CN105327613A - Desulfurizing agent and application thereof - Google Patents
Desulfurizing agent and application thereof Download PDFInfo
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- CN105327613A CN105327613A CN201510706602.3A CN201510706602A CN105327613A CN 105327613 A CN105327613 A CN 105327613A CN 201510706602 A CN201510706602 A CN 201510706602A CN 105327613 A CN105327613 A CN 105327613A
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Abstract
The invention discloses a desulfurizing agent and application thereof. The desulfurizing agent comprises a component A and a component B, wherein the component A is a catalyst and the component B is a desulfurizing and activating agent. The component A comprises MgO, CaO, dolomite and CaCO<3>; the component B comprises dicalcium silicate and calcium olivine. The desulfurizing agent comprises the component A and the component B, and the component A is from smoke generated in the process of calcining the raw material dolomite at the temperature of 1423-1473 K; the component B is from residues left after pellets made of calcined dolomite, silicon iron and fluorite are subjected to high temperature calcination in a reduction furnace; the component A serves as the active catalyst, the component B serves as the desulfurizing and activating agent, the component A and the component B are mixed together and jointly serve as the desulfurizing agent, the desulfurization activity of the component B is catalyzed through adding of the component A, desulfurization efficiency is improved, meanwhile, the combined action of calcium groups and magnesium groups is utilized, and a new path is opened up for the desulfurization technology.
Description
Technical field
The present invention relates to desulfurizing agent and application thereof, concrete waste material in Pidgeon process smelting magnesium technique is carried out recovery make desulfurizing agent, then apply it to the desulfurization of flue gas, is namely a kind of desulfurizing agent and application thereof.
Background technology
The major way of current domestic product magnesium metal is Pidgeon process, this with in state-owned abundant magnesium ore resources, the energy, auxiliary material and cheap labour etc. are closely related.Along with Pidgeon process smelting magnesium technology China universal, promote, the magnesium output of China reaches 87.38 ten thousand tons in 2014 from 0.53 ten thousand ton of nineteen ninety, is rapid development.Meanwhile, due to the defect that Pidgeon process is intrinsic, add that China's refining magnesium industry technology innovation is delayed, China's refining magnesium industry does not still break away from traditional growth pattern of " produce in a large number; consume in a large number, discard in a large number ", and this pattern causes energy utilization rate low, comprehensive utilization of resources level is low, consequently severe contamination environment.For Shanxi Province, magnesium output in 2005 330000 tons of meters, estimate about can produce the sulfur dioxide gas scale of construction about 21.78 ten thousand tons, Dust Capacity about 2.178 ten thousand tons, reducing slag about 1,650,000 tons, reduction furnace exhaust gas volumn about 313.5 ten thousand stere.Wherein reducing slag output is huge and do not have value, brings white elephant to environment.How improving comprehensive resource utilization rate, turn waste into wealth, is the problem that we are concerned about to alleviate environmental pressure.
The main purpose of flue gas desulfurization is the discharge capacity of the pollutants such as the sulfur dioxide in order to produce in Controlling Technology process.According to EPA (EPA) statistics, the sulfur dioxide control technology of countries in the world exploitation, research, use has reached 189 kinds, estimates that current quantity will more than 200 kinds.These technology sum up and can be divided into four classes, i.e. the trans-utilization technology of desulfurization in desulfurization (desulfurization of coal) before burning, burning, coal and the rear desulfurization (flue gas desulfurization) of burning.The main mode adopting flue gas desulfurization in the sulfur removal technology of current China, because other modes can't be competed with it economically, technically.
Sulfur removal technology difference can be divided into wet desulphurization again, dry desulfurization and semi-dry desulphurization according to desulfurization reaction product and desulfurization product.Wet Flue Gas Desulfurization Technique mainly comprises lime (lime stone) method, Dual alkali, sodium method, magnesium processes, ammonia process, seawater method, phospho-ammonium fertilizer method etc.; Desulfurization by dry method mainly comprises active carbon adsorption, electron beam irradiation method, plasma desulfuration method, catalytic oxidation and reducing process etc.; Semi-dry desulphurization technology mainly comprises flue gas circulating fluidized bed technology, spraying dry, in-furnace calcium spraying/humidification activation desulfur technology, and the various desulfurizing agents wherein related to have the advantage of oneself uniqueness.
