CN106582244B - A kind of wet process removes mercurous, sulphur and mercury in sulfur-containing smoke gas method - Google Patents
A kind of wet process removes mercurous, sulphur and mercury in sulfur-containing smoke gas method Download PDFInfo
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- CN106582244B CN106582244B CN201611192723.1A CN201611192723A CN106582244B CN 106582244 B CN106582244 B CN 106582244B CN 201611192723 A CN201611192723 A CN 201611192723A CN 106582244 B CN106582244 B CN 106582244B
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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
-
- 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
Abstract
The present invention relates to flue gas wet purification technology fields, especially a kind of wet process removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, after being prepared into ore pulp to pyrolusite, it places it in reactive tank, flue gas is sprayed by way of injection sulfur-bearing, mercury fume and is reacted, and the control action time is 10-20min, and the sulphur in flue gas, mercury ingredient is effectively made to have obtained a large amount of removing, so that the removal efficiency of sulphur mercury ingredient has reached 80% or more, discharge sulfureous in flue gas, mercury content are effectively reduced；And cost is relatively low for treatment process, and raw material is easy to get, and the cost of high degree reduced using pyrolusite processing sulfur-bearing, mercury fume reduces the discharge amount of sulfureous in flue gas, mercury ingredient.
Description
Technical field
The present invention relates to flue gas wet purification technology field, especially a kind of wet process removing is mercurous, in sulfur-containing smoke gas sulphur and
The method of mercury.
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, and in industry
On, it is all using activated carbon adsorption demercuration, so that the discharge of mercury is controlled effectively, but since the price of active carbon is high mostly
It is expensive, so that largely using active carbon demercuration higher cost；Moreover, most of is all to carry out individually for flue gas desulfurizing and hydrargyrum-removing
Isolated removing, and for carrying out flue gas desulfurizing and hydrargyrum-removing disposably to combine the investigative technique of removing also relatively fewer, but also have
A small amount of document occurs, if Patent No. ZL03135926 carries out desulfurization process using pyrolusite and manganese spar, and in the processing
In the process, undesirable for demercuration effect using wet desulphurization, but its substantially there is also the oxidation to mercury ingredient is de-
It removes；For another example the desulfuration demercuration for carrying out flue gas using middle-low grade pyrolusite that number of patent application is 201610149557 is handled, should
Method is mainly handled using desulfuration demercuration in dry method fixed bed reactors；In addition to this, there are also some for desulfuration demercuration mistake
The research of the sulfur and mercury removing agent used in journey, still, these sulfur and mercury removing agents are not that desulfuration demercuration efficiency is undesirable, are exactly raw material
It is difficult to obtain, higher cost, such as the sulfur and mercury removing agent of Patent No. 200810118580, magnetic iron oxide is used to produce for self-control
Product, and this product preparation difficulty is larger so that market acquiring way is less, cause its preparation cost, application cost compared with
It is high；For another example the desulfurization denitration demercuration agent that number of patent application is 201410026774, it is undesirable for the removal efficiency of desulfuration demercuration.
Summary of the invention
In order to solve the above technical problems existing in the prior art, the present invention provides a kind of wet process removing mercurous, sulfur-bearing
The method of sulfureous in flue gas and mercury.
It is achieved particular by following technical scheme:
A kind of wet process removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, and pyrolusite powder is broken into powder, water is added to be prepared into
Ore pulp is fitted into reactive tank；Mercurous, sulfur-containing smoke gas temperature is controlled at 80-180 DEG C, from reactive tank in a manner of injection
Entrance, which enters, to be sprayed into ore pulp, and the position that spray site is located at reactive tank enables to the mine in mercurous, sulfur-containing smoke gas and reactive tank
Slurry time of contact reaches 10-20min, passes through the outlet drain of setting at the top of reactive tank with the flue gas after ore pulp contact action.It adopts
It is fixed in reactive tank with by pyrolusite ore pulp, and is sprayed into reactive tank by mercurous, sulfur-containing smoke gas using injecting type, so that instead
It answers the ore pulp in slot to flow, so that ore pulp realizes circulating contact flue gas, realizes the desulfuration demercuration to flue gas, and in this process
In, so that the contact area of ore pulp and flue gas increases, so that desulfuration demercuration efficiency is improved, relatively traditional is sprayed using ore pulp
Leaching or using fixed bed bed processing flue gas for, can effectively avoid ore pulp spray during generate steam cause with
Smoke contacts are insufficient, and ore pulp is difficult to realize recycle.The present invention during processing, passes through slurry in control reactive tank
PH value >=3.5, the sulphur ingredient removal efficiency that can be realized in flue gas reach 90% or more.
