CN107399753A - A kind of device and oxidation modifying method for sintering semi-dry desulphurization ash oxidation modification - Google Patents
A kind of device and oxidation modifying method for sintering semi-dry desulphurization ash oxidation modification Download PDFInfo
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Abstract
The invention discloses a kind of device and oxidation modifying method for sintering semi-dry desulphurization ash oxidation modification, belong to Desulphurization recycling application field.The pro-oxygenic agent injection unit of the present invention includes pro-oxygenic agent container and fluid pipeline, pro-oxygenic agent container is connected with fluid pipeline, pro-oxygenic agent injection unit is used to inject pro-oxygenic agent solution into Desulphurization mixed liquor, when being blown into oxygen-containing gas into the mixed liquor of Desulphurization and water, by the collective effect of reaction member, air supply unit and pro-oxygenic agent injection unit, it is molten that pro-oxygenic agent with water is mixed to get pro-oxygenic agent；And pro-oxygenic agent solution is uniformly injected into Desulphurization mixed liquor bottom, the pro-oxygenic agent includes acid additive, the pKa of acid additive1Acidity coefficient is between sulfurous acid and the pKa of sulfuric acid1Between acidity coefficient.The method of the oxidation modification of the present invention, by changing the reaction interface in Desulphurization oxidizing process, accelerates the oxidation efficiency of Desulphurization, is laid a good foundation for the recycling application of Desulphurization.
Description
Technical field
The present invention relates to Desulphurization recycling application field, and semi-dry desulphurization ash oxygen is sintered more specifically to one kind
Change modified device and oxidation modifying method.
Background technology
Global crude steel total output is up to 16.285 hundred million tons within 2016, increases by 0.8% on a year-on-year basis；Wherein crude steel yield in China's is
8.084 hundred million tons (account for global crude steel yield 49.6%), still increase by 1.2% on year-on-year basis.Sintering circuit produces as modern steel to flow
Important step in journey, and the SO in the main pollutant emission source, wherein steel and iron industry more than 70% of steel and iron industry2From sintering
Process.By SO in " the steel and iron industry emission standard " of newest revision2Emission control as one of important content, force
Property regulation steel industry wants time limit to realize CER and flue gas qualified discharge.In Iron and Steel Enterprises in China, the SO of iron and steel enterprise's discharge2
Middle 50%-70% comes from sintering circuit, and flue gas desulfurization is sintered using semi-dry desulphurization technology, not only invests low, and desulfurization
Rate is higher, but substantial amounts of Desulphurization is generated during semi-dry desulphurization, and only small part Desulphurization obtains profit both at home and abroad
With the overwhelming majority is abandoned, if do not utilized rationally, it will cause secondary pollution and take a large amount of soils.
With China environmental protection realize reinforcement, sintering deposit flue gas desulfurization ash comprehensive utilization in terms of research gradually by
To the concern of people, and the utilization of sintering deposit flue gas desulfurization ash can reduce because stack consumed fund, land occupation and
Environmental pollution, the dosage of the natural gypsum is reduced, and then reduce the yield of the natural gypsum, preserved the ecological environment.Therefore, many height
School and enterprise such as utilize sintering flue gas desulfurization ash system to having carried out substantial amounts of research in terms of the comprehensive utilization of sintering deposit flue gas desulfurization ash
Standby sulfuric acid, cement retarder, gypsum building material and calcium sulfate crystal whiskers etc..Wherein, sulfuric acid is prepared using sintering flue gas desulfurization ash
Calcium pyroborate has higher added value, and calcium sulfate crystal whiskers are a kind of chopped fibers grown with single crystal form, and it has uniform
Cross section, complete profile and highly perfect internal structure, compared with glass fibre, it is high strong that advantage is that it has
Degree, trickle size, is more easy to be combined with organic high molecular compounds such as resin, rubber, plastics, and the presentation quality of product is excellent
It is good.Can be widely used for automobile, Aero-Space, chemical industry, metallurgy, national defence, machinery, electrically, many necks such as ship, oil and building materials
Domain.Pollution of the desulfurated plaster to environment can not only be reduced by preparing calcium sulfate crystal whiskers as raw material using desulfurated plaster, can also be saved
Natural gypsum resource, and new way is opened for the high value added utilization of desulfurated plaster, but existing Desulphurization prepares sulphur
The method of sour calcium pyroborate is not perfect so that calcium sulfate crystal whiskers it is second-rate, seriously limit the high efficient resourcing of Desulphurization
Using.
Through patent retrieval, the Shi Peiyang of Northeastern University has also carried out first closing research, and has applied for Patents, utilizes sintering
Ore deposit flue gas desulfurization byproduct prepares the method (application number of calcium sulfate crystal whiskers：201010545829.1；The applying date：2010.11.16)
With the method (application number that calcium sulfate crystal whiskers are prepared using desulfurized gesso of flue gas：200810011193.5；The applying date：
2008.04.25), this method provides a kind of approach for the recycling application of Desulphurization.In addition, a kind of utilize semi-dry desulphurization
Ash and spent acid prepare the technique and device (application number of crystal whisker of gypsum：201210405335.2 the applying date：2012.10.22), it is real
The recycling application of Desulphurization is showed.But the calcium sulfate crystal whiskers that existing method produces to obtain are second-rate, limit desulfurization
The value added applications of ash.In addition, applicant explores by prolonged before this, have been achieved for a series of breakthrough
Anxiety, a kind of flue gas desulfurization ash modification processing method (application number of patent of invention is applied for：201611068316X), a kind of flue gas
Desulphurization low-temperature oxidation device (application number：2016110682881), modification of this method to Desulphurization has obvious action；
Again after this, invention again this break original technical thought, rebuild brand-new desulfurization ash handling equipment and processing method
Method, and the method for developing the brand-new acid oxidation based on pro-oxygenic agent oxidation, promote the recycling application of Desulphurization.
The content of the invention
1. invention technical problems to be solved
The problem of it is an object of the invention to overcome the oxidation efficiency of semi-dry desulphurization in the prior art poor, there is provided a kind of
Sinter the device and oxidation modifying method of semi-dry desulphurization ash oxidation modification；
A kind of sintering semi-dry desulphurization ash oxidation unit wherein provided, passes through reaction member, air supply unit and pro-oxygenic agent
The collective effect of injection unit, pro-oxygenic agent solution is uniformly injected into Desulphurization mixed liquor bottom, the pro-oxygenic agent can change
Reaction interface in Desulphurization oxidizing process, and then the oxidation efficiency of Desulphurization can be accelerated；
A kind of method using oxidation unit oxidation sweetening ash wherein provided, desulfurization is uniformly injected into by pro-oxygenic agent solution
Grey mixed liquor bottom, the pro-oxygenic agent can change the reaction interface in Desulphurization oxidizing process, and then can accelerate desulfurization
The oxidation efficiency of ash；It is possible to further improve the purity of calcium sulphate dihydrate in reaction product.