Investigation is learnt, the sulfur removal technology that the flue gas desulfurization of current Lian Mei factory or large coal-fired boiler adopts usually is wet desulphurization, and the desulfurizing agent of employing is quick lime (calcium oxide).For maintaining the normal operation of Lian Mei factory desulphurization system, within one day, need consume lime and be approximately 3-4 ton, desulfurizing agent accounts for 48% of total desulphurization cost, estimates by 300 yuan/ton, market price lime, and the input of annual desulphurization system is about 68 ~ 920,000 yuan, and cost drops into very large.And quick lime activity is not high, desulfuration efficiency is not high.
Summary of the invention
For defect or the deficiency of prior art, in order to improve comprehensive resource utilization rate, alleviate environmental pressure, increase economic efficiency, the present invention passes through systematic research, to be prepared into the high and desulfurizing agent that can reuse of a kind of desulfuration efficiency after the mixing of produce in production of magnesium by pidgeonprocess process two kinds of waste materials, this desulfurizing agent can be applied to the desulfurization process to the flue gas containing sulfur dioxide.
For achieving the above object, the present invention takes following scheme to solve:
A kind of desulfurizing agent, comprise component A and B component, component A is catalyst component, and B component is desulphurizing activated composition; Described component A comprises MgO, CaO, dolomite, CaCO
3, SiO
2and zeolite; Described B component comprises dicalcium silicate and lime-olivine.
Concrete, count in mass ratio, component A: B component is 7:35 ~ 45.
More specifically, component A: B component is 7:40.
Concrete, by mass percentage, in waste material A, magnesia is 38% ~ 42%, and calcium oxide is 22% ~ 26%, and dolomite is 17% ~ 21%, and calcium carbonate is 8% ~ 12%, SiO
2be 2% ~ 4%, zeolite is 3% ~ 4%; Waste material B mesosilicic acid dicalcium is 44% ~ 50%, and lime-olivine is 50% ~ 56%.
More specifically, by mass percentage, in component A, MgO is 40%, CaO is 24%, and dolomite is 19%, CaCO
3be 10%, SiO
2be 3%, zeolite is 4%; B component mesosilicic acid dicalcium be 47% and lime-olivine be 53%.
In addition, the preparation method of described component A is: namely the flue dust collecting produced in 1150 ~ 1250 DEG C of temperature lower calcination white clouds ore processes is obtained component A, and the product after calcining is white for forging;
The preparation method of described B component is: by white for forging of obtaining of preparation component A mix with ferrosilicon and fluorite after make pelletizing through temperature range be 1190 ~ 1210 DEG C calcine after remaining residue namely obtain B component;
And the particle diameter of described flue dust is less than 40 μm; The particle diameter of described residue is less than 40 μm, and the unit weight of described pelletizing is 1195 ~ 2105g/cm
3.
Described desulfurizing agent is used for the application of the flue gas desulfurization containing sulfur dioxide.
Described desulfurizing agent is for removing the application containing sulfur dioxide FGD produced in Pidgeon process smelting magnesium technique.
Beneficial effect of the present invention is:
(1) desulfurizing agent provided by the invention comprises component A and B component, and the source of component A is the flue dust produced at 1150 ~ 1250 DEG C of temperature lower calcination raw material white clouds ores; The source of waste material B be utilization forge white, ferrosilicon and fluorite make pelletizing in reduction furnace after high-temperature calcination remaining residue; Wherein component A is as active catalyst, B component is as desulphurizing activated dose, common as desulfurizing agent after component A is mixed with B component, component A adds the desulphurizing activated of catalysis B component, improve desulfuration efficiency, and employ the acting in conjunction of calcium base and magnesium base, for desulfur technology opens new approach simultaneously;
(2) adopt the proportioning of the proportioning of component A: B component=7:40 preparation desulfurizing agent (HBF) to be through experiment and consider the optimum proportioning that the output of two kinds of waste materials in actual production process obtains simultaneously, at this moment desulfurized effect can reach best, practical application proves, as long as maintain pH value can meet desulfurization requirement about 12, component A and B component are reasonably used, not only increase the comprehensive utilization ratio of resource, significantly reduce the burden of environment, and decrease the input of desulphurization cost in production process, economic benefit is improved;
(3) the present invention is mainly used in a large amount of sulfur dioxide produced in reduction furnace in removing Pidgeon process smelting magnesium technological process reduction flow process, can give play to its advantage when being applied in this Pidgeon process smelting magnesium field to the full extent; Certainly, as long as there is the field that sulfur dioxide produces in production process, desulfurizing agent of the present invention can be applied.
