CN105327613B - A kind of desulfurizing agent and its application - Google Patents
A kind of desulfurizing agent and its application Download PDFInfo
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- CN105327613B CN105327613B CN201510706602.3A CN201510706602A CN105327613B CN 105327613 B CN105327613 B CN 105327613B CN 201510706602 A CN201510706602 A CN 201510706602A CN 105327613 B CN105327613 B CN 105327613B
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Abstract
The invention discloses a kind of desulfurizing agent and its application, including component A and component B, component A are catalyst, and component B is desulphurizing activated dose；Described component A includes MgO, CaO, dolomite and CaCO3；Described component B includes dicalcium silicate and lime-olivine.The desulfurizing agent that the present invention is provided includes component A and component B, and component A source is the flue dust produced in 1423~1473K temperature lower calcination raw material white clouds ore；Waste material B source is that white, ferrosilicon is forged in utilization and pelletizing remaining residue after high-temperature calcination in reduction furnace is made in fluorite；Wherein component A is used as active catalyst, component B is used as desulphurizing activated dose, collectively as desulfurizing agent after component A is mixed with component B, component A addition has been catalyzed the desulphurizing activated of component B, improve desulfuration efficiency, and the collective effect of calcium base and magnesium-based has been used simultaneously, it is that desulfurization technology opens new approach.
Description
Technical field
The present invention relates to desulfurizing agent and its application, specifically the waste material progress recovery in Pidgeon process smelting magnesium technique is made de-
Sulphur agent, then the desulfurization of flue gas is applied it to, it is a kind of desulfurizing agent and its application.
Background technology
The major way of current domestic product magnesium metal is Pidgeon process, and this has abundant magnesium ore resources with China, and the energy is auxiliary
Material and cheap labour etc. are closely related.With Pidgeon process smelting magnesium technology China popularization, promote, the magnesium yield of China from
0.53 ten thousand tondals of nineteen ninety, to 87.38 ten thousand tons of 2014, are rapid development.At the same time, due to Pidgeon process
Intrinsic defect, it is delayed to add China's refining magnesium industry technology innovation, China's refining magnesium industry do not break away from still " a large amount of productions, greatly
It is amount consumption, a large amount of discarded " traditional growth pattern, this pattern causes energy utilization rate low, and comprehensive utilization of resources level is low, its
The result environment that has been severe contamination.By taking Shanxi Province as an example, the 330000 tons of meters of magnesium yield in 2005, estimation can about produce sulfur dioxide gas
About 21.78 ten thousand tons of the scale of construction, about 2.178 ten thousand tons of Dust Capacity, about 1,650,000 tons of reducing slag, about 313.5 ten thousand cubes of reduction furnace exhaust gas volumn
Rice.Wherein reducing slag yield is huge and without value, and white elephant is brought to environment.How resource comprehensive profit is improved
With rate, turn waste into wealth, be our problems of concern to mitigate environmental pressure.
The main purpose of flue gas desulfurization is for the discharge of the pollutants such as the sulfur dioxide produced by controlling in technical process
Amount.Counted according to EPA (EPA), the sulfur dioxide control technology that countries in the world are developed, studied, using is up to 189 kinds, in advance
The current quantity of meter will be more than 200 kinds.These technologies, which are summed up, can be divided into four classes, that is, desulfurization (desulfurization of coal), combustion before burning
Desulfurization (flue gas desulfurization) after desulfurization, the trans-utilization technology of coal and burning in burning.Mainly used in the sulfur removal technology of current China
The mode of flue gas desulfurization, because other modes economically, can't be competed technically therewith.
Sulfur removal technology Bu Tong can be divided into wet desulphurization, dry desulfurization again according to desulfurization reaction product and desulfurization product
And semi-dry desulphurization.Wet Flue Gas Desulfurization Technique mainly include lime (lime stone) method, Dual alkali, sodium method, magnesium processes, ammonia process, seawater method,
Phospho-ammonium fertilizer method etc.；Desulfurization by dry method mainly includes active carbon adsorption, electron beam irradiation method, plasma desulfuration method, catalysis
Oxidation and reducing process etc.；Semi-dry desulphurization technology mainly includes flue gas circulating fluidized bed technology, spray drying, in-furnace calcium spraying/increasing
Wet activation desulfurization technology, the various desulfurizing agents being directed to have oneself unique advantage.