The pyrolusite powder is crossed during being prepared into ore pulp using microwave radiation processing；Or it is preparing
After ore pulp, crossed using microwave radiation processing.
The microwave irradiation time is 10-20min, microwave irradiation power 100-300W.
The ore pulp, liquid-solid ratio 2-3.8:1.
Mercurous, the sulfur-containing smoke gas sprays into reactive tank, is 10-15L/min in the flow velocity of spray site.
The ore pulp, wherein being additionally added the phosphoric acid for accounting for pyrolusite quality 10-20% and accounting for pyrolusite quality 5-8%'s
Urea.It is added using phosphoric acid and urea, the temperature by flue gas is in the range of 80-180 DEG C, so that the temperature in ore pulp
It gradually rises, so that phosphoric acid and urea is in ore pulp, as exhaust gas volumn is gradually passed through, the continuous raising of slurry temperature, so that phosphorus
Urea phosphate recurring structure alienation in the excessive environment of phosphoric acid that acid is formed with urea 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 being acted on sulfate radical, is formed
Sulfate, realization significantly remove mercury ion and sulphur ingredient, and in pyrolusite under the action 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 lower so that for flue gas demercuration desulfurization process cost compared with
It is low.
The phosphoric acid, is substituted using phosphorus ore, and is added in terms of phosphorus pentoxide.It is directly substituted using phosphorus ore, it can not only
Enough so that the cost of desulfuration demercuration more reduces, and contain part calcium constituent in phosphorus ore, which can make with sulfate radical
With increase pH value improves the removal efficiency to sulphur ingredient.
The method, further include the reaction slurry in reactive tank pH be reduced to≤4.2 after, using manganese spar plus
Enter, adjusting pH value is neutrality.
The manganese spar is to be ground into 50-80 mesh powder by microwave radiation processing 10-20min.
The researcher of the invention is in order to prove the technical effect of the invention, to the technology of the invention
Scheme is specifically made that experimental study below during realization:
Test column 1:
By pyrolusite 150g, it is ground into powder, water is added to be configured to ore pulp, is fitted into reactive tank, control liquid consolidates mass ratio and is
The ore pulp import for adding ore pulp and the sealing of reaction slurry outlet are closed, using injection apparatus, injection apparatus are protruded into instead by 2:1
It answers in slot, mercurous, sulfur-containing smoke gas is sprayed into, and detect sulfur-bearing, the sulfur content in mercury fume, mercury content before penetrating, and will spray
The oral area that exit point is chosen at reactive tank flue gas injection inlet port is sprayed, jet velocity 10L/min, so that flue gas enters
Afterwards, 5min just has flue gas to emit from discharge outlet, and detect the sulfur content in the flue gas that reactive tank discharge outlet emits and
Mercury content, as a result: the sulfur content in flue gas that discharge outlet emits 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 flue gas that discharge outlet emits account for the mercury in flue gas content that flue gas injection inlet port goes out
23.7%.
Test column 2:
By the position of spray site to flue gas injection inlet port position to bottom offset, so that after flue gas enters reactive tank, 15min
Just there is flue gas to come out from discharge outlet afterwards, other according to test column 1, as a result:: the sulphur in flue gas that discharge outlet emits
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 flue gas that discharge outlet emits accounts for
The 13.57% of the mercury in flue gas content that flue gas injection inlet port goes out.
Test column 3:
By the position of spray site to flue gas injection inlet port position to bottom offset, so that after flue gas enters reactive tank, 10min
Just there is flue gas to come out from discharge outlet afterwards, other according to test column 1, as a result: the sulphur in flue gas that discharge outlet emits
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 flue gas that discharge outlet emits accounts for
The 12.15% of the mercury in flue gas content that flue gas injection inlet port goes out.
Test column 4:
By the position of spray site to flue gas injection inlet port position to bottom offset, so that after flue gas enters reactive tank, 9min
Just there is flue gas to come out from discharge outlet afterwards, other according to test column 1, as a result: the sulphur in flue gas that discharge outlet emits
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 flue gas that discharge outlet emits
Account for the 22.16% of the mercury in flue gas content that flue gas injection inlet port goes out.
