CN106512699B - A kind of ethylenediamine is used for flue gas desulfurizing and hydrargyrum-removing processing method - Google Patents
A kind of ethylenediamine is used for flue gas desulfurizing and hydrargyrum-removing processing method Download PDFInfo
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- CN106512699B CN106512699B CN201611193673.9A CN201611193673A CN106512699B CN 106512699 B CN106512699 B CN 106512699B CN 201611193673 A CN201611193673 A CN 201611193673A CN 106512699 B CN106512699 B CN 106512699B
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- flue gas
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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
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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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
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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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- 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
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
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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 present invention relates to desulfuration demercuration technical fields, especially a kind of ethylenediamine is used for flue gas desulfurizing and hydrargyrum-removing processing method, after pyrolusite is prepared into powder, and water is added to be prepared into slurry, it is added in slurry using ethylenediamine, ultrasonication, so that manganese dioxide active constituent improves in pyrolusite, so that being the sulfur dioxide in flue gas, when Elemental Mercury contacts, quickly react, so that sulfur dioxide is oxidized to sulfuric acid, Elemental Mercury is oxidized to ionic mercury, realize sulfureous in flue gas, the removing of mercury ingredient, improve the sulphur in flue gas, the removal efficiency of mercury ingredient, so that reaching 90% or more.
Description
Technical field
The present invention relates to desulfuration demercuration technical field, especially a kind of ethylenediamine is used for flue gas desulfurizing and hydrargyrum-removing processing method.
Background technique
Currently, position is at the forefront in the world for the discharge capacity of China's sulfur dioxide, become the third-largest Acid Rain Zone in the whole world, every year by
It is gradually increased to the acid rain extent of injury, has reached hundred billion yuan or more, for the source of sulfur dioxide, mainly sintering flue gas, and
And in most sintering flue gas, the process of acid rain also is formed so that sulfur dioxide is getting into the air containing mercury ingredient,
Mercury ingredient also enters in environment, and mercury is the virose heavy metal component of tool, after entering in environment with rainwater, be easy into
Enter organism, is converted to methyl mercury in vivo, and methyl mercury can significantly influence the metabolism of organism, cause
The threat that the health of organism is subject to.
Therefore, desulfurization is carried out for sintering flue gas, demercuration is processed into for necessity；It is most of both at home and abroad to go back for desulfurization
It is based on wet desulphurization, it is all generally to use limestone-gypsum method and sodium alkali etc. that wet desulphurization, which occupies 85% or more,
These methods are not only invested and operating cost is high, in sweetening process, are easy fouling blockage equipment, and the byproduct valence after desulfurization
Lattice are low, and waste residue application value is little, be easy to cause secondary pollution；For this purpose, for desulfurization technology gradually appeared semidry method and
Dry desulfurizing process.For demercuration, demercuration before burning is related generally to, demercuration after demercuration and burning in burning, in these three ranks
The non-cleaner demercuration of technology, the adsorbent demercuration, catalysis oxidation demercuration, wet flue gas desulfurizer that the demercuration of section relates generally to
Demercuration, solution absorption method demercuration, still, for demercuration in flue gas, technology is all also in undesirable state.According to statistics, when
The preceding technology for being applied to industrialization desulfuration demercuration, the removal efficiency removed simultaneously to sulphur and mercury is lower, most of to maintain 80%
Left and right causes the sulphur for also still having the overwhelming majority in flue gas, the discharge of mercury ingredient, causes the pollution of environment.
Ethylenediamine is colourless or yellowish oily or watery liquid, there is the smell of similar ammonia.In strong basicity, have centainly
Corrosivity.
Summary of the invention
In order to solve the above technical problems existing in the prior art, the present invention provides a kind of ethylenediamine for flue gas desulfurization
Demercuration processing method.
It is achieved particular by following technical scheme:
A kind of ethylenediamine is used for flue gas desulfurizing and hydrargyrum-removing processing method, takes pyrolusite to be prepared into powder, and powder is added water system
It is standby to be mixed at slurry, then by the slurry with ethylenediamine according to mass ratio for 1-7:0.01-0.05, use ultrasonic frequency for 20-
40Hz handles 20-30min and obtains liquid sulfur and mercury removing agent after adjustment liquid-solid ratio is 6-9:1；And by the liquid sulfur and mercury removing agent
In spray absorber, sulfur-bearing, mercury flue gas are passed through according to flow velocity for 7-9L/min, so that flue gas and liquid sulfur and mercury removing agent exist
Haptoreaction in spray absorber.