Investigation learns, the sulfur removal technology that the flue gas desulfurization of current Lian Mei factories or large coal-fired boiler is generally used is wet method
Desulfurization, the desulfurizing agent used is quick lime (calcium oxide).To maintain the normal operation of Lian Mei factories desulphurization system, stone need to be consumed within one day
Ash is about 3-4 tons, and desulfurizing agent accounts for the 48% of total desulphurization cost, is estimated by 300 yuan/ton of market price lime, annual desulfurization system
The input of system is about 68~920,000 yuan, and cost input is very big.And quick lime activity is not high, desulfuration efficiency is not high.
The content of the invention
For the defect or deficiency of prior art, in order to improve comprehensive resource utilization rate, mitigate environmental pressure, improve economical
Benefit, the present invention is prepared into a kind of de- by systematic research after produced during production of magnesium by pidgeonprocess two kinds of waste materials are mixed
Sulphur efficiency height and the desulfurizing agent that can be reused, the desulfurizing agent can be applied to the desulfurization process to the flue gas containing sulfur dioxide.
To achieve the above object, the present invention takes following scheme to solve：
A kind of desulfurizing agent, including component A and component B, component A are catalyst component, and component B is desulphurizing activated composition；It is described
Component A include MgO, CaO, dolomite, CaCO3、SiO2And zeolite；Described component B includes dicalcium silicate and lime-olivine.
Specifically, counting in mass ratio, component A：Component B is 7：35~45.
More specifically, component A：Component B is 7：40.
Specifically, by mass percentage, in waste material A, magnesia is 38%~42%, and calcium oxide is 22%~26%,
Dolomite is 17%~21%, and calcium carbonate is 8%~12%, SiO2For 2%~4%, zeolite is 3%~4%；Silicon in waste material B
Sour dicalcium is 44%~50%, and lime-olivine is 50%~56%.
More specifically, by mass percentage, MgO is that 40%, CaO is 24% in component A, and dolomite is 19%, CaCO3
For 10%, SiO2For 3%, zeolite is 4%；Dicalcium silicate is 47% in component B and lime-olivine is 53%.
In addition, described component A preparation method is：It will be produced during 1150~1250 DEG C of temperature lower calcination white clouds ores
Raw flue dust collecting produces component A, and the product after calcining is white to forge；
Described component B preparation method is：Ball is made after preparing that forging of obtaining of component A is white and being mixed with ferrosilicon and fluorite
Group produces component B through temperature range for remaining residue after 1190~1210 DEG C of calcinings；
And, the particle diameter of described flue dust is less than 40 μm；The particle diameter of described residue is less than 40 μm, the unit weight of described pelletizing
For 1195~2105g/cm3。
Described desulfurizing agent is used for the application of the flue gas desulfurization containing sulfur dioxide.
Described desulfurizing agent is used to remove the application containing sulfur dioxide FGD produced in Pidgeon process smelting magnesium technique.
The beneficial effects of the present invention are：
(1) desulfurizing agent that the present invention is provided includes component A and component B, and component A source is in 1150~1250 DEG C of temperature
The flue dust that lower calcining raw materials white clouds ore is produced；Waste material B source is that white, ferrosilicon is forged in utilization and pelletizing is made in reduction in fluorite
In stove after high-temperature calcination remaining residue；Wherein component A is as active catalyst, and component B is as desulphurizing activated dose, by group
Divide A to be catalyzed the desulphurizing activated of component B collectively as desulfurizing agent, component A addition after being mixed with component B, improve desulfurization effect
Rate, and the collective effect of calcium base and magnesium-based has been used simultaneously, it is that desulfurization technology opens new approach；
(2) using component A：Component B=7:The proportioning that 40 proportioning prepares desulfurizing agent (HBF) is considered simultaneously by experiment
The optimum proportioning that the yield of two kinds of waste materials is obtained in actual production process, desulfurized effect at this moment can reach most preferably, practical application
Prove, as long as maintaining pH value to meet desulfurization requirement 12 or so, component A and component B is reasonably used, not only
The comprehensive utilization ratio of resource is improved, the burden of environment is significantly reduced, and reduces the throwing of desulphurization cost in production process
Enter, economic benefit is improved；
(3) present invention is mainly applied to remove the technological process of Pidgeon process smelting magnesium reduction flow in produced in reduction furnace it is big
The sulfur dioxide of amount, its advantage can have been given play to the full extent at this Pidgeon process smelting magnesium field by applying；Certainly, as long as
There is the field that sulfur dioxide is produced in production process, can be using desulfurizing agent of the invention.