Test column 5:
By the position of spray site to flue gas injection inlet port position to bottom offset, so that after flue gas enters reactive tank, 20min
Just there is flue gas to come out from discharge outlet afterwards, other according to test column 1, as a result:: the sulphur in flue gas that discharge outlet emits
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 flue gas that discharge outlet emits accounts for
The 11.46% of the mercury in flue gas content that flue gas injection inlet port goes out.
Test column 6:
By the position of spray site to flue gas injection inlet port position to bottom offset, so that after flue gas enters reactive tank, 25min
Just there is flue gas to come out from discharge outlet afterwards, other according to test column 1, as a result: the sulphur in flue gas that discharge outlet emits
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 flue gas that discharge outlet emits accounts for
The 12.89% of the mercury in flue gas content that flue gas injection inlet port goes out.
Test column 7:
By the position of spray site to flue gas injection inlet port position to bottom offset, so that after flue gas enters reactive tank, 21min
Just there is flue gas to come out from discharge outlet afterwards, other according to test column 1, as a result: the sulphur in flue gas that discharge outlet emits
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 flue gas that discharge outlet emits accounts for
The 11.43% of the mercury in flue gas content that flue gas injection inlet port goes out.
Test column 8:
Pyrolusite is prepared into ore pulp according to test column 1, and is passed directly by sulfur-bearing, containing mercury gas, it is steady to enter reaction
In slot, and the time acted in reactive tank is 20min, and carries out detection removal effect according to the mode of operation of test column 1, is tied
Fruit shows are as follows: before flue gas sulfur content enters reactive tank relatively in discharge outlet, content has reached 65.1%；Mercury content is opposite to be entered
Before reactive tank, reach 78.35%.
Injecting type processing gas is contacted with the ore pulp of standing from can be seen that as the result is shown for test column 1-8, it can
So that ore pulp rolls, promote sulfur dioxide, mercury ingredient in ore pulp catalysis oxidation flue gas, and realize and take off to mercury, sulfur dioxide
It removes, and for relatively complete stationary contact, can significantly reduce sulphur, mercury content, reduce flue gas emission to environment
Pollution.
Further, the researcher of the invention during processing, has also passed through and has prepared to before ore pulp preparation with ore pulp
The test of microwave radiation processing in the process has specifically carried out test column 9, test column 10, as follows:
Test column 9:
According to test column 1, pyrolusite is first used into microwave radiation processing, microwave irradiation power 200W, when microwave radiation
Between be 15min, after radiation treatment, it is prepared into ore pulp according to test column 1, according to test 1 processing mode of column carry out it is mercurous, contain
Sulphur fume treatment, detects its desulfurization, demercuration efficiency, and result is that the sulfur content in the flue gas that discharge outlet emits accounts for flue gas injection
The 7.5% of the sulfureous in flue gas content that inlet port goes out, the mercury content in flue gas that discharge outlet emits accounts for flue gas injection inlet port
The 8.91% of mercury in flue gas content out.
Test column 10
Microwave 200W, radiation treatment 15min are used after pyrolusite crushing is prepared into ore pulp according to test column 1,
And the ore pulp is used in reactive tank, the processing of sulfur-bearing, mercury fume is carried out according to test column 1, as a result discharge outlet discharges
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 discharge outlet 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 column 1, test column 9, test column 10, can significantly learn, it, can be effective for microwave radiation processing
Improve ore pulp to the sulphur in sulfur-bearing, mercury fume, mercury removal rate, so that 90% or more sulphur ingredient is removed, 87% or more
Mercury ingredient removed, the sulfur content reduced in flue gas and mercury content of high degree.
This researcher is during test process, also by some additives are added to, so that desulfurization, demercuration efficiency
It is improved, the test specifically done is test column 11, test column 12, test column 13:
Test column 11:
According to test column 1, pyrolusite powder is prepared into ore pulp, and the phosphorus for accounting for pyrolusite powder quality 10% is added into ore pulp
Acid is added into reactive tank, carries out the processing of sulfur-bearing, mercury fume according to the processing mode of test column 1, and it is handled
As a result it is detected, result is that the sulfur content in the flue gas that discharge outlet emits accounts for the sulfureous in flue gas that flue gas injection inlet port goes out
The 15.1% of content, the mercury content in flue gas that discharge outlet emits account for the mercury in flue gas content that flue gas injection inlet port goes out
20.57%.