2. technical scheme
To reach above-mentioned purpose, technical scheme provided by the invention is：
A kind of sintering semi-dry desulphurization ash oxidation unit of the present invention, including reaction member, the reaction member include reaction
Device inner chamber, reactor inner chamber are used to contain oxidized Desulphurization mixed liquor；Air supply unit, the gas pipeline of the air supply unit are stretched
Enter the bottom of reactor inner chamber, air supply unit is used to be blown into oxygen-containing gas into Desulphurization mixed liquor；Pro-oxygenic agent injection unit, should
Pro-oxygenic agent injection unit includes pro-oxygenic agent container and fluid pipeline, and pro-oxygenic agent container is connected with fluid pipeline, pro-oxygenic agent injection
Unit is used to inject pro-oxygenic agent solution into Desulphurization mixed liquor.
Preferably, described fluid pipeline stretches into the bottom of reactor inner chamber, and fluid pipeline bottom is provided with liquid outlet,
And the tracheae outlet of gas pipeline is correspondingly arranged with liquid outlet, and tracheae outlet is sprayed towards liquid outlet.
Preferably, described fluid pipeline is stretched into gas pipeline, and the pro-oxygenic agent solution in pro-oxygenic agent container is single in supply
Enter the bottom of reactor inner chamber under the driving of member.
Preferably, the bottom of described fluid pipeline is provided with bubble generator, and bubble generator causes gas and helps oxygen
Agent solution is uniformly distributed in reactor inner chamber.
Preferably, described reactor lumen outer is provided with constant temperature exocoel, and the constant temperature exocoel is used to keep in reactor
Chamber is in steady temperature.
A kind of method using oxidation unit oxidation sweetening ash of the present invention, is comprised the following steps that：
S1, removal of impurities drying
Take Desulphurization raw material to be mixed with water, and bulky grain insoluble matter is gone by water sieve, then after being filtered by vacuum and being cleaned
Desulphurization；
S2, configuration Desulphurization solution
The Desulphurization that S1 steps obtain is mixed with deionized water, and the solid-to-liquid ratio of Desulphurization and deionized water be 1/20~
1/50, Desulphurization mixed liquor is obtained after fully shaking；
S3, the oxidation of Desulphurization acid
(1) mass ratio of pro-oxygenic agent and the Desulphurization after filtering and impurity removing is 0.2-0.3, and pro-oxygenic agent is dissolved in into deionized water obtains
To pro-oxygenic agent solution, then pro-oxygenic agent solution is added to the pro-oxygenic agent container of desulphurized ash oxidation device, described oxidation unit
For the oxidation unit described in the claims any one of 1-5；Described pro-oxygenic agent includes acid additive, the acid additive
pKa1Acidity coefficient is between sulfurous acid and the pKa of sulfuric acid1Between acidity coefficient, the pro-oxygenic agent is for the sulfurous in oxidation sweetening ash
Sour calcium；
(2) Desulphurization mixed liquor is added in reactor inner chamber, and opens inner chamber agitator, blown into Desulphurization mixed liquor
Enter oxygen-containing gas, the pro-oxygenic agent solution in pro-oxygenic agent container is uniformly injected into Desulphurization mixed liquor during oxidation sweetening ash
Bottom, and the Desulphurization aoxidized.
Preferably, the time of Desulphurization mixed liquor oxidation reaction is 80-150min in described S3 steps (2), and helps oxygen
The time of agent solution injection is identical with the time reacted.
Preferably, described acid additive is soluble in water, pKa of the described acid additive in 25 DEG C of water1Acidity coefficient
For：1.00-1.89.
Preferably, described acid additive is the combination of oxalic acid or dichloroacetic acid or both.
Preferably, in addition to additive, pro-oxygenic agent are formed by following mass parts：
Acid additive 10-20 parts；
Additive 8-12 parts；
Wherein, described additive includes triammonium citrate and pyruvic acid.
3. beneficial effect
Using technical scheme provided by the invention, compared with existing known technology, there is following remarkable result：
(1) a kind of method using oxidation unit oxidation sweetening ash of the invention, pro-oxygenic agent solution is uniformly injected into de-
Sulphur ash mixed liquor bottom, the pKa of the acid additive in the pro-oxygenic agent1Acidity coefficient is between sulfurous acid and the pKa of sulfuric acid1Acidity system
Between number, the reaction interface in Desulphurization oxidizing process is changed, and then the oxidation efficiency of Desulphurization can be accelerated, is dropped simultaneously
Low energy consumption of reaction, and then improve industrial economic benefit；
(2) a kind of method using oxidation unit oxidation sweetening ash of the invention, add after pro-oxygenic agent in Desulphurization
CaSO3Form ionic condition and enter solution, change the reaction interface in Desulphurization oxidizing process, realize in open condition
Oxidation in lower to Desulphurization, while slowly the uniform pro-oxygenic agent that adds is easy, efficiently avoid SO2Escape；
(3) a kind of method using oxidation unit oxidation sweetening ash of the invention, substantially increase anti-after Desulphurization aoxidizes
The content of the calcium sulphate dihydrate in product is answered, and the purity of the calcium sulphate dihydrate in dried powder is higher, is the equal of in desulfurization
It is purified in grey oxidizing process, laid a good foundation subsequently to prepare whisker；
(4) a kind of sintering semi-dry desulphurization ash oxidation unit of the invention, passes through reaction member, air supply unit and pro-oxygenic agent
The collective effect of injection unit, pro-oxygenic agent solution is uniformly injected into Desulphurization mixed liquor bottom, the pro-oxygenic agent can change
Reaction interface in Desulphurization oxidizing process, and then the oxidation efficiency of Desulphurization can be accelerated；
(5) a kind of sintering semi-dry desulphurization ash oxidation unit of the invention, flow control valve are used to control adding for pro-oxygenic agent solution
Enter speed, and then regulate and control the addition time of pro-oxygenic agent solution, it is ensured that the time and the time of reaction of pro-oxygenic agent solution injection
Identical, pro-oxygenic agent solution is slow all the time, is uniformly injected into Desulphurization mixed liquor bottom, after addition pro-oxygenic agent in Desulphurization
CaSO3Form ionic condition and enter solution, while also avoid SO2Escape；
(6) a kind of sintering semi-dry desulphurization ash oxidation unit of the invention, the tracheae outlet of gas pipeline and liquid outlet
It is correspondingly arranged, and tracheae outlet is sprayed towards liquid outlet so that during pro-oxygenic agent solution is that Desulphurization combines, desulfurization
CaSO in ash3Formed after ionic condition enters solution, H that oxygen-containing gas can rapidly with solution state2SO3With reference to concurrently
Raw oxidation reaction generation SO4 2-, and then accelerate the speed of reaction.
