CN106582244A - Method for removing sulfur and mercury in mercury-containing and sulfur-containing smoke with wet process - Google Patents
Method for removing sulfur and mercury in mercury-containing and sulfur-containing smoke with wet process Download PDFInfo
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- CN106582244A CN106582244A CN201611192723.1A CN201611192723A CN106582244A CN 106582244 A CN106582244 A CN 106582244A CN 201611192723 A CN201611192723 A CN 201611192723A CN 106582244 A CN106582244 A CN 106582244A
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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
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
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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 relates to the technical field of wet-process purification of smoke, in particular to a method for removing sulfur and mercury in mercury-containing and sulfur-containing smoke with a wet process. Ore pulp prepared from pyrolusite is put in a reaction tank, mercury-containing and sulfur-containing smoke is sprayed into the reaction tank for a reaction, the action time is controlled to last for 10-20 min, the sulfur and mercury components in the smoke are massively and effectively removed, the removal rate of the sulfur and mercury components reaches 80% or higher, and the content of sulfur and mercury in the smoke is effectively reduced; the cost of the treatment process is low, raw materials are easy to obtain, the cost for treating the mercury-containing and sulfur-containing smoke through pyrolusite is greatly reduced, and emission of the sulfur and mercury components in the smoke is reduced.
Description
Technical field
The present invention relates to flue gas wet purification technology field, especially a kind of wet method remove in mercurous, sulfur-containing smoke gas sulphur and
The method of mercury.
Background technology
At present, position is at the forefront in the world for the discharge capacity of China's sulfur dioxide, becomes global the third-largest Acid Rain Zone, receives every year
Gradually increase to the acid rain extent of injury, reached more than hundred billion yuan, for the source of sulfur dioxide, mainly sinter flue gas, and
And in most sintering flue gas, also containing mercury composition so that sulfur dioxide is getting into the air, and forms the process of acid rain,
During mercury composition is also into environment, and mercury is the virose heavy metal component of tool, after it is entered in environment with rainwater, is easily entered
Enter organism, methyl mercury is changed in vivo, and methyl mercury can significantly affect the metabolism of organism, cause
What the health of organism was subject to threatens.
Therefore, it is processed into for necessity for sintering flue gas carries out desulfurization, demercuration；For desulfurization, both at home and abroad great majority are gone back
It is that based on desulfurization in a wet process, wet desulphurization occupies more than 85%, is all generally to adopt limestone-gypsum method and sodium alkali etc.,
These methods not only invest high with operating cost, in sweetening process, easy fouling and clogging equipment, and the byproduct valency after desulfurization
Lattice are low, and waste residue using value less, easily causes secondary pollution；For this purpose, for desulfurization technology engendered semidry method and
Dry desulfurizing process.For demercuration, related generally to burning before demercuration, burning in demercuration and burning after demercuration, in these three ranks
The non-cleaner demercuration of technology, adsorbent demercuration, catalysis oxidation demercuration, wet flue gas desulfurizer that the demercuration of section is related generally to
Demercuration, solution absorption method demercuration, but, for demercuration in flue gas, its technology all also in undesirable state, and in industry
On, all it is using charcoal absorption demercuration mostly so that the discharge of mercury is controlled effectively, but because the price of activated carbon is held high
It is expensive so that substantial amounts of use activated carbon demercuration is relatively costly；And, for flue gas desulfurizing and hydrargyrum-removing, great majority are all to carry out individually
Detached removing, and it is also relatively fewer for the investigative technique that flue gas desulfurizing and hydrargyrum-removing is carried out disposable combination removing, but also have
A small amount of document occurs, and such as Patent No. ZL03135926 carries out desulfurization process using pyrolusite and manganese spar, and manages in this place
During, it uses wet desulphurization, undesirable for demercuration effect, but it substantially there is also the oxidation to mercury composition and takes off
Remove；For another example number of patent application be 201610149557 employing middle-low grade pyrolusite carry out flue gas desulfuration demercuration process, should
Method mainly uses desulfuration demercuration in dry method fixed bed reactors and processes；In addition, more also for desulfuration demercuration mistake
The research of the sulfur and mercury removing agent adopted in journey, but, these sulfur and mercury removing agents are not that desulfuration demercuration efficiency is undesirable, are exactly raw material
It is difficult to obtain, relatively costly, such as the sulfur and mercury removing agent of Patent No. 200810118580, it adopts magnetic iron oxide and produces for self-control
Product, and this product prepare difficulty it is larger so that market acquiring way is less, cause its preparation cost, application cost compared with
It is high；For another example number of patent application is 201410026774 desulfurization denitration demercuration agent, and it is undesirable for the removal efficiency of desulfuration demercuration.
