CN105417797B - A kind of technique of desulfurization slurry dechlorination - Google Patents
A kind of technique of desulfurization slurry dechlorination Download PDFInfo
- Publication number
- CN105417797B CN105417797B CN201511007845.4A CN201511007845A CN105417797B CN 105417797 B CN105417797 B CN 105417797B CN 201511007845 A CN201511007845 A CN 201511007845A CN 105417797 B CN105417797 B CN 105417797B
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- CN
- China
- Prior art keywords
- dechlorination
- chlorine
- filtrate
- ammonium sulfate
- desulfurization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- 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
-
- 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
- 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
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
Abstract
The application is related to a kind of method of desulfurization slurry dechlorination, belongs to coal-fired flue-gas process field.Furthermore, it is the removing to chlorion in sulphur ammonium limestone-based process flue gas desulfurization glue size, take and the mode being electrolysed after ammonium sulfate is supplemented to the dehydrated filtrate of desulfurated plaster, directly discharge hydrogen and chlorine, agitated kettle further discharges chlorine again, the filtered fluid of dechlorination sends absorption tower back to, so that chlorinity reduces in slurries.The beneficial effect of the application：(1) the direct dechlorination of non-slurries, but dechlorination is carried out to desulfurated plaster dehydration filtrate, avoid interference of the desulfurization intermediate product to dechlorination in desulfurization slurry.(2) directly to use electrolysis dechlorination after the ammonium sulfate concentrate filtrate of supplement, flow is simple.(3) chlorine not discharged in time in a cell promotes chlorine further to discharge under stirred tank high-speed stirred.(4) chloride ion content problem in control desulfurization slurry is satisfactorily resolved, reduces discharge of wastewater.
Description
Technical field
The invention belongs to boiler exhaust gas process field.The present invention relates to a kind of technique of desulfurization slurry dechlorination, more specifically
Say, the removing to chlorion in sulphur ammonium-limestone-based process flue gas desulfurization glue size, take and sulfuric acid is supplemented to the dehydrated filtrate of desulfurated plaster
The mode being electrolysed after ammonium, hydrogen and chlorine are directly discharged, then chlorine is further discharged through a stirred tank, the filtered fluid of dechlorination is sent back to
Absorption tower, so that chlorinity reduces in slurries.
Background technology
Chlorion has two main sources in desulfurization slurry：First, chloride in fire coal form chloride with flue gas by burning
Into desulfurizing tower, desulfurization slurry is entered under wet scrubbing；Second, being brought into process water, moisture evaporates in desulfurizing tower, chlorine from
Subproduct, which is tired out, to get off.
Research shows that the ＞ 1000mg/L in water have high polarity to promote corrosion reaction to chlorion for a long time, have very strong again
Penetrability, the diaphragm of metal surface is penetrated readily through, gap corrosion and pitting.In chemical industry, many austenite stainless
Steel equipment anti-chlorine ion corrosion poor-performing.And chloride ion content is more than 10000mg/ in current many power plant's wet desulphurization slurries
L, operation risk is very big, how to control chloride ion content ≯ 5000mg/L in desulfurization slurry, turns into the index of power plant's control chlorine.
The harm of chlorion is also mainly reflected in two aspects in slurries：When corrosion of the chlorion to desulfurization tower internals,
Particularly to strengthening gas-liquid contact in tower after environmental requirement minimum discharge or improving the increased moving components such as demisting efficiency
Corrosion；Second, increasing desulfurated plaster chloride ion content, the value of by-product is influenceed.
Some enterprises of power plant, for the safe for operation of equipment and the problem of outlet of reply desulfurated plaster, conscious control takes off
Chloride ion content in sulphur slurries, but the method controlled is to take water-reducible mode, that is, takes the mode of increase waste discharge.This
Kind waste water is containing heavy metals such as mercury, and the pollution to environment is very serious.Therefore, the flue gas desulfurization waste-water that should keep under strict control discharges, then
The problem of how controlling chloride ion content, i.e. dechlorination in desulfurization slurry is urgently to be resolved hurrily.
