It is evaporated in vacuo the Na in bittern2SO4Condensing crystallizing, obtains anhydrous sodium sulfate after drying.The technical process energy consumption is larger, greatly
Some Enterprises have power houses and produced, and consume contain in a large amount of thermal coals, the flue gas that coal combustion process is produced every year
Higher SO2, it is qualified discharge, typically sulphur is fixed with 20%-30% soda bath, the alkali lye after desulfurization returns mine note
Well, while solving the process problem of doctor solution.
With the continuous exploitation and the continuous diffusion of note well alkali lye of mirabilite resource, saltcake grade constantly declines, part ore deposit
Contain more NaHCO in the bittern of well extraction3、Na2CO3, had a strong impact on the sustainable development of the sector.How to solve to work as
Preceding predicament and to improve industrial profit extremely urgent.
For above-mentioned situation, most of enterprise's selection is opened a mine again obtains the higher mirabilite resource of grade or using in acid adding
The method of sum excludes the interference of system neutral and alkali component, but opens a mine again and easily cause the waste of resource and be not recycled, resource
Using being unable to reach in maximization, acid adding and needing to consume a large amount of sulfuric acid, virtually improve the operating cost of enterprise, it is long this with
Toward the sound development for being unfavorable for industry.
CN101503204B discloses a kind of with containing NaHCO3Alkali halogen wet decomposition evaporation alkali-making process, will contain NaHCO3's
Bittern is used to produce heavy soda ash.Disclosed method complex process, energy consumption be larger, to NaHCO in bittern3Content requirement is higher,
It is not particularly suited for practical condition.
The content of the invention
For drawbacks described above, it is used for flue gas desulfurization-oxidation it is an object of the invention to provide the low-grade bittern containing alkali of one kind
The method of nitre processed, is decreased obviously solving nitre raw material grade processed, and low-grade bittern containing alkali is same the problem of can not make full use of
When, the SO in flue gas can be removed again2So that flue gas reaches discharge standard.
The present invention is achieved by the following technical solutions：
A kind of low-grade bittern containing alkali is used for the method for flue gas desulfurization-oxidation nitre, comprises the following steps：
A. bittern containing alkali by slurry feeding pump from desulfurization tower bottom squeeze into desulfurizing tower top spray or atomization system, using spray or
The mode of atomization is distributed, and the flow of bittern containing alkali is 100-200m3/ h, pH value control is 6.5-7.5；
B. boiler smoke is blasted by blower fan from desulfurization tower bottom, with halogen buck reverse flow, contact desulfuriation, into desulfurizing tower
The liquid-gas ratio of bittern containing alkali and boiler smoke is 1:0.9-1.8 L/m3, flue gas after desulfurization discharges from desulfurizing tower top exit,
By on-line checking, SO in the flue gas after desulfurization2Concentration is 100-200 mg/Nm3, meet discharge standard；
C. the deoxidation reactor of bittern containing alkali being used for after flue gas desulfurization, the NaHSO that oxidation sweetening process is produced3、Na2SO3；
D. when the pH value for the absorbing liquid that the tail gas that oxidation reactor overflows is gone in device for absorbing tail gas, device for absorbing tail gas is less than 5
It is recycled to oxidation reactor；
E. the bittern of oxidized reactor enters NaHSO remaining in deep oxidization reactor, oxidation system3、Na2SO3；
F. the bittern after deep oxidation goes to be acidified kettle, adjusts the pH value of bittern to 5.5-6；
G. nitre workshop processed is gone to be refining to obtain glauber salt after the bittern filtering after acid adjustment.
Further improvement of the present invention scheme is：
The main component of bittern containing alkali described in step a is NaHCO3、Na2CO3、NaCl、Na2SO4, wherein NaHCO3Content is 5-30g/
L, Na2CO3Content is 5-20g/L, and NaCl contents are 30-120g/L, Na2SO4Content is 100-320g/L, and total alkali is 5-
50g/L, total alkali is preferably 10-15g/L.
SO in boiler smoke described in step b2Concentration is 1000-2000mg/Nm3。
Oxidant in oxidation reactor described in step c is bittern flow 100-200 m in chlorine, oxidation reactor3/h,
Chlorine flowrate 120-220 m3/h。
Device for absorbing tail gas described in step d is absorption tower or absorption cell, and absorbing liquid is saturation NaHCO3Solution.
Oxidant is NaClO, NaClO in deep oxidization reactor described in step e2、HClO、O3、O2、H2O2；Preferably
H2O2, NaHSO in the mole and system of oxidant3、Na2SO3Integral molar quantity ratio be 1.05:1.