The content of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention provides a kind of wet method and removes mercurous, sulfur-bearing
The method of sulfureous in flue gas and mercury.
It is achieved particular by technical scheme below：
A kind of method that wet method removes sulphur and mercury in mercurous, sulfur-containing smoke gas, by pyrolusite powder powder is broken into, and is added water and is prepared into
Ore pulp, in being fitted into reactive tank；By mercurous, sulfur-containing smoke gas temperature controls at 80-180 DEG C, from reactive tank in the way of spraying
Entrance is entered and sprayed in ore pulp, and spray site is located at the position of reactive tank and enables to mercurous, sulfur-containing smoke gas and the ore deposit in reactive tank
Slurry time of contact reaches 10-20min, the outlet drain arranged by reactive tank top with the flue gas after ore pulp contact action.Adopt
With pyrolusite ore pulp is fixed in reactive tank, and sprayed in reactive tank using injecting type through mercurous, sulfur-containing smoke gas so that anti-
Answer the ore pulp in groove to flow so that ore pulp realizes circulating contact flue gas, realize the desulfuration demercuration to flue gas, and in this process
In so that ore pulp increases with the contact area of flue gas so that desulfuration demercuration efficiency is improved, relatively conventional employing ore pulp spray
Drench or using fixed bed bed process flue gas for, its can effectively avoid ore pulp spray during produce steam cause with
Smoke contacts are insufficient, and ore pulp is difficult to recycle.The present invention in processing procedure, by controlling reactive tank in slip
PH value >=3.5, you can realize that the sulphur composition removal efficiency in flue gas reaches more than 90%.
Described pyrolusite powder is crossed during ore pulp is prepared into using microwave radiation processing；Or preparing
After ore pulp, crossed using microwave radiation processing.
Described microwave irradiation time is 10-20min, and microwave irradiation power is 100-300W.
Described ore pulp, liquid-solid ratio is 2-3.8:1.
Described mercurous, sulfur-containing smoke gas, it is sprayed in reactive tank, is 10-15L/min in the flow velocity of spray site.
Described ore pulp, wherein be additionally added and accounting for the phosphoric acid of pyrolusite quality 10-20% and accounting for pyrolusite quality 5-8%
Urea.Added using phosphoric acid and urea, its temperature for passing through flue gas is in the range of 80-180 DEG C so that the temperature in ore pulp
Gradually rise so that phosphoric acid and urea in ore pulp, as exhaust gas volumn is gradually passed through, the continuous rising of slurry temperature so that phosphorus
The urea phosphate that acid is formed with urea recurring structure alienation in the excessive environment of phosphoric acid, forms the ion with chelating function, should
The structural formula of ion is as follows：
In the effect of the above-mentioned ion, the mercury ion entered in flue gas is chelated, while acting on sulfate radical, formed
Sulfate, realization is significantly removed mercury ion and sulphur composition, and in pyrolusite in the presence of manganese dioxide, energy
Enough promote the sulfur dioxide in flue gas, molecule mercury to be constantly transformed into sulfate radical and ionic mercury, improve to sulfur dioxide in flue gas,
The removing of mercury, reduces environmental pollution.
And the procurement cost of above-mentioned phosphoric acid and urea is relatively low so that for flue gas demercuration desulfurization process cost compared with
It is low.
Described phosphoric acid, is substituted using phosphorus ore, and is added in terms of phosphorus pentoxide.Directly substituted using phosphorus ore, can not only
Enough so that the cost of desulfuration demercuration is more reduced, and contain part calcium constituent in phosphorus ore, the calcium constituent can be made with sulfate radical
With, increase pH value, improve the removal efficiency to sulphur composition.
