CN108211759A - The processing method of the salt slurry waste generated in chlorine industry and its application - Google Patents
The processing method of the salt slurry waste generated in chlorine industry and its application Download PDFInfo
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- CN108211759A CN108211759A CN201611201151.9A CN201611201151A CN108211759A CN 108211759 A CN108211759 A CN 108211759A CN 201611201151 A CN201611201151 A CN 201611201151A CN 108211759 A CN108211759 A CN 108211759A
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- salt slurry
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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
Abstract
The present invention relates to the processing methods of salt slurry waste generated in a kind of chlorine industry, comprise the steps of：Salt slurry liquid is subjected to washing process, obtains supernatant and concentration salt slurry liquid；Concentration salt slurry liquid is subjected to filter-press dehydration processing, obtains filtrate and dehydration salt slurry；Screening process is ground to dehydration salt slurry, obtains powder salt slurry.After salt slurry liquid is by method provided by the invention processing, alternative part commodity desulfurizing agent calcium lime powder, for boiler smoke semi-dry desulphurization.Salt slurry liquid process flow is short in the present invention, method is simple to operation, processing cost is low, processing procedure is discharged without " three wastes ", solve the disposal difficulties of chlorine industry salt slurry liquid, waste recycling is realized again, need not be changed original sulfur removal technology using the desulfurizing agent, be reduced the desulphurization cost of boiler smoke.
Description
Technical field
The present invention relates to a kind of application of solid waste salt slurry in boiler flue gas desulfurization of chlorine industry, and in particular to
Part commodity desulfurizing agent calcium lime powder is substituted for boiler smoke semi-dry desulphurization for the salt slurry after a kind of be effectively treated, and belongs to solid
Body utilization of waste as resource field and field of environment protection.
Background technology
Chlorine industry produces NaOH, Cl by being electrolysed the method for saturation NaCl solution2And H2, and produced using them as raw material
A series of chemical products.Chlorine industry is removed using crude salt as raw material, in the saturation NaCl solution that crude salt is obtained by salt dissolving mainly to be contained
Outside NaCl, also containing a small amount of Ca2+And Mg2+, if do not removed it, in alkali producing process, they can form precipitation, be attached to and set
It on standby or duct wall or remains in alkali, influence normal operating or reduces product purity, therefore needed before being electrolysed to obtained full
Removal Ca therein is refined with NaCl solution2+And Mg2+。
In industrial production, usually by adding double alkali NaOH-Na2CO3Method saturation NaCl solution is refined, at this
During one, a certain amount of solid waste salt slurry liquid is given off.Due to crude salt place of production difference, impurity content is different, salt slurry
The discharge capacity of slurries is also different, and the discharge capacity for usually producing 1 ton of caustic soda salt slurry liquid is 0.4~0.8m3.Salt slurry liquid moisture content
80% or so, the main component of butt is CaCO3、Mg(OH)2With Ca (OH)2, also containing a small amount of Na2CO3With NaCl etc..Mesh
Before, the country is to note well or landfill as solid waste to the main method of disposal of salt slurry liquid, this method not only waste of resource, but also
Environment is polluted, while also needs to inject capital into, increases the operating cost of enterprise.
Contain a large amount of SO in the flue gas of discharged from coal-fired boiler2.Flue gas desulfurization is generally by desulfurizing agent and SO2Reaction life
Into stable compound by SO2Immobilization.It is divided into wet method, semidry method by how much sulfur removal technologies of desulfurizing agent moisture content and does
Method.Can have much as the substance of desulfurizing agent, what is be commonly used is resourceful calcium type desulfurizing agent, i.e. lime stone or stone
Ash, other desulfurizing agents also have caustic soda, soda ash, magnesium hydroxide, ammonia and seawater etc..
The main component of salt slurry butt is the active ingredient of desulfurizing agent, as can by salt slurry for boiler flue gas desulfurization, a side
Face reduces discharge of the salt slurry as solid waste, on the other hand can also realize the recycling of salt slurry, has certain environment
Benefit and economic benefit.