The slurry, liquid-solid ratio 2-4:1.
The pyrolusite is after microwave radiation processing, is crushed, is ground, and 30-80 mesh is crossed.
The microwave radiation, radiant power 80-130W, radiated time 30-50min.
The sulfur-bearing, mercury flue gas, temperature are 80-140 DEG C.
The pyrolusite, after being prepared into powder, being also added thereto has the cupric oxide powder for accounting for pyrolusite quality 3-8%
End, and adjusting temperature is that 120-180 DEG C of processing 3-7min is added water after mixing evenly and be prepared into slurry.
The water, wherein containing mass concentration be 4-8% lithium hydroxide and/or mass concentration be 1-3% Gao Meng
Sour potassium.
Compared with prior art, the technical effect of the invention is embodied in:
After pyrolusite is prepared into powder, and water is added to be prepared into slurry, is added in slurry using ethylenediamine, ultrasonic wave
Processing, so that manganese dioxide active constituent improves in pyrolusite, when so that being the sulfur dioxide in flue gas, Elemental Mercury contact,
Quickly react so that sulfur dioxide is oxidized to sulfuric acid, Elemental Mercury is oxidized to ionic mercury, realize sulfureous in flue gas, mercury at
Point removing, improve flue gas in sulphur, mercury ingredient removal efficiency so that reaching 90% or more.
Specific embodiment
It is limited below with reference to specific embodiment technical solution of the present invention is further, but claimed
Range is not only limited to made description.
In certain embodiments, ethylenediamine is used for flue gas desulfurizing and hydrargyrum-removing processing method, takes pyrolusite to be prepared into powder, and will
Powder adds water to be prepared into slurry, then the slurry is mixed with ethylenediamine according to mass ratio for 1-7:0.01-0.05, using ultrasonic wave
Frequency is that 20-40Hz handles 20-30min, adjusts liquid-solid ratio to obtain liquid sulfur and mercury removing agent after 6-9:1；And the liquid is taken off
Sulphur mercury removal agent is passed through in spray absorber, by sulfur-bearing, mercury flue gas according to flow velocity for 7-9L/min, so that flue gas and liquid desulfurization
Mercury removal agent haptoreaction in spray absorber.
In certain embodiments, the slurry, liquid-solid ratio 2-4:1.Suitable liquid-solid ratio facilitates at ultrasonic wave
Extent of cavitation during reason improves pyrolusite and the mutual effect degree of ethylenediamine, improve activity in pyrolusite at
Point, improve desulfuration demercuration removal efficiency.
In certain embodiments, the pyrolusite is after microwave radiation processing, is crushed, is ground, and 30-80 is crossed
Mesh.The activation that microwave radiation enables to the manganese dioxide in pyrolusite preparatory improves pyrolusite removing sulphur, mercury ingredient effect
Rate.
In certain embodiments, the microwave radiation, radiant power 80-130W, radiated time 30-50min.
The processing of suitable microwave irradiation power and radiated time, can not only avoid energy consumption excessively high, and enable to soft manganese
The preactivated processing of manganese dioxide in mine enhances, so that can largely change subsequent with ethylenediamine mechanism
Kind activation grade, improves removal efficiency.
In certain embodiments, the sulfur-bearing, mercury flue gas, temperature are 80-140 DEG C.So that subtractive process is suitable
It is acted under the conditions of temperature, improves the activity of sulfur and mercury removing agent, be conducive to improve removal efficiency.
In certain embodiments, the pyrolusite is also added thereto after being prepared into powder and accounts for pyrolusite quality
The cupric oxide powder of 3-8%, and adjusting temperature is that 120-180 DEG C of processing 3-7min adds water preparation and be slurried after mixing evenly
Material.Copper oxide can be realized manganese dioxide desulfurization in pyrolusite, the precision of demercuration improves, and be conducive to improve removal efficiency.
In certain embodiments, the water, wherein dense containing the lithium hydroxide and/or quality that mass concentration is 4-8%
Degree is the potassium permanganate of 1-3%.
Embodiment 1
Ethylenediamine is used for flue gas desulfurizing and hydrargyrum-removing processing method, takes pyrolusite to be prepared into powder, and add water to be prepared into powder
Slurry, liquid-solid ratio 2:1, then by the slurry and ethylenediamine according to mass ratio be that 1-7:0.01 is mixed, use ultrasonic frequency for
20Hz handles 20min and obtains liquid sulfur and mercury removing agent after adjustment liquid-solid ratio is 6:1；And the liquid sulfur and mercury removing agent is being sprayed
It is 80 DEG C of sulfur-bearings, mercury flue gas by temperature is that 7L/min is passed through according to flow velocity in absorption tower, so that flue gas and liquid sulfur and mercury removing agent
The haptoreaction in spray absorber.