Brief description of the drawings
Fig. 1 is the structural representation of the oxidation unit of embodiments of the invention 1；
Fig. 2 is the structural representation of the oxidation unit of embodiments of the invention 2；
Fig. 3 is the structural representation of the oxidation unit of embodiments of the invention 3.
Label declaration in accompanying drawing：
100th, reaction member；110th, reactor inner chamber；111st, inner chamber agitator；112nd, thermocouple；120th, constant temperature exocoel；
121st, refrigerant import；122nd, refrigerant exit；
200th, air supply unit；210th, air feed bottle；211st, cylinder outlet；212nd, gas cooling mechanism；220th, gas control valve；
221st, valve inlet；230th, flowmeter；240th, gas pipeline；241st, tracheae exports；242nd, bubble generator；
300th, pro-oxygenic agent injection unit；310th, pro-oxygenic agent container；320th, flow control valve；330th, fluid pipeline；331st, liquid discharge
Mouthful.
Embodiment
Hereafter to the detailed description of exemplary embodiment of the invention, although these exemplary embodiments are by fully in detail
Description is to enable those skilled in the art to implement the present invention, it is to be understood that can realize other embodiment and can not depart from
To the present invention, various changes can be made in the case of the spirit and scope of the present invention.Hereafter the more detailed of embodiments of the invention is retouched
State and be not limited to required the scope of the present invention, and just to be illustrated and do not limit the spy to the present invention
The description of point and feature, best mode of the invention is performed with proposition, and be sufficient so that those skilled in the art to implement this
Invention.Therefore, the scope of the invention is only defined by the appended claims.
Embodiment 1
As shown in figure 1, a kind of sintering semi-dry desulphurization ash oxidation unit of the present invention, including reaction member 100, supply are single
Member 200 and pro-oxygenic agent injection unit 300, wherein reaction member 100 include reactor inner chamber 110, and reactor inner chamber 110 is used to contain
The oxidized Desulphurization mixed liquor of dress, the middle part of reactor inner chamber 110 are provided with inner chamber agitator 111, and inner chamber agitator 111 is used for
Desulphurization mixed liquor in reactor inner chamber 110 is stirred, promotes reaction to homogenize；It is provided with reactor inner chamber 110
Thermocouple 112, it is used for the temperature for monitoring the mixed liquor in reactor inner chamber 110.Above-mentioned air supply unit 200 includes air feed bottle
210th, gas control valve 220, flowmeter 230 and gas pipeline 240, air feed bottle 210 is through gas control valve 220 and gas pipeline
240 are connected, and the cylinder outlet 211 of air feed bottle 210 is connected with the valve inlet 221 of gas control valve 220, gas control valve 220
The other end is connected with gas pipeline 240, and flowmeter 230 is arranged on gas pipeline 240, and flowmeter 230 can detect and be blown into gas
The flow of body, the gas pipeline 240 stretch into the bottom of reactor inner chamber 110, and air supply unit 200 is used for into Desulphurization mixed liquor
It is blown into oxygen-containing gas, the bottom that oxygen-containing gas is blown into reactor inner chamber 110 enhances the stirring of Desulphurization solution, promotes reaction
Progress, while accelerate the oxidation reaction of Desulphurization.
The pro-oxygenic agent injection unit 300 of the present embodiment is used to inject pro-oxygenic agent solution into Desulphurization mixed liquor, and this helps oxygen
Agent injection unit 300 includes pro-oxygenic agent container 310, flow control valve 320 and fluid pipeline 330, pro-oxygenic agent container 310 and fluid pipeline
330 are connected, and flow control valve 320 is arranged on fluid pipeline 330, and flow control valve 320 is used for the addition speed for controlling pro-oxygenic agent solution,
And then regulate and control the addition time of pro-oxygenic agent solution, it thereby may be ensured that the time of pro-oxygenic agent solution injection and the time phase reacted
Together, i.e., pro-oxygenic agent solution terminates since reaction to reaction, and pro-oxygenic agent solution is slow all the time, is uniformly injected into Desulphurization mixed liquor
Bottom, add the CaSO in Desulphurization after pro-oxygenic agent3Form ionic condition and enter solution, while also avoid SO2Escape, tool
Have and significantly improve.
The fluid pipeline 330 of the present embodiment stretches into the bottom of reactor inner chamber 110, and the bottom of fluid pipeline 330 is provided with liquid
Body outlet 331, and the tracheae outlet 241 of gas pipeline 240 is correspondingly arranged with liquid outlet 331, and tracheae exports 241 towards liquid
The injection of body outlet 331, so that during pro-oxygenic agent solution is that Desulphurization combines, the CaSO in Desulphurization3Formed from
After sub- state enters solution, H that oxygen-containing gas can rapidly with solution state2SO3With reference to, and oxidation reaction generation occurs
SO4 2-, and then accelerate the speed of reaction.
Constant temperature exocoel 120 is provided with outside the reactor inner chamber 110 of the present embodiment, the constant temperature exocoel 120 is used to keep anti-
Device inner chamber 110 is answered to be in steady temperature, constant temperature exocoel 120 can be electric control constant incubator, while can also be the perseverance for injecting refrigerant
Warm exocoel 120, the side of described constant temperature exocoel 120 are provided with refrigerant import 121, and corresponding opposite side is provided with refrigerant
Outlet 122, and the level height of refrigerant exit 122 is higher than the level height of refrigerant import 121, cooling media is by refrigerant import
121 enter, and are flowed out by refrigerant exit 122, and reactor inner chamber 110 is cooled down.
