CN108722165A - Wet process of FGD composite synergistic additive and its preparation method and application - Google Patents
Wet process of FGD composite synergistic additive and its preparation method and application Download PDFInfo
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- CN108722165A CN108722165A CN201810587095.XA CN201810587095A CN108722165A CN 108722165 A CN108722165 A CN 108722165A CN 201810587095 A CN201810587095 A CN 201810587095A CN 108722165 A CN108722165 A CN 108722165A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2251/602—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/00—Sources of waste gases
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Abstract
The invention discloses a kind of wet process of FGD composite synergistic additives and its preparation method and application, belong to Chemical composition that technical field.Wherein, which is obtained after mixing by each component of following mass fraction：30~70 parts of L MALIC ACID, 4~25 parts of ammonium lauryl sulfate, 4~25 parts of sodium acetate, 5~35 parts of sodium humate, simultaneously, the additive of the present invention is added in lime stone slurry the liquid that is absorbed, then by the absorbing liquid and the reverse contact desulfuriation of former flue gas, has reached higher desulfuration efficiency.The present invention has the advantages that whole process global optimization promotes wet desulfurization of flue gas by limestone-gypsum method device performance, it is in particular in buffering desulfurization slurry pH value, reduction consumption of limestone, promotes dissolution of calcium carbonate, promote calcium sulfite oxidation, improve gypsum qualitt, improving desulfuration efficiency aspect, and environmentally friendly, at low cost, the easy industrialization promotion of the present invention.
Description
Technical field
The present invention relates to flue gas desulfurization additives, belong to Chemical composition that technical field, are specifically related to a kind of wet method cigarette
Desulfurization composite synergistic additive and its preparation method and application.
Background technology
For wet process of FGD because its technology maturation, desulfuration efficiency are high, absorbent lime stone abundance is cheap, secondary
The features such as product gypsum can utilize, for a long time in occupation of the leading position of coal fired power plant flue gas desulfurization, wet desulphurization device is about at present
Account for the 80% of the desulfurizer built up in the world.But the existing thermal power plant lime stone-gypsum wet cigarette in China
The problem of high, to coal sulfur the adaptability difference of desulfurization device generally existing high energy consumption, operating cost.New《Thermal power plant
Atmosphere pollutants emission standards》(GB13223-2011) to SO2Emission reduction proposes stringenter the binding indicator so that at present
80% or more fired power generating unit faces desulfurization synergistic transformation problem.Synergistic additives can be without desulphurization system capacity-increasing transformation
Under the premise of, it improves desulfuration efficiency, reduce desulphurization plant energy consumption, have a vast market foreground.
The country is broadly divided into three classes currently used for the synergist of wet desulfurizing process：Efficiently but the big sodium salt of dosage, ammonium salt,
The inorganic additives such as magnesium salts, such as patent ZL201110169685, ZL201310528824, ZL201510883841；It works slow
But the organic additives such as the small organic acid of dosage, organic dibasic acid, organic multicomponent acid, such as patent
ZL200810096744,ZL201310423630,ZL201510166371；And compound additive made of the above two is mixed,
Although existing compound additive overcomes the disadvantage that dosage is big, action is slow, but be formulated complexity, expensive, such as
ZL201010593203,ZL201110033630,ZL201210137703,ZL201310241042,ZL201510044710.Through
Access and investigation are crossed, although currently, synergist patent concern removing SO of the above-mentioned three classes for wet desulphurization2Basic role,
But do not pay attention to reducing the actual demand of power plant's energy consumption, and the application of above-mentioned patent is random larger, to high-sulfur atmosphere adaptability
Difference, without reliable additive selection evaluation of programme, it is of high cost be not easy to industrialization promotion, so wet in existing limestone-gypsum
On the basis of method flue gas desulfurization, a kind of whole process global optimization promotion wet desulfurization of flue gas by limestone-gypsum method performance (buffering is researched and developed
Desulfurization slurry pH value reduces consumption of limestone, promotes dissolution of calcium carbonate, promote calcium sulfite oxidation, improve gypsum qualitt, improve
Desulfuration efficiency improves sulfur adaptability, improves gypsum qualitt), promote energy-saving, at low cost, the easy industrialization of desulfurization subsidiary engine to push away
Wide wet process of FGD composite synergistic additive is particularly important.