Accompanying drawing explanation
Fig. 1 is Pidgeon process smelting magnesium process chart;
Fig. 2 is desulfurization flow chart, and in Fig. 2, each label is expressed as: 1-dissolving tank, 2-regenerated reactor, 3-sedimentation basin, 4-regulating reservoir, 5-dehydration between, 6-desulfurization zone, 7-demister, 8-catalyst (waste material A), 9-circulating pump, 10-smoke inlet, 11-desulfurizing tower top, 12-desulfurizing tower, 13-chimney;
Fig. 3 is the pH graph of a relation under different waste material B content;
Fig. 4 is the pH graph of a relation under different waste material A content;
Fig. 5 is the grain size distribution of waste material A;
Fig. 6 is the grain size distribution of waste material B;
Below in conjunction with specification drawings and specific embodiments, the present invention is illustrated.
Detailed description of the invention
Pidgeon process produces magnesium metal, and to comprise with dolime is raw material, ferrosilicon is reducing agent, fluorite carries out batching for catalyst; Suppress balling-up by after batching grinding, be called pelletizing; Loaded by pelletizing in reductive jar, be heated to 1200 ± 10 DEG C, inside is evacuated to 13.3 ~ 10Pa and produces magnesium vapor, and magnesium vapor forms Crystalline Magnesium in the condenser of reductive jar front end, also known as crude magnesium; Again through flux-refining, output commodity magnesium ingot, i.e. smart magnesium.
Production of magnesium by pidgeonprocess production process comprises:
(1) dolomite calcination: dolomite is heated to 1150 DEG C ~ 1250 DEG C in rotary kiln or shaft furnace, burns till and forges white (MgOCaO);
(2) to prepare burden ball processed: will forge white, ferrosilicon powder and Fluorspar Powder batching, grinding, and then be pressed into pelletizing, the unit weight of pelletizing pressure group (in amygdaliform, amygdaloidal) pellet afterwards should reach 1195 ~ 2105g/cm
3;
(3) reduce: pellet is heated to 1200 ± 10 DEG C in reductive jar, and under the vacuum condition of 13.3 ~ 10Pa, keep 8 ~ 12 hours, magnesia is reduced into magnesium vapor, becomes crude magnesium after condensation;
(4) refining ingot casting: by crude magnesium heat fused, under 680 ~ 740 DEG C of high temperature, after solvent refined, casts magnesium ingot, also known as smart magnesium.
(5) pickling: by magnesium ingot sulfuric acid or nitric acid clean surface, removing surface is mingled with, and makes surface aesthetic.
Investigation finds, can produce two kinds of waste materials in Pidgeon process smelting magnesium technological process (see Fig. 1).The technological process of Pidgeon process smelting magnesium only has this kind of, although the development through for many years makes technological process constantly be optimized, in production process, still waste material A and waste material B (waste material A of the present invention and waste material B is called component A and B component in desulfurizing agent) can be produced.
Waste material A, its source is the flue dust produced in calcining raw materials white clouds ore process in rotary kiln under 1150 ~ 1250 DEG C of temperature conditions, claims this operation to be calcination process.If these flue dust are discharged into air, serious pollution will be caused to atmospheric environment.Correlative study shows, if the flue dust particle diameter produced in calcination process is less than 40 μm, will containing MgO37% ~ 39% in flue dust, and increase because specific grain surface is long-pending, magnesium base activity will significantly improve, and this will promote the active grow of neutralization reaction.Therefore, the dust that particle diameter is less than 40 μm in afterbody sack cleaner is to flue gas traps, and utilizes pulse oscillating mode to collect waste material A, used as active catalyst.
Waste material B, its source for utilization forge pelletizing that white (chemical formula is MgOCaO), ferrosilicon and fluorite be made up of marble forming machine in reduction furnace after high temperature (1200 ± 10 DEG C) calcining remaining residue, claim this operation to be reduce operation.Because its output is very large, and do not have any value usually can cause very large burden to environment.Test finds that the main component in B is 2CaOSiO
2, be rich in calcium base, and its close to 90% particle diameter be all less than 40 μm, be very suitable as desulfurizing agent.