Described method, the pH of the reaction slurry being additionally included in reactive tank is reduced to≤4.2 after, using manganese spar plus
Enter, adjust pH value for neutrality.
Described manganese spar is the powder that 50-80 mesh is ground to form through microwave radiation processing 10-20min.
The researcher of the invention is in order to proving the technique effect of the invention, the technology to the invention
Scheme is specifically made that following experimental study during realization：
Test row 1：
By pyrolusite 150g, powder is ground into, adds water and be configured to ore pulp, in being fitted into reactive tank, controlling the solid mass ratio of liquid is
2:1, the ore pulp import and the sealing of reaction slurry outlet that add ore pulp are closed, using injection apparatus, injection apparatus is stretched into instead
In answering groove, mercurous, sulfur-containing smoke gas are sprayed into, and detect sulfur content, the mercury content sprayed in front sulfur-bearing, mercury fume, and will spray
Exit point is chosen at the oral area of reactive tank flue gas injection inlet port and is sprayed, and jet velocity is 10L/min so that flue gas is entered
Afterwards, 5min just has flue gas to emit from floss hole, and detect the sulfur content in the flue gas that reactive tank floss hole is emitted and
Mercury content, its result is：Sulfur content in the flue gas that floss hole is emitted accounts for the sulfureous in flue gas that flue gas injection inlet port goes out and contains
The 13.45% of amount, the mercury content in the flue gas that floss hole is emitted accounts for the mercury in flue gas content that flue gas injection inlet port goes out
23.7%.
Test row 2：
By the position of spray site to flue gas injection inlet port position to bottom offset so that flue gas is entered after reactive tank, 15min
Just have afterwards flue gas from floss hole out,, according to test row 1, its result is for other：：Sulphur in the flue gas that floss hole is emitted
Content accounts for the 9.15% of the sulfureous in flue gas content that flue gas injection inlet port goes out, and the mercury content in the flue gas that floss hole is emitted is accounted for
The 13.57% of the mercury in flue gas content that flue gas injection inlet port goes out.
Test row 3：
By the position of spray site to flue gas injection inlet port position to bottom offset so that flue gas is entered after reactive tank, 10min
Just have afterwards flue gas from floss hole out,, according to test row 1, its result is for other：Sulphur in the flue gas that floss hole is emitted
Content accounts for the 9.13% of the sulfureous in flue gas content that flue gas injection inlet port goes out, and the mercury content in the flue gas that floss hole is emitted is accounted for
The 12.15% of the mercury in flue gas content that flue gas injection inlet port goes out.
Test row 4：
By the position of spray site to flue gas injection inlet port position to bottom offset so that flue gas is entered after reactive tank, 9min
Just have afterwards flue gas from floss hole out,, according to test row 1, its result is for other：Sulphur in the flue gas that floss hole is emitted
Content accounts for the 12.79% of the sulfureous in flue gas content that flue gas injection inlet port goes out, the mercury content in the flue gas that floss hole is emitted
Account for the 22.16% of the mercury in flue gas content that flue gas injection inlet port goes out.
Test row 5：
By the position of spray site to flue gas injection inlet port position to bottom offset so that flue gas is entered after reactive tank, 20min
Just have afterwards flue gas from floss hole out,, according to test row 1, its result is for other：：Sulphur in the flue gas that floss hole is emitted
Content accounts for the 8.78% of the sulfureous in flue gas content that flue gas injection inlet port goes out, and the mercury content in the flue gas that floss hole is emitted is accounted for
The 11.46% of the mercury in flue gas content that flue gas injection inlet port goes out.
Test row 6：
By the position of spray site to flue gas injection inlet port position to bottom offset so that flue gas is entered after reactive tank, 25min
Just have afterwards flue gas from floss hole out,, according to test row 1, its result is for other：Sulphur in the flue gas that floss hole is emitted
Content accounts for the 9.11% of the sulfureous in flue gas content that flue gas injection inlet port goes out, and the mercury content in the flue gas that floss hole is emitted is accounted for
The 12.89% of the mercury in flue gas content that flue gas injection inlet port goes out.
