CN104338435A - Method for removing mercury in flue gas by use of waste desulfurizer after being used for recycling elemental sulfur - Google Patents
Method for removing mercury in flue gas by use of waste desulfurizer after being used for recycling elemental sulfur Download PDFInfo
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- CN104338435A CN104338435A CN201410376165.9A CN201410376165A CN104338435A CN 104338435 A CN104338435 A CN 104338435A CN 201410376165 A CN201410376165 A CN 201410376165A CN 104338435 A CN104338435 A CN 104338435A
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Abstract
The invention provides a method for removing mercury in flue gas by use of a waste desulfurizer after being used for recycling elemental sulfur, and relates to an environment-friendly treatment method in which a heat-treated waste ferric oxide desulfurizer is used as a coal-fired flue gas mercury remover. According to the method comprises, rich elemental sulfur in the waste desulfurizer is recycled by use of carrier gas under a heating condition, wherein based on the total amount of the waste desulfurizer, the content of the total sulfur in the waste ferric oxide desulfurizer in 17wt%-21wt%, and the content of the elemental sulfur in the waste ferric oxide desulfurizer is 6wt%-7wt%; the condition that pores of the desulfurizer are blocked by the elemental sulfur is improved. The content of the elemental sulfur in the heat-treated waste desulfurizer is 1-2wt%; the heat-treated waste ferric oxide desulfurizer has the excellent activity to zero-valence mercury, and is capable of finally converting adsorbed mercury into stabilized mercury sulfide. The method for removing the mercury in the flue gas by use of the waste desulfurizer after being used for recycling the elemental sulfur is used for solving the problem of recycling the waste desulfurizer; as a result, a sulfur product can be obtained, and furthermore, an efficient and cheap waste gas mercury remover is found out, and the environment protection treatment cost can be reduced.
Description
Technical field
The present invention relates to a kind of eco-friendly processing method and application direction waste desulfurizing agent after heat treatment being used as coal-fired flue gas mercury removal agent, be specifically related to a kind of method utilizing the waste desulfurizing agent after reclaiming elemental sulfur to remove the mercury in flue gas.
Background technology
Mercury is that one has permanent cumulative noxious material in vivo with in food chain, and the toxicity of mercury has accumulation property often to be needed several years or the more than ten years just have performance to coerce very large to the health of crowd.Simultaneously the hypertoxicity that has of mercury and atmospheric residence time long, it can not be ignored the harm of environment.
Mercury is mainly through the discharge of nature and human factor and entered environment.Naturally discharge mainly refers to volcano eruption etc.Anthropogenic discharge's amount accounts for the larger ratio of total release, about 3/4, and the mercury proportion of wherein coal-fired release is comparatively large, accounts for 1/3.The whole world mercury that only coal-fired power plant discharges every year just can reach 1470t, and wherein Asia coal-burning power plant discharges mercury quantity is every year 860t, and North America is 105t.China is that global range Mercury In The Air pollutes one of region the most serious, and it is large that coal in China accounts for energy resource structure ratio, also will account for 62.6%, even if still account for more than 50% to the year two thousand fifty coal according to predicting coal in 2015.Visible within a quite long from now on period, the energy consumption structure of China based on coal will be difficult to change, and therefore in coal conversion process, mercury pollution is more outstanding.Can predict, prevent mercury pollution in coal conversion process from being one of current and later a period of time most important environmental protection subject.
Coal-burning power plant's mercury emissions has received increasing concern, and various demercuration scheme also occurs in succession, but thinks that the most promising coal-fired flue-gas mercury control technology has three kinds at present: sorbent injection, washing and coal preparation technology.Sorbent injection method mainly utilizes the Hg in adsorbent flue gas
0and Hg
2+, making them be enriched in adsorbent becomes particulate Hg, and particulate Hg is caught through cleaner, reaches the object of flue gas demercuration.Flue gas demercuration technology at present closest to application sprays into powdered active carbon demercuration method in flue gas, but this technical operation cost is very high.Although wet scrubbing technology can utilize wet desulphurization device can reach Hg
2+control, but for water-fast Hg
0removal efficiency low.The mercury removal efficiency that coal preparation technology can reach is larger with coal relation, new coal preparation technology is just in development, but the mercury residued in coal still needs to remove with additive method, and coal separation removal of mercury cost is high, needs just can reach satisfied demercuration effect with other control technology conbined usage.The discharge utilizing existing pollutant catabolic gene equipment to control coal-fired plant boiler in conjunction with sorbent injection method is a kind of economically viable method, and can it focus on finding the cheap raw material be applicable to prepare mercury absorbent.