Invention content
In order to solve the above technical problems, the invention discloses a kind of not only cost of material is low, but also application effect is preferable
Wet process of FGD composite synergistic additive and its preparation method and application.
To achieve the above object, the invention discloses a kind of wet process of FGD composite synergistic additives, it is characterised in that：
It is grouped as by each group of following mass fraction：30~70 parts of L MALIC ACID, 4~25 parts of ammonium lauryl sulfate, sodium acetate 4~
25 parts, 5~35 parts of sodium humate.
Further, 40~60 parts of L MALIC ACID, 5~20 parts of ammonium lauryl sulfate, 5~20 parts of sodium acetate, humic acid
10~30 parts of sodium.
Further, the L MALIC ACID is 45~50 parts.
Further, the ammonium lauryl sulfate is 10~15 parts.
Preferably, the wet process of FGD composite synergistic additive is grouped as by each group of following mass fraction：L- apples
20 parts of 40 parts of tartaric acid, 20 parts of ammonium lauryl sulfate, 20 parts of sodium acetate, sodium humate compositions.
Preferably, the wet process of FGD composite synergistic additive is grouped as by each group of following mass fraction：L- apples
30 parts of 60 parts of tartaric acid, 5 parts of ammonium lauryl sulfate, 5 parts of sodium acetate, sodium humate compositions.
Preferably, the wet process of FGD composite synergistic additive is grouped as by each group of following mass fraction：L- apples
20 parts of 50 parts of tartaric acid, 10 parts of ammonium lauryl sulfate, 20 parts of sodium acetate, sodium humate compositions.
Preferably, the wet process of FGD composite synergistic additive is grouped as by each group of following mass fraction：L- apples
25 parts of 50 parts of tartaric acid, 15 parts of ammonium lauryl sulfate, 10 parts of sodium acetate, sodium humate compositions.
In order to preferably achieve the object of the present invention, the invention also discloses a kind of additions of wet process of FGD composite synergistic
The preparation method of agent is particularly mixed using each ingredient in above-mentioned wet process of FGD composite synergistic additive equal
It is even.
At the same time, the invention also discloses a kind of above-mentioned wet process of FGD composite synergistic additives fires suitable for power plant
In the flue gas desulfurization device for the wet desulfurization system that coal burning boiler is configured.
It is that above-mentioned compound increasing is added in sweetening process in addition, the invention also discloses a kind of wet flue gas desulfurization method
Additive is imitated to promote the effect of desulfurization, is included the following steps：
1) composite synergistic additive is added in the lime stone slurry that mass percent is 1~3%, is stirred
It is even, obtain absorbing liquid；
2) former flue gas enters and the absorbing liquid that enters from bottom to top along flue gas desulfurization device from the lower part of flue gas desulfurization device
Reverse contact, it is 3.5~6s to control former flue gas and absorbing liquid time of contact.
Further, the absorbing liquid temperature in step 2) is 25~65 DEG C.
Further, the liquid-gas ratio in step 2) is 11~23L/m3。
Further, every liter of lime stone slurry of a concentration of 0.5~1.4g of composite synergistic additive described in step 1).
Preferably, every liter of lime stone slurry of a concentration of 0.5g of composite synergistic additive described in step 1).
Preferably, every liter of lime stone slurry of a concentration of 1.4g of composite synergistic additive described in step 1).
Preferably, every liter of lime stone slurry of a concentration of 1.0g of composite synergistic additive described in step 1).