Test row 7：
By the position of spray site to flue gas injection inlet port position to bottom offset so that flue gas is entered after reactive tank, 21min
Just have afterwards flue gas from floss hole out,, according to test row 1, its result is for other：Sulphur in the flue gas that floss hole is emitted
Content accounts for the 8.91% of the sulfureous in flue gas content that flue gas injection inlet port goes out, and the mercury content in the flue gas that floss hole is emitted is accounted for
The 11.43% of the mercury in flue gas content that flue gas injection inlet port goes out.
Test row 8：
Pyrolusite is prepared into into ore pulp according to test row 1, and is passed directly into by sulfur-bearing, containing mercury gas, it is steady to enter reaction
In groove, and the time acted in reactive tank is 20min, and the mode of operation according to test row 1 carries out detection removal effect, ties
Fruit is shown as：Flue gas sulfur content is relative in floss hole enters before reactive tank, and its content has reached 65.1%；Mercury content is relative to be entered
Before reactive tank, 78.35% has been reached.
Show from the result of test row 1-8 and can be seen that for injecting type processing gas are contacted with the ore pulp for standing, can
So that ore pulp rolling, promotes sulfur dioxide, the mercury composition in ore pulp catalysis oxidation flue gas, and realize taking off mercury, sulfur dioxide
Remove, and for relatively complete stationary contact, it can significantly reduce sulphur, mercury content, reduce fume emission to environment
Pollution.
Further, prepare with ore pulp before the researcher of the invention has passed through to prepare ore pulp in processing procedure, also
During microwave radiation processing test, specifically carried out test row 9, test row 10, it is as follows：
Test row 9：
According to test row 1, pyrolusite is first adopted microwave radiation processing, microwave irradiation power is 200W, during microwave
Between be 15min, after radiation treatment, by its according to test row 1 be prepared into ore pulp, according to test the processing mode of row 1 carry out it is mercurous, contain
Sulphur fume treatment, detects its desulfurization, demercuration efficiency, and the sulfur content in the flue gas for as a result emitting for floss hole accounts for flue gas injection
The 7.5% of the sulfureous in flue gas content that inlet port goes out, the mercury content in the flue gas that floss hole is emitted accounts for flue gas injection inlet port
The 8.91% of the mercury in flue gas content for going out.
Test row 10
According to test row 1, pyrolusite is crushed and is prepared into after ore pulp, adopted microwave 200W, radiation treatment 15min,
And the ore pulp is used in reactive tank, the process of sulfur-bearing, mercury fume is carried out according to test row 1, its result is floss hole discharge
The sulfur content in flue gas out accounts for the 9.27% of the sulfureous in flue gas content that flue gas injection inlet port goes out, what floss hole was emitted
Mercury content in flue gas accounts for the 11.98% of the mercury in flue gas content that flue gas injection inlet port goes out.
By test row 1, test row 9, test row 10, can significantly learn, for microwave radiation processing, can be effective
Improve ore pulp to the sulphur in sulfur-bearing, mercury fume, mercury removal rate so that more than 90% sulphur composition is removed, more than 87%
Mercury composition removed, the sulfur content reduced in flue gas of high degree and mercury content.
During test process, it is also by the addition of some additives for this researcher so that desulfurization, demercuration efficiency
It is improved, the test specifically done is test row 11, test row 12, test row 13：
Test row 11：
According to test row 1, pyrolusite powder is prepared into into ore pulp, and the phosphorus for accounting for pyrolusite powder quality 10% is added in ore pulp
Acid, in being added into reactive tank, according to the processing mode of test row 1 process of sulfur-bearing, mercury fume is carried out, and it is processed
As a result detected, the sulfur content in the flue gas for as a result emitting for floss hole accounts for the sulfureous in flue gas that flue gas injection inlet port goes out
The 15.1% of content, the mercury content in the flue gas that floss hole is emitted accounts for the mercury in flue gas content that flue gas injection inlet port goes out
20.57%.
Test row 12
According to test row 1, pyrolusite powder is prepared into into ore pulp, and the phosphorus for accounting for pyrolusite powder quality 10% is added in ore pulp
Acid and the urea for accounting for pyrolusite powder quality 8%, in being added into reactive tank, carry out sulfur-bearing, contain according to the processing mode of test row 1
The process of mercury flue gas, and the result that it is processed is detected, the sulfur content in the flue gas for as a result emitting for floss hole is accounted for
The 0.35% of the sulfureous in flue gas content that flue gas injection inlet port goes out, the mercury content in the flue gas that floss hole is emitted accounts for flue gas spray
Inject the 1.37% of the mercury in flue gas content that entrance goes out.