Research finds, all alkalescence is presented after waste material A and waste material B is water-soluble, waste material A is rich in magnesium base and calcium base, after water-soluble, its pH value can reach 12.7, waste material B has been rich in calcium base, dissolve pH value by a certain percentage and can reach 11, but the pH value of waste material B is less than normal, and calcium base activity is weak, be not suitable for making desulfurizing agent to use, and add certain proportion waste material A (active catalyst) afterwards pH value Absorbable organic halogens 12, and form the synthetic sweetening agent (HBF) of calcium base and magnesium base of knowing clearly, substantially increase desulfurized effect.
So can consider to utilize these two kinds of materials of waste material A (active catalyst) and waste material B to replace original used desulfurizing agent calcium oxide, be applied to desulfurizing tower and produce a large amount of sulfur dioxide gas (or flue gas desulfurization of large-scale coal-burning boiler) for removing in reduction furnace.Because the output of waste material A and B and water-soluble alkalescence there are differences, come as a kind of novel desulfurizing agent (HBF) by carrying out specific mixing match to A and B, waste material A and B produced in technical process can be utilized to greatest extent, under the prerequisite meeting sulfur removal technology demand, improve comprehensive resource utilization rate.After estimating technical optimization, it is over half that desulphurization system can save desulphurization cost.Meanwhile, because the specific area of main matter in waste material A and B is large, therefore desulfuration efficiency also can be further enhanced.
Wet Flue Gas Desulfurization Technique mainly comprises lime (lime stone) method, Dual alkali, sodium method, magnesium processes, ammonia process, seawater method, phospho-ammonium fertilizer method etc., it is one matter desulfurization, and the mixed desulfurizing agent (HBF) more obtained than method of waste material A (active catalyst) and waste material B, new mixing than method desulfur technology is defined in Wet Flue Gas Desulfurization Technique, employ the acting in conjunction of calcium base and magnesium base, for desulfur technology opens new approach simultaneously.
One, the feasibility analysis of scheme:
(1) composition test of waste material A, B
Adopt the EMPYREAN type X-ray diffraction analysis instrument of PANalytical company of the U.S. to carry out the mensuration of composition and ratio to two waste materials, result is as follows.
The main component of waste material A is magnesia (MgO), calcium oxide (CaO), dolomite and calcium carbonate (CaCO
3), it has accounted for 93% of total content, and all the other are SiO
2and zeolite, concrete composition is in table 1.
Table 1
| Composition | MgO | CaO | Dolomite | CaCO 3 | SiO 2 | Zeolite |
| Mass percent | 40％ | 24％ | 19％ | 10％ | 3％ | 4％ |
Waste material B is mainly containing two kinds of materials, dicalcium silicate and lime-olivines.Lime-olivine is the another kind of version of dicalcium silicate, and both only exist the difference of physical property.Its chemical formula is all 2CaOSiO
2, there is identical chemical property.When discussing its chemical property, can think same material, the concrete composition in waste material B is in table 2.
Table 2
| Composition | Dicalcium silicate | Lime-olivine |
| Mass percent | 47％ | 53％ |
Can see from waste material constituent analysis, wherein can with sulfurous acid (SO
2water-soluble product) composition that reacts accounts for more than 90% of total amount, for desulfurization object highly beneficial.
According to the otherness that different manufacturers adopts production of magnesium by pidgeonprocess to produce, by mass percentage, in waste material A, magnesia (MgO) can be 38% ~ 42%, calcium oxide (CaO) can be 22% ~ 26%, dolomite can be 17% ~ 21%, calcium carbonate (CaCO
3) can be 8% ~ 12%, it has accounted for 93% of total content, and all the other are SiO
2and zeolite, SiO
2can be 2% ~ 4%, zeolite can be 3% ~ 4%;
Waste material B mesosilicic acid dicalcium can be 44% ~ 50%, and lime-olivine can be 50% ~ 56%.
(2) proportioning of waste is on the impact of pH value of water solution
Because solution ph in existing desulfurization method is 12, desulfuration efficiency is now in higher level, so we still expect that the slurry pH value be equipped with is 12.
(1) B is dissolved separately
The distilled water that waste material B and the 100ml of different quality is got in experiment mixes, and after abundant dissolving, records the pH value of solution under different B content.Can find out the increase of the content along with the B added from table 3 and in Fig. 3, the pH value of solution constantly increases.But along with the increase of B, the change of pH value is more and more slower.When the content of B equals 54g, the pH of solution can reach 12.