Brief description of the drawings
Fig. 1 is Pidgeon process smelting magnesium process chart；
Fig. 2 is desulfurization flow chart, and each label is expressed as in Fig. 2：1- dissolving tanks, 2- regenerated reactors, 3- sedimentation basins, 4- regulations
Pond, 5- dehydration between, 6- desulfurization zones, 7- demisters, 8- catalyst (waste material A), 9- circulating pumps, 10- smoke inlets, 11- desulfurizing towers
Top, 12- desulfurizing towers, 13- chimneys；
Fig. 3 is the pH graphs of a relation under different waste material B contents；
Fig. 4 is the pH graphs of a relation under different waste material A contents；
Fig. 5 is waste material A grain size distribution；
Fig. 6 is waste material B grain size distribution；
The present invention is illustrated below in conjunction with specification drawings and specific embodiments.
Embodiment
Pidgeon process production magnesium metal is included by raw material of dolime, ferrosilicon is reducing agent, fluorite is that catalyst is carried out
Batching；Balling-up, referred to as pelletizing will be suppressed after dispensing grinding；Pelletizing is fitted into reductive jar, 1200 ± 10 DEG C are heated to, it is interior
Portion 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 thick
Magnesium；Again through flux-refining, output commodity magnesium ingot, i.e., smart magnesium.
Production of magnesium by pidgeonprocess production process includes：
(1) dolomite calcination：Dolomite is heated to 1150 DEG C~1250 DEG C in rotary kiln or shaft furnace, burn till forge it is white
(MgOCaO)；
(2) dispensing ball：White, ferrosilicon powder and Fluorspar Powder batching, grinding will be forged, pelletizing, pelletizing pressure is then pressed into
(in amygdaliform, amygdaloidal), the unit weight of pellet should reach 1195~2105g/cm after group3；
(3) reduce：Pellet is heated to 1200 ± 10 DEG C in reductive jar, under 13.3~10Pa vacuum condition, protected
Hold 8~12 hours, magnesia is reduced into magnesium vapor, turn into crude magnesium after condensation；
(4) ingot casting is refined：Crude magnesium is heated and melted, under 680~740 DEG C of high temperature, after solvent refined, magnesium ingot is cast,
Also known as smart magnesium.
(5) pickling：Magnesium ingot is cleaned into surface with sulfuric acid or nitric acid, surface is removed and is mingled with, make surface aesthetic.
Investigation is found, two kinds of waste materials can be produced in Pidgeon process smelting magnesium technological process (see Fig. 1).Pidgeon process smelting magnesium technique stream
Journey only has this kind of, although technological process is continuously available optimization by development for many years, but in production process or can produce
Raw waste material A and waste material B (waste material A and waste material B of the present invention are referred to as component A and component B in desulfurizing agent).
Waste material A, its originate be under 1150~1250 DEG C of temperature conditionss in rotary kiln calcining raw materials white clouds ore process
The flue dust of middle generation, this process is called calcination process.If these flue dust are discharged into air, it will atmospheric environment is caused sternly
The pollution of weight.Correlative study shows, if the flue dust particle diameter produced in calcination process is less than 40 μm, MgO37% will be contained in flue dust
~39%, increase because specific grain surface is accumulated, magnesium-based activity will be greatly improved, this will promote neutralization reaction activity to become strong.Therefore,
Afterbody with sack cleaner to flue gas in particle diameter be less than 40 μm of dust and trap, collect waste material using pulse oscillating mode
A, is used as active catalyst.
Waste material B, its originate be utilization forge white (chemical formula is MgOCaO), the pelletizing that ferrosilicon and fluorite are made up of marble forming machine
In reduction furnace after the calcining of (1200 ± 10 DEG C) of high temperature remaining residue, this process be called to reduce process.Due to its production
Amount is very big, and what value very big burden would generally be caused to environment without.Test finds the main component in B
For 2CaOSiO2, rich in calcium base, and it is both less than 40 μm close to 90% particle diameter, is highly suitable as desulfurizing agent.
