CN105921104A - Industrial sulfur-containing waste gas modified carbon-based adsorbent and preparation method and application thereof - Google Patents
Industrial sulfur-containing waste gas modified carbon-based adsorbent and preparation method and application thereof Download PDFInfo
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- CN105921104A CN105921104A CN201610288796.4A CN201610288796A CN105921104A CN 105921104 A CN105921104 A CN 105921104A CN 201610288796 A CN201610288796 A CN 201610288796A CN 105921104 A CN105921104 A CN 105921104A
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- adsorbent
- exhaust gas
- sulphur
- containing exhaust
- carbon
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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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
- B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
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- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses an industrial sulfur-containing waste gas modified carbon-based adsorbent and a preparation method thereof. A carbon-based adsorbent is put into a flowing industrial sulfur-containing waste gas modifier, heating treatment is carried out, and the industrial sulfur-containing waste gas modified carbon-based adsorbent is obtained. The invention further discloses application of the industrial sulfur-containing waste gas modified carbon-based adsorbent in flue gas demercuration and an application method of the industrial sulfur-containing waste gas modified carbon-based adsorbent. Compared with the prior art, by modifying the carbon-based adsorbent with the industrial sulfur-containing waste gas, the demercuration performance of the adsorbent is improved, the effect of treating waste with waste is achieved, desorption and recycling of mercury are achieved at the same time, the content of total mercury entering the atmosphere is reduced, and meanwhile waste of the valuable natural resource mercury is reduced.
Description
Technical field
The invention belongs to field of environment protection, be specifically related to a kind of industry sulphur-containing exhaust gas carbon modified base adsorbent and preparation side thereof
Method and application.
Background technology
Hydrargyrum is the heavy metal element of a kind of hypertoxicity, and natural environment and human health in serious threat.Hydrargyrum become the dust that continues,
SOx、NOxThe fourth-largest pollutant in coal-fired plant flue gas afterwards.Coal-burning power plant's mercury emissions standard that China is current and warp
Efficient demercuration technology of helping lags behind the most far away World Developed Countries.China Council for International Cooperation on Environment and Development in 2011
The mercury emissions limit value of the coal-fired thermal power generation that China is performed by special policies seminar (SPS Team) suggestion at present is further
Strict: to be changed to 3 μ g/Nm to the year two thousand twenty3.It is main that development course prevented and treated by the most ripe coal fired power plant mercury pollution
There is the front demercuration of burning, utilize additive demercuration and flue gas injection in coal-burning power plant's existing pollutant catabolic gene device demercuration, coal
Adsorbent demercuration etc..But although hydrargyrum in coal can be transferred in coal washing liquid by any of the above demercuration technology effectively, or removing
Hydrargyrum in flue gas, or hydrargyrum is transferred in flying dust or low slag, effectively reduce the mercury content entering in atmospheric environment, but
All it is not carried out the recycling of hydrargyrum and the circular regeneration of demercuration adsorbent, causes natural resources serious waste and become with demercuration
This high problem.Therefore, in the face of the mercury emissions requirement of increasingly stringent, the flue gas demercuration technology gesture of economical and efficient is developed
Must go.
Carbon-based adsorbent has highly developed pore structure, determines that it not only has stronger physical absorption ability, simultaneously
Also for the supporting of various active components, and then produce powerful chemisorbed and provide active sites.But, non-modified
Carbon-based adsorbent there is no efficient orientation removing ability to Elemental Mercury.Sulfur affinity great to hydrargyrum, sulfur modification can be obviously enhanced
The hydrargyrum adsorbing and removing ability of carbon-based adsorbent, and also can be by the hydrargyrum of ADSORPTION STATE by methods such as decompression, intensification or electrochemistry
Carry out being desorbed, be enriched with, reclaim, utilize.Therefore, utilize the industrial waste gas of sulfur compound as modifying agent to strengthen carbon back
The demercuration activity of adsorbent can not only obtain the ability of high-efficient mercury removing, and carry the carbon-based adsorbent after sulfur and can also realize
The potential physicochemical property that hydrargyrum desorption reclaims.On the one hand reduce flue gas demercuration cost realizes the money of trade waste to this method
Sourceization utilizes, and on the other hand achieves recycling and the regeneration of adsorbent of rare valuable natural resources hydrargyrum, is formed
Adsorbent demercuration and the circulating system of regeneration, have important theory significance and a potential industrial application value.
At present, patent CN102258936A discloses device and the side that a kind of mercury in smoke multi-pollutant control technology reclaims
Method, but this method step is more complicated, needs to add various medicaments, and creates NO pollutant in course of reaction.