Table 3 waste material B lysate pH value changes
| The content (g) of B | PH value |
| 10 | 11.40 |
| 15 | 11.67 |
| 25 | 11.84 |
| 35 | 11.93 |
| 45 | 11.96 |
| 54 | 11.99 |
(2) A and B mixing
In refining magnesium process, the generation of waste material B will far away more than the generation of waste material A.Experiment is got 10gB waste material and is mixed with 100ml distilled water, then the A waste material adding different quality fully mixes, and the pH value change recording the aqueous solution is very fast, in table 4 and Fig. 4.When the A added reaches 1.75g, the pH value of solution can reach 12.
The change of table 4A and B aggregate sample lysate pH value
| The content (g) of A | PH value |
| 0 | 11.40 |
| 0.5 | 11.68 |
| 1.5 | 11.93 |
| 1.75 | 12.00 |
(3) the antacid ability of waste material
If utilize waste material A and B to carry out desulfurization, terminate from preparing alkaline slurry to as the desulfurization of desulfurization medium, the chemical reaction occurred in process is mainly as follows:
1) reaction of the water-soluble generation of waste material A and B:
CaO+H
2O→Ca(OH)
2(1)MgO+H
2O→Mg(OH)
2(2)
2) waste material A and B water-soluble after, the reaction occurred with sulfurous acid:
MgO+H
2SO
3→MgSO
3+H
2O(3)
Mg(OH)
2+H
2SO
3→MgSO
3+2H
2O(4)
Ca(OH)
2+H
2SO
3→CaSO
3·2H
2O(5)
CaCO
3MgCO
3+2H
2SO
3→CaSO
3+MgSO
3+2CO
2↑+2H
2O(6)
CaCO
3+H
2SO
3→CaSO
3+CO
2↑+H
2O(7)
2CaO·SiO
2+2H
2SO
3→2CaSO
3+H
2SiO
3+H
2O(8)
3) CaSO after oxygenation
3, MgSO
3be converted into CaSO
4, MgSO
4the chemical reaction of Shi Fasheng:
CaSO
3·2H
2O+0.5O
2→CaSO
4·H
2O(9)
MgSO
3+0.5O
2→MgSO
4(10)
As can be seen from above-mentioned chemical equation, the composition that in waste material A and B, main and sulfurous acid reacts has MgO, CaO, dolomite, CaCO
3, 2CaOSiO
2deng, its content reaches more than 90%.Finally main product is MgSO
4, CaSO
4deng.Wherein CaSO
4content very high, the raw material of industry or construction material can be considered as.
Test the proportioning being determined A and B by test waste material A and B two kinds of antacid abilities of the aqueous solution.Because sulfurous acid solution is volatile acid solution, and the SO volatilized
2gas all can produce significant damage to human body and environment, is difficult under experimental conditions control.Therefore consider to adopt the aqueous solution of the sulfuric acid solution and waste material A and B that have similar quality with it to react.
The product that A and the B aqueous solution and sulfuric acid solution react main has MgSO
4, CaSO
4, CO
2and H
2o.The product that A and the B aqueous solution and sulfurous acid solution react main has MgSO
3, CaSO
3, CO
2and H
2o.If can find out the AB aqueous solution that will consume identical amount from the equation of the reaction of table 5, then the sulfuric acid solution consumed is the same with the amount of sulfurous acid solution.And sulfurous acid solution is identical with the product that sulfuric acid solution and waste material react after oxygenation, the end product that namely the waste material AB aqueous solution and sulfurous acid and sulfuric acid solution react is consistent.Therefore it is rational for adopting the aqueous solution of sulfuric acid solution and waste material A and B to carry out reaction in experimentation.
Contrast between table 5 waste material A and B and acid reaction
Waste material A and the B aqueous solution and sulfuric acid carry out the experiment of neutralization reaction.Get waste material A respectively, each 10g of B, fully mixes with 100ml distilled water, obtains suspension.Adopt the dilution heat of sulfuric acid of 1mL/L to carry out neutralization reaction, solution ph is neutralized to 7.Consume the volume of sulfuric acid solution in table 6: by contrast can find out, the sulfuric acid solution of the aqueous solution consumption of A waste material is almost 11 times of B waste material.A waste material is obviously better than B waste material to the neutralising capacity of acid solution.
