CN103263835B - Iron bromide mercury removal compound liquid and method for removing mercury of flue gas by use of same - Google Patents
Iron bromide mercury removal compound liquid and method for removing mercury of flue gas by use of same Download PDFInfo
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- CN103263835B CN103263835B CN201310199654.7A CN201310199654A CN103263835B CN 103263835 B CN103263835 B CN 103263835B CN 201310199654 A CN201310199654 A CN 201310199654A CN 103263835 B CN103263835 B CN 103263835B
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- mercury
- flue gas
- ferric bromide
- compositional liquor
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Abstract
The invention relates to an iron bromide mercury removal compound liquid and a method for removing mercury of flue gas by use of the same. The compound liquid is an iron bromide mercury removal compound liquid which is prepared by taking iron chloride and calcium bromide as main active raw material components and adding hydrogen peroxide with certain concentration, wherein the molar ratio of iron chloride to calcium bromide is 2:3, the mass concentration of iron chloride is 1-10%, and the mass concentration of hydrogen peroxide is 0.1-2.0%. The method for removing mercury of flue gas by use of the iron bromide mercury removal compound liquid comprises the following steps of: uniformly spraying the iron bromide mercury removal compound liquid into the coal-fired flue gas according to certain proportion; generating active bromine atoms or molecules through the oxidation effect of iron ions and hydrogen peroxide on the bromine ions, and converting zero-valence mercury in the flue gas into bivalence mercury by use of the active bromine atoms or molecules; and finally, synchronously absorbing and removing the bivalence mercury and residual iron bromide compound liquid in the flue gas by a wet desulfurization device to achieve an aim of removing mercury in the flue gas. Compared with the prior art, the method provided by the invention can improve the oxidation efficiency of zero-valance mercury in the coal-fired flue gas, avoid secondary pollution and save cost.
Description
Technical field
The present invention relates to the control technology of a kind of environmental protection technical field Mercury In Coal Combustion Flue Gas discharge, specifically a kind of ferric bromide removal of mercury compositional liquor and carry out the method for fume mercury-removing with it.
Background technology
Due to mercury there is stronger toxicity, cumulative bad, atmospheric residence time are longer, it has obvious harmfulness to human health and living environment.Mercury is one of the most volatile heavy metal element in fire coal, and due to the whole world, to fire the consumption of coal every year huge, causes the artificial mercury emissions source that coal-fired flue-gas has become main.As one of country that global mercury pollution is the most serious, China has started the emission control focusing on coal-fired flue-gas mercury pollution, and in desulfurization and dedusting process cooperation-removal mercury research in achieve certain achievement.But in technological development and popularization, need further deeply, and emphasis is considered from the efficient removal nonvalent mercury (Hg coal-fired flue-gas
0) technology.
Mercury in coal-fired flue-gas is mainly with particulate Hg (Hg
p), gaseous state bivalent mercury (Hg
2+) and gaseous state nonvalent mercury (Hg
0) three kinds of forms exist, wherein the ratio shared by each component and the halogen in fire coal (as bromine, chlorine etc.) content closely related.If halogen element content is lower, in flue gas, the ratio of nonvalent mercury is higher.Hg
pgenerally can be removed by dust arrester, Hg
2+more soluble in water, in wet method fume desulfurizing system (WFGD), the Hg of about 90% can be removed
2+, and Hg
0volatile, difficulty is adsorbed and is insoluble in water, and wet desulfurizer does not almost remove effect to it.Halogen element content in China's fire coal is general lower, Hg
0ratio shared in coal-fired flue-gas is higher, and therefore, how effectively control the difficult point of coal-fired flue-gas mercury emissions and key technical problem is control Hg
0discharge.At present, external main active carbon spraying technique (ACI) that adopts is to Hg
0remove, but removal effect is undesirable, and its operating cost is very high, causes the carbon content in flying dust too high, affect its comprehensive utilization; Also utilize catalytic oxidation by Hg in flue gas
0be converted into Hg
2+, but SO in flue gas
2existence to the toxic effect of catalyst, still being difficult at present to find can the catalyst effectively used steady in a long-term, and adopt catalytic oxidation to need to increase a catalytic conversion unit in original flue gas treating process, add complexity and the cost of investment of flue gas purification system.Therefore, develop effective mercury control technology under existing situation and seem particularly urgent.