Research finds that waste material A and waste material B, which are dissolved in after water, is all presented alkalescence, and waste material A is rich in magnesium-based and calcium base, be dissolved in water it
Its pH value can reach 12.7 afterwards, and waste material B dissolves pH value rich in there is calcium base, by a certain percentage can reach 11, but waste material B pH value is inclined
It is small, and calcium base activity is weak, be not suitable for making desulfurizing agent and use, and add certain proportion waste material A (active catalyst) pH value can afterwards
Stabilization forms the synthetic sweetening agent (HBF) of know clearly calcium base and magnesium-based 12, substantially increases desulfurized effect.
So it is contemplated that original used de- using waste material A (active catalyst) and waste material B both materials replacements
Sulphur agent calcium oxide, is used to remove substantial amounts of sulfur dioxide gas (or large-scale fire coal is produced in reduction furnace applied to desulfurizing tower
The flue gas desulfurization of boiler).Due to waste material A and B yield and be dissolved in the alkalescence of water and have differences, it is specific by being carried out to A and B
Mixing match come as a kind of new desulfurizing agent (HBF), the waste material A that produces in technical process can be utilized to greatest extent
And B, on the premise of sulfur removal technology demand is met, improve comprehensive resource utilization rate.It is expected that after technical optimization, desulphurization system can
Save desulphurization cost more than half.Simultaneously as the specific surface area of main matter is big in waste material A and B, therefore desulfuration efficiency also can
It is further enhanced.
Wet Flue Gas Desulfurization Technique mainly includes lime (lime stone) method, Dual alkali, sodium method, magnesium processes, ammonia process, seawater method, phosphorus ammonium
Fertile method etc., is single substance desulfurization, and waste material A (active catalyst) and waste material B is used and mixed than desulfurizing agent made from method (HBF),
Form new mixed than method desulfurization technology in Wet Flue Gas Desulfurization Technique, be desulfurization while having used the collective effect of calcium base and magnesium-based
Technology opens new approach.
First, the feasibility analysis of scheme：
(1) waste material A, B composition test
Using the EMPYREAN type X-ray diffraction analysis instrument of PANalytical companies of the U.S. two waste materials have been carried out into
Divide the measure with ratio, it is as a result as follows.
Waste material A main component is magnesia (MgO), calcium oxide (CaO), dolomite and calcium carbonate (CaCO3), it is accounted for
The 93% of total content, remaining is SiO2And zeolite, specific composition is shown in Table 1.
Table 1
| Composition | MgO | CaO | Dolomite | CaCO3 | SiO2 | Zeolite |
| Mass percent | 40% | 24% | 19% | 10% | 3% | 4% |
Waste material B mainly contains two kinds of materials, dicalcium silicate and lime-olivine.Lime-olivine is another knot of dicalcium silicate
Configuration formula, both only exist the difference of physical property.Its chemical formula is all 2CaOSiO2, with identical chemical property.
When its chemical property is discussed, it is believed that be that specific composition in same material, waste material B is shown in Table 2.
Table 2
| Composition | Dicalcium silicate | Lime-olivine |
| Mass percent | 47% | 53% |
It can see from waste material constituent analysis, wherein can be with sulfurous acid (SO2Be dissolved in the product of water) reaction composition account for always
More than the 90% of amount, it is highly beneficial for the purpose of desulfurization.
The otherness that production of magnesium by pidgeonprocess is produced is used according to different manufacturers, by mass percentage, in waste material A, magnesia
(MgO) can be able to be that 22%~26%, dolomite can be 17%~21%, carbonic acid for 38%~42%, calcium oxide (CaO)
Calcium (CaCO3) can be 8%~12%, it has accounted for the 93% of total content, and remaining is SiO2And zeolite, SiO2Can for 2%~
4%, zeolite can be 3%~4%；
Dicalcium silicate can be 44%~50% in waste material B, and lime-olivine can be 50%~56%.
(2) influence of the proportioning of waste to pH value of water solution
Because solution ph is 12 in existing desulfurization method, desulfuration efficiency now is in higher level, so I
Still expect be equipped with slurry pH value be 12.