Test column 12
According to test column 1, pyrolusite powder is prepared into ore pulp, and the phosphorus for accounting for pyrolusite powder quality 10% is added into ore pulp
Acid and the urea for accounting for pyrolusite powder quality 8%, are added into reactive tank, carry out sulfur-bearing according to the processing mode of test column 1, contain
The processing of mercury flue gas, and the result that it is handled is detected, result is that the sulfur content in the flue gas that discharge outlet emits accounts for
The 0.35% of the sulfureous in flue gas content that flue gas injection inlet port goes out, the mercury content in flue gas that discharge outlet emits account for flue gas spray
Inject the 1.37% of the mercury in flue gas content that entrance goes out.
Test column 13
According to test column 1, pyrolusite powder is prepared into ore pulp, and the urine for accounting for pyrolusite powder quality 8% is added into ore pulp
Element is added into reactive tank, carries out the processing of sulfur-bearing, mercury fume according to the processing mode of test column 1, and it is handled
As a result it is detected, result is that the sulfur content in the flue gas that discharge outlet emits accounts for the sulfureous in flue gas that flue gas injection inlet port goes out
The 14.57% of content, the mercury content in flue gas that discharge outlet emits account for the mercury in flue gas content that flue gas injection inlet port goes out
22.18%.
It after the invention is by being prepared into ore pulp to pyrolusite, places it in reactive tank, passes through injection sulfur-bearing, mercurous
The mode of flue gas, which sprays into flue gas, reacts, and the control action time is 10-20min, effectively makes the sulphur in flue gas, mercury at getting
A large amount of removing has been arrived, so that the removal efficiency of sulphur mercury ingredient has reached 80% or more, has effectively reduced discharge sulfureous in flue gas, mercury contains
Amount；And cost is relatively low for treatment process, and raw material is easy to get, and reducing for high degree handles sulfur-bearing, mercurous cigarette using pyrolusite
The cost of gas reduces the discharge amount of sulfureous in flue gas, mercury ingredient.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the reactive tank used in the invention.
1- discharge outlet 2- groove body 3- flue gas injection inlet port 4- reaction slurry outlet 5- ore pulp import.
The structural schematic diagram is to carry out the realization original in flue gas desulfurizing and hydrargyrum-removing treatment process in order to illustrate the invention
Reason can completely fill full reactive tank, and stretch to centainly by injection apparatus after ore pulp is sent into reactive tank
Position realize desulfuration demercuration processing so that flue gas is entered in ore pulp liquid by injecting type, and by the cigarette of desulfuration demercuration processing
Gas is discharged by discharge outlet, and reaction mass after the reaction was completed, is excluded by reaction slurry outlet, handled once again, flue gas
Being injected into entrance is that can according to need to be adjusted, and setting position protrudes into injection apparatus inside reactive tank, and combines
The selection of spray site, the time that flue gas is contacted with ore pulp reaches 10-20min, and enters processing in flue gas injection
During, ore pulp import, reaction slurry outlet are in completely enclosed state.
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.
As shown in Figure 1, the invention during realization, is that ore pulp is packed by discharge outlet 1, groove body 2, flue gas injection
The reactive tank or the similar reaction that can be realized the invention that inlet port 3, reaction slurry outlet 4, ore pulp import 5 form
In equipment, and during the work time, reaction slurry outlet 4, ore pulp import 5 can be completely enclosed, and pass through flue gas injection
Inlet port carries out flue gas to spurt into slot, and in course of injection limit injection flow velocity realize 10-15L/min so that flue gas into
After entering, promote ore pulp rolling, so that sufficiently acting on and reacting, improves the removing to sulfur dioxide, mercury ingredient, reduce discharge outlet
The sulphur in flue gas, the mercury component content emitted, reduces environmental pollution.
