CN106390722A - Method for applying dilute waste alkali to treating tail gas from sulfuric acid plants - Google Patents
Method for applying dilute waste alkali to treating tail gas from sulfuric acid plants Download PDFInfo
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- CN106390722A CN106390722A CN201610973227.3A CN201610973227A CN106390722A CN 106390722 A CN106390722 A CN 106390722A CN 201610973227 A CN201610973227 A CN 201610973227A CN 106390722 A CN106390722 A CN 106390722A
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- Prior art keywords
- sulfuric acid
- tail gas
- dilute
- salkali waste
- gas treatment
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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
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a method for applying dilute waste alkali to treating tail gas from sulfuric acid plants. The method includes steps of directly applying the dilute waste alkali to treating the tail gas from the sulfuric acid plants in a spray mode. The pH (potential of hydrogen) of sprayed circulating liquid is higher than or equal to 4.50 under the control in sulfuric acid tail gas treatment procedures, and the concentration of the detected sulfuric acid tail gas SO2 is lower than 400 mg/m<3>. The method has the advantages that regeneration liquid from cathode beds can be completely collected in desalted water preparation working procedures and can be directly applied to removing sulfur from the tail gas from the sulfuric acid plants, and accordingly waste materials can be recycled; the sulfuric acid tail gas emission can be far lower than national standards, and accordingly the method has excellent economical and environmental protection significance.
Description
Technical field
The present invention relates to a kind of method that dilute salkali waste is used for sulfuric acid apparatus vent gas treatment, belong to sulfuric acid tail gas process field.
Background technology
Before the eighties in 20th century, gas washing in SA production adopts one turn of one suction technique, in order to reduce environmental pollution, domestic once enters
Went substantial amounts of sulfuric acid tail gas Processing Technology Research and application.After the nineties in 20th century, with technological innovation and progress, sulfuric acid
Produce and mostly adopt double conversion double absorption acid-making process, exhaust emissions is substantially all and reaches GB16297 1996《Atmosphere pollution is comprehensive
Discharge standard》Require, the research and development progress of tail gas disposal technique accordingly slows down.2010, national environmental protection portion promulgated
GB2132—2010《Sulfuric acid industry pollutant emission standard》.New standard clear stipulaties new device in 1 day March in 2011,
Existing apparatus started to execute new discharge standard, tail gas ρ (SO in 1 day October in 20132) emission limit be 400mg/m3, acid
Mist emission limit is 30mg/m3.In order to realize qualified discharge, some enterprises are using filling high performance catalyst, optimization conversion work
The method of skill, some enterprises adopt tail gas desulfurization technique.
At present, sulfuric acid plant's tail gas desulfurization technology mainly has ammonia-acid process, sodium alkali, new catalytic method, activated coke method, organic
Amine method etc., desulfuration efficiency is all more than 90% it is ensured that sulfuric acid plant's exhaust emissions meets new standard.Which kind of tail Sulphuric Acid Enterprises adopt
Desulfurization technology, should suit measures to local conditions to consider the problems such as source of desulfurizing agent, the market of accessory substance and investment, operating cost.
Sodium alkali is one of important method that sulfuric acid tail gas are processed, and according to the difference of accessory substance, can be divided into sodium-sulfurous acid
Hydrogen sodium method, sodium-Arbiso process and sodium-sodium sulphate method., inhale tower from sulfuric acid apparatus two taking sodium-sodium bisulfite method as a example
Gas is entered first grade absorption tower and is inversely contacted with NaOH solution, and sour gas and alkali lye are fully contacted generation acid-base neutralization reaction；
Go out first grade absorption tower gas absorb again through second level absorption tower after, by chimney qualified discharge.NaOH absorbing liquid is by the second level
Tail gas absorber adds, and controls circulation fluid pH value to be 9.5；When the pH value of primary cycle groove is down to 4.5～5.0, output sulfurous
Sour hydrogen sodium solution, and part circulation fluid entrance primary cycle groove is sealed in by secondary cycle groove.Sodium alkali desulfurization technology main feature
Have：(1) desulfurizing agent NaOH solution source is guaranteed.(2) NaOH and SO2Affinity extremely strong, absorptivity is high, and desulfurization is imitated
Rate, more than 95%, reach and 1 section of sodium alkali identical gas cleaning rate, and ammonia-acid process generally requires to arrange 2 sections or 3 sections suctions
Receive.(3) compared with ammonia process, another advantage of sodium alkali is cation non-volatility, do not exist as ammonia process absorption process because
The volatilization of ammonia produces ammonia mist.
But the subject matter of sodium alkali is alkali lye price so that sulfuric acid becomes to produce cost improves, and product competitiveness reduces,
And in order to save alkali consumption, generally require the first order absorption of complexity, two grades of absorptions, device is complicated, and operating cost is not also low.
Wash in production process of titanium pigment, steam, reagent preparation is required for using a large amount of desalted waters with improve product quality.
