CN102657999A - Poly (tetramethylguandium acrylate) aqueous solution desulfurization agent and preparation method thereof - Google Patents
Poly (tetramethylguandium acrylate) aqueous solution desulfurization agent and preparation method thereof Download PDFInfo
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- CN102657999A CN102657999A CN2012101748311A CN201210174831A CN102657999A CN 102657999 A CN102657999 A CN 102657999A CN 2012101748311 A CN2012101748311 A CN 2012101748311A CN 201210174831 A CN201210174831 A CN 201210174831A CN 102657999 A CN102657999 A CN 102657999A
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Abstract
The invention relates to a preparation method and an application method of poly (tetramethylguandium acrylate) desulfurization agent. The poly (tetramethylguandium acrylate) desulfurization agent can be used for flue gas desulfurization of a thermal power plant and a metallurgic plant, and has excellent selective absorption for sulfur dioxide as well as good lasting absorption property and multi-time cycle absorption and desorption stability. The desulfurization agent is characterized by comprising the components: poly (tetramethylguandium acrylate), water, antioxidant, corrosion inhibitor and defoaming agent. The preparation method comprises the steps of: adding solvent into a polymerizing pot, then adding initiator into the solvent, slowly heating to 120-140 DEG C when stirring, and dripping acrylic acid within 2-4h at the temperature of 120-140 DEG C; then removing the solvent under pressure reduction, and grinding to obtain polyacrylic acid; adding polyacrylic acid and water into a reaction flask and stirring; controlling the temperature to be 0-5 DEG C by ice-water bath, dripping 1,1,3,3-tetramethyl guanidine, reacting for 1h and then stopping the reaction; and adding right amount of antioxidant, corrosion inhibitor and defoaming agent, and evenly stirring to obtain poly (tetramethylguandium acrylate) aqueous solution, wherein the aqueous solution is the target desulfurization agent product.
Description
Technical field
The present invention relates to a kind of aqueous solutions of polymers desulfurizing agent and application process thereof, specifically is to serve as to absorb the desulfurizing agent of composition and with the application process of its aqueous solution form absorbing sulfur dioxide with the polyacrylic acid TMG.
Technical background
The SO of China's discharging
290% comes from fire coal.A large amount of fire coals cause China SO together with other economic activities
2The acid deposition of polluting and causing is thus polluted, and causes the large-area acid rain of China, and agricultural, industry and human ecology have been produced significant damage, and flue gas desulfurization technique is effectively to control SO
2One of important behave of polluting.
Flue gas desulfurization technique is varied, roughly is divided into wet process of FGD, three types of semi-dry process flue gas desulphurization and dry flue gas desulphurizations.Wet process of FGD is SO in the flue
2Most widely used method accounts for 80% of total treating capacity.This method maturation that possesses skills, rate of sulphur expulsion is fast, the efficient advantages of higher, but system complex, and investment, operating cost are all very high.Be prone to cause secondary pollution problems.Semi-dry desulfurizing process has some characteristics of dry method and wet method concurrently; Be desulfurizing agent desulfurization under drying regime, regeneration or desulfurization under wet condition under wet condition, the flue gas desulfurization technique of processing desulfurization product under dried state; It is fast to have the wet desulphurization reaction speed; The advantage that desulfuration efficiency is high, having dry method does not again have sewage and spent acid and gets rid of, the easy-to-handle advantage of desulfurization afterproduct and receive people and pay close attention to widely.Dry desulfurizing process spray absorbent technology compares with the wet scrubbing technology of routine that to have investment cost lower, need not to install demister and reheater, and equipment is not perishable.Its shortcoming is that the utilization rate of absorbent is lower than wet flue gas desulfurization technology.
In the fume desulfurizing agent that industrialization is at present used always, the wet process of FGD agent has lime stone, monoethanolamine, and natrium citricum, ionic liquid etc., the dry flue gas desulphurization agent has active carbon.Chinese patent CN101979128A is through 1,1,3; 3-TMG and 'alpha '-hydroxy acids mix stirring; Add free radical inhibitors successively to the main body species then, the complexing of metal ion agent, thinners etc. are prepared the little molecule composite desulfurizing agent of TMG hydroxy-acid salt; It has desulfuration efficiency height, by-product recovery, and to be worth high, few secondary pollution, absorption liquid renewable and advantage such as recycle; But its absorbent is solvent-free absorbent, and cost is high, and it is big to be applied to flue gas desulphurization owner economic pressures.Chinese patent CN1884315A is with carboxylic vinyl monomer and 1,1,3, and the 3-TMG carried out neutralization reaction in 1: 1 in molar ratio～1: 2, obtained 1; 1,3, the cationic vinyl monomer of 3-TMG makes 1 through the free radical polymerisation in bulk then; 1,3,, the cation type polymer of 3-TMG; This polymer can be used as solid-state desulfurizing agent, absorbing sulfur dioxide, and it is high to absorb selectivity, and absorptive capacity is big and speed is fast; And the polymer desulfurizing agent can repeatedly recycle, but solid-state desulfurizing agent can only be used the just inevitable low shortcoming of absorbent utilization rate with the form of dry desulfurization in Desulfurization Application.Consider solid desulfurating agent low shortcoming of absorbent utilization rate in industrial applications, the polyacrylic acid TMG is deviate from SO 2 from fume with the mode of wet desulphurization and is not seen that also patent report is arranged, and has promptly practiced thrift cost, has remedied the shortcoming of dry desulfurization again.