(1) B is individually dissolved
Experiment takes the waste material B of different quality to be mixed with 100ml distilled water, after after abundant dissolving, measures different B and contains
The pH value of the lower solution of amount.It can be seen that the increase of the content with the B of addition, the pH value of solution constantly increases from table 3 and in Fig. 3
Plus.But with B increase, the change of pH value is more and more slower.When B content is equal to 54g, the pH of solution can reach
12。
The waste material B lysates pH value of table 3 changes
| B content (g) | 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
The yield that waste material B yield will be far more than waste material A during refining magnesium.Experiment takes 10gB waste materials and 100ml
Distilled water is mixed, and the A waste materials for adding different quality are sufficiently mixed, and the pH value change for measuring the aqueous solution quickly, is shown in Table 4 and Fig. 4.
When the A of addition reaches 1.75g, the pH value of solution can reach 12.
A the and B aggregate sample lysates pH value of table 4 changes
| A content (g) | 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 carrying out desulfurization using waste material A and B, terminate from alkaline slurry is prepared to as desulfurization medium desulfurization, during
The chemical reaction occurred is mainly as follows：
1) waste material A and B are dissolved in the reaction of water generation：
CaO+H2O→Ca(OH)2 (1)
MgO+H2O→Mg(OH)2 (2)
2) waste material A and B are dissolved in after water, the reaction occurred with sulfurous acid：
MgO+H2SO3→MgSO3+H2O (3)
Mg(OH)2+H2SO3→MgSO3+2H2O (4)
Ca(OH)2+H2SO3→CaSO3·2H2O (5)
CaCO3MgCO3+2H2SO3→CaSO3+MgSO3+2CO2↑+2H2O (6)
CaCO3+H2SO3→CaSO3+CO2↑+H2O (7)
2CaO·SiO2+2H2SO3→2CaSO3+H2SiO3+H2O (8)
3) CaSO after being oxygenated3、MgSO3It is converted into CaSO4、MgSO4Shi Fasheng chemical reaction：
CaSO3·2H2O+0.5O2→CaSO4·H2O (9)
MgSO3+0.5O2→MgSO4 (10)
From above-mentioned chemical equation can be seen that waste material A and B in the composition that reacts of main and sulfurous acid have
MgO, CaO, dolomite, CaCO3、2CaO·SiO2Deng, its content up to more than 90%.Final main product is MgSO4、
CaSO4Deng.Wherein CaSO4Content it is very high, it may be considered that be used as industry or construction material raw material.
Experiment determines A and B proportioning by testing two kinds of antacid abilities of the aqueous solution of waste material A and B.Due to sulfurous acid
Solution is volatile acid solution, and the SO volatilized2Gas can all produce significant damage to human body and environment, in experiment condition
Lower is difficult control.Therefore the aqueous solution of the sulfuric acid solution and waste material A and B that are considered as having similar quality with it is reacted.
A the and B aqueous solution and sulfuric acid solution, which react main product, MgSO4、CaSO4、CO2And H2O.A the and B aqueous solution
Reacting main product with sulfurous acid solution has MgSO3、CaSO3、CO2And H2O.Can from the equation of the reaction of table 5
If going out to consume the same amount of AB aqueous solution, then as the sulfuric acid solution consumed is with the amount of sulfurous acid solution.And oxygenation
Sulfurous acid solution and sulfuric acid solution are identical with the product that waste material reacts afterwards, i.e. the waste material AB aqueous solution and sulfurous acid and sulfuric acid is molten
The final product of liquid reaction is consistent.Therefore, reacted in experimentation using the aqueous solution of sulfuric acid solution and waste material A and B
It is rational.
Contrast between the waste material A of table 5 and B and acid reaction
Waste material A and the B aqueous solution carry out the experiment of neutralization reaction with sulfuric acid.Waste material each 10g of A, B is taken respectively, is distilled with 100ml
Water is sufficiently mixed, and obtains suspension.Neutralization reaction is carried out using 1mL/L dilution heat of sulfuric acid, solution ph is neutralized to 7.Institute
The volume of consumption sulfuric acid solution is shown in Table 6：By contrast as can be seen that the sulfuric acid solution that the aqueous solution of A waste materials is consumed is almost B useless
11 times of material.A waste materials are significantly stronger than B waste materials to the neutralising capacity of acid solution.