Table 6 waste material A and B is respectively to the consumption of sulfuric acid
Mix according to the ratio of waste material A to be 1.75g and waste material B be 10g, be fully dissolved in 100ml distilled water, and carry out neutralization reaction with the dilution heat of sulfuric acid of 1ml/L.Result is as shown in table 7: in the CaO adopted at present and time, under same pH, the dilute sulfuric acid of about 50ml can be consumed.After doubling according to the above ratio, namely 3.5g waste material A, 20g waste material B is fully dissolved in 100ml distilled water, the dilute sulfuric acid of consumption, close to existing technique, reaches identical desulfurized effect substantially.So we adopt waste material A in practical application: the proportioning mode of waste material B=7:40, the requirement both having met desulfurization reasonably make use of two kinds of waste materials simultaneously.
The mixture of table 7 waste material A and B is to the consumption of sulfuric acid
(4) desulfuration efficiency
Research shows, calcium silicates exists hole, and its specific area is much larger than the specific area of calcium hydroxide, and this is conducive to improving desulfuration efficiency.Adopt laser fineness gage, the particle diameter of waste material A, B is measured, as can be seen from domain size distribution Fig. 5, Fig. 6 of waste material A and waste material B, in waste material A, B, the component content of particle diameter below 40 μm is close to 90%, and less particle diameter will cause their specific area very large.Especially, the particle diameter that waste material A is less, be also the main cause of adopting the active catalyst used it as in HBF desulfurizing agent, this way improves the reactivity in sweetening process, and desulfuration efficiency is improved.In addition, the product of calcium hydroxide and silicic acid also can improve the utilization rate of calcium base in sweetening process, thus reduces the use amount of desulfurizing agent, and this is undoubtedly the another one advantage after desulfur technology improvement.
Two, conclusion:
Waste material A and B can be prepared into the alkaline solution of pH value more than 12 through rational proportion, and is rich in calcium base and magnesium base, and these two kinds of materials can be utilized to replace original used desulfurizing agent calcium oxide.Here employing waste material A serves as the active catalyst in desulfurizing agent (HBF), and its existence can make desulfuration efficiency greatly improve.Although in the aqueous solution of waste material A and strong than waste material B of the ability of sulfurous acid, and waste material A completely can separately as desulfurizing agent, but consider that the amount of the waste material A collected from deduster is less, in order to make full use of two kinds of waste materials, adopt the proportioning mode of waste material A: waste material B=7:40, also be that the mode of dissolving 3.5gA and 20gB in 100ml distilled water prepares desulfurizing agent (HBF), the desulfurizing agent (HBF) of new preparation has confirmed the requirement that can meet former desulfurizing agent in Practical Project.By the monitoring form after Liang Jia unit application desulfurizing agent (HBF), desulfuration efficiency improves 1% ~ 2% compared with before application.According to the Rational Pre measured value of the composition to waste material A and waste material B, waste material A: the scope of the proportional quantity of waste material B is 7:35 ~ 45.
After optimizing, obtain desulphurization system, make desulphurization cost over half, desulfuration efficiency have also been obtained raising simultaneously.Under the prerequisite meeting desulfurization object, reasonably make use of waste material A and waste material B, improve comprehensive resource utilization rate, not only make economic benefit be improved, and alleviate the burden of environment to a great extent.
Embodiment 1:
Composition graphs 2, the waste material B produced in production process is directly poured in dissolving tank 1, put into running water simultaneously and be full of dissolving tank 1, and stir with agitator the dissolving promoting waste material B continuously, the solubilized composition in waste material B enters regenerated reactor 2 by pipe network in the mode of flow by gravity with lysate.In regulating reservoir 4, add appropriate waste material A, make the pH value of slurries in regulating reservoir 4 about 12.The slurries regulating pH value squeeze into desulfurizing tower 12 by circulating pump 9, the flue gas generation desulphurization reaction entered with smoke inlet 10 in desulfurization zone 6, flue gas after purification enters chimney through demister 7 from desulfurizing tower top 11, the slurries absorbing sulfur dioxide enter regenerated reactor 2 by flow by gravity bottom desulfurizing tower, mix with the alkaline matter flowed out in dissolving tank 1, after reacting, desulfurization absorbing liquid is regenerated.Reaction mixture in regenerated reactor 2 flows into sedimentation basin 3, and wherein supernatant flows into regulating reservoir 4, after adjusted to ph, squeeze into desulfurizing tower by circulating pump, circulation desulfurization, sediment through transport pump to dehydration between 5, focus on after dehydration, 13 is chimneys, effect be desulfurization after flue gas be discharged in air.8 is waste material A, and effect is catalyst in desulfurizing agent and pH value regulator.