Patent application No. is 201310391191.4 is after lime-flue gas method two level salt slurry is washed, and is added with water to solid
Content is 5~30% slurries, then the organic additive of salt slurry quality 0.05~1% is added in into slurries, after mixing
It substitutes agstone and is used for smoke-gas wet desulfurization；Patent application No. is 201310389205.9 is to wash two alkaline process salt slurries
Afterwards, the slurries that solid content is 5~30% are added with water to, then the organic acid addition of salt slurry quality 0.05~1% is added in into slurries
Agent substitutes agstone and is used for smoke-gas wet desulfurization after mixing；Patent CN101219328A is modulated into salt slurry and water
Slurries absorbing sulfur dioxide in flue simultaneously aoxidizes, and absorbs serum recycle Reusability, and control liquid-gas ratio is 6~15L/m3, pH value
It is 5~7.
These inventions are all using salt slurry as raw material, for smoke-gas wet desulfurization.The present invention is the salt using salt slurry liquid as raw material
Slurry liquid is used for the semidry method of flue gas after being effectively treated after uniformly being mixed according to a certain percentage with commodity desulfurizing agent calcium lime powder
Desulfurization does not need to change original semi-dry desulphurization facility and sulfur removal technology.
Invention content
The purpose of the present invention is to provide a kind of methods of disposal of the salt slurry liquid of chlorine industry, and salt slurry liquid is through effectively place
After reason, alternative part commodity desulfurizing agent calcium lime powder, for boiler smoke semi-dry desulphurization.Both chlorine industry salt slurry had been solved
The disposal difficulties of slurries, and waste recycling is realized, reduce the desulphurization cost of boiler smoke.
The present invention discloses the processing method of salt slurry waste generated in a kind of chlorine industry, comprises the steps of：
(1) the salt slurry liquid by three layers of mud cleaning bucket discharge carries out washing process, obtains supernatant and concentration salt slurry liquid；
(2) above-mentioned concentration salt slurry liquid is transported to progress filter-press dehydration processing in plate and frame filter press, obtains filtrate and taken off
Water salt slurry；
(3) screening process is ground to above-mentioned dehydration salt slurry, obtains powder salt slurry.
The processing method of salt slurry of the present invention, wherein, in the step (1), the volume ratio of salt slurry liquid and water is excellent
It is selected as 1:1~2, washing times are preferably 1~2 time.
The processing method of salt slurry of the present invention, wherein, in step (1), Na in the concentration salt slurry liquid+、K+With
Cl-Percentage composition based on salt slurry butt is preferably respectively Na+＜ 0.5%, K+＜ 0.1%, Cl-＜ 0.4%.
The processing method of salt slurry of the present invention, wherein, in step (1), preferably described supernatant is back to salt dissolving tank
It is dissolved for crude salt, recycles salinity therein.
The processing method of salt slurry of the present invention, wherein, in step (2), the moisture content of the dehydration salt slurry is preferably
10~15%.
The processing method of salt slurry of the present invention, wherein, in step (2), preferably described filtrate is back to salt dissolving tank use
It is dissolved in crude salt, recycles salinity therein.
The processing method of salt slurry of the present invention, wherein, in the step (3), the preferred grain size of powder salt slurry<1mm.
The processing method of salt slurry of the present invention, wherein, in the step (3), 90% powder salt slurry grain size is preferred
In 0.5~0.9mm.
The powder salt slurry that processing method of the present invention obtains preferably is preparing the semi-dry desulphurization as boiler smoke
With the application in desulfurizing agent.
Application of the present invention, wherein, the weight ratio of the powder salt slurry and commodity desulfurizing agent calcium lime powder is preferably
0.2~0.4:1.
Using three layers of mud cleaning bucket, washing fresh water is inversely contacted with salt mud every time washes washing process of the present invention
It washs, once washing divides three phases to carry out, i.e., often washed once, and has actually carried out triphasic washing, washing effect is good, more has
Conducive to the wash-off of sodium, potassium, chlorion in salt slurry liquid.
Present invention concentration salt slurry dewatering slurries process is dehydrated, dehydration 20 using plate and frame filter press under -0.8 atmospheric pressure
Minute can reach 10~15% moisture content, and the dehydration salt slurry of gained is directly entered grinding screening machine, is carried out after grinding
Screening, oversize return to system and are ground again again.