Demineralized Water Production technique, also known as Pure water preparation technique or advanced desalination hydraulic art, refers generally to the strong conduction being easily removed in water
Matter removes and removes the weak electrolytes such as the silicic acid and the carbon dioxide that are difficult in water remove to a certain degree of water again.Early stage people institute
Known to Demineralized Water Production technique be mainly pretreatment+cation bed+anion bed+mixed bed full ion-exchange process, that is, Traditional Method process
Flow process.Long-term practice is it was demonstrated that Traditional Method handling process is a kind of ripe effectively water treatment technology.
After ion exchange resin is using a period of time, the impurity of absorption, is used it is necessary to carry out regeneration process close to saturation state
The ion that resin is adsorbed by chemical agent and other impurities wash-out remove, and are allowed to recover original composition and performance.Desalted water
In preparation process, the regeneration of anion bed resin generally adopts 5.0% about NaOH solution, and the alkaline consumption of 1 ton of desalted water is mainly regenerated
The species of agent, temperature, concentration and flushing water quality impact, according to the difference of raw water quality, folding hundred alkaline consumption of 1 ton of desalted water is in 50-
Fluctuate between 500g, 1 ton of desalted water alkaline consumption of most of producers is in 250g, but NaOH in production application
Practical efficiency only has 50% about, often produces ton desalted water and will produce 2.0% about sodium hydroxide waste liquor about 6.25kg, with day
As a example producing the manufacturer of 700 tons of titanium dioxides, about 130 ton 2.0% about of spent lye will be produced daily, due to this alkali lye machinery
Impurity is many, and concentration is low, color and luster weight, and containing about 400ppm about Cl ion, therefore it is carried out with removal of impurities, decolouring is reclaimed economical
Feasibility less, and because Cl ion is exceeded, is also not useable for calcining tail gas in production process of titanium pigment and sprays (because calcining tail gas
Spray often has lead electric demister, when 60 DEG C about, high chlorinity alkali lye meeting corroding lead).This alkali lye often directly enters sewage
Process, cause serious waste.
Content of the invention
The problem being existed according to prior art, the present invention provides a kind of dilute salkali waste to be used for the side of sulfuric acid apparatus vent gas treatment
Method.
Technical scheme is as follows：
A kind of method that dilute salkali waste is used for sulfuric acid apparatus vent gas treatment, comprises the following steps：Dilute salkali waste is directly used in sulphur
Sour device exhaust is processed, and using spray mode, controls pH >=4.50 of Sprayer Circulation liquid in sulfuric acid tail gas processing procedure, detects sulphur
Sour tail gas SO2Concentration is less than 400mg/m3.
Wherein, described dilute salkali waste is derived from anion bed regeneration during ion-exchange produces desalted water and produces；Or it is described
Dilute salkali waste be derived from anion bed resin regeneration process in produce mother liquor, washing lotion or the mixture of the two.
The concentration of described dilute salkali waste is 5-100g/l.
Described sulfuric acid tail gas spray can spray mode using one or more levels.
Described dilute salkali waste needs not move through any pretreatment and is directly used in sulfuric acid apparatus vent gas treatment, and pretreatment includes dropping
The steps such as temperature, removal of impurities, decolouring；On the premise of sig water abundance, the pH of Sprayer Circulation liquid controls the higher vent gas treatment obtaining
Effect is better；
The relevant device material being related in sulfuric acid tail gas processing procedure must resistance to Cl be corroded, preferably plastic material.
The tail gas of sulfuric acid apparatus mainly contains sulfur dioxide, nitrogen dioxide, oxygen and nitrogen, wherein sulfur dioxide and titanium dioxide
Nitrogen is major pollutants, in order to ensure the qualified discharge of tail gas, the main reflection equation generally being sprayed using NaOH
Formula：
2NaOH+SO2=Na2SO3+H2O
Na2SO3+SO2+H2O=2NaHSO3
4NaOH+4NO2+O2=4NaNO3+2H2O
In sulfuric acid tail gas, sulfur dioxide adopts iodimetric titration, is to analyze one of technology of sulfur dioxide earliest, and it is using suction
After receiving the fixing sulfur dioxide of liquid, titrate the content of sulfur dioxide with iodine standard solution.
Beneficial effect
In the present invention, anion bed regenerated liquid in desalted water preparation section is all collected, is directly used in sulfuric acid apparatus tail gas
Desulfurization, accomplishes to turn waste into wealth, and not only has preferable economic implications, it may have preferably environment protection significance.With 200,000 tons of titanium dioxides
Factory, supporting 1,800,000 tons of sulfuric acid apparatus calculate, and hundred liquid caustic soda about 10kg is rolled in annualization water station consumption, produce about 2000 tons of salkali waste total amount,
Carry out tail gas spray as being effectively recycled to sulfuric acid apparatus, every year about 5,000,000 yuan of producible economic benefit, sulfuric acid tail can be made simultaneously
Gas discharges well below national standard, economical and environmentally friendly all has positive effect.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is described in further detail.It should be appreciated that specific embodiment described herein, only in order to explain the present invention, does not limit
In the present invention.