It is H that the acid used in kettle is acidified described in step f2SO4、HCl；Preferably H2SO4。
The present invention will be unable to be directly used in being used for low-grade bittern containing alkali in boiler flue gas desulfurization, removing flue gas of nitre processed
SO2So that while flue gas reaches discharge standard, generate NaHSO3、Na2SO3By aoxidizing generation Na2SO4, Na in bittern2SO4
Content increase, can be directly used as producing the raw material of glauber salt.
Compared with prior art, beneficial effects of the present invention are：
First, the invention activation value of the low-grade bittern containing alkali, solves that the pre-treatment of bittern containing alkali cost is high, value is low
The problem of, the production cost of company is reduced, being truly realized turns waste into wealth, had a high potential in terms of practical application；In not shadow
Ring under conditions of existing equipment operating, realize the low cost removing of boiler smoke sulfur-bearing composition, again the sulphur of removing is returned in time
Receive, business burden is transformed to company interest, the production of glauber salt and boiler flue gas desulfurization are combined.
2nd, the present invention need not consume a large amount of sulfuric acid to carry out brine refining, it is not necessary to the higher hydroxide of use value
Sodium carries out desulfurization, it is not required that the alkali lye blowback mine after desulfurization is noted into well, therefore, present invention reduces entreprise cost；This hair
The compositing characteristic of bright reasonable utilization low grade brine, the sulfur content in boiler smoke is effectively reduced by desulfurization-oxidation technology, is made
Qualified discharge；Utilized for the bittern original place after desulfurization, the sulphur of removing is fixed into reproduction, energy consumption is effectively reduced, the present invention
While entreprise cost is reduced, the discharge of waste water and gas is also reduced, with higher application value and environmental benefit.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Embodiment
The bittern containing alkali selected the following is embodiment is that Huaian Region is used to produce in the mirabilite ore that glauber salt is produced
Low grade brine, main component is NaHCO3、Na2CO3、NaCl、Na2SO4, pH value is 8.5, and alkali content is 10-15g/L, with
HCO3 -Meter.
Embodiment 1
A. bittern containing alkali squeezes into desulfurizing tower top by slurry feeding pump from desulfurization tower bottom, is distributed using spray mode, falls on de-
Desulfurizing tower top spray system is squeezed into from desulfurization tower bottom by slurry feeding pump again during sulphur tower bottom, so circulation, bittern containing alkali
Flow is 100m3/ h, pH value control is 7.5；
B. boiler smoke is blasted by blower fan from desulfurization tower bottom, and halogen buck reverse flow, contact desulfuriation, and flue gas flow is
180000m3/ h, the liquid-gas ratio of bittern containing alkali and boiler smoke into desulfurizing tower is 1:1.8 L/m3, flue gas after desulfurization is from de-
Sulphur top of tower outlet discharge, by on-line checking, SO in the flue gas after desulfurization2Concentration is 100 mg/Nm3, meet discharge standard；
C. the deoxidation reactor of bittern containing alkali being used for after flue gas desulfurization, oxidant is chlorine, what oxidation sweetening process was produced
NaHSO3、Na2SO3, the m of bittern flow 100 in oxidation reactor3/ h, the m of chlorine flowrate 1203/h；
D. the absorbing liquid that the tail gas that oxidation reactor overflows is gone in device for absorbing tail gas, device for absorbing tail gas is saturation NaHCO3It is molten
Liquid, oxidation reactor is recycled to when the pH value of absorbing liquid is less than 5；
E. the bittern of oxidized reactor enters deep oxidization reactor, and oxidant is H2O2, it is remaining in oxidation system
NaHSO3、Na2SO3, normative reference《HG/T 2967-2010 industry anhydrous sodium sulfites》In the method analysis bittern of middle offer
NaHSO3、Na2SO3Content, hydrogen peroxide mole excessive 5%；
F. the bittern after deep oxidation go be acidified kettle, with sulfuric acid and system in remaining NaHCO3、Na2CO3, adjust bittern
PH value to 5.5-6；Now constituted in bittern with NaCl, Na2SO4Based on, contain a small amount of NaHCO3, NaHCO3Content it is low
In 0.8 g/L.
After the insolubility impurity such as the flyash brought into the g. bittern filtering after acid adjustment, removing sweetening process, nitre processed is removed
Workshop is refining to obtain the glauber salt for meeting national standard.