A kind of method using oxidation unit oxidation sweetening ash of the present invention, wherein used pro-oxygenic agent helps including acidity
Agent, the acidity of the acid additive is between sulfurous acid and sulfuric acid, i.e. the pKa of acid additive1Acidity coefficient between sulfurous acid with
The pKa of sulfuric acid1Between acidity coefficient, the pro-oxygenic agent is readily soluble for the calcium sulfite in oxidation sweetening ash, described acid additive
Yu Shui, pKa of the acid additive in 25 DEG C of water1Acidity coefficient is：1.00-1.89, wherein described pKa1For the one of acid additive
Level acidity coefficient, the acid additive of the present embodiment are oxalic acid, its pKa1For 1.27；Pro-oxygenic agent in the present embodiment is oxalic acid,
Pro-oxygenic agent solution is obtained after oxalic acid is mixed with water.Wherein：Acidity coefficient (pKa), also known as acid dissociation constant, it is acid dissociation balance
The opposite number of the common logarithm of constant, its definition are pKa=-lg (Ka).
Desulphurization and water are then mixed to get Desulphurization mixed liquor, then oxalic acid solution is injected in mixed liquor, pro-oxygenic agent
Mass ratio with the Desulphurization after filtering and impurity removing is 0.2-03, i.e., oxalic acid powder pure material and Desulphurization mass ratio are 0.2-0.3.
As shown in figure 1, a kind of method using oxidation unit oxidation sweetening ash of the present invention, is comprised the following steps that：
S1, removal of impurities drying
Take Desulphurization raw material to be mixed with water, and the upper bulky grain insoluble matter of sieve is removed by 200 mesh water sieves, pass through vacuum filtration
Desulphurization after being cleaned, then Desulphurization is put into drying box, 4h is dried at 105 DEG C；
S2, configuration Desulphurization solution
The Desulphurization 20g that S1 steps obtain is mixed with deionized water, and the solid-to-liquid ratio of Desulphurization and deionized water is 1/
50, the fully shaking 30min under 50 DEG C of environment is put into gas bath concussion case, obtains Desulphurization mixed liquor；
S3, the oxidation of Desulphurization acid
(1) mass ratio of pro-oxygenic agent and the Desulphurization after filtering and impurity removing is 0.2-0.3, and the present embodiment takes 0.2, takes 4g to help oxygen
Agent is dissolved in deionized water and obtains pro-oxygenic agent solution, and the mass ratio of pro-oxygenic agent and deionized water is 0.05-0.2, and this implementation is excellent
0.05 is selected, obtains 84g pro-oxygenic agent solution, and pro-oxygenic agent solution is added in pro-oxygenic agent container 310；
(2) Desulphurization mixed liquor is added in reactor inner chamber 110, the thermostat temperature of control constant temperature exocoel 120, and kept
Temperature in reactor inner chamber 110 is 5 DEG C, and the gas control valve 220 for opening air supply unit 200 is blown into Desulphurization mixed liquor
Oxygen-containing gas, described oxygen-containing gas are air；At the same time the flow control valve 320 of pro-oxygenic agent injection unit 300, pro-oxygenic agent are opened
Solution injects the bottom of reactor inner chamber 110 by pro-oxygenic agent container 310 through fluid pipeline 330, and pro-oxygenic agent solution is in oxidation sweetening ash
During be uniformly injected into Desulphurization mixed liquor bottom, reaction time 150min；According to gas control valve 220 in course of reaction
The flow that is blown into of the oxygen-containing gas regulated and controled with flowmeter 230 is 15ml/min, and the tracheae of gas pipeline 240 exports 241 and liquid
Body outlet 331 is correspondingly arranged, and tracheae outlet 241 is sprayed towards liquid outlet 331 so that pro-oxygenic agent solution is Desulphurization knot
During conjunction, the CaSO in Desulphurization3Formed after ionic condition enters solution, oxygen-containing gas can rapidly and solution state
H2SO3With reference to, and oxidation reaction generation SO occurs4 2-, and then accelerate the speed of reaction；Reaction terminates to obtain oxidation modification
Desulphurization, in the present invention modification to Desulphurization be to desulfurization can oxidation processes, therefore oxidation modification can also claim
For oxidation.What deserves to be explained is：The time of pro-oxygenic agent solution injection is identical with the time reacted, i.e. pro-oxygenic agent solution is opened from reaction
Begin to reaction to terminate, pro-oxygenic agent solution is slow all the time, is uniformly injected into Desulphurization mixed liquor bottom, i.e. the pro-oxygenic agent solution of 84g
Slowly it is uniformly injected into 150min reaction time.Reaction obtains reactant precipitation, the temperature to being deposited in 100 DEG C after terminating
Lower heat drying obtains dried powder, and the content of the calcium sulphate dihydrate in dried powder reaches 96.1%, improves reaction product
The purity of middle calcium sulphate dihydrate, be the equal of that it is purified in Desulphurization oxidizing process, so as to be subsequently to prepare whisker
Lay a good foundation.
Existing technical staff to the calcium sulfite in Desulphurization often in order to carry out oxidation processes, often by height
The airtight condition of warm (about 300 DEG C) high pressure, oxidant is added into Desulphurization mixed liquor to the calcium sulfite progress in Desulphurization
Oxidation.Although this method has certain effect in the oxidation processes tool to Desulphurization.But semidry method sintering flue gas desulfurization is grey
Composition is complex, in addition to containing substantial amounts of calcium sulfite, calcium oxide and calcium carbonate also containing part of sulfuric acid calcium, residual
Deng although part research shows that above-mentioned Desulphurization method for oxidation has certain oxidation effectiveness, can not be by desulfurization product
In impurity remove；It is past in open reactor because solubility of the sulfurous acid in water is relatively low in open reactor
It is past to be difficult to CaSO3Quick Oxidation, therefore oxygen is first often carried out using high temperature, the airtight condition of high pressure in the prior art
Change, and then avoid SO2Escape.In addition, its obtained product of oxidation not only aoxidizes cost is high, efficiency is low, and oxygen
The purity for the product that change obtains is poor, and higher oxidizing temperature significantly increases the energy consumption of commercial Application, has had a strong impact on desulfurization
The recycling application of ash.