In the present invention, the moisture content of dehydration salt slurry is preferably 10~15% after filter-press dehydration processing, this moisture content
It is to be more advantageous to required by subsequent process of lapping and moisture content as semi-dry desulphurization agent addition agent.
In the present invention, it is preferred to the grain size of 90% powder salt slurry, in 0.5~0.9mm, this particle size is that semidry method takes off
Particle size required by sulphur agent, grain size are more than 0.9mm, and desulfuration efficiency declines；Grain size is less than 0.5mm, in flue gas after desulfurization
Dust concentration can bigger.
The content of magnesium hydroxide is higher in the powder salt slurry of the present invention, due to magnesium hydroxide and a kind of good desulfurization
Agent, and magnesium hydroxide has hygroscopicity, is more advantageous to the progress of sweetening process, i.e. and salt slurry of the invention is added to commodity desulfurization
Generated increased desulfurization benefit part can be attributed to the presence of magnesium hydroxide in powder salt slurry in agent.
The powder salt slurry of the present invention can also directly as desulfurizing agent for flue gas desulfurization, but directly as desulfurizing agent,
Desulfuration efficiency is relatively low, below 70%；With commodity desulphurizer mixing desulfurization, in the case where various operating modes are constant, desulfuration efficiency
More than 6% can be improved, total desulfuration efficiency reaches more than 92%.The powder salt slurry of the present invention exists with the mixing ratio of commodity desulfurizing agent
0.4:When less than 1, desulfurization effect increases with the increase of mixing ratio, when more than 0.4:When 1, desulfuration efficiency does not increase again substantially
Add.
The salt slurry of the present invention has catalytic and hygroscopicity, and the salt slurry of the present invention is added in commodity desulfurizing agent, can be increased
Add more than 6% desulfurization benefit.
In the present invention, the split salt slurry of the magnesium hydroxide containing high-content is after commodity desulphurizer mixing for desulfurization
When completely without the device for changing original calcium desulfurizing.
Beneficial effects of the present invention：
(1) present invention gives birth to by the solid waste salt slurry liquid of chlorine industry discharge through being effectively treated with commodity desulfurizing agent
For boiler smoke semi-dry desulphurization after pulverized limestone mixing, not only solved the disposal difficulties of chlorine industry salt slurry liquid, but also realize
Waste recycling reduces the desulphurization cost of flue gas.
(2) salt slurry liquid process flow is short, and method is simple to operation, and processing cost is low, supernatant and dehydration after washing
Filtrate recycle dissolved in the salt dissolving tank of device for crude salt, recycle salinity therein, processing procedure is discharged without " three wastes ".
(3) present invention, without changing original sulfur removal technology, takes off without being transformed to original semidry process desulfurizer
Sulphur ash is disposed by original processing method.
Specific embodiment
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
The technological parameter of actual conditions is not specified in example, usually according to normal condition.
Embodiment 1：
By the salt slurry liquid of three layers of mud cleaning bucket discharge in certain enterprise's electrolysis unit refining crude salt unit by volume 1:1 adds water
Agitator treating 2 times, Na in salt slurry liquid+Content be 0.03%, K+Content be 0.01%, Cl-Content for 0.03%, wash
It washs the supernatant after precipitation and is back to salt dissolving tank for crude salt dissolving, recycle salinity therein.Salt slurry liquid after washing is defeated
Plate and frame filter press is sent to, under the pressure of 0.4MPa, filter-press dehydration is after 15 minutes, CaCO in salt slurry3Content be 49.8%, Mg
(OH)2Content for 25.9%, moisture content 12%, insoluble substance content is 10.6%, and the salts substances of dissolving are
1.5%.After the dewatered ground screening of salt slurry, all salt slurry grain sizes are in 0.5~0.9mm.