Its source of waste material A is the flue dust produced in calcining raw materials white clouds ore process in rotary kiln under 1150 ~ 1250 DEG C of temperature conditions, and flue dust particle diameter is less than 40 μm;
Waste material B, its source for utilization forge pelletizing that white (chemical formula is MgOCaO), ferrosilicon and fluorite be made up of marble forming machine in reduction furnace after high temperature (1200 ± 10 DEG C) is calcined remaining residue, residue particle diameter is less than 40 μm;
By mass percentage, in component A, MgO is 40%, CaO is 24%, dolomite is 19%, CaCO
3be 10%, SiO
2be 3% and zeolite be 4%; B component mesosilicic acid dicalcium be 47% and lime-olivine be 53%.
Waste material A is waste material A with the mass ratio of waste material B: obtain desulfurizing agent (HBF) after waste material B=7:40 mixes.
Desulfurizing agent (HBF) obtains application in several magnesium metal factory, and desulfurizing tower diameter 4.0m, height overall 12m, desulfurization slurry PH are 12, and liquid-gas ratio is 8.0L/m
3, achieved extraordinary effect according to above-mentioned detailed description of the invention, sulfur content reaches 700mg/m
3flue gas desulfurization after sulfur content can be reduced to 20mg/m
3within, far below international standard.
Desulfuration efficiency after application desulfurizing agent (HBF) is 97.1%, improves 1%-2% than desulfuration efficiency before.Liang Jia unit extends benzin source coalification Co., Ltd and pseudo-classic Wanyuan Mei Ye Co., Ltd goes out according to the online monitoring data obtained from environmental administration, in table 6; As can be seen from Table 6, SO in emission gases
2content be less than 10mg/m
3. well below the 200mg/m that national standard requires
3.
Table 8
Claims (9)
1. a desulfurizing agent, is characterized in that, comprises component A and B component, and component A is catalyst component, and B component is desulphurizing activated composition;
Described component A comprises MgO, CaO, dolomite, CaCO
3, SiO
2and zeolite;
Described B component comprises dicalcium silicate and lime-olivine.
2. desulfurizing agent as claimed in claim 1, is characterized in that, count in mass ratio, component A: B component is 7:35 ~ 45.
3. desulfurizing agent as claimed in claim 2, it is characterized in that, by mass percentage, in waste material A, magnesia is 38% ~ 42%, and calcium oxide is 22% ~ 26%, and dolomite is 17% ~ 21%, and calcium carbonate is 8% ~ 12%, SiO
2be 2% ~ 4%, zeolite is 3% ~ 4%;
Waste material B mesosilicic acid dicalcium is 44% ~ 50%, and lime-olivine is 50% ~ 56%.
4. desulfurizing agent as claimed in claim 1, is characterized in that, count in mass ratio, component A: B component is 7:40.
5. desulfurizing agent as claimed in claim 4, it is characterized in that, by mass percentage, in component A, MgO is 40%, CaO is 24%, and dolomite is 19%, CaCO
3be 10%, SiO
2be 3%, zeolite is 4%; B component mesosilicic acid dicalcium be 47% and lime-olivine be 53%.
6. the desulfurizing agent as described in claim 1,2,3,4 or 5, is characterized in that, the preparation method of described component A is: namely the flue dust collecting produced in 1150 ~ 1250 DEG C of temperature lower calcination white clouds ore processes is obtained component A, and the product after calcining is white for forging;
The preparation method of described B component is: by white for forging of obtaining of preparation component A mix with ferrosilicon and fluorite after make pelletizing through temperature range be 1190 ~ 1210 DEG C calcine after remaining residue namely obtain B component.
7. desulfurizing agent as claimed in claim 6, it is characterized in that, the particle diameter of described flue dust is less than 40 μm; The particle diameter of described residue is less than 40 μm, and the unit weight of described pelletizing is 1195 ~ 2105g/cm
3.