Desulfurizing agent is widely used in the industry such as oil, chemical industry, metallurgy, electric power, and along with industrial fast development since reform and opening-up, industries concerned is as day by day increased the demand of desulfurizing agent to produce the industry such as coal gas, natural gas and synthetic material gas.Wherein iron oxide process desulfurization is a kind of classical and one of effective method, and it has, and technique is simple, safe and reliable, simple to operate, low power consumption and other advantages.Along with the increase of ferric oxide desulfurizer consumption, the quantity of this solid waste containing a large amount of noxious material is also increasing, defines the new pollution sources being more and more difficult to dispose, so reasonably processing these waste desulfurizing agents has been the task of top priority.Iron oxide desulphurizing agent is in the process of desulfurization and regeneration, and the hydrogen sulfide major part be adsorbed onto on desulfurizing agent can be converted into sulphur, and also some can be converted into metal sulfide.Desulfurizing agent after regeneration, elemental sulfur accumulates in desulfurizing agent surface and pore, when desulfurizing agent repeated regeneration, constantly reduce the elemental sulfur that makes new advances with time wherein, active component in desulfurizing agent will gradually cover by elemental sulfur encirclement, pore is blocked by elemental sulfur, finally causes desulfurizing agent to lose activity.Now, just this part desulfurizing agent will be discarded, this not only wastes a large amount of resources, and disposal cost is also very high.But, if sulphur abundant in these discarded desulfurizing agents can be reclaimed, and utilize desulfurizing agent to prepare demercuration adsorbent as raw material, both saved valuable Sulphur ressource, can waste desulfurizing agent have been effectively utilized again, reached the effect of the treatment of wastes with processes of wastes against one another.New through looking into, at present about to the method preparing mercury removal agent after waste desulfurizing agent Recovered sulphur, there is not been reported.
Summary of the invention
The object that spent ferric oxide fimily desulfurizing agent of the present invention reclaims sulphur had both been to reclaim valuable sulphur resource, more be greatly to alleviate desulfurizing agent surface and hole by the situation of sulfur plug, the specific area of desulfurizing agent is increased, enhance the reactivity of elemental sulfur and mercury, thus obtain a kind of very good material preparing mercury removal agent.Solve in existing mercury pollution control procedure and need the mercury removal agent that a large amount of price is higher, and spent ferric oxide fimily desulfurizing agent is difficult to the problems such as process application, can also significantly improve the adsorption effect to nonvalent mercury in mercury fume.
The present invention is achieved through the following technical solutions, carrier gas is utilized to reclaim elemental sulfur abundant in spent ferric oxide fimily desulfurizing agent in a heated condition, the adsorption capacity of spent ferric oxide fimily desulfurizing agent to the nonvalent mercury in mercury fume after heat treatment significantly improves, and finally adsorbed mercury is converted into stable mercuric sulphide.
The invention provides a kind of method utilizing spent ferric oxide fimily desulfurizing agent to prepare flue gas demercuration agent, described spent ferric oxide fimily desulfurizing agent is the discarded desulfurizing agent of conventional load type iron oxide desulphurizing agent after desulphurization reaction, (wherein with spent ferric oxide fimily desulfurizing agent total amount, in described spent ferric oxide fimily desulfurizing agent, total sulfur content is 17-21wt %, simple substance sulfur content is 6-7wt%), it is characterized in that comprising the steps:
A) described spent ferric oxide fimily desulfurizing agent is pulverized;
B) in logical carrier gas situation, spent ferric oxide fimily desulfurizing agent is heat-treated, after heat treatment, elemental sulfur in described waste desulfurizing agent is transformed into steam sulphur and enters cooling device with carrier gas, the elemental sulfur be recycled after cooling, the elemental sulfur of described spent ferric oxide fimily desulfurizing agent after heat treatment only containing 1-2wt%;
C) the described spent ferric oxide fimily desulfurizing agent after heat treatment only containing 1-2wt% elemental sulfur is used as flue gas demercuration agent.
The present invention is the claimed flue gas demercuration agent prepared according to the method described above also.