Based on above-mentioned analysis, if by certain chemical treatment method, by Hg
0be converted into the bivalent mercury of solubility, then WFGD system can be utilized it to be removed together with sulfur dioxide, thus reach the object of the multiple pollutant comprehensive regulation, simplify technical matters simultaneously, and significantly reduce investment outlay and operating cost.Through finding the retrieval of prior art, the oxidant added in flue gas is at present to strengthen Hg in flue gas
0the method of oxidation extensively explored, wherein utilize the method for adding halogen oxidant (particularly chlorine and bromine) to be paid attention to most.The salts such as halide are directly sprayed into the conversion strengthening nonvalent mercury in heat smoke by patent CA2418578, but the oxidation activity of this kind of material is lower, must be combined just can obtain better effects with other adsorbent; Patent US2008107579 proposes by adding the salts such as chloride to improve the method promoting that the nonvalent mercury in flue gas transforms in fire coal, but this method will accelerate the corrosion of boiler furnace and heat-transfer surface.
Chloride or the brominated salt that said process uses, more weak to the oxidation activity of nonvalent mercury, cause the dosage of chlorine or bromine to strengthen, both caused wastage of material, and may secondary pollution be caused again.
Summary of the invention
Object of the present invention is exactly provide a kind of ferric bromide removal of mercury compositional liquor to overcome defect that above-mentioned prior art exists and carry out the method for fume mercury-removing with it.
Object of the present invention can be achieved through the following technical solutions: a kind of ferric bromide removal of mercury compositional liquor, it is characterized in that, this compositional liquor is for chief active raw material components with iron chloride and calcium bromide, and add certain density hydrogen peroxide, the ferric bromide removal of mercury compositional liquor of composition, wherein the mol ratio of iron chloride and calcium bromide is 2: 3, and chlorination iron speciation is 1% ~ 10%, and the mass concentration of hydrogen peroxide is 0.1% ~ 2.0%.
Ferric bromide removal of mercury compositional liquor carries out a method for fume mercury-removing, and it is characterized in that, the method comprises the following steps:
The first step, utilizes iron chloride and calcium bromide solution as raw material, it is contained in container at 2: 3 in molar ratio, and dissolved with distilled water, be configured to ferric bromide combination solution;
Second step, instills in ferric bromide combination solution by a certain percentage by the hydrogenperoxide steam generator prepared, and makes required ferric bromide removal of mercury compositional liquor, and by a certain percentage ferric bromide removal of mercury compositional liquor is injected coal-fired flue-gas, makes it fully mix with flue gas;
3rd step, injects the ferric bromide removal of mercury compositional liquor of flue gas and gasifies at flue gas, and generates and release active bromine or molecule, and the nonvalent mercury in these active bromines or molecule and flue gas reacts, and is oxidized to bivalent mercury;
4th step, flue gas is through wet desulphurization device, and bivalent mercury wherein can be desulfurized liquid and absorb, thus reaches the object of fume mercury-removing, and in flue gas, the ferric bromide removal of mercury compositional liquor of residual minim is desulfurized liquid absorption removal equally simultaneously.
Described in second step by a certain percentage ferric bromide removal of mercury compositional liquor is injected the bromine of coal-fired flue-gas ferric bromide removal of mercury compositional liquor and the mol ratio of flue gas nonvalent mercury is 10 ~ 10000: 1.
Described in second step is 120 ~ 700 DEG C by ferric bromide removal of mercury compositional liquor injection coal-fired flue-gas flue-gas temperature.
Described in second step by ferric bromide removal of mercury compositional liquor inject coal-fired flue-gas, its injection mode sprays in flue by ferric bromide removal of mercury compositional liquor through atomizer, and the liquid-drop diameter after atomization is below 100 microns.
Ferric bromide removal of mercury compositional liquor is injected coal-fired flue-gas itself and flue gas are fully mixed is according to every 0.25m described in second step
2flue area of section a nozzle is set principle in the distribution of flue sectional uniform, to guarantee that ferric bromide removal of mercury compositional liquor is fully and smoke contacts.
Research shows, under certain condition, bromide ion by ferrous ions oxidation, can generate bromine simple substance.Under normal temperature and pressure, this reaction is relatively slower, if but after a small amount of hydrogen peroxide is added ferric bromide compositional liquor, can accelerate the carrying out of this reaction.In addition, due to unstable after ferric bromide heating, in high-temperature flue gas, also can there is decomposition reaction, form more active atomic state bromine, accelerate the oxidation to nonvalent mercury.In addition, the oxidation of the iron containing compounds that ferric bromide generates in the presence of hydrogen peroxide to nonvalent mercury also has catalytic action, further promotes the oxidation of nonvalent mercury.In above process, involved main chemical reactions is as follows:
Fe
3++Br
-→Br
2+Fe
Hg
0+Br
2→HgBr
2
FeBr
3→FeBr
2+Br
Hg
0+Br→HgBr
HgBr+Br
2→HgBr
2+Br
The present invention proposes to utilize the compositional liquor containing ferric bromide based on above-mentioned principle just, and this material can be oxidized the nonvalent mercury in flue gas under certain condition.