Preferably, composite synergistic additive is added in lime stone slurry in step 1), control mixing speed be 100~
300r/min, mixing time are 5~20min.
Preferably, the mass percent of lime stone slurry is 3% in step 1).
Preferably, the absorbing liquid temperature in step 2) is 50 DEG C.
Preferably, the liquid-gas ratio in step 2) is 20L/m3。
The desulfurization principle for the desulfurization composite synergistic additive that the present invention designs is as follows：
The L MALIC ACID that the present invention uses is as pH buffer, and so that slurry pool is maintained pH=5.5 or so, (system is most preferably grasped
Make pH=5.0~6.2), the skill that the lime stone slurry maintenance best desulfurization pH value of slurry pool is added need to be relied on by solving power plant scene
Art problem can be effectively reduced the overall consumption of lime stone.Wherein, L MALIC ACID promotes calcium carbonate as calcium carbonate chaotropic agent
High desulfurization efficiency is realized in dissolving, is improved to high-sulfur adaptability.
The ammonium lauryl sulfate that the present invention uses can promote calcium sulfite oxidation as surfactant, promote stone
Cream quality.
The sodium acetate and sodium humate that the present invention uses promote slurries mass transfer ability as slurries activator, assist desulfurization,
Wherein metal sodium ion plays the role of catalytic desulfurization reaction, improves reactivity.
To sum up, L MALIC ACID of the invention, ammonium lauryl sulfate and sodium acetate, sodium humate synergy, in wet method
Flue gas desulfurization whole process global optimization promotes desulfurization performance, while reducing desulphurization plant energy consumption.
The beneficial effects are mainly as follows following aspects：
(1) the desulfurization composite synergistic additive that the present invention designs has buffering desulfurization slurry pH value, saves consumption of limestone
Advantage.Wherein, L MALIC ACID is as pH buffer, and weak acid radical ion is in high concentration H+When, in conjunction with H+At weak electrolyte point
Son, in low concentration H+When, weak electrolyte molecular ionization goes out H+, effective buffering slurries pH value can be played the role of, it is existing to solve power plant
Field adjusts the high power consumption of subsidiary engine and consumption of limestone caused by slurry pool maintains best desulfurization pH value by lime stone slurry is added
Big problem can be effectively reduced the overall consumption of lime stone；
(2) the desulfurization composite synergistic additive that the present invention designs, which has, promotes dissolution of calcium carbonate, promotes calcium sulfite oxidation
Effect, and gypsum crystal quality can be improved.Wherein, L MALIC ACID ionizes out H as calcium carbonate chaotropic agent+Promote calcium carbonate
The CO of dissolving3 2-Generate HCO3 -, to promote the dissolving of calcium carbonate, while organic acid anions carry H+Enhance liquid phase main body
H+Mass transfer ability promotes dissolution of calcium carbonate；And ammonium lauryl sulfate makes gas-liquid surface activity increase as surfactant,
To increase the O of gas-liquid interface2Mass transfer ability, makes O2It can effectively be reacted much sooner with calcium sulfite and generate gypsum, promoted sub-
Calcium sulfate aoxidizes, and the gypsum of generation is presented the quality structure of short prism-shaped, improves the quality of gypsum；
(3) the raw material composition for the desulfurization composite synergistic additive that the present invention designs is at low cost, prepares simple, application effect
Good, market prospects are big, easy industrialization promotion, and whole process global optimization promotes desulfurization performance, and desulfuration efficiency is high, and is unfavorable for
The anion of desulfurization.The additive that the present invention designs (leads to crystalline lamellae without the chlorion that can reduce gypsum crystal quality
Change), without heavy metals such as cadmium, lead.Inventive desulfurization efficiency > 96.5%, and preparation manipulation is simple, application scheme is with pervasive
Property, price down to 0.4133 ten thousand yuan/ton, better than existing Desulfurization synergist price (at present price 10,000/ton~20,000/ton it
Between), " high performance-price ratio " of the invention determines that the present invention is more prone to industrialization promotion.