Through the above method treated salt slurry by weight 0.3:1 uniformly mixed with commodity desulfurizing agent calcium lime powder after formed
New desulfurizing agent, with Mr. Yu enterprise fire coal boiler fume semi-dry desulphurization.Exhaust gas volumn after electric precipitation is 136000Nm3/ h, cigarette
SO in gas2A concentration of 1680mg/Nm3, desulfurizing tower entrance flue gas temperature is 149 DEG C, using humidification cycle fluid bed outside Desulphurization half
Dry desulfurizing process, control Ca/S are 1.4, and Desulphurization recycle ratio is 150, and the flue gas after desulfurization discharges after bag-type dust, outside
Smoke discharging SO2A concentration of 131mg/Nm3, desulfurizing tower exit flue-gas temperature is 77 DEG C, smoke desulfurization efficiency 92.2%.
Embodiment 2：
By the salt slurry liquid of three layers of mud cleaning bucket discharge in certain enterprise's electrolysis unit refining crude salt unit by volume 1:1 adds water
Agitator treating 1 time, the Na in salt slurry liquid+Content be 0.04%, K+Content be 0.01%, Cl-Content for 0.04%,
Supernatant after washing precipitation is back to salt dissolving tank and is dissolved for crude salt, recycles salinity therein.By the salt slurry liquid after washing
Plate and frame filter press is transported to, under the pressure of 0.4MPa, filter-press dehydration is after 18 minutes, CaCO in salt slurry3Content for 50.8%,
Mg(OH)2Content for 26.3%, moisture content 10.5%, insoluble substance content is 10.7%, and the salts substances of dissolving are
1.5%.After the dewatered ground screening of salt slurry, all salt slurry grain sizes are in 0.5~0.9mm.
Through the above method treated salt slurry by weight 0.4:1 uniformly mixed with commodity desulfurizing agent calcium lime powder after formed
New desulfurizing agent, for 1 same fire coal boiler fume semi-dry desulphurization of embodiment.Exhaust gas volumn after electric precipitation is
136000Nm3/ h, SO in flue gas2A concentration of 1680mg/Nm3, desulfurizing tower entrance flue gas temperature is 149 DEG C, is increased using outside Desulphurization
Wet circulating fluid bed semi-drying method sulfur removal technology, control Ca/S are 1.4, and Desulphurization recycle ratio is 150, and the flue gas after desulfurization is through cloth bag
It is discharged after dedusting, discharged gas fume SO2A concentration of 124mg/Nm3, desulfurizing tower exit flue-gas temperature is 76 DEG C, smoke desulfurization efficiency
It is 92.6%.
As seen from the above-described embodiment, because the powder salt slurry of the present invention has moisture retention and catalytic, in the powder of the present invention
Body salt slurry is added to as additive in commodity desulfurizing agent, and above two property can improve desulfurization benefit, therefore desulfurization ratio can
To be less than 1.5, indirectly for saved the consumption of desulfurizing agent, realize waste recycling, use powder salt slurry and the quotient of the present invention
The mixture of product desulfurizing agent need not change original sulfur removal technology when as desulfurizing agent, reduce the desulphurization cost of boiler smoke.
Claims (10)
1. the processing method of salt slurry waste generated in a kind of chlorine industry, comprises the steps of：
(1) the salt slurry liquid by three layers of mud cleaning bucket discharge carries out washing process, obtains supernatant and concentration salt slurry liquid；
(2) above-mentioned concentration salt slurry liquid is transported to progress filter-press dehydration processing in plate and frame filter press, obtains filtrate and dehydration salt
Mud；
(3) screening process is ground to above-mentioned dehydration salt slurry, obtains powder salt slurry.
2. the processing method of salt slurry as described in claim 1, which is characterized in that in the step (1), salt slurry liquid and water
Volume ratio is 1:1~2, washing times are 1~2 time.
3. the processing method of salt slurry as described in claim 1, which is characterized in that in step (1), in the concentration salt slurry liquid
Na+、K+And Cl-Percentage composition based on salt slurry butt is respectively Na+＜ 0.5%, K+＜ 0.1%, Cl-＜ 0.4%.
4. the processing method of salt slurry as described in claim 1, which is characterized in that in step (1), being back to of supernatant
Salt tank dissolves for crude salt, recycles salinity therein.
5. the processing method of salt slurry as described in claim 1, which is characterized in that described to be dehydrated the aqueous of salt slurry in step (2)
Rate is 10~15%.
6. the processing method of salt slurry as described in claim 1, which is characterized in that in step (2), the filtrate is back to salt dissolving
Bucket dissolves for crude salt, recycles salinity therein.