8. the desulfurizing agent described in claim 1,2,3,4,5,6 or 7 is used for the application of the flue gas desulfurization containing sulfur dioxide.
9. the desulfurizing agent described in claim 1,2,3,4,5,6 or 7 is for removing the application containing sulfur dioxide FGD produced in Pidgeon process smelting magnesium technique.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597701A (en) * | 2016-03-17 | 2016-05-25 | 杭州富阳高博信息技术服务有限公司 | Adsorbent for boiler fume treatment |
| CN108079776A (en) * | 2017-11-24 | 2018-05-29 | 北京绿岩环保科技有限责任公司 | A kind of new dry process rotary kiln catalytic desulfurizing agent and its preparation and application |
| CN108479373A (en) * | 2016-04-22 | 2018-09-04 | 何超 | A kind of preparation method of the flue gas desulfurization pulvis of environmental protection |
| CN109331620A (en) * | 2018-06-29 | 2019-02-15 | 邢台县旭东工贸有限责任公司 | A kind of calcium and magnesium composite desulfurizing agent and its calcium and magnesium compound desulfurizing process |
| CN114146545A (en) * | 2020-11-19 | 2022-03-08 | 衢州科尔钙业科技有限公司 | Composite desulfurizer and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3384435B2 (en) * | 1997-03-28 | 2003-03-10 | 出光興産株式会社 | Fluidized bed furnace exhaust gas desulfurization method |
| CN101302576A (en) * | 2008-06-16 | 2008-11-12 | 东北大学 | Dolomite-based desulfurizer based on in-situ reduction and preparation thereof |
| CN101591571A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of solid desulfurating agent |
| CN201454381U (en) * | 2009-06-24 | 2010-05-12 | 武建国 | Desulfurizer conveying device for coal-fired boiler |
| CN102755829A (en) * | 2012-08-06 | 2012-10-31 | 北京世能中晶能源科技有限公司 | Desulfurizer and application thereof |
| CN103537177A (en) * | 2013-10-30 | 2014-01-29 | 武汉钢铁(集团)公司 | Modified calcium-based desulfurizing agent for dry desulfurization of sintering gas and preparation method of modified calcium-based desulfurizing agent |
-
2015
- 2015-10-27 CN CN201510706602.3A patent/CN105327613B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3384435B2 (en) * | 1997-03-28 | 2003-03-10 | 出光興産株式会社 | Fluidized bed furnace exhaust gas desulfurization method |
| CN101591571A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of solid desulfurating agent |
| CN101302576A (en) * | 2008-06-16 | 2008-11-12 | 东北大学 | Dolomite-based desulfurizer based on in-situ reduction and preparation thereof |
| CN201454381U (en) * | 2009-06-24 | 2010-05-12 | 武建国 | Desulfurizer conveying device for coal-fired boiler |
| CN102755829A (en) * | 2012-08-06 | 2012-10-31 | 北京世能中晶能源科技有限公司 | Desulfurizer and application thereof |
| CN103537177A (en) * | 2013-10-30 | 2014-01-29 | 武汉钢铁(集团)公司 | Modified calcium-based desulfurizing agent for dry desulfurization of sintering gas and preparation method of modified calcium-based desulfurizing agent |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597701A (en) * | 2016-03-17 | 2016-05-25 | 杭州富阳高博信息技术服务有限公司 | Adsorbent for boiler fume treatment |
| CN105597701B (en) * | 2016-03-17 | 2018-09-11 | 浙江嘉昱达机械有限公司 | A kind of adsorbent for handling boiler smoke |
| CN108479373A (en) * | 2016-04-22 | 2018-09-04 | 何超 | A kind of preparation method of the flue gas desulfurization pulvis of environmental protection |
| CN108079776A (en) * | 2017-11-24 | 2018-05-29 | 北京绿岩环保科技有限责任公司 | A kind of new dry process rotary kiln catalytic desulfurizing agent and its preparation and application |
| CN109331620A (en) * | 2018-06-29 | 2019-02-15 | 邢台县旭东工贸有限责任公司 | A kind of calcium and magnesium composite desulfurizing agent and its calcium and magnesium compound desulfurizing process |
| CN114146545A (en) * | 2020-11-19 | 2022-03-08 | 衢州科尔钙业科技有限公司 | Composite desulfurizer and preparation method and application thereof |
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