In addition; the present invention is a kind of claimed method utilizing spent ferric oxide fimily desulfurizing agent to remove the mercury in flue gas also; described spent ferric oxide fimily desulfurizing agent is that the discarded desulfurizing agent of conventional load type iron oxide desulphurizing agent after desulphurization reaction is (wherein with spent ferric oxide fimily desulfurizing agent total amount; in described spent ferric oxide fimily desulfurizing agent, total sulfur content is 17-21wt%; simple substance sulfur content is 6-7wt%), it is characterized in that comprising the steps:
A) described spent ferric oxide fimily desulfurizing agent is pulverized;
B) in logical carrier gas situation, spent ferric oxide fimily desulfurizing agent is heat-treated, after heat treatment, elemental sulfur in described spent ferric oxide fimily desulfurizing agent is transformed into steam sulphur and enters cooling device with carrier gas, the elemental sulfur be recycled after cooling, the elemental sulfur of described waste desulfurizing agent after heat treatment only containing about 1-2wt%;
C) the spent ferric oxide fimily desulfurizing agent of the elemental sulfur only containing about 1-2wt% after above-mentioned heat treatment is used as flue gas demercuration agent, described flue gas demercuration agent is with filled type or directly spray into the form of flue gas and mercury fume carries out haptoreaction, mercury in flue gas is converted into mercuric sulphide, thus reaches the object of flue gas demercuration.
The concrete operations of wherein said step b) are: under the temperature range of 270-450 DEG C, carrier gas is passed in the quartz ampoule that spent ferric oxide fimily desulfurizing agent is housed and heat-treats, time controling is at 1-10min, and at the elemental sulfur that the afterbody installation cooling device recovery carrier gas of quartz ampoule is carried, the rate of recovery of elemental sulfur reaches about 70-80%, the elemental sulfur of described spent ferric oxide fimily desulfurizing agent after heat treatment only containing 1-2%.
The carrier of described conventional load type iron oxide desulphurizing agent to be preferably selected from active carbon, molecular sieve, silica, aluminium oxide and imvite one or more.
Described carrier gas is N
2, CO
2, one or more in Ar, He, described carrier gas purity is more than 99.7%.
Described spent ferric oxide fimily desulfurizing agent also comprises use electric drying oven with forced convection to the withering step of described waste desulfurizing agent before pulverizing, the condition of dry process is 120 DEG C, 2-6h, air atmosphere.
Described flue gas demercuration agent carries out haptoreaction with the form of filled type and mercury fume, and the thickness of mercury removal agent packed layer is 10-100mm; Or described flue gas demercuration agent carries out haptoreaction with the form directly sprayed into and mercury fume, spraying into the mercury removal agent in mercury fume with the ratio of flue gas volume is 100-2000mg/m
3.
Described flue gas demercuration agent is with filled type or directly spray into the form of flue gas and mercury fume carries out catalytic reaction temperature for 80-240 DEG C.
Because the total mercury concentration in flue gas is 40 μ g/m
3left and right, belongs to contaminant trace species, and existing mercury removal agent is very undesirable to the removal effect of Trace Hg pollutant.And utilize the waste desulfurizing agent after reclaiming elemental sulfur to remove in the method for the mercury in flue gas of the present invention, after heat treatment only containing in the waste desulfurizing agent of about 1-2% sulphur, remaining elemental sulfur is highly dispersed on carrier, its pore structure and specific area prosperity, flue gas demercuration agent is used as with the waste desulfurizing agent that this after heat treatment only contains about 1-2% sulphur, wherein remaining a small amount of elemental sulfur can react with mercury, generates stable mercuric sulphide, can remove nonvalent mercury efficiently.Therefore utilize described in the application reclaim that method that the waste desulfurizing agent after elemental sulfur removes the mercury in flue gas not only rationally can solve mercury in flue gas remove problem, fume emission outlet mercury concentration is controlled at 5 μ g/Nm
3below, can also produce the sulfur product of high-quality, purity can reach 93 ~ 95%, and sulfur recovery rate can reach about 70 ~ 80%.
Compared with prior art, feature of the present invention is: 1, waste desulfurizing agent is after this heat treatment, significantly increases the adsorption capacity of the gas mercury comprising nonvalent mercury, and the consumption of adsorbent in mercury fume processing procedure is significantly reduced; 2, containing a large amount of elemental sulfurs in the waste desulfurizing agent adopted, reclaimed the sulphur of more than 70% by heat treatment, saved valuable Sulphur ressource, turned waste into wealth; 3, use waste desulfurizing agent as the raw material of mercury removal agent, both solved the process problem of waste desulfurizing agent, and reached the effect of the treatment of wastes with processes of wastes against one another.Reduce the cost of flue gas demercuration more to a great extent.