The present invention has broken the technology prejudice of prior art, in oxidation reaction process, by into Desulphurization mixed liquor
Pro-oxygenic agent is slowly added, to the oxidation of Desulphurization in realizing in an open condition, the pro-oxygenic agent in the present embodiment is
Oxalic acid, add the CaSO in Desulphurization after pro-oxygenic agent3Form ionic condition and enter solution, effectively avoid SO2Escape, and
H is generated in the solution2SO3, so as to change the reaction interface in Desulphurization oxidizing process, carry out ionic reaction oxidation, Jin Erjia
The fast progress of Desulphurization oxidation reaction, the degree of oxidation of Desulphurization is improved as pro-oxygenic agent from oxalic acid, simultaneously effective
Avoid SO2Escape.At the same time, what this hair was creative proposes low-temperature oxidation (the temperature dimension of the present embodiment oxidizing process
Hold at 5 DEG C), under normal circumstances in order to improve oxidation rate, existing researcher is often subconscious to go to improve reaction temperature
Spend and then improve the speed of reaction, and the present invention is by reducing reaction temperature, and during improving calcium sulfite oxidation
Reaction interface, and then reaction efficiency is greatly improved, and unexpected effect is reached, the present invention has non-obvious
Property, there are prominent substantive distinguishing features and significant progress.
Comparative example 1
The substance of this comparative example is with embodiment 1, and difference is, this comparative example does not use the experiment of embodiment 1
Device, reaction terminate after obtain reactant precipitation, reaction time 180min, to being deposited in 100 DEG C at a temperature of heat drying
Obtain dried powder, the content of the calcium sulphate dihydrate in dried powder reaches 95.2%.
It can be found that the content of the calcium sulphate dihydrate of embodiment 1 further improves compared with comparative example 1, and accelerate anti-
Answer efficiency；Its reason is：Regulate and control the addition time of pro-oxygenic agent solution using flow control valve 320, it is ensured that pro-oxygenic agent solution is noted
The time entered is identical with the time reacted, i.e., pro-oxygenic agent solution starts to reaction to terminate since reaction, pro-oxygenic agent solution is slow all the time,
It is uniformly injected into Desulphurization mixed liquor bottom, adds the CaSO in Desulphurization after pro-oxygenic agent3Form ionic condition and enter solution, together
When also avoid SO2Escape；And the tracheae outlet 241 of gas pipeline 240 is correspondingly arranged with liquid outlet 331, and tracheae
Sprayed towards liquid outlet 331 outlet 241 so that during pro-oxygenic agent solution is that Desulphurization combines, in Desulphurization
CaSO3Formed after ionic condition enters solution, H that oxygen-containing gas can rapidly with solution state2SO3With reference to, and aoxidize
Reaction generation SO4 2-, and then accelerate the speed of reaction.
Embodiment 2
With embodiment 1, difference is the substance of the present embodiment：A kind of as shown in Fig. 2 sintering of the present embodiment
Semi-dry desulphurization ash oxidation unit, fluid pipeline 330 are stretched into gas pipeline 240, the pro-oxygenic agent solution in pro-oxygenic agent container 310
Enter the bottom of reactor inner chamber 110 under the driving of air supply unit 200.The bottom of fluid pipeline 330 is provided with bubble
Device 242, bubble generator 242 cause gas and pro-oxygenic agent solution to be uniformly distributed in reactor inner chamber 110.So that pro-oxygenic agent
During solution is that Desulphurization combines, the CaSO in Desulphurization3Formed after ionic condition enters solution, oxygen-containing gas can be with
Rapidly with the H of solution state2SO3With reference to, and oxidation reaction generation SO occurs4 2-, and then accelerate the speed of reaction.
Acid additive is dichloroacetic acid (CHCl2COOH), its pKa in 25 DEG C of water1For 1.30, helping in the present embodiment
Oxygen agent is dichloroacetic acid, and pro-oxygenic agent solution is obtained after dichloroacetic acid is mixed with water.Carried significantly using the pro-oxygenic agent of the present invention
The high oxidation efficiency of Desulphurization, and become to realize and Desulphurization is aoxidized under conditions of open container low temperature.Instead
The Desulphurization that reactant precipitation is oxidation modification is obtained after should terminating, and heat drying obtains at a temperature of 100 DEG C by it
Dried powder, the content of the calcium sulphate dihydrate in dried powder reach 96.1%.
Embodiment 3
With embodiment 1, difference is the substance of the present embodiment：As shown in figure 3, the air feed bottle of the present embodiment
Gas cooling mechanism 212 is provided with pipeline between 210 and gas control valve 220, the gas cooling mechanism 212 is used for pipe
The gas in road is cooled down so that and the gas being blown into Desulphurization mixed liquor is cryogenic gas, and gas temperature is 0 DEG C, so as to
Promote by reducing reaction temperature, and improve the reaction interface during calcium sulfite oxidation, and then greatly improve
Reaction efficiency.The acid additive of the present embodiment is made up of oxalic acid and dichloroacetic acid, and the mass ratio of oxalic acid and dichloroacetic acid is 2:
1, the pro-oxygenic agent of the present embodiment is made up of oxalic acid and dichloroacetic acid.Desulphurization is substantially increased using the pro-oxygenic agent of the present invention
Oxidation efficiency, and become to realize and Desulphurization is aoxidized under open container cryogenic conditions, reaction obtains anti-after terminating
The Desulphurization that thing precipitation is oxidation modification is answered, and heat drying obtains dried powder, xeraphium at a temperature of 100 DEG C by it
The content of calcium sulphate dihydrate in end reaches 95.2%.
Embodiment 4
With embodiment 1, difference is the substance of the present embodiment：Pro-oxygenic agent includes acid additive and additive；
And acid additive and additive are formed by following mass parts：10 parts of acid additive, wherein 8 parts of additive, the acidity of the present embodiment
Auxiliary agent is oxalic acid；Additive includes triammonium citrate and pyruvic acid, is formed by following mass parts：Triammonium citrate 2-4 parts, acetone
Acid：6-8 parts；2 parts of the present embodiment optimization citric acid triamine, pyruvic acid：6 parts.Substantially increased using the pro-oxygenic agent of the present invention de-
The oxidation efficiency of sulphur ash, and become to realize and Desulphurization is aoxidized under open container cryogenic conditions.