Embodiment 1
Ion-exchange produces desalted water, and anion bed regeneration, using 5.0% NaOH solution, collects institute after resin activated end
There is regeneration mother liquor, mother liquor is directly used in sulfuric acid apparatus tail gas desulfurization and processes, using one-level spray, control Sprayer Circulation liquid pH ＞
4.5, detect sulfuric acid tail gas SO2=250mg/m3.
Embodiment 2
Ion-exchange produces desalted water, and anion bed regeneration, using 5.0% NaOH solution, collects institute after resin activated end
There is regeneration mother liquor, mother liquor is directly used in sulfuric acid apparatus tail gas desulfurization and processes, using multi-stage spray, control Sprayer Circulation liquid pH ＞
9.0, detect sulfuric acid tail gas SO2=50mg/m3.
Embodiment 3
Ion-exchange produces desalted water, and anion bed regeneration, using 5.0% NaOH solution, collects institute after resin activated end
There is washing lotion it is ensured that sig water concentration is more than 2.0%, mother liquor is directly used in sulfuric acid apparatus tail gas desulfurization and processes, using one-level spray
Drench, control Sprayer Circulation liquid pH ＞ 4.5, detect sulfuric acid tail gas SO2=300mg/m3.
Claims (6)
1. a kind of dilute salkali waste be used for sulfuric acid apparatus vent gas treatment method it is characterised in that：Comprise the following steps：Will be straight for dilute salkali waste
Connect for sulfuric acid apparatus vent gas treatment, using spray mode, control the pH of Sprayer Circulation liquid in sulfuric acid tail gas processing procedure >=
4.50, detect sulfuric acid tail gas SO2Concentration is less than 400mg/m3.
2. a kind of dilute salkali waste according to claim 1 be used for sulfuric acid apparatus vent gas treatment method it is characterised in that：Described
Dilute salkali waste be derived from ion-exchange produce desalted water during anion bed regeneration produce.
3. a kind of dilute salkali waste according to claim 1 be used for sulfuric acid apparatus vent gas treatment method it is characterised in that：Described
Dilute salkali waste be derived from anion bed resin regeneration process in produce mother liquor, washing lotion or the mixture of the two.
4. a kind of dilute salkali waste according to claim 1 be used for sulfuric acid apparatus vent gas treatment method it is characterised in that：Described
The concentration of dilute salkali waste is 5-100g/l.
5. a kind of dilute salkali waste according to claim 1 be used for sulfuric acid apparatus vent gas treatment method it is characterised in that：Described
Spray mode adopt one or more levels spray mode.
6. a kind of dilute salkali waste according to claim 1 be used for sulfuric acid apparatus vent gas treatment method it is characterised in that：Described
Dilute salkali waste need not move through any pretreatment and be directly used in sulfuric acid apparatus vent gas treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610973227.3A CN106390722A (en) | 2016-11-04 | 2016-11-04 | Method for applying dilute waste alkali to treating tail gas from sulfuric acid plants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610973227.3A CN106390722A (en) | 2016-11-04 | 2016-11-04 | Method for applying dilute waste alkali to treating tail gas from sulfuric acid plants |
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| Publication Number | Publication Date |
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| CN106390722A true CN106390722A (en) | 2017-02-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610973227.3A Pending CN106390722A (en) | 2016-11-04 | 2016-11-04 | Method for applying dilute waste alkali to treating tail gas from sulfuric acid plants |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004076829A1 (en) * | 2003-02-26 | 2004-09-10 | Umicore Ag & Co. Kg | Exhaust-gas purification system for the selective catalytic reduction of nitrogen oxides in the lean exhaust gas of internal combustion engines and method of exhaust-gas purification |
| CN102755815A (en) * | 2012-07-06 | 2012-10-31 | 江苏恒丰伟业科技工程有限公司 | Titanium dioxide acidolysis tail gas treatment method |
| CN204338172U (en) * | 2014-12-05 | 2015-05-20 | 天津市瑞德赛恩水业有限公司 | Anion bed regeneration liquid waste recycling device |
-
2016
- 2016-11-04 CN CN201610973227.3A patent/CN106390722A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004076829A1 (en) * | 2003-02-26 | 2004-09-10 | Umicore Ag & Co. Kg | Exhaust-gas purification system for the selective catalytic reduction of nitrogen oxides in the lean exhaust gas of internal combustion engines and method of exhaust-gas purification |
| CN102755815A (en) * | 2012-07-06 | 2012-10-31 | 江苏恒丰伟业科技工程有限公司 | Titanium dioxide acidolysis tail gas treatment method |
| CN204338172U (en) * | 2014-12-05 | 2015-05-20 | 天津市瑞德赛恩水业有限公司 | Anion bed regeneration liquid waste recycling device |
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Application publication date: 20170215 |