Test row 13
According to test row 1, pyrolusite powder is prepared into into ore pulp, and the urine for accounting for pyrolusite powder quality 8% is added in ore pulp
Element, in being added into reactive tank, according to the processing mode of test row 1 process of sulfur-bearing, mercury fume is carried out, and it is processed
As a result detected, the sulfur content in the flue gas for as a result emitting for floss hole accounts for the sulfureous in flue gas that flue gas injection inlet port goes out
The 14.57% of content, the mercury content in the flue gas that floss hole is emitted accounts for the mercury in flue gas content that flue gas injection inlet port goes out
22.18%.
The invention by being prepared into pyrolusite after ore pulp, in being placed on reactive tank, by spraying sulfur-bearing, mercurous
The mode of flue gas sprays into flue gas reacts, and the control action time is 10-20min, effectively causes the sulphur in flue gas, mercury into getting
Substantial amounts of removing is arrived so that the removal efficiency of sulphur mercury composition has reached more than 80%, has effectively reduced discharge sulfureous in flue gas, mercury and contain
Amount；And the cost of processing procedure is relatively low, raw material is easy to get, and reducing for high degree processes sulfur-bearing, mercurous cigarette using pyrolusite
The cost of gas, reduces sulfureous in flue gas, the discharge capacity of mercury composition.
Description of the drawings
Fig. 1 is the structural representation of the reactive tank adopted in the invention.
1- floss hole 2- cell body 3- flue gas injection inlet port 4- reaction slurry outlet 5- ore pulp imports.
The structural representation is former in order to illustrate realization of the invention in flue gas desulfurizing and hydrargyrum-removing processing procedure is carried out
Reason, after ore pulp is sent in reactive tank, it can completely fill full reactive tank, and be stretched to necessarily by injection apparatus for it
Position so that flue gas by injecting type enter ore pulp liquid in, realize desulfuration demercuration process, and by desulfuration demercuration process cigarette
Gas is discharged through floss hole, after the completion of reaction mass reaction, is excluded through reaction slurry outlet, is processed once again, flue gas
It can be to be adjusted as needed to be injected into entrance, and set location causes injection apparatus to stretch into inside reactive tank, and combines
The selection of spray site so that the time that flue gas is contacted with ore pulp can reach 10-20min, and enter process in flue gas injection
During, ore pulp import, reaction slurry outlet are in completely enclosed state.
Specific embodiment
Technical scheme is further limited with reference to specific embodiment, but claimed
Scope is not only limited to description.
As shown in figure 1, the invention is during realization, it is to load ore pulp by floss hole 1, cell body 2, flue gas injection
Inlet port 3, reaction slurry outlet 4, the reactive tank of the composition of ore pulp import 5 or the similar reaction that can realize the invention
In equipment, and in the course of the work, reaction slurry outlet 4, ore pulp import 5 can be completely enclosed, and through flue gas injection
Flue gas is carried out spurting into and limit in groove, and course of injection injection flow velocity and realize 10-15L/min by inlet port so that flue gas enters
After entering, promote ore pulp rolling so that fully effect and reaction, improve to sulfur dioxide, the removing of mercury composition, reduce floss hole
Sulphur, mercury component content in the flue gas for emitting, reduces environmental pollution.
It is to carry out operating realization according to following examples specifically in processing procedure：
In certain embodiments, a kind of method that wet method removes sulphur and mercury in mercurous, sulfur-containing smoke gas, pyrolusite powder is broken into
Powder, adds water and is prepared into ore pulp, in being fitted into reactive tank；By mercurous, sulfur-containing smoke gas temperature controls at 80-180 DEG C, with what is sprayed
Mode is entered from the entrance of reactive tank and sprayed in ore pulp, and spray site is located at the position of reactive tank and enables to mercurous, sulfur-containing smoke gas
10-20min is reached with the ore pulp time of contact in reactive tank, is arranged by reactive tank top with the flue gas after ore pulp contact action
Outlet drain；PH value >=3.5 of ore pulp, in pH value 3.5 are less than in control reactive tank, then more renew ore pulp.