Patent CN101406794A discloses a kind of method to preparing exhaust gas mercury-removing reagent from modification of waste desulfurizing agent, and this method is by by halogen
Race's element is supported on waste desulfurizer surface, improves its activity and strengthens the characteristic of removing nonvalent mercury, but this method is the most real
The recycling of existing hydrargyrum, wastes the natural resources of preciousness.Patent CN104338435A discloses a kind of utilization and reclaims list
The method of the hydrargyrum in waste desulfurizing agent removing flue gas after matter sulfur, it is achieved that the purpose of the treatment of wastes with processes of wastes against one another, but the most only hydrargyrum is carried out
Adsorbing and removing, is not reaching to the purpose of hydrargyrum resource reclaim recycling.Although patent CN104888743A proposes one
The apparatus and method that mercurous load sulfur activated coke regenerative process hydrargyrum separates, but this technique is also it is emphasised that to high-concentration sulfur dioxide
The recovery of middle Sulphur ressource, not for the recovery of hydrargyrum.Additionally this technology uses high-concentration sulfur dioxide purging to realize absorption
Agent regenerates.The present invention is directed industry sulphur-containing exhaust gas is at 600-700 DEG C of carbon modified base adsorbent flue gas, simultaneously with mercurous
Flue gas carries out adsorption reaction, is then fed in desorption apparatus realizing hydrargyrum desorption at 250-400 DEG C and reclaiming, finally inhales
Attached dose is re-fed in reforming apparatus realizing regeneration.Therefore, the feature of overall circulation of the present invention determines that it has significant environment
And social benefit.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of industry sulphur-containing exhaust gas carbon modified base adsorbent, to solve existing skill
The desorption effect that art exists is the best, it is impossible to realize the problem such as recycling of resource.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows:
A kind of preparation method of industry sulphur-containing exhaust gas carbon modified base adsorbent, it prepares by the following method:
Being placed in by carbon-based adsorbent in the industrial sulphur-containing exhaust gas modifying agent of flowing, heat treated, by sulfide with multiple sulfur-bearing
The form of functional group is enriched in adsorbent surface, obtains industrial sulphur-containing exhaust gas carbon modified base adsorbent；Reaction equation is as follows:
Wherein, described carbon-based adsorbent is activated carbon, biomass char or petroleum coke, and described industrial sulphur-containing exhaust gas modifying agent is
The industrial waste gas of sulfur compound；Wherein, in industrial waste gas, the mass fraction of sulfide is 0.2～5%.If sulfur herein
Compound excessive concentration, can produce competitive Adsorption with hydrargyrum, suppress the adsorbent adsorption to hydrargyrum.
Wherein, the flow velocity of industry sulphur-containing exhaust gas modifying agent is 1～5m/s.
Wherein, in described heat treated, heating-up temperature is 600～700 DEG C, and heating treatment time is 1～5s.
The industrial sulphur-containing exhaust gas carbon modified base adsorbent that above-mentioned any one prepares also protection scope of the present invention it
In.
Above-mentioned industry the application in flue gas demercuration of the sulphur-containing exhaust gas carbon modified base adsorbent also protection scope of the present invention it
In.
Wherein, described application process is:
(1) being sprayed into by industry sulphur-containing exhaust gas carbon modified base adsorbent and carry out haptoreaction in mercury fume, phase hydrargyrum is with HgS
Form be combined in adsorbent surface, the industrial sulphur-containing exhaust gas carbon modified base adsorbent of isolated richness hydrargyrum；Reaction equation is as follows:
Hg(g)+C-S(s)→C-HgS(s)；
(2) by the industrial sulphur-containing exhaust gas carbon modified base adsorbent of the rich hydrargyrum of gained in step (1) under inert gas shielding
Carry out adding thermal desorption, rest on the HgS on carbon-based adsorbent surface again with gaseous state Hg0Form discharge completely, brought about the desired sensation
State hydrargyrum reclaims in noble gas is delivered to condensing unit；Reaction equation is as follows:
CAC-HgS(s)→Hg(g)+CAC-S(s)；
(3) being reacted with sulphur-containing exhaust gas by the adsorbent after desorption in step (2), it is modified that regeneration obtains industry sulphur-containing exhaust gas
Carbon-based adsorbent；Reaction equation is as follows:
In step (1), the amount ratio of industry sulphur-containing exhaust gas carbon modified base adsorbent and mercury fume is 100～2000mg:
1m3；Wherein, in haptoreaction, the response time is 1～2s.
In step (2), described adds in thermal desorption, and reaction temperature is 250～400 DEG C, and the response time is 1～2s.
In step (2), described noble gas is any one or a few the combination in nitrogen, helium and argon.