Embodiment 2
A. bittern containing alkali squeezes into desulfurizing tower top by slurry feeding pump from desulfurization tower bottom, is distributed using spray mode, halogen containing alkali
Water-carrying capacity is 200m3/ h, pH value control is 6.5；
B. boiler smoke is blasted by blower fan from desulfurization tower bottom, and halogen buck reverse flow, contact desulfuriation, and flue gas flow is
220000m3/ h, the liquid-gas ratio of bittern containing alkali and boiler smoke into desulfurizing tower is 1:1.1 L/m3, flue gas after desulfurization is from de-
Sulphur top of tower outlet discharge, by on-line checking, SO in the flue gas after desulfurization2Concentration is 200mg/Nm3, meet discharge standard；
C. the deoxidation reactor of bittern containing alkali being used for after flue gas desulfurization, oxidant is chlorine, what oxidation sweetening process was produced
NaHSO3、Na2SO3, the m of bittern flow 200 in oxidation reactor3/ h, the m of chlorine flowrate 2203/h；
D. the absorbing liquid that the tail gas that oxidation reactor overflows is gone in device for absorbing tail gas, device for absorbing tail gas is saturation NaHCO3It is molten
Liquid, oxidation reactor is recycled to when the pH value of absorbing liquid is less than 5；
E. the bittern of oxidized reactor enters deep oxidization reactor, and oxidant is H2O2, it is remaining in oxidation system
NaHSO3、Na2SO3, normative reference《HG/T 2967-2010 industry anhydrous sodium sulfites》In the method analysis bittern of middle offer
NaHSO3、Na2SO3Content, hydrogen peroxide mole excessive 5%；
F. the bittern after deep oxidation go be acidified kettle, with sulfuric acid and system in remaining NaHCO3、Na2CO3, adjust bittern
PH value to 5.5-6, now constituted in bittern with NaCl, Na2SO4Based on, contain a small amount of NaHCO3, NaHCO3Content it is low
In 0.8 g/L.
After the insolubility impurity such as the flyash brought into the g. bittern filtering after acid adjustment, removing sweetening process, nitre processed is removed
Workshop is refining to obtain the glauber salt for meeting national standard.
Embodiment 3
A. bittern containing alkali squeezes into desulfurizing tower top by slurry feeding pump from desulfurization tower bottom, is distributed using spray mode, falls on de-
Desulfurizing tower top spray system is squeezed into from desulfurization tower bottom by slurry feeding pump again during sulphur tower bottom, so circulation, bittern containing alkali
Flow is 150m3/ h, pH value control is 7；
B. boiler smoke is blasted by blower fan from desulfurization tower bottom, and halogen buck reverse flow, contact desulfuriation, and flue gas flow is
135000m3/ h, the liquid-gas ratio of bittern containing alkali and boiler smoke into desulfurizing tower is 1:0.9 L/m3, flue gas after desulfurization is from de-
Sulphur top of tower outlet discharge, by on-line checking, SO in the flue gas after desulfurization2Concentration is 150mg/Nm3, meet discharge standard；
C. the deoxidation reactor of bittern containing alkali being used for after flue gas desulfurization, oxidant is chlorine, what oxidation sweetening process was produced
NaHSO3、Na2SO3, the m of bittern flow 150 in oxidation reactor3/ h, the m of chlorine flowrate 1703/h；
D. the absorbing liquid that the tail gas that oxidation reactor overflows is gone in device for absorbing tail gas, device for absorbing tail gas is saturation NaHCO3It is molten
Liquid, oxidation reactor is recycled to when the pH value of absorbing liquid is less than 5；
E. the bittern of oxidized reactor enters deep oxidization reactor, and oxidant is H2O2, it is remaining in oxidation system
NaHSO3、Na2SO3, normative reference《HG/T 2967-2010 industry anhydrous sodium sulfites》In the method analysis bittern of middle offer
NaHSO3、Na2SO3Content, hydrogen peroxide mole excessive 5%；
F. the bittern after deep oxidation go be acidified kettle, with sulfuric acid and system in remaining NaHCO3、Na2CO3, adjust bittern
PH value to 5.5-6, now constituted in bittern with NaCl, Na2SO4Based on, contain a small amount of NaHCO3, NaHCO3Content it is low
In 0.8 g/L.
After the insolubility impurity such as the flyash brought into the g. bittern filtering after acid adjustment, removing sweetening process, nitre processed is removed
Workshop is refining to obtain the glauber salt for meeting national standard.
Claims (8)
1. a kind of low-grade bittern containing alkali is used for the method for flue gas desulfurization-oxidation nitre, it is characterised in that comprise the following steps：
A. bittern containing alkali by slurry feeding pump from desulfurization tower bottom squeeze into desulfurizing tower top spray or atomization system, boiler smoke by
Blower fan is blasted from desulfurization tower bottom；
C. the deoxidation reactor of bittern containing alkali being used for after flue gas desulfurization, the NaHSO that oxidation sweetening process is produced3、Na2SO3；
D. the tail gas of oxidation reactor effusion removes device for absorbing tail gas；
E. the bittern of oxidized reactor enters remaining NaHSO in deep oxidization reactor, oxidation system3、Na2SO3；
F. the bittern after deep oxidation goes to be acidified kettle；
G. nitre workshop processed is gone to be refining to obtain glauber salt after the bittern filtering after acid adjustment.