In certain embodiments, described pyrolusite powder is to adopt microwave radiation processing during ore pulp is prepared into
Cross；Or after ore pulp is prepared, crossed using microwave radiation processing.
In certain embodiments, described microwave irradiation time is 10-20min, and microwave irradiation power is 100-300W.
In certain embodiments, described ore pulp, liquid-solid ratio is 2-3.8:1.
In certain embodiments, described mercurous, sulfur-containing smoke gas, it is sprayed in reactive tank, is 10- in the flow velocity of spray site
15L/min。
In certain embodiments, described ore pulp, wherein be additionally added and accounting for the phosphoric acid of pyrolusite quality 10-20% and accounting for soft
The urea of manganese ore quality 5-8%.
In certain embodiments, described phosphoric acid, is substituted using phosphorus ore, and is added in terms of phosphorus pentoxide.
In certain embodiments, described method, the pH of the reaction slurry being additionally included in reactive tank is reduced to≤4.2
Afterwards, added using manganese spar, adjust pH value for neutrality.
In certain embodiments, described manganese spar is, through microwave radiation processing 10-20min, to grind to form 50-80 purposes
Powder.
Embodiment 1
A kind of method that wet method removes sulphur and mercury in mercurous, sulfur-containing smoke gas, comprises the following steps：
(1) ore pulp is prepared：Pyrolusite is taken, powder is ground into, is added water and is prepared into ore pulp, control liquid-solid ratio for 2:1, load anti-
In answering groove；
(2) flue gas desulfurization, demercuration process：It is 80-180 DEG C by mercurous, sulfur-containing smoke gas temperature controls, and by it with injection
Mode spray in ore pulp, spray site is located at the position of reactive tank and enables to mercurous, sulfur-containing smoke gas and ore pulp time of contact is
10min, the flow velocity of spray site flue gas is 10L/min, and controls slurry pH >=3.5 in reactive tank；
(3) reaction slurry is processed：After slurry pH in reactive tank is less than 3.5, released, in changing reactive tank
After slip, then it is processed according to step (1), step (2), and the reaction slurry that will be released, it is diluted with water 10-20
After times quality, by its direct filtration, filter residue and filtrate are obtained, filter residue is used for calcining and reclaims mercury, and filtrate condensing crystallizing reclaims sulfuric acid
Manganese.
Embodiment 2
A kind of method that wet method removes sulphur and mercury in mercurous, sulfur-containing smoke gas, comprises the following steps：
(1) ore pulp is prepared：Pyrolusite is taken, powder is ground into, is added water and is prepared into ore pulp, control liquid-solid ratio for 3.8:1, then will
It adopts power for microwave radiation processing 10min of 100W, in being fitted into reactive tank；
(2) flue gas desulfurization, demercuration process：It is 80-180 DEG C by mercurous, sulfur-containing smoke gas temperature controls, and by it with injection
Mode spray in ore pulp, spray site is located at the position of reactive tank and enables to mercurous, sulfur-containing smoke gas and ore pulp time of contact is
20min, the flow velocity of spray site flue gas is 15L/min, and controls slurry pH >=3.5 in reactive tank；
(3) reaction slurry is processed：After slurry pH in reactive tank is less than 3.5, released, in changing reactive tank
After slip, then it is processed according to step (1), step (2), and the reaction slurry that will be released, it is diluted with water 10-20
After times quality, by its direct filtration, filter residue and filtrate are obtained, filter residue is used for calcining and reclaims mercury, and filtrate condensing crystallizing reclaims sulfuric acid
Manganese.