Description of the drawings
Fig. 1 is different SO2The desulfuration efficiency datagram of composite synergistic additive of the present invention under concentration；
Fig. 2 is the different composite synergistic additives of the present invention using concentration to SO2The influence datagram of absorption rate；
Fig. 3 is the corresponding sulfurous of composite synergistic additive 1h that the present invention uses a concentration of 500mg/L, 1000mg/L respectively
Sour calcium oxidation rate figure；
Fig. 4 is composite synergistic additive 1h corresponding dissolution of calcium carbonate rate data of the present invention using a concentration of 1000mg/L
Figure；
Fig. 5 is desulfuration efficiency datagram of the embodiment of the present invention.
Fig. 6 is the SEM figures for the gypsum crystal that the embodiment of the present invention is prepared；
Fig. 7 is the SEM figures for the gypsum crystal that the embodiment of the present invention is prepared；
Fig. 8 is the SEM figures for the gypsum crystal that the embodiment of the present invention is prepared；
Specific implementation mode
Following three processes are related generally in the synergist limestone-gypsum method flue gas desulfurization system of the present invention：Lime stone
Dissolving, sulfur dioxide absorb, sulfite oxidation is sulfate.Wherein, specific chemical equation is as follows：
CaCO3(s)→Ca2++CO3 2-
SO3 2-+Ca2++1/2H2O(l)→CaSO3·1/2H2O(s)↓
CaSO3·1/2H2O(s)+1/2O2(aq)+3/2H2O(l)→CaSO4·2H2O(s)
In order to preferably explain the present invention, below in conjunction with the specific embodiment main contents that the present invention is furture elucidated, but
Present disclosure is not limited solely to following embodiment.
Embodiment 1
A kind of wet process of FGD composite synergistic additive, it is stirred at normal temperatures and pressures by each component of following mass fraction
It mixes uniformly mixed：40 parts of L MALIC ACID, 5 parts of ammonium lauryl sulfate, 5 parts of sodium acetate, 10 parts of sodium humate.
The above-mentioned wet process of FGD composite synergistic additive being prepared is added to the lime that mass percent is 1%
In stone slurries, control mixing speed is 100r/min, stirs 10min, absorbing liquid is obtained after being uniformly mixed, wherein compound increasing
Imitate every liter of lime stone slurry of a concentration of 0.5g of additive；
It is 25 that former flue gas, which enters from the lower part of flue gas desulfurization device with the temperature entered from bottom to top along flue gas desulfurization device,
DEG C absorbing liquid inversely contact, it is 3.5s to control former flue gas and absorbing liquid time of contact, and liquid-gas ratio is in flue gas desulfurization device
15L/m3, flue gas after final purification is discharged from the top of flue gas desulfurization device, completes the absorbing liquid after desulfurization and enter absorbing liquid
Regenerative system.
The flue gas desulfurization device of the present embodiment is in flue gas SO2It is run under the high-sulfur atmosphere of concentration 3750ppm, it can in conjunction with Fig. 5
Know, the desulfuration efficiency of the present embodiment>96.5%, and Fig. 3 is combined it is found that the desulfurization composite synergistic additive that the present embodiment uses
The case where corresponding calcium sulfite oxidation rate is apparently higher than no Synergistic additives, while the by-product that the present embodiment desulfurization obtains
Gypsum crystal structure is as shown in fig. 6, as seen from Figure 6, the gypsum crystal of the present embodiment is in short prism-shaped quality structure, crystal grain
30 μm of diameter > is conducive to vacuum dehydration into gypsum storehouse.
Embodiment 2
A kind of wet process of FGD composite synergistic additive, it is stirred at normal temperatures and pressures by each component of following mass fraction
It mixes uniformly mixed：50 parts of L MALIC ACID, 15 parts of ammonium lauryl sulfate, 15 parts of sodium acetate, 20 parts of sodium humate.