Specifically during processing, it is to carry out operation realization according to the following examples:
In certain embodiments, a kind of wet process removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, and pyrolusite powder is broken into
Powder adds water to be prepared into ore pulp, is fitted into reactive tank；Mercurous, sulfur-containing smoke gas temperature is controlled at 80-180 DEG C, with injection
Mode enters from the entrance of reactive tank to be sprayed into ore pulp, and the position that spray site is located at reactive tank enables to mercurous, sulfur-containing smoke gas
Reach 10-20min with the ore pulp time of contact in reactive tank, with the flue gas after ore pulp contact action by being arranged at the top of reactive tank
Outlet drain；PH value >=3.5 of ore pulp then more renew ore pulp in pH value less than 3.5 in control reactive tank.
In certain embodiments, the pyrolusite powder is using microwave radiation processing during being prepared into ore pulp
It crosses；Or after preparing ore pulp, crossed using microwave radiation processing.
In certain embodiments, the microwave irradiation time is 10-20min, microwave irradiation power 100-300W.
In certain embodiments, the ore pulp, liquid-solid ratio 2-3.8:1.
In certain embodiments, mercurous, the sulfur-containing smoke gas spray into reactive tank, are 10- in the flow velocity of spray site
15L/min。
In certain embodiments, the ore pulp, wherein being additionally added the phosphoric acid for accounting for pyrolusite quality 10-20% and accounting for soft
The urea of manganese ore quality 5-8%.
In certain embodiments, the phosphoric acid, is substituted using phosphorus ore, and is added in terms of phosphorus pentoxide.
In certain embodiments, the method further includes that the pH of the reaction slurry in reactive tank is reduced to≤4.2
Afterwards, it is added using manganese spar, adjusting pH value is neutrality.
In certain embodiments, the manganese spar is to be ground into 50-80 purpose by microwave radiation processing 10-20min
Powder.
Embodiment 1
A kind of wet process removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, comprising the following steps:
(1) it prepares ore pulp: taking pyrolusite, be ground into powder, water is added to be prepared into ore pulp, control liquid-solid ratio is 2:1, is packed into anti-
It answers in slot；
(2) flue gas desulfurization, demercuration processing: it is 80-180 DEG C that mercurous, sulfur-containing smoke gas temperature, which is controlled, and by it with injection
Mode spray into ore pulp, the position that spray site is located at reactive tank enables to mercurous, sulfur-containing smoke gas and ore pulp time of contact is
The flow velocity of 10min, spray site flue gas are 10L/min, and control slurry pH >=3.5 in reactive tank；
(3) reaction slurry is handled: after slurry pH in reactive tank is less than 3.5, being released, is replaced in reactive tank
After slurry, then it is handled according to step (1), step (2), and by the reaction slurry of releasing, is diluted with water 10-20
After times quality, it is directly filtered, obtains filter residue and filtrate, filter residue recycles sulfuric acid for calcining recycling mercury, filtrate condensing crystallizing
Manganese.
Embodiment 2
A kind of wet process removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, comprising the following steps:
(1) it prepares ore pulp: taking pyrolusite, be ground into powder, water is added to be prepared into ore pulp, control liquid-solid ratio is 3.8:1, then will
It uses power for the microwave radiation processing 10min of 100W, is fitted into reactive tank；
(2) flue gas desulfurization, demercuration processing: it is 80-180 DEG C that mercurous, sulfur-containing smoke gas temperature, which is controlled, and by it with injection
Mode spray into ore pulp, the position that spray site is located at reactive tank enables to mercurous, sulfur-containing smoke gas and ore pulp time of contact is
The flow velocity of 20min, spray site flue gas are 15L/min, and control slurry pH >=3.5 in reactive tank；
(3) reaction slurry is handled: after slurry pH in reactive tank is less than 3.5, being released, is replaced in reactive tank
After slurry, then it is handled according to step (1), step (2), and by the reaction slurry of releasing, is diluted with water 10-20
After times quality, it is directly filtered, obtains filter residue and filtrate, filter residue recycles sulfuric acid for calcining recycling mercury, filtrate condensing crystallizing
Manganese.