Embodiment 3
A kind of method that wet method removes sulphur and mercury in mercurous, sulfur-containing smoke gas, comprises the following steps：
(1) ore pulp is prepared：Pyrolusite is taken, powder is ground into, is added water and is prepared into ore pulp, control liquid-solid ratio for 3.8:1, then will
It adopts power for microwave radiation processing 20min of 300W, in being fitted into reactive tank；
(2) flue gas desulfurization, demercuration process：It is 80-180 DEG C by mercurous, sulfur-containing smoke gas temperature controls, and by it with injection
Mode spray in ore pulp, spray site is located at the position of reactive tank and enables to mercurous, sulfur-containing smoke gas and ore pulp time of contact is
15min, the flow velocity of spray site flue gas is 13L/min, and controls slurry pH >=3.5 in reactive tank；
(3) reaction slurry is processed：After slurry pH in reactive tank is less than 3.5, released, in changing reactive tank
After slip, then it is processed according to step (1), step (2), and the reaction slurry that will be released, it is diluted with water 10-20
After times quality, by its direct filtration, filter residue and filtrate are obtained, filter residue is used for calcining and reclaims mercury, and filtrate condensing crystallizing reclaims sulfuric acid
Manganese.
Embodiment 4
A kind of method that wet method removes sulphur and mercury in mercurous, sulfur-containing smoke gas, comprises the following steps：
(1) ore pulp is prepared：Pyrolusite is taken, powder is ground into, then is adopted power for the microwave radiation processing of 300W
10min, adds water and is prepared into ore pulp, controls liquid-solid ratio for 2.5:1, in being fitted into reactive tank；
(2) flue gas desulfurization, demercuration process：It is 80-180 DEG C by mercurous, sulfur-containing smoke gas temperature controls, and by it with injection
Mode spray in ore pulp, spray site is located at the position of reactive tank and enables to mercurous, sulfur-containing smoke gas and ore pulp time of contact is
17min, the flow velocity of spray site flue gas is 12L/min, and controls slurry pH >=3.5 in reactive tank；
(3) reaction slurry is processed：After slurry pH in reactive tank is less than 3.5, released, in changing reactive tank
After slip, then it is processed according to step (1), step (2), and the reaction slurry that will be released, it is diluted with water 10-20
After times quality, by its direct filtration, filter residue and filtrate are obtained, filter residue is used for calcining and reclaims mercury, and filtrate condensing crystallizing reclaims sulfuric acid
Manganese.
Embodiment 5
A kind of method that wet method removes sulphur and mercury in mercurous, sulfur-containing smoke gas, comprises the following steps：
(1) ore pulp is prepared：Pyrolusite is taken, powder is ground into, then is adopted power for the microwave radiation processing of 200W
20min, adds water and is prepared into ore pulp, controls liquid-solid ratio for 3.5:1, in being fitted into reactive tank；
(2) flue gas desulfurization, demercuration process：It is 80-180 DEG C by mercurous, sulfur-containing smoke gas temperature controls, and by it with injection
Mode spray in ore pulp, spray site is located at the position of reactive tank and enables to mercurous, sulfur-containing smoke gas and ore pulp time of contact is
16min, the flow velocity of spray site flue gas is 14L/min, and controls slurry pH >=3.5 in reactive tank；
(3) reaction slurry is processed：After slurry pH in reactive tank is less than 3.5, released, in changing reactive tank
After slip, then it is processed according to step (1), step (2), and the reaction slurry that will be released, it is diluted with water 10-20
After times quality, by its direct filtration, filter residue and filtrate are obtained, filter residue is used for calcining and reclaims mercury, and filtrate condensing crystallizing reclaims sulfuric acid
Manganese.
Embodiment 6
On the basis of embodiment 1, during ore pulp is prepared, it is added thereto to account for the phosphorus of pyrolusite quality 10%
Acid and the urea for accounting for pyrolusite quality 8%.
Embodiment 7
On the basis of embodiment 2, during ore pulp is prepared, it is added thereto to account for the phosphorus of pyrolusite quality 20%
Acid and the urea for accounting for pyrolusite quality 5%.
Embodiment 8
On the basis of embodiment 4, during ore pulp is prepared, it is added thereto to account for the phosphorus of pyrolusite quality 15%
Acid and the urea for accounting for pyrolusite quality 7%.
Embodiment 9
On the basis of embodiment 5, during ore pulp is prepared, it is added thereto to account for the phosphorus of pyrolusite quality 10%
Acid and the urea for accounting for pyrolusite quality 5%.
Embodiment 10
On the basis of embodiment 9, described phosphoric acid is substituted using phosphorus ore, and is added in terms of phosphorus pentoxide contained by phosphorus ore
Enter.