Using a kind of method using oxidation unit oxidation sweetening ash of the present invention, comprise the following steps that：
S1, removal of impurities drying
Take Desulphurization raw material to be mixed with water, and the upper bulky grain insoluble matter of sieve is removed by 200 mesh water sieves, pass through vacuum filtration
Desulphurization after being cleaned, then Desulphurization is put into drying box, 4h is dried at 105 DEG C；
S2, configuration Desulphurization solution
The Desulphurization 25g that S1 steps obtain is mixed with deionized water, and the solid-to-liquid ratio of Desulphurization and deionized water is 1/
30, the fully shaking 30min under 50 DEG C of environment is put into gas bath concussion case, obtains Desulphurization mixed liquor；
S3, the oxidation of Desulphurization acid
(1) mass ratio of pro-oxygenic agent and the Desulphurization after filtering and impurity removing is 0.2-0.3, and the present embodiment takes 0.3；7.5g is taken to help
Oxygen agent is dissolved in deionized water and obtains pro-oxygenic agent solution, and the mass ratio of pro-oxygenic agent and deionized water is 0.05-0.2, this implementation
It is preferred that 0.2, obtain 45g pro-oxygenic agent solution；The specific collocation method of pro-oxygenic agent is：First acid additive is mixed with water, then will
Additive, which is added in acid additive solution, obtains pro-oxygenic agent solution, i.e., in the present embodiment first by 4.17g oxalic acid powder with
37.5g water mixing, then additive is added in acid additive solution and obtains pro-oxygenic agent solution, and pro-oxygenic agent solution is added and helped
In oxygen agent container 310.
(2) Desulphurization mixed liquor is added in reactor inner chamber 110, the thermostat temperature of control constant temperature exocoel 120, and it is interior
Temperature is 0 DEG C, and the gas control valve 220 for opening air supply unit 200 is blown into oxygen-containing gas into Desulphurization mixed liquor, and described contains
Carrier of oxygen is oxygen-enriched air, and the oxygen volume ratio in oxygen-enriched air is 40-60%, the present embodiment preferably 45%；At the same time, beat
The flow control valve 320 of pro-oxygenic agent injection unit 300 is opened, pro-oxygenic agent solution injects reaction by pro-oxygenic agent container 310 through fluid pipeline 330
The bottom of device inner chamber 110, pro-oxygenic agent solution are uniformly injected into Desulphurization mixed liquor bottom, reaction time during oxidation sweetening ash
For 100min；It is according to the flow that is blown into of gas control valve 220 and the oxygen-containing gas of the regulation and control of flowmeter 230 in course of reaction
12ml/min, and the tracheae outlet 241 of gas pipeline 240 is correspondingly arranged with liquid outlet 331, and tracheae exports 241 towards liquid
The injection of body outlet 331 so that during pro-oxygenic agent solution is that Desulphurization combines, the CaSO in Desulphurization3Form ion like
After state enters solution, H that oxygen-containing gas can rapidly with solution state2SO3With reference to, and oxidation reaction generation SO occurs4 2-, enter
And accelerate the speed of reaction.What deserves to be explained is：The time of pro-oxygenic agent solution injection is identical with the time reacted, i.e. pro-oxygenic agent
Solution terminates since reaction to reaction, and pro-oxygenic agent solution is slow all the time, is uniformly injected into Desulphurization mixed liquor bottom, i.e. 45g
Pro-oxygenic agent solution be slowly uniformly injected into 100min reaction time.Reaction obtains reactant precipitation after terminating be to aoxidize
Modified Desulphurization, and by it, heat drying obtains dried powder at a temperature of 100 DEG C, the calcium sulphate dihydrate in dried powder
Content reach 96.6%, the oxidation efficiency of Desulphurization is substantially increased using the pro-oxygenic agent of the present invention, and become and realize
Desulphurization is aoxidized under conditions of open container low temperature.
Embodiment 5
With embodiment 4, difference is the substance of the present embodiment：The pro-oxygenic agent of the present embodiment includes acid additive
And additive；And acid additive and additive are formed by following mass parts：15 parts of acid additive, 10 parts of additive, wherein adding
Agent includes triammonium citrate, pyruvic acid and ethanol, is formed by following mass parts：2 parts of triammonium citrate, pyruvic acid：4 parts, ethanol：
4 parts.The oxidation efficiency of Desulphurization is substantially increased using the pro-oxygenic agent of the present invention, and change is realized in the low of open container
Desulphurization is aoxidized under the conditions of temperature, the content of the calcium sulphate dihydrate after oxidation in dried powder reaches 95.8%, so as to big
The big cost for reducing Desulphurization oxidation processes, triammonium citrate, acid additive and ethanol solution it is common, change Desulphurization
Reaction interface in the oxidizing process of sulfite calcium, and then to SO under ionic condition3 2-, at the same time also improve solution
In to H2SO3Solubility, and then extend H2SO3Residence time in the solution, so as to improve Desulphurization sulfite calcium
Oxidation efficiency, avoid SO2Escape.
Embodiment 6
With embodiment 4, difference is the substance of the present embodiment：The pro-oxygenic agent of the present embodiment includes acid additive
And additive；And acid additive and additive are formed by following mass parts：15 parts of acid additive, 10 parts of additive, wherein adding
Agent includes triammonium citrate, pyruvic acid, ethanol and CaCl2, formed by following mass parts：2 parts of triammonium citrate, pyruvic acid：3
Part, ethanol：4 parts, CaCl2：1 part.The oxidation efficiency of Desulphurization is substantially increased using the pro-oxygenic agent of the present invention, and becomes realization
Desulphurization is aoxidized in open container, under conditions of low temperature, the calcium sulphate dihydrate after oxidation in dried powder
Content reaches 95.2%.CaCl2The precipitation for being incorporated as calcium sulfate provide sufficient Ca2+, so as to be the H so as to promote2SO3
The generation of deposit after oxidation, promotes the quick progress of reaction, and improves H2SO3Utilization rate.
Embodiment 7
With embodiment 4, difference is the substance of the present embodiment：The pro-oxygenic agent of the present embodiment includes acid additive
And additive；And acid additive and additive are formed by following mass parts：15 parts of acid additive, 11 parts of additive, wherein adding
Agent includes triammonium citrate, pyruvic acid, ethanol and sodium ethylene diamine tetracetate, is formed by following mass parts：2 parts of triammonium citrate,
Pyruvic acid：4 parts, ethanol：4 parts, sodium ethylene diamine tetracetate：1 part.It is worth noting that, sodium ethylene diamine tetracetate is insoluble in ethanol,
Therefore additive is difficult to be sufficiently mixed in itself, and the specific collocation method of pro-oxygenic agent is：First acid additive is mixed with water, then will
The sodium ethylene diamine tetracetate of additive is added in acid additive solution, and the other components of additive finally are added sequentially into acid
Pro-oxygenic agent solution is obtained in property compounding agent solution.The oxidation efficiency of Desulphurization is substantially increased using the pro-oxygenic agent of the present invention, and
Change realizes to be aoxidized under open container, cryogenic conditions to Desulphurization, the calcium sulphate dihydrate after oxidation in dried powder
Content reach 96.7%.