The consumption of table 6 waste material A and B respectively to sulfuric acid
The ratio that according to waste material A be 1.75g and waste material B is 10g is mixed, and is substantially soluble in 100ml distilled water, and with
1ml/L dilution heat of sulfuric acid carries out neutralization reaction.As a result it is as shown in table 7：In the CaO used at present and when, can under same pH
To consume about 50ml dilute sulfuric acid.After doubling according to the above ratio, i.e., 3.5g waste material A, 20g waste materials B is substantially soluble in 100ml and steamed
In distilled water, the dilute sulfuric acid of consumption basically reaches identical desulfurized effect close to existing process.So we adopt in practical application
Use waste material A：Waste material B=7:40 proportioning mode, had both met the requirement of desulfurization while reasonably make use of two kinds of waste materials.
Consumption of table 7 waste material A and the B mixture to sulfuric acid
(4) desulfuration efficiency
Research shows that calcium silicates has hole, and its specific surface area is much larger than the specific surface area of calcium hydroxide, and this is conducive to carrying
High desulfurization efficiency.Using laser fineness gage, waste material A, B particle diameter are measured, from waste material A and waste material B particle diameter point
Cloth Fig. 5, Fig. 6 can be seen that in waste material A, B that component content of the particle diameter below 40 μm is close to 90%, and less particle diameter will be led
Cause their specific surface area very big.Especially, the less particle diameters of waste material A, are also to adopt the activity used it as in HBF desulfurizing agents to urge
The main cause of agent, this way improves the reactivity in sweetening process, desulfuration efficiency is improved.In addition,
The reaction product of calcium hydroxide and silicic acid can also improve the utilization rate of calcium base in sweetening process, so as to reduce the use of desulfurizing agent
Amount, this is undoubtedly another advantage after desulfurization technological improvement.
2nd, conclusion：
Waste material A and B can be prepared into alkaline solution of the pH value more than 12 by rational proportion, and rich in calcium base and magnesium
Base, it is possible to use both materials replace original used desulfurizing agent calcium oxide.Here desulfurizing agent is served as using waste material A
(HBF) active catalyst in, its presence can greatly improve desulfuration efficiency.Although in the waste material A aqueous solution and sulfurous
The ability of acid is strong than waste material B, and waste material A completely can be separately as desulfurizing agent, but considers to be collected into from deduster
Waste material A amount it is less, in order to make full use of two kinds of waste materials, using waste material A：Waste material B=7:40 proportioning mode, namely
The mode for dissolving 3.5gA and 20gB in 100ml distilled water prepares desulfurizing agent (HBF), and the desulfurizing agent newly prepared (HBF) is in reality
Confirm that the requirement of former desulfurizing agent can be met in engineering.By the monitoring form after two unit application desulfurizing agents (HBF), with
The desulfuration efficiency that compares before improves 1%~2%.According to the reasonable prediction value to waste material A and waste material B composition,
Waste material A：The scope of waste material B proportional quantity is 7:35~45.
After optimization desulphurization system, make desulphurization cost more than half, while desulfuration efficiency is also improved.
On the premise of meeting desulfurization purpose, waste material A and waste material B are reasonably make use of, comprehensive resource utilization rate is improved, not only makes economy
Benefit is improved, and largely alleviates the burden of environment.
Embodiment 1：
With reference to Fig. 2, the waste material B produced in production process is directly poured into dissolving tank 1, while being put into running water full of molten
Solve pond 1, and continuously stirred with agitator with promote the dissolvable composition in waste material B dissolving, waste material B with lysate by pipe network with
The mode of flow by gravity enters regenerated reactor 2.Appropriate waste material A is added into regulating reservoir 4, makes the pH value of slurries in regulating reservoir 4 12
Left and right.The slurries for regulating pH value squeeze into desulfurizing tower 12 by circulating pump 9, the flue gas entered in desulfurization zone 6 with smoke inlet 10
Generation desulphurization reaction, the flue gas after purification is discharged into chimney by demister 7 from the top of desulfurizing tower 11, absorbs the slurry of sulfur dioxide
Liquid enters regenerated reactor 2 in desulfurization tower bottom by flow by gravity, is mixed with the alkaline matter flowed out in dissolving tank 1, occurs
Desulfurization absorbing liquid is regenerated after reaction.Reaction mixture in regenerated reactor 2 flows into sedimentation basin 3, and wherein supernatant, which is flowed into, adjusts
Pond 4 is saved, is adjusted after pH value and desulfurizing tower is squeezed into by circulating pump, circulation desulfurization, sediment is through being pumped into 5 between dehydration, after dehydration
Focused on, 13 be chimney, and effect is that the flue gas after desulfurization is discharged in air.8 be waste material A, during effect is desulfurizing agent
Catalyst and pH value regulator.