Compared with prior art, the invention provides a kind of ferric bromide removal of mercury compositional liquor and carry out the method for fume mercury-removing with it, nonvalent mercury in flue gas is converted into easily by the mercury compound that solution absorbs, recycles existing wet type desulfurizing equipment and it is synchronously removed with the sulfur dioxide in flue gas.There is following beneficial effect:
(1) when not increasing capital equipment, the discharge of nonvalent mercury in flue gas is effectively controlled;
(2) utilize the removal of mercury compositional liquor invented, realizing the Quick Oxidation of nonvalent mercury simultaneously, making full use of and having activated the bromine component in compositional liquor, improve its oxidation efficiency to nonvalent mercury, decrease the consumption of bromide, reduce operating cost;
(3) the present invention is combined with common flue gas desulfur device, can obtain good effect, and not produce secondary pollution;
(4) the present invention is also applicable to the flue gas purification system of waste incineration, and the emission control of the system mercury such as smelting industry gas cleaning.
Detailed description of the invention
Be further described below by way of specific embodiment.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.
Embodiment 1
The preparation of compositional liquor: take 1.625g iron chloride and 1.665g calcium bromide (analyzing pure, > 98%) is inserted in the beaker of 500ml, then dissolved with 200ml distilled water, be mixed with the ferric bromide combination solution of 0.05mol/L; Measure 0.2ml mass concentration be 30 ~ 33% hydrogenperoxide steam generator stand-by.
Utilize the stainless steel tube that diameter is 100mm, length is 5m to be reactor, upstream has a hot plate to add hot-air, and utilizes blower fan by situ configuration simulated flue gas ([NO]=200ppm, [Hg
0]=20 μ g/m
3, [SO
2]=1000ppm, all the other are the hot-air of 140 DEG C of heating by electric cooker) with 160m
3the flow of/h passes into reactor continuously.Then immediately ferric bromide compositional liquor and hydrogenperoxide steam generator mixing are also sprayed in reactor continuously in reactor upstream, the straying quatity of ferric bromide removal of mercury compositional liquor is 100mL/h, and the concentration mol ratio making to spray into nonvalent mercury in bromo element concentration in simulated flue gas and flue gas is about 1000: 1.When reaction reaches stable, record nonvalent mercury oxygenation efficiency and reach more than 85%.Recycling simulation desulfurization alkali lye absorbs tail gas, obtains total removal efficiency of mercury more than 90%.
Embodiment 2
The preparation method of compositional liquor: main preparation condition is identical with embodiment 1.
Utilize the stainless steel tube that diameter is 100mm, length is 5m to be reactor, upstream has a hot plate to add hot-air, and utilizes blower fan by situ configuration simulated flue gas ([NO]=200ppm, [Hg
0]=20 μ g/m
3, [SO
2]=1000ppm, all the other are the hot-air of 140 DEG C of heating by electric cooker) with 160m
3the flow of/h passes into reactor continuously, adds a certain amount of flying dust simultaneously, guarantee that the flying dust concentration in simulated flue gas is about 5g/m in reactor
3.Then immediately ferric bromide compositional liquor and hydrogenperoxide steam generator mixing are also sprayed in reactor continuously in reactor upstream, the straying quatity of ferric bromide removal of mercury compositional liquor is 100mL/h, and the concentration mol ratio making to spray into nonvalent mercury in bromo element concentration in simulated flue gas and flue gas is about 1000: 1.When reaction reaches stable, record nonvalent mercury oxygenation efficiency and reach more than 90%.Recycling simulation desulfurization alkali lye absorbs tail gas, obtains total removal efficiency of mercury more than 95%.Experiment can find thus, when containing a certain amount of flying dust in coal-fired flue-gas, uses the oxidation effectiveness of ferric bromide removal of mercury compositional liquor to nonvalent mercury better.