Embodiment 8
With embodiment 1, difference is the substance of the present embodiment：The pro-oxygenic agent of the present embodiment includes acid additive
And additive；And acid additive and additive are formed by following mass parts：15 parts of acid additive, 10 parts of additive, wherein acid
Auxiliary agent is oxalic acid, and additive includes triammonium citrate, pyruvic acid, ethanol, ether and hydrogen peroxide, is formed by following mass parts：Lemon
Lemon acid triamine 1-2 parts；Pyruvic acid 3-4 parts；Ethanol 3-4 parts；Ether 0.5-1 parts；Hydrogen peroxide 0.5-1 parts；The preferred lemon of the present embodiment
2 parts of lemon acid triamine, 3 parts of pyruvic acid, 4 parts of ethanol, 0.5 part of ether, 0.5 part of hydrogen peroxide.
Using a kind of method using oxidation unit oxidation sweetening ash of the present invention, comprise the following steps that：
S1, removal of impurities drying
Take Desulphurization raw material to be mixed with water, and the upper bulky grain insoluble matter of sieve is removed by 200 mesh water sieves, pass through vacuum filtration
Desulphurization after being cleaned, then Desulphurization is put into drying box, 4h is dried at 105 DEG C；
S2, configuration Desulphurization solution
The Desulphurization 30g that S1 steps obtain is mixed with deionized water, and the solid-to-liquid ratio of Desulphurization and deionized water is 1/
20, the fully shaking 30min under 50 DEG C of environment is put into gas bath concussion case, obtains Desulphurization mixed liquor；
S3, the oxidation of Desulphurization acid
(1) mass ratio of pro-oxygenic agent and the Desulphurization after filtering and impurity removing is 0.2-0.3, and the present embodiment takes 0.2；6g is taken to help oxygen
Agent is dissolved in deionized water and obtains pro-oxygenic agent solution, and the mass ratio of pro-oxygenic agent and deionized water is 0.05-0.2, and this implementation is excellent
0.1 is selected, obtains 66g pro-oxygenic agent solution；The specific collocation method of pro-oxygenic agent is：First acid additive is mixed with water, then will be added
Add agent to be added in acid additive solution and obtain pro-oxygenic agent solution, i.e., first by 3.6g oxalic acid powder and 60g in the present embodiment
Water is mixed, then 2.4g additive is added in acid additive solution and obtains pro-oxygenic agent solution, and pro-oxygenic agent solution is added and helped
In oxygen agent container 310.
(2) Desulphurization mixed liquor is added in reactor inner chamber 110, the thermostat temperature of control constant temperature exocoel 120, and kept
Temperature in reactor is 10 DEG C, open air supply unit 200 gas control valve 220 be blown into Desulphurization mixed liquor it is oxygenous
Body, described oxygen-containing gas are oxygen-enriched air；At the same time, the flow control valve 320 of pro-oxygenic agent injection unit 300, pro-oxygenic agent are opened
Solution injects the bottom of reactor inner chamber 110 by pro-oxygenic agent container 310 through fluid pipeline 330, and pro-oxygenic agent solution is in oxidation sweetening ash
During be uniformly injected into Desulphurization mixed liquor bottom, reaction time 80min；According to gas control valve 220 in course of reaction
The flow that is blown into of the oxygen-containing gas regulated and controled with flowmeter 230 is 10ml/min, and the tracheae of gas pipeline 240 exports 241 and liquid
Body outlet 331 is correspondingly arranged, and tracheae outlet 241 is sprayed towards liquid outlet 331 so that pro-oxygenic agent solution is Desulphurization knot
During conjunction, the CaSO in Desulphurization3Formed after ionic condition enters solution, oxygen-containing gas can rapidly and solution state
H2SO3With reference to, and oxidation reaction generation SO occurs4 2-, and then accelerate the speed of reaction.What deserves to be explained is：Pro-oxygenic agent is molten
The time of liquid injection is identical with the time reacted, i.e., pro-oxygenic agent solution terminates since reaction to reaction, and pro-oxygenic agent solution is all the time
Slowly, Desulphurization mixed liquor bottom is uniformly injected into, i.e. the pro-oxygenic agent solution of 14g is slowly uniform in 80min reaction time
Injection.Reaction terminate after obtain reactant precipitation, to being deposited in 100 DEG C at a temperature of heat drying obtain dried powder, dry
The content of calcium sulphate dihydrate in powder reaches 97.3%, and the oxidation that Desulphurization is substantially increased using the pro-oxygenic agent of the present invention is imitated
Rate, and become to realize and Desulphurization is aoxidized under conditions of open container low temperature.
Its reaction mechanism for promoting Desulphurization to aoxidize is probably the pro-oxygenic agent of the present invention afterwards in Desulphurization mixed liquor is added：
H is ionized out after oxalic acid in pro-oxygenic agent is soluble in water+, triammonium citrate and oxalic acid collective effect promote the SO in sulfurous acid3 2-
Into solution, at the same time, the addition of ethanol solution is improved in solution to H2SO3Solubility, and in hydrogen peroxide and oxygen
So as to promoting H under effect2SO3Oxidation generation H2SO4, aoxidize the SO of generation4 2-Will be with Ca2+Generation precipitation.The second of pro-oxygenic agent
After ether is added in Desulphurization mixed liquor, the top of solution can be swum in, due to SO2Ether is dissolved in, so as to the SO limited2Escape
Ease, at the same time, the sulfur dioxide that the ethanol in solution system can make to be dissolved in ether, which is come back in solution system, joins
With oxidation reaction, the part hydrogen peroxide of the interior dissolving of certain ethanol equally can be with the SO in ether oxygen2, and then improve SO2Oxygen
Change efficiency, at the same time, limit SO2Escape.
The present invention is described in detail above in conjunction with specific exemplary embodiment.It is understood, however, that it can not take off
Various modifications and variations are carried out in the case of from the scope of the present invention being defined by the following claims.Detailed description should only by
It is considered illustrative and not restrictive, if there is any such modifications and variations, then they fall within
In the scope of the present invention of this description.In addition, background technology is intended to illustrate the Development Status of this technology and meaning, not purport
In the limitation present invention or the application field of the application and the present invention.