The content of the invention
For harm existing for the accumulation of wet desulphurization slurry chlorion, a kind of technique of desulfurization slurry dechlorination is proposed, with
Reaching reduces chloride ion content in slurries, makes the safe operation of absorption tower internals and reduces the purpose of discharge of wastewater.
A kind of technique of desulfurization slurry dechlorination, is the removing to chlorion in sulphur ammonium-limestone-based process flue gas desulfurization glue size, adopts
Take and the mode being electrolysed after ammonium sulfate is supplemented to the dehydrated filtrate of desulfurated plaster, directly discharge hydrogen and chlorine, then agitated kettle
Chlorine is further discharged, the filtered fluid of dechlorination sends absorption tower back to, so that chlorinity reduces in slurries；
Comprise the following steps：
A, filtrate supplement ammonium sulfate
It is dissolved in the ammonium sulfate of supplement in filtrate, obtains the ammonium sulfate of 25~35% concentrates；
B, it is electrolysed dechlorination
Directly using the ammonium sulfate of concentrate as raw material, at a temperature of 30~60 DEG C, anode is made using Pt, Pb makees negative electrode,
Polytetrafluoroethylene (PTFE) cationic membrane is barrier film, and the APP additive of positive level addition 0.05%, electrolysis produces hydrogen and chlorine, point
Do not extract out；
Key reaction formula is as follows：
Anode reaction：2Cl-=Cl2+2e
Cathode reaction：2H++ 2e=H2
Cell reaction：2Cl-+2H+=Cl2+H2
C, the further release chlorine of high-speed stirred
The chloride filtrate not discharged in time in a cell, stirred in stirred tank high speed, liquid stream is transported along reactor wall
Dynamic, liquid layer thickness reduces, and promotes chlorine release, and the filtrate after dechlorination sends desulfuration absorbing tower back to so that in desulfurization slurry chlorine from
Sub- content reduces.
The present invention be embodied in it is following some：
(1) the direct dechlorination of non-slurries, but dechlorination is carried out to desulfurated plaster dehydration filtrate, strengthen dechlorination efficiency, avoid taking off
Interference of the desulfurization intermediate product to dechlorination in sulphur slurries.
(2) it is dissolved in the ammonium sulfate of supplement in desulfurated plaster dehydration filtrate, 25~35% solution is prepared, directly with this
Ammonium sulfate is raw material, discharges hydrogen and chlorine using electrolysis, reaches the purpose of dechlorination, technological process is simple.
(3) the chloride filtrate not discharged in time in a cell, stirred in stirred tank high speed, make liquid stream along reactor wall
Motion, liquid layer thickness reduce, and promote chlorine release.
(4) filtered fluid of dechlorination sends absorption tower back to, so that chlorinity reduces in slurries；Satisfactorily resolve control desulfurization slurry
Middle chloride ion content problem, reduce discharge of wastewater.
The specific implementation process of the present invention：
When chloride ion content is more than 5000mg/L in slurries, allow desulfurated plaster dehydration filtrate to pass through stirred tank, in kettle not
The disconnected ammonium sulfate for adding supplement, is directly electrolysed to chloride ion-containing filtrate after ammonium sulfate concentrate, discharges hydrogen and chlorine, uses
Vavuum pump is extracted out respectively, and the filtered fluid of dechlorination sends absorption tower back to, so that chlorinity reduces in slurries, maintains chlorine in desulfurization slurry
Ion concentration ≯ 5000mg/L.
Brief description of the drawings
Accompanying drawing 1 is the process flow diagram of inventive embodiments 1
Embodiment
Embodiment 1
Ammonium sulfate dissolution kettle 1 in Fig. 1, electrolytic cell 2, stirred tank 3；Filtrate A, ammonium sulfate B, hydrogen C, chlorine D, dechlorination filtrate
E。
When chloride ion content is 5000mg/L in slurries, filter is dissolved in the ammonium sulfate B of supplement in ammonium sulfate dissolution kettle 1
In liquid A, the ammonium sulfate of 25~35% concentrates is obtained；Directly using the ammonium sulfate of concentrate as raw material, in 30~60 DEG C of temperature
Under degree, anode is made using Pt, Pb makees negative electrode, and polytetrafluoroethylene (PTFE) cationic membrane is barrier film, the APP of positive level addition 0.05%
Additive, the electrolysis generation hydrogen C and chlorine D in electrolytic cell 2, extract out send post processing respectively；Not release in time in a cell
Chloride filtrate, the high speed of stirred tank 3 stir, liquid stream is moved along reactor wall, liquid layer thickness reduce, promote chlorine D release
Put dechlorination filtrate E chloride ion contents and be reduced to 1000mg/L and send absorption tower back to, so that chlorinity reduces in slurries.