Embodiment 11
On the basis of embodiment 1, described method, the pH of the reaction slurry being additionally included in reactive tank is reduced to≤
After 4.2, added using manganese spar, it is neutrality to adjust pH value, and when addition adjusts pH value, stops the penetrating of flue gas, and is adjusted
To neutrality, released immediately, and changed the slip in reactive tank, you can.
Embodiment 12
On the basis of embodiment 11, described manganese spar is the powder that 50 mesh are ground to form through microwave radiation processing 15min
End.The process can realize the activation of manganese carbonate, promote the quick formation of manganese ion, realize the purpose of quick regulation pH value, drop
Corrosion of the sulfuric acid that low ore pulp is produced in sulfur dioxide absorption process to equipment, reduces processing cost.
Above example and test are not the restriction of the technical scheme to the invention, are intended merely to art technology
Personnel are capable of the invention thinking of correct understanding the invention, the reality of the non-protruding that those skilled in the art make on this basis
The improvement of matter feature and non-significant progress, belongs to the protection domain of the invention.
Claims (9)
1. a kind of method that wet method removes sulphur and mercury in mercurous, sulfur-containing smoke gas, it is characterised in that pyrolusite powder is broken into into powder,
Add water and be prepared into ore pulp, in being fitted into reactive tank；By mercurous, sulfur-containing smoke gas temperature controls at 80-180 DEG C, in the way of spraying
Enter from the entrance of reactive tank and spray in ore pulp, spray site be located at the position of reactive tank enable to mercurous, sulfur-containing smoke gas with it is anti-
The ore pulp time of contact in groove is answered to reach 10-20min, with flue gas the going out by reactive tank top setting after ore pulp contact action
Mouth discharge；PH value >=3.5 of ore pulp, in pH value 3.5 are less than in control reactive tank, then more renew ore pulp.
2. the method that wet method as claimed in claim 1 removes sulphur and mercury in mercurous, sulfur-containing smoke gas, it is characterised in that described
Pyrolusite powder is crossed during ore pulp is prepared into using microwave radiation processing；Or be using micro- after ore pulp is prepared
What wave radiation was processed.
3. the method that wet method as claimed in claim 2 removes sulphur and mercury in mercurous, sulfur-containing smoke gas, it is characterised in that described
Microwave irradiation time is 10-20min, and microwave irradiation power is 100-300W.
4. the method that wet method as claimed in claim 1 removes sulphur and mercury in mercurous, sulfur-containing smoke gas, it is characterised in that described
Ore pulp, liquid-solid ratio is 2-3.8:1.
5. the method that wet method as claimed in claim 1 removes sulphur and mercury in mercurous, sulfur-containing smoke gas, it is characterised in that described
Mercurous, sulfur-containing smoke gas, it is sprayed in reactive tank, is 10-15L/min in the flow velocity of spray site.
6. the method that wet method as claimed in claim 1 removes sulphur and mercury in mercurous, sulfur-containing smoke gas, it is characterised in that described
Ore pulp, wherein being additionally added the phosphoric acid for accounting for pyrolusite quality 10-20% and the urea for accounting for pyrolusite quality 5-8%.
7. the method that wet method as claimed in claim 6 removes sulphur and mercury in mercurous, sulfur-containing smoke gas, it is characterised in that described
Phosphoric acid, is substituted using phosphorus ore, and is added in terms of phosphorus pentoxide.
8. the method that wet method as claimed in claim 1 removes sulphur and mercury in mercurous, sulfur-containing smoke gas, it is characterised in that described
Method, the pH of the reaction slurry being additionally included in reactive tank is reduced to≤4.2 after, added using manganese spar, adjust during pH value is
Property.
9. the method that wet method as claimed in claim 8 removes sulphur and mercury in mercurous, sulfur-containing smoke gas, it is characterised in that described
Manganese spar is the powder that 50-80 mesh is ground to form through microwave radiation processing 10-20min.
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| CN113041838A (en) * | 2021-05-06 | 2021-06-29 | 昆明理工大学 | Method for cooperatively removing low-concentration sulfur dioxide and mercury in smelting flue gas |
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