7. the processing method of salt slurry as described in claim 1, which is characterized in that in the step (3), the grain size of powder salt slurry
<1mm。
8. the processing method of salt slurry as claimed in claim 7, which is characterized in that in the step (3), 90% powder salt slurry
Grain size is in 0.5~0.9mm.
9. the powder salt slurry that the processing method described in claim 1-8 obtains is preparing the semi-dry desulphurization use as boiler smoke
Application in desulfurizing agent.
10. application as claimed in claim 9, which is characterized in that the weight of the powder salt slurry and commodity desulfurizing agent calcium lime powder
Amount is than being 0.2~0.4:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611201151.9A CN108211759A (en) | 2016-12-22 | 2016-12-22 | The processing method of the salt slurry waste generated in chlorine industry and its application |
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| CN201611201151.9A CN108211759A (en) | 2016-12-22 | 2016-12-22 | The processing method of the salt slurry waste generated in chlorine industry and its application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563426A (en) * | 2019-10-21 | 2019-12-13 | 河南城建学院 | Steam-cured high-strength brick prepared from mine salt mud and preparation method thereof |
| CN112125416A (en) * | 2020-08-18 | 2020-12-25 | 中盐金坛盐化有限责任公司 | Technology for washing salt mud by lime flue gas method |
| CN112456832A (en) * | 2020-12-09 | 2021-03-09 | 泰安燊豪化工有限公司 | Treatment method of salt mud containing high calcium sulfate |
| CN114873890A (en) * | 2022-04-12 | 2022-08-09 | 博华工程技术有限公司 | Treatment process for semi-dry salt mud generated by wastewater treatment by doping desulfurizer |
| CN115321776A (en) * | 2022-09-22 | 2022-11-11 | 中国轻工业长沙工程有限公司 | Comprehensive recycling process for waste residue and waste water in chlor-alkali industry |
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| CN101274206A (en) * | 2007-12-25 | 2008-10-01 | 江苏省井神盐业有限公司 | Method for producing sulfur absorbing agent by 'salty mud' |
| CN103551015A (en) * | 2013-08-31 | 2014-02-05 | 中盐金坛盐化有限责任公司 | Sulfur dioxide absorbent prepared from two-alkali salt slurry |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4990677A (en) * | 1972-12-29 | 1974-08-29 | ||
| CN101219328A (en) * | 2007-10-08 | 2008-07-16 | 史汉祥 | Sulphur dioxide salty mud absorbent |
| CN101274206A (en) * | 2007-12-25 | 2008-10-01 | 江苏省井神盐业有限公司 | Method for producing sulfur absorbing agent by 'salty mud' |
| CN103551015A (en) * | 2013-08-31 | 2014-02-05 | 中盐金坛盐化有限责任公司 | Sulfur dioxide absorbent prepared from two-alkali salt slurry |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563426A (en) * | 2019-10-21 | 2019-12-13 | 河南城建学院 | Steam-cured high-strength brick prepared from mine salt mud and preparation method thereof |
| CN110563426B (en) * | 2019-10-21 | 2021-12-21 | 河南城建学院 | Steam-cured high-strength brick prepared from mine salt mud and preparation method thereof |
| CN112125416A (en) * | 2020-08-18 | 2020-12-25 | 中盐金坛盐化有限责任公司 | Technology for washing salt mud by lime flue gas method |
| CN112125416B (en) * | 2020-08-18 | 2022-11-15 | 中盐金坛盐化有限责任公司 | Technology for washing salt mud by lime flue gas method |
| CN112456832A (en) * | 2020-12-09 | 2021-03-09 | 泰安燊豪化工有限公司 | Treatment method of salt mud containing high calcium sulfate |
| CN114873890A (en) * | 2022-04-12 | 2022-08-09 | 博华工程技术有限公司 | Treatment process for semi-dry salt mud generated by wastewater treatment by doping desulfurizer |
| CN115321776A (en) * | 2022-09-22 | 2022-11-11 | 中国轻工业长沙工程有限公司 | Comprehensive recycling process for waste residue and waste water in chlor-alkali industry |
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Application publication date: 20180629 |