More specifically, although the exemplary embodiment of the present invention has been described herein, but the invention is not limited in
These embodiments, but including those skilled in the art according to above detailed description it can be appreciated that it is modified, omit,
Any and whole embodiments of (such as between each embodiment) combination, adaptive change and/or replacement.In claim
Restriction can widely be explained according to the language used in claim, and be not limited in foregoing detailed description or in reality
The example described during this application is applied, these examples are considered as nonexcludability.For example, in the present invention, term is " preferably
Ground " not exclusively, preferably, here it means that " but be not restricted to that ".It is in office where method or process claims
In any step for enumerating can in any order perform and be not limited to the order proposed in claim.Therefore, it is of the invention
Scope only should be determined by appended claims and its legal equivalents, rather than by descriptions and examples given above Lai
It is determined that.
Claims (10)
1. one kind sintering semi-dry desulphurization ash oxidation unit, it is characterised in that：Including
Reaction member (100), the reaction member (100) include reactor inner chamber (110), and reactor inner chamber (110) are used to contain
Oxidized Desulphurization mixed liquor；
Air supply unit (200), the gas pipeline (240) of the air supply unit (200) stretch into the bottom of reactor inner chamber (110), supply
Gas unit (200) is used to be blown into oxygen-containing gas into Desulphurization mixed liquor；
Pro-oxygenic agent injection unit (300), the pro-oxygenic agent injection unit (300) include pro-oxygenic agent container (310) and fluid pipeline
(330), pro-oxygenic agent container (310) is connected with fluid pipeline (330), and pro-oxygenic agent injection unit (300) is used to mix to Desulphurization
Close and pro-oxygenic agent solution is injected in liquid.
A kind of 2. sintering semi-dry desulphurization ash oxidation unit according to claim 1, it is characterised in that：Described liquid line
Road (330) stretches into the bottom of reactor inner chamber (110), and fluid pipeline (330) bottom is provided with liquid outlet (331), and gas
The tracheae outlet (241) of pipeline (240) is correspondingly arranged with liquid outlet (331), and tracheae exports (241) towards liquid outlet
(331) spray.
A kind of 3. sintering semi-dry desulphurization ash oxidation unit according to claim 1, it is characterised in that：Described liquid line
Road (330) is stretched into gas pipeline (240), driving of the pro-oxygenic agent solution in pro-oxygenic agent container (310) in air supply unit (200)
The lower bottom for entering reactor inner chamber (110).
A kind of 4. sintering semi-dry desulphurization ash oxidation unit according to claim 3, it is characterised in that：Described liquid line
The bottom in road (330) is provided with bubble generator (242), and bubble generator (242) is such that gas and pro-oxygenic agent solution are uniform
It is distributed in reactor inner chamber (110).
A kind of 5. sintering semi-dry desulphurization ash oxidation unit according to claim any one of 1-4, it is characterised in that：It is described
Reactor inner chamber (110) outside be provided with constant temperature exocoel (120), the constant temperature exocoel (120) be used for keep reactor inner chamber
(110) it is in steady temperature.
A kind of 6. method using oxidation unit oxidation sweetening ash, it is characterised in that：Comprise the following steps that：
S1, removal of impurities drying
Take Desulphurization raw material to be mixed with water, and bulky grain insoluble matter is gone by water sieve, then be filtered by vacuum the desulfurization after being cleaned
Ash；
S2, configuration Desulphurization solution
The Desulphurization that S1 steps obtain is mixed with deionized water, and the solid-to-liquid ratio of Desulphurization and deionized water is 1/20~1/
50, Desulphurization mixed liquor is obtained after fully shaking；
S3, the oxidation of Desulphurization acid
(1) mass ratio of pro-oxygenic agent and the Desulphurization after filtering and impurity removing is 0.2-0.3, and pro-oxygenic agent is dissolved in into deionized water is helped
Oxygen agent solution, then pro-oxygenic agent solution is added to the pro-oxygenic agent container (310) of desulphurized ash oxidation device, described oxidation unit
For the oxidation unit described in the claims any one of 1-5；Described pro-oxygenic agent includes acid additive, the acid additive
pKa1Acidity coefficient is between sulfurous acid and the pKa of sulfuric acid1Between acidity coefficient, the pro-oxygenic agent is for the sulfurous in oxidation sweetening ash
Sour calcium；
(2) Desulphurization mixed liquor is added in reactor inner chamber (110), and opens inner chamber agitator (111), mixed to Desulphurization
Oxygen-containing gas is blown into liquid, the pro-oxygenic agent solution in pro-oxygenic agent container (310) is uniformly injected into during oxidation sweetening ash
Desulphurization mixed liquor bottom, and the Desulphurization aoxidized.
A kind of 7. method using oxidation unit oxidation sweetening ash according to claim 6, it is characterised in that：Described S3
The time of Desulphurization mixed liquor oxidation reaction is 80-150min in step (2), and the time of pro-oxygenic agent solution injection and reaction
Time is identical.
A kind of 8. method using oxidation unit oxidation sweetening ash according to claim 6, it is characterised in that：Described acid
Property auxiliary agent is soluble in water, pKa of the described acid additive in 25 DEG C of water1Acidity coefficient is：1.00-1.89.
A kind of 9. method using oxidation unit oxidation sweetening ash according to claim 8, it is characterised in that：Described acid
Property auxiliary agent be oxalic acid or dichloroacetic acid or both combination.
A kind of 10. method using oxidation unit oxidation sweetening ash according to claim 9, it is characterised in that：Also include
Additive, pro-oxygenic agent are formed by following mass parts：
Acid additive 10-20 parts；
Additive 8-12 parts；
Wherein, described additive includes triammonium citrate and pyruvic acid.
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|---|---|---|---|---|
| CN103551029A (en) * | 2013-10-22 | 2014-02-05 | 重庆大学 | Modification method for semi-dry sintering flue gas desulfurization ash |
| CN105819480A (en) * | 2016-03-18 | 2016-08-03 | 株洲醴陵旗滨玻璃有限公司 | Semi-dry process flue gas desulfurized ash modification treatment method |
| CN206553205U (en) * | 2017-03-03 | 2017-10-13 | 安徽工业大学 | One kind sintering semi-dry desulphurization ash oxidation unit |
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| CN103551029A (en) * | 2013-10-22 | 2014-02-05 | 重庆大学 | Modification method for semi-dry sintering flue gas desulfurization ash |
| CN105819480A (en) * | 2016-03-18 | 2016-08-03 | 株洲醴陵旗滨玻璃有限公司 | Semi-dry process flue gas desulfurized ash modification treatment method |
| CN206553205U (en) * | 2017-03-03 | 2017-10-13 | 安徽工业大学 | One kind sintering semi-dry desulphurization ash oxidation unit |
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