The above-mentioned wet process of FGD composite synergistic additive being prepared is added to the stone that mass percent is 1.2%
In lime stone slurries, control mixing speed is 200r/min, stirs 10min, absorbing liquid is obtained after being uniformly mixed, wherein compound
Every liter of lime stone slurry of a concentration of 1g of Synergistic additives；
It is 50 that former flue gas, which enters from the lower part of flue gas desulfurization device with the temperature entered from bottom to top along flue gas desulfurization device,
DEG C absorbing liquid inversely contact, it is 5s to control former flue gas and absorbing liquid time of contact, and liquid-gas ratio is 19L/ in flue gas desulfurization device
m3, flue gas after final purification is discharged from the top of flue gas desulfurization device, completes the absorbing liquid after desulfurization and enter regeneration of absorption solution
System.
The flue gas desulfurization device of the present embodiment is in flue gas SO2It is run under the high-sulfur atmosphere of concentration 3750ppm, it can in conjunction with Fig. 5
Know, the desulfuration efficiency of the present embodiment>98.5%, and Fig. 3 is combined it is found that the desulfurization composite synergistic additive that the present embodiment uses
The case where corresponding calcium sulfite oxidation rate is apparently higher than no Synergistic additives, in conjunction with Fig. 4 it is found that the present embodiment use takes off
The case where corresponding dissolution of calcium carbonate rate of sulphur composite synergistic additive is apparently higher than no Synergistic additives, while the present embodiment desulfurization
As shown in fig. 7, as seen from Figure 7, the gypsum crystal of the present embodiment column that is square is excellent for obtained by-product gypsum crystal structure
Matter structure, 36 μm of crystal particle diameter > are conducive to vacuum dehydration into gypsum storehouse.
Embodiment 3
A kind of wet process of FGD composite synergistic additive, it is stirred at normal temperatures and pressures by each component of following mass fraction
It mixes uniformly mixed：60 parts of L MALIC ACID, 20 parts of ammonium lauryl sulfate, 20 parts of sodium acetate, 30 parts of sodium humate.
The above-mentioned wet process of FGD composite synergistic additive being prepared is added to the stone that mass percent is 1.5%
In lime stone slurries, control mixing speed is 300r/min, stirs 15min, absorbing liquid is obtained after being uniformly mixed, wherein compound
Every liter of lime stone slurry of a concentration of 1.4g of Synergistic additives；
It is 65 that former flue gas, which enters from the lower part of flue gas desulfurization device with the temperature entered from bottom to top along flue gas desulfurization device,
DEG C absorbing liquid inversely contact, it is 6s to control former flue gas and absorbing liquid time of contact, and liquid-gas ratio is 23L/ in flue gas desulfurization device
m3, flue gas after final purification is discharged from the top of flue gas desulfurization device, completes the absorbing liquid after desulfurization and enter regeneration of absorption solution
System.
The flue gas desulfurization device of the present embodiment is in flue gas SO2It is run under the high-sulfur atmosphere of concentration 3750ppm, it can in conjunction with Fig. 5
Know, the desulfuration efficiency of the present embodiment>98.6%, while by-product gypsum crystal structure such as Fig. 8 institutes that the present embodiment desulfurization obtains
Show, as seen from Figure 8, the gypsum crystal of the present embodiment is in ball bulk quality structure, and it is de- that 40 μm of crystal particle diameter > is conducive to vacuum
Water is into gypsum storehouse.
Embodiment 4
A kind of wet process of FGD composite synergistic additive, it is stirred at normal temperatures and pressures by each component of following mass fraction
It mixes uniformly mixed：30 parts of L MALIC ACID, 4 parts of ammonium lauryl sulfate, 4 parts of sodium acetate, 5 parts of sodium humate.