The removal efficiency of sulfureous in flue gas, mercury ingredient, sulfur removal rate 94.6% are detected, mercury removal rate is 90.3%.
Embodiment 2
Ethylenediamine is used for flue gas desulfurizing and hydrargyrum-removing processing method, takes pyrolusite, the microwave for being 80W by radiant power, radiation
After handling 30min, is crushed, ground, 30 meshes of mistake, and add water to be prepared into slurry in powder, liquid-solid ratio 4:1, then should
Slurry is that 7:0.05 is mixed according to mass ratio with ethylenediamine, uses ultrasonic frequency to handle 30min for 40Hz, adjustment liquid-solid ratio is
After 9:1, liquid sulfur and mercury removing agent is obtained；And by the liquid sulfur and mercury removing agent in spray absorber, temperature is 140 DEG C and is contained
Sulphur, mercury flue gas are passed through according to flow velocity for 9L/min, so that flue gas and liquid sulfur and mercury removing agent haptoreaction in spray absorber,
?.
The removal efficiency of sulfureous in flue gas, mercury ingredient, sulfur removal rate 96.7% are detected, mercury removal rate is 95.8%.
Embodiment 3
Ethylenediamine is used for flue gas desulfurizing and hydrargyrum-removing processing method, takes at the microwave radiation that pyrolusite is 130W by radiant power
After managing 50min, is crushed, ground, 80 meshes of mistake, and add water to be prepared into slurry in powder, liquid-solid ratio 3:1, then by the slurry
Material is that 5:0.03 is mixed according to mass ratio with ethylenediamine, uses ultrasonic frequency to handle 25min for 30Hz, adjustment liquid-solid ratio is 7:
After 1, liquid sulfur and mercury removing agent is obtained；And by the liquid sulfur and mercury removing agent in spray absorber, by temperature be 100 DEG C of sulfur-bearings,
Mercury flue gas is passed through according to flow velocity for 8L/min, so that flue gas and liquid sulfur and mercury removing agent haptoreaction in spray absorber, i.e.,
It can.
The removal efficiency of sulfureous in flue gas, mercury ingredient, sulfur removal rate 93.5% are detected, mercury removal rate is 95.6%.
Embodiment 4
Ethylenediamine is used for flue gas desulfurizing and hydrargyrum-removing processing method, takes at the microwave radiation that pyrolusite is 90W by radiant power
It after managing 40min, crushed, ground, cross 70 meshes, the cupric oxide powder for accounting for pyrolusite quality 3% is added, and adjust temperature and be
120 DEG C of processing 3min add water to be prepared into slurry after mixing evenly, liquid-solid ratio 2.5:1, then by the slurry and ethylenediamine according to
Mass ratio is 6:0.01 mixing, uses ultrasonic frequency to handle 30min for 20Hz and it is de- to obtain liquid after adjustment liquid-solid ratio is 7:1
Sulphur mercury removal agent；It is 120 DEG C of sulfur-bearings, mercury flue gas according to flow velocity by temperature and by the liquid sulfur and mercury removing agent in spray absorber
It is passed through for 7L/min, so that flue gas and liquid sulfur and mercury removing agent haptoreaction in spray absorber.
The removal efficiency of sulfureous in flue gas, mercury ingredient, sulfur removal rate 96.4% are detected, mercury removal rate is 96.7%.
Embodiment 5
Ethylenediamine is used for flue gas desulfurizing and hydrargyrum-removing processing method, takes at the microwave radiation that pyrolusite is 110W by radiant power
It after managing 39min, crushed, ground, cross 78 meshes, the cupric oxide powder for accounting for pyrolusite quality 8% is added, and adjust temperature and be
160 DEG C of processing 5min add water to be prepared into slurry after mixing evenly, liquid-solid ratio 3.5:1, containing mass concentration are 7% in water
Lithium hydroxide, then the slurry is mixed with ethylenediamine according to mass ratio for 5:0.04, use ultrasonic frequency for 40Hz processing
20min obtains liquid sulfur and mercury removing agent after adjustment liquid-solid ratio is 9:1；And by the liquid sulfur and mercury removing agent in spray absorber
In, it be 80 DEG C of sulfur-bearings, mercury flue gas by temperature according to flow velocity is that 9L/min is passed through, so that flue gas is being sprayed with liquid sulfur and mercury removing agent
Haptoreaction in absorption tower.