In step (3), the adsorbent after desorption reacts with sulphur-containing exhaust gas, and regeneration obtains industry sulphur-containing exhaust gas modification carbon back
The method of adsorbent is: in the industrial waste gas of the sulfur compound that the adsorbent after desorption is placed in flowing, at 600～700 DEG C
Heat treated 1～5s, obtains industrial sulphur-containing exhaust gas carbon modified base adsorbent；Wherein, in industrial waste gas, the quality of sulfide
Mark is 0.2～5%, if sulfide concentration is too high, can produce competitive Adsorption with hydrargyrum, and the absorption of hydrargyrum is made by suppression adsorbent
With；The flow velocity of the industrial waste gas of sulfur compound is 1～5m/s.
Beneficial effect:
Compared with prior art, the present invention has the advantage that
(1) by low concentration sulfur-bearing industrial waste gas resource, turn waste into wealth；
(2) utilize industry sulphur-containing exhaust gas carbon modified base adsorbent, strengthen the demercuration performance of adsorbent, the treatment of wastes with processes of wastes against one another；
(3) desorption realizing hydrargyrum recycles, and reduces the total mercury content entering air, decreases the nature of preciousness simultaneously
The waste of resource hydrargyrum；
(4) carbon-based adsorbent can obtain activating and regenerating and recycle, and decreases the consumption of adsorbent, largely
On reduce demercuration cost；
(5) achieve absorption demercuration-add thermal desorption-gas modified active and regenerate continuous cyclic process.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of preparation, demercuration and the regeneration of industry sulphur-containing exhaust gas carbon modified base adsorbent in embodiment 1.
Detailed description of the invention
Embodiment 1
As it is shown in figure 1, a kind of industry sulphur-containing exhaust gas carbon modified base adsorbent flue gas demercuration that the present invention relates to and renovation process,
Sulfur activated reactor 3, dedusting capture segregation apparatus 6, hydrargyrum desorption reaction device 8, hydrargyrum separating reaction is carried including carbon-based adsorbent
Device 10 and hydrargyrum condensate recycling device 12, sulfur-bearing industrial waste gas 1 enters carbon-based adsorbent from bottom to top and carries sulfur activated reactor
3；Load sulfur absorbent 4 after activation is injected directly in mercury fume 5, and the outlet of mixture captures segregation apparatus 6 with dedusting
Connect；The rich mercury absorbent 7 in dedusting capture segregation apparatus 6 exit is connected with the bottom of hydrargyrum desorption reaction device 8；Desorption
The outlet of reactor 8 is connected by the weary pipe material of adsorbent 9 with hydrargyrum separate reactor 10；A left side for hydrargyrum separate reactor 10
Bringing out mouth and connect carbon-based adsorbent load sulfur activated reactor 3 by the weary pipe material of adsorbent 2, top exit is by hydrargyrum outlet tube
Road 11 connects hydrargyrum condensate recycling device 12, and hydrargyrum condensate recycling device 12 is connected with pure hydrargyrum conveyance conduit 13.
Containing SO2Concentration be 2% industrial waste gas enter carbon-based adsorbent with the speed of 3m/s and carry sulfur activated reactor 3, with
Time the weary material of adsorbent enter reactor 3 by pipeline 2, under the temperature conditions of 650 DEG C, both are fully contacted,
Sulfide is enriched in adsorbent surface with the form of multiple sulfur-bearing functional group, it is thus achieved that highly active load sulfur absorbent 4；Obtain
The demercuration adsorbent 4 obtained is injected directly in the mercury fume 5 that temperature is 135 DEG C, and gas phase hydrargyrum is combined in the form of HgS
Adsorbent surface, the ratio spraying into adsorbent in mercury fume and flue gas volume is 1000mg/m3.Reacted rich hydrargyrum is inhaled
It is delivered to desorption reaction device 8 after being captured separation by dust arrester 6 for attached dose 7, adds under the conditions of 300 DEG C of temperature nitrogen atmospheres
Heat carries out the desorption of hydrargyrum, stays in the HgS on carbon-based adsorbent surface again with gaseous state Hg0Form discharge completely.Release
Hg0Material weary with adsorbent is delivered to hydrargyrum separate reactor 10, Hg by pipeline 90It is delivered to by inert carrier gas pipeline 11
Condensate recycling device 12 enriching and recovering, the weary material of adsorbent is entered activated reactor 3 and containing SO by pipeline 22Industrial waste gas
Regenerate under the conditions of 650 DEG C, it is achieved carbon modified base adsorbent flue gas mercury removal reclaims and the cyclic process of adsorbent reactivation.
Use said method, containing SO after activation2Sulfide content when waste gas is got rid of is less than 0.1%, and the response rate of hydrargyrum can
More than 80%, the recovery utilization rate of carbon-based adsorbent reaches more than 90%.