Accompanying drawing explanation
Fig. 1 is spent ferric oxide fimily desulfurizing agent at the thermal gravimetric analysis results figure of temperature programming to 900 DEG C.Thermogravimetric analysis condition: atmosphere is N
2, gas flow is 100ml/min, and sample size is 20mg, and heating rate is 20 DEG C/min.
Fig. 2 is that mercury removal agent prepared by embodiment 1 carries out the Activity evaluation of the Hg removed in flue gas in fixed bed reactors.Temperature 120 DEG C, time 500min.
Fig. 3 is that mercury removal agent prepared by embodiment 2 carries out the Activity evaluation of the Hg removed in flue gas in fixed bed reactors.Temperature 240 DEG C, time 500min.
Fig. 4 is the Activity evaluation that in embodiment 5, mercury removal agent carries out the Hg removed in flue gas in fixed bed reactors.Temperature 160 DEG C, time 30h.
Detailed description of the invention
Below embodiments of the invention are elaborated: the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
First in waste desulfurizing agent, change the temperature of steam sulphur according to elemental sulfur into, the heat treated temperature of waste desulfurizing agent is in optimized selection.For verifying elemental sulfur gasification temperature suitable in waste desulfurizing agent, sample thief does thermogravimetric analysis (DTG), and thermogravimetric analysis condition is atmosphere: N
2, gas flow is 100ml/min, and sample size is 20mg, and heating rate is 20 DEG C/min.As can be seen from DTG curve, there is an obvious weightless peak 250-320 DEG C of stage, and maximum weight loss rate peak temperature is close to 290 DEG C, this weightless peak is because elemental sulfur is heated vaporization with weightless.There is another obvious weightless peak 400-680 DEG C of stage, and maximum weight loss rate peak temperature is close to 600 DEG C, this weightless peak is because metal sulfide such as iron sulfide etc. decomposes with weightless.According to the result of thermogravimetric analysis, carried out the heat treatment experiment of a series of different temperatures different time, and the waste desulfurizing agent after heat treatment is carried out demercuration activity rating, final optimization pass has gone out the best heat treated temperature and time of waste desulfurizing agent.When heat treatment temperature is 270-400 DEG C, when the time is 1-10min, in the spent ferric oxide fimily desulfurizing agent after heat treatment, simple substance sulfur content is 1-2wt%.Spent ferric oxide fimily desulfurizing agent now shows fabulous flue gas demercuration ability, by its with filled type or directly spray into flue gas form contact with mercury fume, be directly used in removing of mercury fume.
Embodiment 1
The spent ferric oxide fimily desulfurizing agent utilizing certain chemical plant to change out is tested.Carbon and sulfur analytical instrument after measured in this spent ferric oxide fimily desulfurizing agent total sulfur content be about 21wt%, wherein simple substance sulfur content is about 7wt%.Described spent ferric oxide fimily desulfurizing agent is positioned over dry 4h in electric drying oven with forced convection, and temperature is set as 120 DEG C.Then take out dried waste desulfurizing agent and be crushed to 40 ~ 60 orders, then take 2g, inserted diameter 8.6mm, quartz ampoule that length is 642mm central authorities, and with silica wool blocking desulfurizing agent two ends, make it fix.Quartz ampoule is placed in tube furnace and heats, and temperature is 290 DEG C.Quartz ampoule entrance passes into N
2, gas flow controls at 300ml/min, and outlet connects a set of gas quench system recovered steam sulphur.Whole waste desulfurizing agent heat treatment process time controling is at about 8min.After heat treatment terminates, take out waste desulfurizing agent, measuring its simple substance sulfur content is 1.3wt%.
Next the waste desulfurizing agent that after utilizing above-mentioned heat treatment, simple substance sulfur content is 1.3wt% is used as flue gas demercuration agent, the activity rating of the Hg removed in flue gas is carried out in described flue gas demercuration agent in fixed bed reactors with filled type, this device mainly comprises 4 parts: source of the gas, mercury generator, LUMEX/RA-915+ mercury vapourmeter and vent gas treatment.Experiment condition: simulation mercury fume consists of 40 μ g/m
3hg, 12v/v%CO
2, 6v/v%O
2, 1500ppmSO
2, 500ppmNO, 10ppmHCl and 1v/v%H
2o, surplus is Balance Air N
2; Flue gas flow 1L/min; Bed temperature 120 DEG C; Flue gas demercuration dosage 0.5g; Reaction time 500min.