Embodiment 3
A kind of wet process removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, comprising the following steps:
(1) it prepares ore pulp: taking pyrolusite, be ground into powder, water is added to be prepared into ore pulp, control liquid-solid ratio is 3.8:1, then will
It uses power for the microwave radiation processing 20min of 300W, is fitted into reactive tank；
(2) flue gas desulfurization, demercuration processing: it is 80-180 DEG C that mercurous, sulfur-containing smoke gas temperature, which is controlled, and by it with injection
Mode spray into ore pulp, the position that spray site is located at reactive tank enables to mercurous, sulfur-containing smoke gas and ore pulp time of contact is
The flow velocity of 15min, spray site flue gas are 13L/min, and control slurry pH >=3.5 in reactive tank；
(3) reaction slurry is handled: after slurry pH in reactive tank is less than 3.5, being released, is replaced in reactive tank
After slurry, then it is handled according to step (1), step (2), and by the reaction slurry of releasing, is diluted with water 10-20
After times quality, it is directly filtered, obtains filter residue and filtrate, filter residue recycles sulfuric acid for calcining recycling mercury, filtrate condensing crystallizing
Manganese.
Embodiment 4
A kind of wet process removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, comprising the following steps:
(1) it prepares ore pulp: taking pyrolusite, be ground into powder, then used power for the microwave radiation processing of 300W
10min adds water to be prepared into ore pulp, and control liquid-solid ratio is 2.5:1, is fitted into reactive tank；
(2) flue gas desulfurization, demercuration processing: it is 80-180 DEG C that mercurous, sulfur-containing smoke gas temperature, which is controlled, and by it with injection
Mode spray into ore pulp, the position that spray site is located at reactive tank enables to mercurous, sulfur-containing smoke gas and ore pulp time of contact is
The flow velocity of 17min, spray site flue gas are 12L/min, and control slurry pH >=3.5 in reactive tank；
(3) reaction slurry is handled: after slurry pH in reactive tank is less than 3.5, being released, is replaced in reactive tank
After slurry, then it is handled according to step (1), step (2), and by the reaction slurry of releasing, is diluted with water 10-20
After times quality, it is directly filtered, obtains filter residue and filtrate, filter residue recycles sulfuric acid for calcining recycling mercury, filtrate condensing crystallizing
Manganese.
Embodiment 5
A kind of wet process removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, comprising the following steps:
(1) it prepares ore pulp: taking pyrolusite, be ground into powder, then used power for the microwave radiation processing of 200W
20min adds water to be prepared into ore pulp, and control liquid-solid ratio is 3.5:1, is fitted into reactive tank；
(2) flue gas desulfurization, demercuration processing: it is 80-180 DEG C that mercurous, sulfur-containing smoke gas temperature, which is controlled, and by it with injection
Mode spray into ore pulp, the position that spray site is located at reactive tank enables to mercurous, sulfur-containing smoke gas and ore pulp time of contact is
The flow velocity of 16min, spray site flue gas are 14L/min, and control slurry pH >=3.5 in reactive tank；
(3) reaction slurry is handled: after slurry pH in reactive tank is less than 3.5, being released, is replaced in reactive tank
After slurry, then it is handled according to step (1), step (2), and by the reaction slurry of releasing, is diluted with water 10-20
After times quality, it is directly filtered, obtains filter residue and filtrate, filter residue recycles sulfuric acid for calcining recycling mercury, filtrate condensing crystallizing
Manganese.
Embodiment 6
On the basis of embodiment 1, during preparing ore pulp, be added has the phosphorus for accounting for pyrolusite quality 10% thereto
Acid and the urea for accounting for pyrolusite quality 8%.
Embodiment 7
On the basis of embodiment 2, during preparing ore pulp, be added has the phosphorus for accounting for pyrolusite quality 20% thereto
Acid and the urea for accounting for pyrolusite quality 5%.
Embodiment 8
On the basis of embodiment 4, during preparing ore pulp, be added has the phosphorus for accounting for pyrolusite quality 15% thereto
Acid and the urea for accounting for pyrolusite quality 7%.
Embodiment 9
On the basis of embodiment 5, during preparing ore pulp, be added has the phosphorus for accounting for pyrolusite quality 10% thereto
Acid and the urea for accounting for pyrolusite quality 5%.
Embodiment 10
On the basis of embodiment 9, the phosphoric acid is substituted using phosphorus ore, and in terms of the phosphorus pentoxide contained by the phosphorus ore plus
Enter.
Embodiment 11
On the basis of embodiment 1, the method, further include the reaction slurry in reactive tank pH be reduced to≤
It after 4.2, is added using manganese spar, adjusting pH value is neutrality, and when adjusting pH value is added, stops the penetrating of flue gas, and adjust
It to neutrality, is released immediately, and replaces the slurry in reactive tank.