Claims (10)
1. the preparation method of an industrial sulphur-containing exhaust gas carbon modified base adsorbent, it is characterised in that it is made by the following method
For obtaining:
Carbon-based adsorbent is placed in the industrial sulphur-containing exhaust gas modifying agent of flowing, heat treated, obtains industrial sulphur-containing exhaust gas and change
Property carbon-based adsorbent.
Preparation method the most according to claim 1, it is characterised in that described carbon-based adsorbent be activated carbon,
Biomass char or petroleum coke, described industrial sulphur-containing exhaust gas modifying agent is the industrial waste gas of sulfur compound；Wherein, Industry Waste
In gas, the mass fraction of sulfide is 0.2～5%.
Preparation method the most according to claim 1, it is characterised in that the flow velocity of industry sulphur-containing exhaust gas modifying agent is
1～5m/s.
Preparation method the most according to claim 1, it is characterised in that in described heat treated, heating-up temperature
Being 600～700 DEG C, heating treatment time is 1～5s.
5. the industrial sulphur-containing exhaust gas carbon modified base adsorbent that in Claims 1 to 4, any one prepares.
6. the application in flue gas demercuration of the industrial sulphur-containing exhaust gas carbon modified base adsorbent described in claim 5.
Application the most according to claim 6, it is characterised in that described application process is:
(1) after industry sulphur-containing exhaust gas carbon modified base adsorbent and mercury fume being carried out haptoreaction, isolated richness hydrargyrum
Industrial sulphur-containing exhaust gas carbon modified base adsorbent；
(2) by the industrial sulphur-containing exhaust gas carbon modified base adsorbent of the rich hydrargyrum of gained in step (1) under inert gas shielding
Carrying out adding thermal desorption, gained gaseous mercury reclaims in noble gas is delivered to condensing unit；
(3) being reacted with sulphur-containing exhaust gas by the adsorbent after desorption in step (2), it is modified that regeneration obtains industry sulphur-containing exhaust gas
Carbon-based adsorbent.
Application process the most according to claim 7, it is characterised in that in step (1), industry sulphur-containing exhaust gas changes
The amount ratio of property carbon-based adsorbent and mercury fume is 100～2000mg:1m3；Wherein, in haptoreaction, during reaction
Between be 1～2s.
Application process the most according to claim 7, it is characterised in that in step (2), described adds thermal desorption
In, reaction temperature is 250～400 DEG C, and the response time is 1～2s.
Application process the most according to claim 7, it is characterised in that in step (3), the absorption after desorption
Agent is reacted with sulphur-containing exhaust gas, and regeneration obtains the method for industry sulphur-containing exhaust gas carbon modified base adsorbent and is: by the absorption after desorption
In the industrial waste gas of the sulfur compound that agent is placed in flowing, heat treated 1～5s at 600～700 DEG C, obtain industrial sulphur-containing exhaust gas
Carbon modified base adsorbent；Wherein, in industrial waste gas, the mass fraction of sulfide is 0.2～5%, if sulfide concentration mistake
Height, can produce competitive Adsorption with hydrargyrum, suppress the adsorbent adsorption to hydrargyrum；The flow velocity of the industrial waste gas of sulfur compound is
1～5m/s.
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| CN201610288796.4A CN105921104A (en) | 2016-05-04 | 2016-05-04 | Industrial sulfur-containing waste gas modified carbon-based adsorbent and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983308A (en) * | 2017-12-11 | 2018-05-04 | 华中科技大学 | A kind of porous carbon adsorbent for removing mercury and preparation method thereof |
| CN108499340A (en) * | 2018-04-28 | 2018-09-07 | 盐城东博环保科技有限公司 | A kind of Mercury In Coal Combustion Flue Gas removing recycling and adsorbent regeneration method based on CLP processes |
| CN109621899A (en) * | 2019-01-17 | 2019-04-16 | 山东大学 | A kind of preparation system and method for demercuration sulfur loading active carbon/coke |
-
2016
- 2016-05-04 CN CN201610288796.4A patent/CN105921104A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983308A (en) * | 2017-12-11 | 2018-05-04 | 华中科技大学 | A kind of porous carbon adsorbent for removing mercury and preparation method thereof |
| CN108499340A (en) * | 2018-04-28 | 2018-09-07 | 盐城东博环保科技有限公司 | A kind of Mercury In Coal Combustion Flue Gas removing recycling and adsorbent regeneration method based on CLP processes |
| CN109621899A (en) * | 2019-01-17 | 2019-04-16 | 山东大学 | A kind of preparation system and method for demercuration sulfur loading active carbon/coke |
| CN109621899B (en) * | 2019-01-17 | 2020-04-28 | 山东大学 | Preparation system and method of demercuration sulfur-carrying activated carbon/coke |
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Application publication date: 20160907 |