Implementation result：Filtrate dechlorination rate >=80%.
The beneficial effects of the invention are as follows：(1) the direct dechlorination of non-slurries, but dechlorination is carried out to desulfurated plaster dehydration filtrate,
Avoid interference of the desulfurization intermediate product to dechlorination in desulfurization slurry.(2) it is electric directly to be used after the ammonium sulfate concentrate filtrate of supplement
Solution dechlorination, flow are simple.(3) chlorine not discharged in time in a cell promotes chlorine to enter under stirred tank high-speed stirred
One step discharges.(4) chloride ion content problem in control desulfurization slurry is satisfactorily resolved, reduces discharge of wastewater.
Claims (1)
1. a kind of technique of desulfurization slurry dechlorination, is the removing to chlorion in sulphur ammonium-limestone-based process flue gas desulfurization glue size, takes
The mode being electrolysed after ammonium sulfate is supplemented to the dehydrated filtrate of desulfurated plaster, directly discharges hydrogen and chlorine, then agitated kettle enters
One step discharges chlorine, and the filtered fluid of dechlorination sends absorption tower back to, so that chlorinity reduces in slurries；
Comprise the following steps：
A, filtrate supplement ammonium sulfate
It is dissolved in the ammonium sulfate of supplement in filtrate, obtains the ammonium sulfate of 25~35% (mass fraction) concentrates；
B, it is electrolysed dechlorination
Directly using the ammonium sulfate of concentrate as raw material, at a temperature of 30~60 DEG C, anode is made using Pt, Pb makees negative electrode, and poly- four
PVF cationic membrane is barrier film, and positive level adds the APP additive of 0.05% (mass fraction), electrolysis produce hydrogen with
Chlorine, extract out respectively；
C, the further release chlorine of high-speed stirred
The chloride filtrate not discharged in time in a cell, stirred in stirred tank high speed, liquid stream is moved along reactor wall, liquid
Thickness degree reduces, and promotes chlorine release, the filtrate after dechlorination sends desulfuration absorbing tower back to, so that chloride ion content in desulfurization slurry
Reduce.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511007845.4A CN105417797B (en) | 2015-12-28 | 2015-12-28 | A kind of technique of desulfurization slurry dechlorination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511007845.4A CN105417797B (en) | 2015-12-28 | 2015-12-28 | A kind of technique of desulfurization slurry dechlorination |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105417797A CN105417797A (en) | 2016-03-23 |
| CN105417797B true CN105417797B (en) | 2017-11-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511007845.4A Active CN105417797B (en) | 2015-12-28 | 2015-12-28 | A kind of technique of desulfurization slurry dechlorination |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1233585A (en) * | 1998-03-30 | 1999-11-03 | 三菱瓦斯化学株式会社 | Process for producing persulfate |
| JP2000317262A (en) * | 1999-05-17 | 2000-11-21 | Mitsubishi Heavy Ind Ltd | Treatment of flue gas desulfurized waste water |
-
2015
- 2015-12-28 CN CN201511007845.4A patent/CN105417797B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1233585A (en) * | 1998-03-30 | 1999-11-03 | 三菱瓦斯化学株式会社 | Process for producing persulfate |
| JP2000317262A (en) * | 1999-05-17 | 2000-11-21 | Mitsubishi Heavy Ind Ltd | Treatment of flue gas desulfurized waste water |
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| Publication number | Publication date |
|---|---|
| CN105417797A (en) | 2016-03-23 |
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