Embodiment 12
On the basis of embodiment 11, the manganese spar is to be ground into the powder of 50 mesh by microwave radiation processing 15min
End.The processing can be realized the activation of manganese carbonate, promote the quick formation of manganese ion, realize the purpose for quickly adjusting pH value, drop
Corrosion of the sulfuric acid that low ore pulp is generated in sulfur dioxide absorption process to equipment, reduces processing cost.
Above embodiments and test are not to be intended merely to art technology to the restriction of the technical solution of the invention
Personnel are capable of the invention thinking of correct understanding the invention, the non-protruding reality that those skilled in the art make on this basis
The improvement of matter feature and non-significant progress belongs to the protection scope of the invention.
Claims (7)
1. a kind of wet process removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, which is characterized in that pyrolusite powder is broken into powder,
Add water to be prepared into ore pulp, is fitted into reactive tank；Mercurous, sulfur-containing smoke gas temperature is controlled at 80-180 DEG C, in a manner of injection
From the entrance of reactive tank enter spray into ore pulp in, the position that spray site is located at reactive tank enable to mercurous, sulfur-containing smoke gas with instead
It answers the ore pulp time of contact in slot to reach 10-20min, is gone out with the flue gas after ore pulp contact action by what is be arranged at the top of reactive tank
Mouth discharge；PH value >=3.5 of ore pulp then more renew ore pulp when pH value is less than 3.5 in control reactive tank；
The ore pulp, wherein the urea for being additionally added the phosphoric acid for accounting for pyrolusite quality 10-20% and accounting for pyrolusite quality 5-8%.
2. wet process as described in claim 1 removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, which is characterized in that described
Pyrolusite powder is crossed during being prepared into ore pulp using microwave radiation processing；It is using micro- or after preparing ore pulp
Wave radiation is processed.
3. wet process as claimed in claim 2 removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, which is characterized in that described
Microwave irradiation time is 10-20min, microwave irradiation power 100-300W.
4. wet process as described in claim 1 removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, which is characterized in that described
Ore pulp, liquid-solid ratio 2-3.8:1.
5. wet process as described in claim 1 removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, which is characterized in that described
Mercurous, sulfur-containing smoke gas sprays into reactive tank, is 10-15L/min in the flow velocity of spray site.
6. wet process as described in claim 1 removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, which is characterized in that described
Method, further include the reaction ore pulp in reactive tank pH be reduced to≤4.2 after, be added, adjusted during pH value is using manganese spar
Property.
7. wet process as claimed in claim 6 removes mercurous, sulphur and mercury in sulfur-containing smoke gas method, which is characterized in that described
Manganese spar is to be ground into 50-80 mesh powder by microwave radiation processing 10-20min.
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| CN104740982A (en) * | 2013-12-25 | 2015-07-01 | 贵州大学 | Method and apparatus for processing sulfur-containing flue gas by lean manganese mine and rhodochrosite |
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| CN105688647A (en) * | 2016-03-16 | 2016-06-22 | 贵州大学 | Method for dry desulfurization and demercuration of sintering flue gas containing mercury by means of low-grade pyrolusite |
| 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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| CN105120982A (en) * | 2013-02-14 | 2015-12-02 | 卡尔冈碳素公司 | Enhanced sorbent formulation for removal of mercury from flue gas |
| CN104740982A (en) * | 2013-12-25 | 2015-07-01 | 贵州大学 | Method and apparatus for processing sulfur-containing flue gas by lean manganese mine and rhodochrosite |
| CN105289261A (en) * | 2015-11-20 | 2016-02-03 | 中南大学 | Washing liquid for eluting mercury in mercury-containing flue gas and method for recovering mercury form mercury-containing flue gas |
| CN105688647A (en) * | 2016-03-16 | 2016-06-22 | 贵州大学 | Method for dry desulfurization and demercuration of sintering flue gas containing mercury by means of low-grade pyrolusite |
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Effective date of registration: 20200929 Address after: 564300 Wuchuan mercury mine, Wuchuan Autonomous County, Zunyi, Guizhou Patentee after: YINYU MINERALS WUCHUAN AUTONOMOUS COUNTY Co.,Ltd. Address before: 550025 Guiyang City, Guizhou Province Huaxi District, Guiyang City, Guizhou Province Patentee before: Guizhou University |
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