As shown in Figure 2, found that, the adsorption effect of desulfurizing agent after heat treatment to nonvalent mercury is remarkable for flue gas demercuration agent demercuration Activity Results, initial demercuration rate reaches 94.5%, in 500 minutes, demercuration rate remains on more than 92% always, and demercuration Activity decline rates is slower.
Embodiment 2
Another spent ferric oxide fimily desulfurizing agent is utilized to test.Mensuration shows that in this waste desulfurizing agent, total sulfur content is about 17wt%, and wherein sulfur content is about 6wt%.Above-mentioned spent ferric oxide fimily desulfurizing agent is positioned over dry 3h in electric drying oven with forced convection, and temperature is set as 120 DEG C.Then take out dried waste desulfurizing agent and be crushed to 40 ~ 60 orders, then take 2g, inserted diameter 8.6mm, quartz ampoule that length is 642mm central authorities, and with silica wool blocking desulfurizing agent two ends, make it fix.Quartz ampoule is placed in tube-type atmosphere furnace and heats, and temperature is 380 DEG C.Quartz ampoule entrance passes into CO
2, gas flow controls at 300ml/min, and outlet connects a set of gas quench system recovered steam sulphur.Whole waste desulfurizing agent heat treatment process time controling is at about 1.5min.After heat treatment terminates, take out waste desulfurizing agent, measure its simple substance sulfur content and be about 1wt%.
Next after utilizing above-mentioned heat treatment, simple substance sulfur content is about the waste desulfurizing agent of 1wt% as flue gas demercuration agent, the activity rating of the Hg removed in flue gas is carried out in described flue gas demercuration agent in fixed bed reactors with filled type, this device mainly comprises 4 parts: source of the gas, mercury generator, LUMEX/RA-915+ mercury vapourmeter and vent gas treatment.Experiment condition: simulation mercury fume consists of 40 μ g/m
3hg, 12v/v%CO
2, 6v/v%O
2, 1500ppmSO
2, 500ppmNO, 10ppmHCl and 1v/v%H
2o, surplus is Balance Air N
2; Flue gas flow 1L/min; Bed temperature 240 DEG C; Flue gas demercuration dosage 0.5g; Reaction time 500min.
Flue gas demercuration agent demercuration Activity Results as shown in Figure 3, found that, after reaction bed temperature brings up to 240 DEG C, initial demercuration rate up to 97.5%, but demercuration rate fall off rate comparatively embodiment 1 is faster, after 450 minutes, demercuration rate drops to less than 90%.
Embodiment 3
The waste desulfurizing agent that in embodiment 1, after heat treatment, sulfur content is 1.3wt% is utilized to be used as the demercuration activity rating that flue gas demercuration agent directly sprays into formula.Experiment is carried out in a simulated flue gas pipeline, by take internal diameter as 20mm, length is 600mm quartz ampoule is vertically placed, and utilizes electrical heating, makes its temperature remain on 80 DEG C.Pass into simulation mercury fume, simulation mercury fume consists of 40 μ g/m
3hg, 12v/v%CO
2, 6v/v%O
2, 1500ppmSO
2, 500ppmNO, 10ppmHCl and 1v/v%H
2o, surplus is Balance Air N
2; Keep mercury fume air-flow to flow through quartz ampoule from top to bottom, the average discharge of mercury fume air-flow is 6m
3/ h, is provided with small cyclones deduster at the gas outlet of quartz ampoule.The waste desulfurizing agent being 1.3wt% by sulfur content after heat treatment in embodiment 1 sprays in pipe with the feed rate of 1.5g/h from the top of quartz ampoule, makes it to mix with air-flow rapidly, and the waste desulfurizing agent flowed out with air-flow from quartz ampoule bottom is removed by deduster.
Measure in real time mercury concentration in quartz ampoule exit flow in above-mentioned situation, result shows, after heat treatment sulfur content be 1.3wt% waste desulfurizing agent adopt and directly spray into formula and carry out flue gas demercuration there is very high adsorption efficiency, on average remain on more than 90%.Although compared with filled type demercuration, the consumption of mercury removal agent will increase, but avoid the frequent operating cost changing flue gas demercuration agent, and the installation cost of fixed adsorption bed, be a kind of feasible industrialization flue gas demercuration path.