Its source of waste material A be under 1150~1250 DEG C of temperature conditionss in rotary kiln during calcining raw materials white clouds ore
The flue dust of generation, flue dust particle diameter is less than 40 μm；
Waste material B, its originate be utilization forge white (chemical formula is MgOCaO), the pelletizing that ferrosilicon and fluorite are made up of marble forming machine
In reduction furnace after the calcining of (1200 ± 10 DEG C) of high temperature remaining residue, residue particle diameter is less than 40 μm；
By mass percentage, MgO is that 40%, CaO is that 24%, dolomite is 19%, CaCO in component A3For 10%,
SiO2It is 3% and zeolite is 4%；Dicalcium silicate is 47% in component B and lime-olivine is 53%.
Waste material A and waste material B mass ratio is waste material A:Waste material B=7：Desulfurizing agent (HBF) is obtained after 40 mixing.
Desulfurizing agent (HBF) is applied in several magnesium metal factories, desulfurizing tower diameter 4.0m, total high 12m, desulfurization slurry
Liquid PH is 12, and liquid-gas ratio is 8.0L/m3, carry out having been achieved for extraordinary effect, sulfur-bearing according to above-mentioned embodiment
Amount reaches 700mg/m3Flue gas desulfurization after sulfur content can be reduced to 20mg/m3Within, far below international standard.
It is 97.1% using the desulfuration efficiency after desulfurizing agent (HBF), 1%-2% is improved than desulfuration efficiency before.Two
Unit extension benzin source coalification Co., Ltd of family and pseudo-classic Wanyuan Mei Ye Co., Ltds go out evidence from existing that environmental administration obtains
Line Monitoring Data, is shown in Table 6；As can be seen from Table 6, SO in discharge gas2Content be less than 10mg/m3Well below country's mark
The 200mg/m of alignment request3。
Table 8
Claims (7)
1. a kind of desulfurizing agent, it is characterised in that including component A and component B, component A is catalyst component, component B is desulphurizing activated
Composition；
Described component A includes MgO, CaO, dolomite, CaCO3、SiO2And zeolite；
Described component B includes dicalcium silicate and lime-olivine；
Count in mass ratio, component A：Component B is 7：35~45；
Described component A preparation method is：The flue dust that will be produced during 1150~1250 DEG C of temperature lower calcination white clouds ores
Collection produces component A, and the product after calcining is white to forge；
Described component B preparation method is：Pelletizing is made after preparing that forging of obtaining of component A is white and mixing with ferrosilicon and fluorite to pass through
Temperature range produces component B for remaining residue after 1190~1210 DEG C of calcinings.
2. in desulfurizing agent as claimed in claim 1, it is characterised in that by mass percentage, component A, magnesia is 38%
~42%, calcium oxide is 22%~26%, and dolomite is 17%~21%, and calcium carbonate is 8%~12%, SiO2For 2%~
4%, zeolite is 3%~4%；
Dicalcium silicate is 44%~50% in component B, and lime-olivine is 50%~56%.
3. desulfurizing agent as claimed in claim 1, it is characterised in that count in mass ratio, component A：Component B is 7：40.
4. MgO is 40%, CaO in desulfurizing agent as claimed in claim 3, it is characterised in that by mass percentage, component A
For 24%, dolomite is 19%, CaCO3For 10%, SiO2For 3%, zeolite is 4%；Dicalcium silicate is 47% and calcium in component B
Olivine is 53%.
5. desulfurizing agent as claimed in claim 1, it is characterised in that the particle diameter of described flue dust is less than 40 μm；Described residue
Particle diameter be less than 40 μm, the unit weight of described pelletizing is 1195~2105g/cm3。
6. the desulfurizing agent described in claim 1,2,3,4 or 5 is used for the application of the flue gas desulfurization containing sulfur dioxide.
What 7. the desulfurizing agent described in claim 1,2,3,4 or 5 was produced for removing in Pidgeon process smelting magnesium technique contains titanium dioxide
The application of sulphur flue gas desulfurization.
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| 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 |
| CN108479373B (en) * | 2016-04-22 | 2021-03-05 | 辽宁基伊能源科技有限公司 | Preparation method of environment-friendly flue gas desulfurization powder |
| 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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