Claims (5)
1. ferric bromide removal of mercury compositional liquor carries out a method for fume mercury-removing, it is characterized in that, the method comprises the following steps:
The first step, utilizes iron chloride and calcium bromide solution as raw material, by its in molar ratio 2:3 contain in container, and to be dissolved with distilled water, be configured to ferric bromide combination solution;
Second step, instills in ferric bromide combination solution by a certain percentage by the hydrogenperoxide steam generator prepared, and makes required ferric bromide removal of mercury compositional liquor, and by a certain percentage ferric bromide removal of mercury compositional liquor is injected coal-fired flue-gas, makes it fully mix with flue gas;
3rd step, injects the ferric bromide removal of mercury compositional liquor of flue gas and gasifies at flue gas, and generates and release active bromine or molecule, and the nonvalent mercury in these active bromines or molecule and flue gas reacts, and is oxidized to bivalent mercury;
4th step, flue gas is through wet desulphurization device, and bivalent mercury wherein can be desulfurized liquid and absorb, thus reaches the object of fume mercury-removing, and in flue gas, the ferric bromide removal of mercury compositional liquor of residual minim is desulfurized liquid absorption removal equally simultaneously;
Chlorination iron speciation is 1% ~ 10%, and the mass concentration of hydrogen peroxide is 0.1% ~ 2.0%.
2. ferric bromide removal of mercury compositional liquor according to claim 1 carries out the method for fume mercury-removing, it is characterized in that, described in second step by a certain percentage ferric bromide removal of mercury compositional liquor is injected the bromine of coal-fired flue-gas ferric bromide removal of mercury compositional liquor and the mol ratio of flue gas nonvalent mercury is 10 ~ 10000:1.
3. ferric bromide removal of mercury compositional liquor according to claim 1 carries out the method for fume mercury-removing, it is characterized in that, described in second step is 120 ~ 700 DEG C by ferric bromide removal of mercury compositional liquor injection coal-fired flue-gas flue-gas temperature.
4. ferric bromide removal of mercury compositional liquor according to claim 1 carries out the method for fume mercury-removing, it is characterized in that, described in second step by ferric bromide removal of mercury compositional liquor inject coal-fired flue-gas, its injection mode sprays in flue by ferric bromide removal of mercury compositional liquor through atomizer, and the liquid-drop diameter after atomization is below 100 microns.
5. ferric bromide removal of mercury compositional liquor according to claim 1 carries out the method for fume mercury-removing, it is characterized in that, ferric bromide removal of mercury compositional liquor is injected coal-fired flue-gas itself and flue gas are fully mixed is according to every 0.25m described in second step
2flue area of section a nozzle is set principle in the distribution of flue sectional uniform, to guarantee that ferric bromide removal of mercury compositional liquor is fully and smoke contacts.
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| CN201310199654.7A CN103263835B (en) | 2013-05-24 | 2013-05-24 | Iron bromide mercury removal compound liquid and method for removing mercury of flue gas by use of same |
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| US8865099B1 (en) | 2014-02-05 | 2014-10-21 | Urs Corporation | Method and system for removal of mercury from a flue gas |
| CN105536499B (en) * | 2014-10-28 | 2018-02-02 | 中国石油天然气股份有限公司 | A kind of mercury removal agent and its preparation method and application |
| CN105749874A (en) * | 2016-03-28 | 2016-07-13 | 柳州联海科技有限公司 | Adsorbent for mercury removal of flue gas and preparation method of adsorbent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101406793A (en) * | 2008-11-13 | 2009-04-15 | 上海交通大学 | Bromine chloride mercury-removing compositional liquor and method for removing mercury in flue gas using the same |
| WO2012068277A2 (en) * | 2010-11-19 | 2012-05-24 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| CN102698753A (en) * | 2012-05-15 | 2012-10-03 | 中国科学院过程工程研究所 | Catalyst for mercury oxidation and preparation method and purpose thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101406793A (en) * | 2008-11-13 | 2009-04-15 | 上海交通大学 | Bromine chloride mercury-removing compositional liquor and method for removing mercury in flue gas using the same |
| WO2012068277A2 (en) * | 2010-11-19 | 2012-05-24 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| CN102698753A (en) * | 2012-05-15 | 2012-10-03 | 中国科学院过程工程研究所 | Catalyst for mercury oxidation and preparation method and purpose thereof |
Non-Patent Citations (1)
| Title |
|---|
| 燃煤烟气中气态Hg0污染物吸附剂的研究进展;张华伟;《环境化学》;20111030;第30卷(第10期);第1805-1813页 * |
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