Embodiment 4
The waste desulfurizing agent that in embodiment 2, after heat treatment, sulfur content is 1wt% is utilized to be used as the demercuration activity rating that flue gas demercuration agent directly sprays into formula.Experiment is carried out in a simulated flue gas pipeline, by take internal diameter as 20mm, length is 600mm quartz ampoule is vertically placed, and utilizes electrical heating, makes its temperature remain on 160 DEG C.Pass into simulation mercury fume, simulation mercury fume consists of 40 μ g/m
3hg, 12v/v%CO
2, 6v/v%O
2, 1500ppmSO
2, 500ppmNO, 10ppmHCl and 1v/v%H
2o, surplus is Balance Air N
2; Keep mercury fume air-flow to flow through quartz ampoule from top to bottom, the average discharge of mercury fume air-flow is 10m
3/ h, is provided with small cyclones deduster at the gas outlet of quartz ampoule.Spray into pipe in the feed rate of 1.5g/h from the top of quartz ampoule by the waste desulfurizing agent after heat treatment in embodiment 2, make it to mix with air-flow rapidly, the waste desulfurizing agent flowed out with air-flow from quartz ampoule bottom is removed by deduster.
Measure in real time mercury concentration in quartz ampoule exit flow in above-mentioned situation, result shows, after heat treatment sulfur content be 1wt% waste desulfurizing agent adopt and directly spray into formula and carry out flue gas demercuration there is very high adsorption efficiency, on average remain on more than 88%.
Embodiment 5
In order to investigate the waste desulfurizing agent after heat treatment, to be used as the long demercuration of flue gas demercuration agent active, gets waste desulfurizing agent that in 1g embodiment 1, after heat treatment, sulfur content is 1.3wt% carries out reaching 30h active appraisal experiment according to the evaluation method described in embodiment 1.Experiment condition: simulation mercury fume consists of 40 μ g/m
3hg, 12v/v%CO
2, 6 v/v%O
2, 1500ppmSO
2, 500ppmNO, 10ppmHCl and 1v/v%H
2o, surplus is Balance Air N
2; Mercury fume gas flow 1L/min; Bed temperature 160 DEG C; Reaction time 30h.
The demercuration Activity Results of described flue gas demercuration agent as shown in Figure 4, found that, adsorbent bed temperature brings up to 160 DEG C by 120 DEG C, mercury removal agent demercuration activity is made to obtain small size raising, in first 600 minutes after starting absorption, demercuration rate remains on more than 90% always, and after 30h, the demercuration efficiency of adsorbent just drops to less than 50%.
It is that the desulfurizing agent of about 1.3wt% not only significantly strengthens the adsorption effect of nonvalent mercury that above-mentioned experimental result shows after heat treatment sulfur content, and demercuration for a long time can be kept active.Greatly reduce the frequent operating cost changing demercuration adsorbent like this.
Claims (10)
1. the method utilizing spent ferric oxide fimily desulfurizing agent to prepare flue gas demercuration agent, described spent ferric oxide fimily desulfurizing agent is that the discarded desulfurizing agent of conventional load type iron oxide desulphurizing agent after desulphurization reaction is (wherein with spent ferric oxide fimily desulfurizing agent total amount, in described spent ferric oxide fimily desulfurizing agent, total sulfur content is 17-21wt%, simple substance sulfur content is 6-7wt%), it is characterized in that comprising the steps:
Described spent ferric oxide fimily desulfurizing agent is pulverized;
In logical carrier gas situation, spent ferric oxide fimily desulfurizing agent is heat-treated, after heat treatment, elemental sulfur in described waste desulfurizing agent is transformed into steam sulphur and enters cooling device with carrier gas, the elemental sulfur be recycled after cooling, the elemental sulfur of described spent ferric oxide fimily desulfurizing agent after heat treatment only containing 1-2wt%;
The described spent ferric oxide fimily desulfurizing agent after heat treatment only containing 1-2wt% elemental sulfur is used as flue gas demercuration agent.
2. the flue gas demercuration agent prepared according to method described in claim 1.