The above-mentioned wet process of FGD composite synergistic additive being prepared is added to the stone that mass percent is 1.8%
In lime stone slurries, control mixing speed is 300r/min, stirs 15min, absorbing liquid is obtained after being uniformly mixed, wherein compound
Every liter of lime stone slurry of a concentration of 1g of Synergistic additives；
It is 40 that former flue gas, which enters from the lower part of flue gas desulfurization device with the temperature entered from bottom to top along flue gas desulfurization device,
DEG C absorbing liquid inversely contact, it is 3.5s to control former flue gas and absorbing liquid time of contact, and liquid-gas ratio is in flue gas desulfurization device
15L/m3, flue gas after final purification is discharged from the top of flue gas desulfurization device, completes the absorbing liquid after desulfurization and enter absorbing liquid
Regenerative system.
The flue gas desulfurization device of the present embodiment is in flue gas SO2It is run under the sulphur atmosphere of concentration 1000ppm, the present embodiment takes off
Sulphur efficiency is 98.7%, while the gypsum crystal knot of by-product gypsum crystal structure and embodiment 1 that the present embodiment desulfurization obtains
Structure is similar, and 40 μm of crystal particle diameter > is conducive to vacuum dehydration into gypsum storehouse.
Embodiment 5
A kind of wet process of FGD composite synergistic additive, it is stirred at normal temperatures and pressures by each component of following mass fraction
It mixes uniformly mixed：50 parts of L MALIC ACID, 15 parts of ammonium lauryl sulfate, 15 parts of sodium acetate, 30 parts of sodium humate.
The above-mentioned wet process of FGD composite synergistic additive being prepared is added to the lime that mass percent is 2%
In stone slurries, control mixing speed is 200r/min, stirs 10min, absorbing liquid is obtained after being uniformly mixed, wherein compound increasing
Imitate every liter of lime stone slurry of a concentration of 0.8g of additive；
It is 45 that former flue gas, which enters from the lower part of flue gas desulfurization device with the temperature entered from bottom to top along flue gas desulfurization device,
DEG C absorbing liquid inversely contact, it is 4.5s to control former flue gas and absorbing liquid time of contact, and liquid-gas ratio is in flue gas desulfurization device
18L/m3, flue gas after final purification is discharged from the top of flue gas desulfurization device, completes the absorbing liquid after desulfurization and enter absorbing liquid
Regenerative system.
The flue gas desulfurization device of the present embodiment is in flue gas SO2It is run under the sulphur atmosphere of concentration 2000ppm, the present embodiment takes off
Sulphur efficiency is 98.1%, and the desulfurization composite synergistic additive that the present embodiment uses is similar to Example 2, corresponding calcium sulfite oxygen
Change the case where rate is apparently higher than no Synergistic additives, the corresponding calcium carbonate of desulfurization composite synergistic additive that the present embodiment uses
Dissolution rate is apparently higher than the case where no Synergistic additives, while by-product gypsum crystal structure this reality that the present embodiment desulfurization obtains
The gypsum crystal for applying example is square column quality structure, and 30 μm of crystal particle diameter > is conducive to vacuum dehydration into gypsum storehouse.
Embodiment 6
A kind of wet process of FGD composite synergistic additive, it is stirred at normal temperatures and pressures by each component of following mass fraction
It mixes uniformly mixed：70 parts of L MALIC ACID, 25 parts of ammonium lauryl sulfate, 25 parts of sodium acetate, 35 parts of sodium humate.
The above-mentioned wet process of FGD composite synergistic additive being prepared is added to the stone that mass percent is 2.5%
In lime stone slurries, control mixing speed is 100r/min, stirs 10min, absorbing liquid is obtained after being uniformly mixed, wherein compound
Every liter of lime stone slurry of a concentration of 0.5g of Synergistic additives；
It is 30 that former flue gas, which enters from the lower part of flue gas desulfurization device with the temperature entered from bottom to top along flue gas desulfurization device,
DEG C absorbing liquid inversely contact, it is 4s to control former flue gas and absorbing liquid time of contact, and liquid-gas ratio is 11L/ in flue gas desulfurization device
m3, flue gas after final purification is discharged from the top of flue gas desulfurization device, completes the absorbing liquid after desulfurization and enter regeneration of absorption solution
System.