The removal efficiency of sulfureous in flue gas, mercury ingredient, sulfur removal rate 97.8% are detected, mercury removal rate is 95.9%.
Claims (5)
1. a kind of ethylenediamine is used for flue gas desulfurizing and hydrargyrum-removing processing method, which is characterized in that take pyrolusite to be prepared into powder, and by powder
End plus water are prepared into slurry, then the slurry is mixed with ethylenediamine according to mass ratio for 1-7:0.01-0.05, using ultrasonic wave frequency
Rate is that 20-40Hz handles 20-30min, adjusts liquid-solid ratio to obtain liquid sulfur and mercury removing agent after 6-9:1；And by the liquid desulfurization
Mercury removal agent is passed through in spray absorber, by sulfur-bearing, mercury flue gas according to flow velocity for 7-9L/min, so that flue gas and liquid desulfurization are de-
Mercurial haptoreaction in spray absorber；
The pyrolusite, after being prepared into powder, being also added thereto has the cupric oxide powder for accounting for pyrolusite quality 3-8%,
And adjusting temperature is that 120-180 DEG C of processing 3-7min is added water after mixing evenly and be prepared into slurry；
The water, wherein containing mass concentration be 4-8% lithium hydroxide and/or mass concentration be 1-3% permanganic acid
Potassium.
2. ethylenediamine as described in claim 1 is used for flue gas desulfurizing and hydrargyrum-removing processing method, which is characterized in that the slurry,
Its liquid-solid ratio is 2-4:1.
3. ethylenediamine as described in claim 1 is used for flue gas desulfurizing and hydrargyrum-removing processing method, which is characterized in that the soft manganese
Mine is after microwave radiation processing, is crushed, is ground, and 30-80 mesh is crossed.
4. ethylenediamine as claimed in claim 3 is used for flue gas desulfurizing and hydrargyrum-removing processing method, which is characterized in that the microwave
Radiation, radiant power 80-130W, radiated time 30-50min.
5. ethylenediamine as described in claim 1 is used for flue gas desulfurizing and hydrargyrum-removing processing method, which is characterized in that the sulfur-bearing,
Mercury flue gas, temperature are 80-140 DEG C.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253847A (en) * | 1998-11-13 | 2000-05-24 | 中国石油化工集团公司 | Desulfurizer for refining gas and its preparation method |
| CN1883764A (en) * | 2006-05-23 | 2006-12-27 | 北京科技大学 | Method for removing sulfur dioxide from flue gas |
| EP2268399A2 (en) * | 2008-04-11 | 2011-01-05 | ExxonMobil Research and Engineering Company | Regeneration and rejuvenation of supported hydroprocessing catalysts |
| CN102179147A (en) * | 2011-03-07 | 2011-09-14 | 中国恩菲工程技术有限公司 | Polymer organic amine desulfurizer |
| CN102755828A (en) * | 2012-08-06 | 2012-10-31 | 北京世能中晶能源科技有限公司 | Desulfurizer composite and application thereof |
| CN205586806U (en) * | 2016-05-12 | 2016-09-21 | 南京凯盛国际工程有限公司 | Cement kiln flue gas desulfurization simultaneously demercuration system |
-
2016
- 2016-12-21 CN CN201611193673.9A patent/CN106512699B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253847A (en) * | 1998-11-13 | 2000-05-24 | 中国石油化工集团公司 | Desulfurizer for refining gas and its preparation method |
| CN1883764A (en) * | 2006-05-23 | 2006-12-27 | 北京科技大学 | Method for removing sulfur dioxide from flue gas |
| EP2268399A2 (en) * | 2008-04-11 | 2011-01-05 | ExxonMobil Research and Engineering Company | Regeneration and rejuvenation of supported hydroprocessing catalysts |
| CN102179147A (en) * | 2011-03-07 | 2011-09-14 | 中国恩菲工程技术有限公司 | Polymer organic amine desulfurizer |
| CN102755828A (en) * | 2012-08-06 | 2012-10-31 | 北京世能中晶能源科技有限公司 | Desulfurizer composite and application thereof |
| CN205586806U (en) * | 2016-05-12 | 2016-09-21 | 南京凯盛国际工程有限公司 | Cement kiln flue gas desulfurization simultaneously demercuration system |
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