3. the method utilizing spent ferric oxide fimily desulfurizing agent to remove the mercury in flue gas, described spent ferric oxide fimily desulfurizing agent is that the discarded desulfurizing agent of conventional load type iron oxide desulphurizing agent after desulphurization reaction is (wherein with spent ferric oxide fimily desulfurizing agent total amount, in described spent ferric oxide fimily desulfurizing agent, total sulfur content is 17-21wt %, simple substance sulfur content is 6-7wt%), it is characterized in that comprising the steps:
Described spent ferric oxide fimily desulfurizing agent is pulverized;
In logical carrier gas situation, spent ferric oxide fimily desulfurizing agent is heat-treated, after heat treatment, elemental sulfur in described spent ferric oxide fimily desulfurizing agent is transformed into steam sulphur and enters cooling device with carrier gas, the elemental sulfur be recycled after cooling, the elemental sulfur of described waste desulfurizing agent after heat treatment only containing about 1-2wt%;
The spent ferric oxide fimily desulfurizing agent of the elemental sulfur only containing about 1-2wt% after above-mentioned heat treatment is used as flue gas demercuration agent, described flue gas demercuration agent is with filled type or directly spray into the form of flue gas and mercury fume carries out haptoreaction, mercury in flue gas is converted into mercuric sulphide, thus reaches the object of flue gas demercuration.
4. the method according to claim 1 or 3, it is characterized in that, the concrete operations of described step b) are: under the temperature range of 270-450 DEG C, carrier gas is passed in the quartz ampoule that spent ferric oxide fimily desulfurizing agent is housed and heat-treats, time controling is at 1-10min, and at the elemental sulfur that the afterbody installation cooling device recovery carrier gas of quartz ampoule is carried, the rate of recovery of elemental sulfur reaches about 70-80%, the elemental sulfur of described spent ferric oxide fimily desulfurizing agent after heat treatment only containing 1-2%.
5. the method according to claim 1 or 3, is characterized in that, the carrier of described conventional load type iron oxide desulphurizing agent to be selected from active carbon, molecular sieve, silica, aluminium oxide and imvite one or more.
6. the method according to claim 1 or 3, is characterized in that, in described step a), spent ferric oxide fimily desulfurizing agent is ground into 40-60 object granule.
7. the method according to claim 1 or 3, is characterized in that, described spent ferric oxide fimily desulfurizing agent also comprises use electric drying oven with forced convection to the withering step of described waste desulfurizing agent before pulverizing.
8. the method according to claim 1 or 3, is characterized in that, described carrier gas is N
2, CO
2, one or more in Ar, He, described carrier gas purity is more than 99.7%.
9. the method according to claim 3 or 4, is characterized in that, described flue gas demercuration agent carries out haptoreaction with the form of filled type and mercury fume, and the thickness of mercury removal agent packed layer is 10-100mm; Or described flue gas demercuration agent carries out haptoreaction with the form directly sprayed into and mercury fume, spraying into the mercury removal agent in mercury fume with the ratio of flue gas volume is 100-2000mg/m
3.
10. the method according to claim 3 or 4, is characterized in that, described flue gas demercuration agent is with filled type or directly spray into the form of flue gas and mercury fume carries out catalytic reaction temperature for 80-240 DEG C.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582250A (en) * | 2016-12-21 | 2017-04-26 | 贵州大学 | Desulfurization and demercuration agent used in fixed bed reactors and preparation method thereof |
| CN106955595A (en) * | 2017-04-19 | 2017-07-18 | 成都天立化工科技有限公司 | The renovation process of desulfurizing agent simple substance sulphur in a kind of desulfurizing tower |
| CN107497829A (en) * | 2017-09-08 | 2017-12-22 | 山西普友气体净化有限公司 | A kind of innoxious use method of useless shaping desulfurizing agent |
| CN107812509A (en) * | 2017-09-14 | 2018-03-20 | 浙江工业大学 | A kind of filter membrane material and its preparation method and application |
| CN107812509B (en) * | 2017-09-14 | 2020-03-17 | 浙江工业大学 | Filtering membrane material and preparation method and application thereof |
| CN114602285A (en) * | 2022-02-08 | 2022-06-10 | 浙江红狮环保股份有限公司 | Method for removing lead compound in flue gas |
| CN115253678A (en) * | 2022-08-05 | 2022-11-01 | 沈阳三聚凯特催化剂有限公司 | Method for recycling zinc oxide desulfurizer and application |
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