The flue gas desulfurization device of the present embodiment is in flue gas SO2It is run under the sulphur atmosphere of concentration 3000ppm, the present embodiment takes off
Sulphur efficiency is 97.4%, and the desulfurization composite synergistic additive that the present embodiment uses is close with embodiment 1, corresponding calcium sulfite oxygen
Change the case where rate is apparently higher than no Synergistic additives, while the gypsum crystal of the present embodiment is in short prism-shaped quality structure, it is brilliant
30 μm of body grain size > is conducive to vacuum dehydration into gypsum storehouse.
Embodiment 7
A kind of wet process of FGD composite synergistic additive, it is stirred at normal temperatures and pressures by each component of following mass fraction
It mixes uniformly mixed：70 parts of L MALIC ACID, 20 parts of ammonium lauryl sulfate, 20 parts of sodium acetate, 35 parts of sodium humate.
The above-mentioned wet process of FGD composite synergistic additive being prepared is added to the lime that mass percent is 3%
In stone slurries, control mixing speed is 200r/min, stirs 10min, absorbing liquid is obtained after being uniformly mixed, wherein compound increasing
Imitate every liter of lime stone slurry of a concentration of 1.3g of additive；
It is 35 that former flue gas, which enters from the lower part of flue gas desulfurization device with the temperature entered from bottom to top along flue gas desulfurization device,
DEG C absorbing liquid inversely contact, it is 5s to control former flue gas and absorbing liquid time of contact, and liquid-gas ratio is 21L/ in flue gas desulfurization device
m3, flue gas after final purification is discharged from the top of flue gas desulfurization device, completes the absorbing liquid after desulfurization and enter regeneration of absorption solution
System.
The flue gas desulfurization device of the present embodiment is in flue gas SO2It is run under the high-sulfur atmosphere of concentration 3500ppm, the present embodiment
Desulfuration efficiency is 98.6%, and the corresponding dissolution of calcium carbonate rate of desulfurization composite synergistic additive that the present embodiment uses is apparently higher than nothing
The case where Synergistic additives, while the gypsum crystal of by-product gypsum crystal structure the present embodiment that the present embodiment desulfurization obtains is in
Square column quality structure, 30 μm of crystal particle diameter > are conducive to vacuum dehydration into gypsum storehouse.
Embodiment 8
A kind of wet process of FGD composite synergistic additive, it is stirred at normal temperatures and pressures by each component of following mass fraction
It mixes uniformly mixed：65 parts of L MALIC ACID, 15 parts of ammonium lauryl sulfate, 20 parts of sodium acetate, 30 parts of sodium humate.
The above-mentioned wet process of FGD composite synergistic additive being prepared is added to the lime that mass percent is 3%
In stone slurries, control mixing speed is 300r/min, stirs 20min, absorbing liquid is obtained after being uniformly mixed, wherein compound increasing
Imitate every liter of lime stone slurry of a concentration of 1.4g of additive；
It is 65 that former flue gas, which enters from the lower part of flue gas desulfurization device with the temperature entered from bottom to top along flue gas desulfurization device,
DEG C absorbing liquid inversely contact, it is 6s to control former flue gas and absorbing liquid time of contact, and liquid-gas ratio is 17L/ in flue gas desulfurization device
m3, flue gas after final purification is discharged from the top of flue gas desulfurization device, completes the absorbing liquid after desulfurization and enter regeneration of absorption solution
System.