2. a kind of low-grade bittern containing alkali according to claim 1 is used for the method for flue gas desulfurization-oxidation nitre, its feature
It is：The main component of bittern containing alkali described in step a is NaHCO3、Na2CO3、NaCl、Na2SO4, wherein NaHCO3Content is 5-
30g/L, Na2CO3Content is 5-20g/L, and NaCl contents are 30-120g/L, Na2SO4Content is 100-320g/L, total alkali
For 5-50g/L.
3. a kind of low-grade bittern containing alkali according to claim 1 or 2 is used for the method for flue gas desulfurization-oxidation nitre, its
It is characterised by：The total alkali of bittern containing alkali described in step a is 10-15g/L, and flow is 100-200m3/ h, pH value is 6.5-7.5.
4. a kind of low-grade bittern containing alkali according to claim 1 is used for the method for flue gas desulfurization-oxidation nitre, its feature
It is：SO in boiler smoke described in step b2Concentration is 1000-2000mg/Nm3, into the bittern containing alkali and boiler smoke of desulfurizing tower
The liquid-gas ratio of gas is 1:0.9-1.8 L/m3。
5. a kind of low-grade bittern containing alkali according to claim 1 is used for the method for flue gas desulfurization-oxidation nitre, its feature
It is：Oxidant in oxidation reactor described in step c is bittern flow 100-200 m in chlorine, oxidation reactor3/ h, chlorine
Throughput 120-220 m3/h。
6. a kind of low-grade bittern containing alkali according to claim 1 is used for the method for flue gas desulfurization-oxidation nitre, its feature
It is：Device for absorbing tail gas described in step d is absorption tower or absorption cell, and absorbing liquid is saturation NaHCO3Solution, absorbing liquid is in pH
Value is recycled to oxidation reactor when being less than 5.
7. a kind of low-grade bittern containing alkali according to claim 1 is used for the method for flue gas desulfurization-oxidation nitre, its feature
It is：Oxidant is NaClO, NaClO in deep oxidization reactor described in step e2、HClO、O3、O2Or H2O2One kind, oxidant
Mole and system in NaHSO3、Na2SO3Integral molar quantity ratio be 1.05:1.
8. a kind of low-grade bittern containing alkali according to claim 1 is used for the method for flue gas desulfurization-oxidation nitre, its feature
It is：It is H that the acid used in kettle is acidified described in step f2SO4Or HCl.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710180085.XA CN107051155B (en) | 2017-03-24 | 2017-03-24 | Method for preparing nitrate by using low-grade alkali-containing brine for flue gas desulfurization-oxidation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710180085.XA CN107051155B (en) | 2017-03-24 | 2017-03-24 | Method for preparing nitrate by using low-grade alkali-containing brine for flue gas desulfurization-oxidation |
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| CN107051155B CN107051155B (en) | 2020-01-10 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114195174A (en) * | 2021-11-18 | 2022-03-18 | 武汉钢铁有限公司 | Method for preparing sodium sulfate from sodium bicarbonate desulfurized fly ash by wet method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4176163A (en) * | 1977-12-12 | 1979-11-27 | Combustion Engineering, Inc. | Sodium oxide fume for sulfur oxide removal |
| CN102530997A (en) * | 2012-02-28 | 2012-07-04 | 信义电子玻璃（芜湖）有限公司 | Desulfurization product recycling technology and system |
| CN205412652U (en) * | 2016-04-05 | 2016-08-03 | 江苏白玫化工有限公司 | Atomizer of former glass gall flue gas neutralizing tower |
-
2017
- 2017-03-24 CN CN201710180085.XA patent/CN107051155B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4176163A (en) * | 1977-12-12 | 1979-11-27 | Combustion Engineering, Inc. | Sodium oxide fume for sulfur oxide removal |
| CN102530997A (en) * | 2012-02-28 | 2012-07-04 | 信义电子玻璃（芜湖）有限公司 | Desulfurization product recycling technology and system |
| CN205412652U (en) * | 2016-04-05 | 2016-08-03 | 江苏白玫化工有限公司 | Atomizer of former glass gall flue gas neutralizing tower |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114195174A (en) * | 2021-11-18 | 2022-03-18 | 武汉钢铁有限公司 | Method for preparing sodium sulfate from sodium bicarbonate desulfurized fly ash by wet method |
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