The flue gas desulfurization device of the present embodiment is in flue gas SO2It is run under the high-sulfur atmosphere of concentration 4000ppm, the present embodiment
Desulfuration efficiency is 98.2%, and the corresponding dissolution of calcium carbonate rate of desulfurization composite synergistic additive that the present embodiment uses is apparently higher than nothing
The case where Synergistic additives, while the gypsum crystal of by-product gypsum crystal structure the present embodiment that the present embodiment desulfurization obtains is in
Square column quality structure, 30 μm of crystal particle diameter > are conducive to vacuum dehydration into gypsum storehouse.
In conjunction with Fig. 1 it is found that difference SO of the invention2Under concentration shown in the desulfuration efficiency data of composite synergistic additive：500
~4000ppm SO2In big concentration segment limit, be more than 97.4% using the desulfuration efficiency of the present invention, high concentration 3500~
4000ppm ranges, desulfuration efficiency are up to 98.2%~98.6%, show the excellent performance that the present invention adapts to sulfur variation.
As Fig. 2 uses the composite synergistic additive of the present invention of various concentration to SO2The influence data of absorption rate are shown：This
When invention is using a concentration of every liter of lime stone slurry of 0.5~1.4g, desulfuration efficiency realizes height in 97.4~99.3% ranges
Imitate desulfurization.
Above example is only best citing, rather than a limitation of the embodiments of the present invention.Except above-described embodiment
Outside, the present invention also has other embodiment.All technical solutions formed using equivalent substitution or equivalent transformation, all fall within the present invention
It is required that protection domain.
Claims (10)
1. a kind of wet process of FGD composite synergistic additive, it is characterised in that：It is grouped as by each group of following mass fraction：
30~70 parts of L MALIC ACID, 4~25 parts of ammonium lauryl sulfate, 4~25 parts of sodium acetate, 5~35 parts of sodium humate.
2. wet process of FGD composite synergistic additive according to claim 1, it is characterised in that：It is by following mass fraction
Each group be grouped as：40~60 parts of L MALIC ACID, 5~20 parts of ammonium lauryl sulfate, 5~20 parts of sodium acetate, sodium humate 10
~30 parts.
3. wet process of FGD composite synergistic additive according to claim 1 or claim 2, it is characterised in that：The L MALIC ACID
It is 45~50 parts.
4. wet process of FGD composite synergistic additive according to claim 1 or claim 2, it is characterised in that：The dodecyl
Ammonium sulfate is 10~15 parts.
5. a kind of preparation method of wet process of FGD composite synergistic additive, it is characterised in that：Claims 1 to 4 is arbitrary
Each ingredient is mixed evenly in wet process of FGD composite synergistic additive described in one.
6. the wet process of FGD composite synergistic additive described in a kind of Claims 1 to 4 any one is suitable for power plant soot
In the flue gas desulfurization device for the wet desulfurization system that boiler is configured.
7. a kind of wet flue gas desulfurization method, it is characterised in that：Claims 1 to 4 any one institute is added in sweetening process
The composite synergistic additive stated is included the following steps with promoting desulfurization effect：
1) composite synergistic additive is added in the lime stone slurry that mass percent is 1~3%, is uniformly mixed, obtains
Absorbing liquid；
2) former flue gas enters reverse with the absorbing liquid that enters from bottom to top along flue gas desulfurization device from the lower part of flue gas desulfurization device
Contact, it is 3.5~6s to control former flue gas with absorbing liquid time of contact.
8. wet flue gas desulfurization method according to claim 7, it is characterised in that：The absorbing liquid temperature in step 2) is
25~65 DEG C.
9. according to the wet flue gas desulfurization method of claim 7 or 8, it is characterised in that：Liquid-gas ratio in step 2) is 11~
23L/m3。
10. wet flue gas desulfurization method according to claim 9, it is characterised in that：Composite synergistic described in step 1) adds
Every liter of lime stone slurry of a concentration of 0.5~1.4g of agent.
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