The present invention is a solute with the polyacrylic acid TMG, and water is that solvent is prepared polyacrylic acid TMG aqueous solution desulfurizing agent.This desulfurizing agent absorbing sulfur dioxide speed is fast, and utilization rate is high, select the absorbing sulfur dioxide performance good, and production cost is lower, is easy to suitability for industrialized production and application.
Summary of the invention
The object of the present invention is to provide to can be recycled, have high absorbing sulfur dioxide speed, high efficiency selected absorbing sulfur dioxide, and lower-cost aqueous solution desulfurizing agent.
Another object of the present invention is to provide a kind of application process of above-mentioned desulfurizing agent.
To achieve these goals, the present invention prepares by following component (mass fraction):
The anti-oxidant that the present invention uses can be as in hydroquinones, tannic acid, the sodium thiosulfate a kind of.
A kind of as in basic copper carbonate, the potassium antimony tartrate of the corrosion inhibiter that the present invention uses.
The antifoaming agent that the present invention uses can be in silicone based antifoaming agent, the mineral oil defoaming agent a kind of.
The present invention also provides a kind of preparation method of above-mentioned desulfurizing agent, and the concrete processing step of this method is following:
(1) with solvent, initator is put into there-necked flask, stirs, and slowly is warming up to 120～140 ℃, and slowly dropwise addition of acrylic acid continues reaction 90～120min, and decompression distillation removes solvent, and pulverizing can obtain low-molecular-weight polyacrylic acid.
(2) under 0～5 ℃, a certain proportion of polyacrylic acid and TMG are stirred neutralization in the aqueous solution, stir 60～90min, form polyacrylic acid TMG aqueous solutions of polymers.
(3) at room temperature in the aqueous solution of polyacrylic acid TMG polymer, adding an amount of anti-oxidant, corrosion inhibiter, antifoaming agent stirs and promptly obtains containing the aqueous solution desulfurizing agent of polyacrylic acid TMG polymer.
The present invention has the following advantages: 1) the absorbent utilization rate is high; 2) rate of sulphur expulsion is fast; 3) can be recycled 4) can select absorbing sulfur dioxide, thus reduce of the influence of the carbon dioxide of higher concentration in the flue gas to desulfurizing agent; 5) production cost is low, and economic and practical is strong.
The specific embodiment
Below the present invention will be described in more detail through specific embodiment.Embodiment only is to a kind of explanation of the present invention, and is not construed as limiting the invention.
Embodiment 1
1) solvent 100ml, 1.00g initator are put into a 250ml there-necked flask; Start stirring, slowly be warming up to 120 ℃, take by weighing 20.00g acrylic acid; Slowly be added drop-wise in the there-necked flask with separatory funnel; Continue stirring reaction 120min, decompression vacuum pumping removes solvent and obtains white solid and be polyacrylic acid, pulverizes.
2) under 0～5 ℃, 18.00g polyacrylic acid and 100ml deionized water are put into the 250ml there-necked flask, stirring and dissolving slowly drips the 28.75g TMG, stirs 60～90min, promptly gets polyacrylic acid TMG aqueous solutions of polymers.
3) in polyacrylic acid TMG aqueous solutions of polymers, add 1.00g hydroquinones anti-oxidant under the room temperature, the 0.50g basic copper carbonate, the 1.00g silicone defoaming agent promptly gets polyacrylic acid TMG aqueous solutions of polymers desulfurizing agent.
Based on the polyacrylic acid TMG aqueous solutions of polymers desulfurizing agent of embodiment 1 gained to the sulfur dioxide cigarette of three kinds of variable concentrations and contain CO
2Concentration is that 10% flue gas is handled, and its result is as shown in table 1.
Table 1
Can know that by table 1 utilize the polyacrylic acid TMG aqueous solutions of polymers desulfurizing agent of the embodiment of the invention that the sulfur dioxide flue gas of any concentration is handled, desulfuration efficiency all can reach more than 98.50%.
Embodiment 2
1) solvent 100ml, 2.00g initator are put into a 250ml there-necked flask; Start stirring, slowly be warming up to 120 ℃, take by weighing 20.00g acrylic acid; Slowly be added drop-wise in the there-necked flask with separatory funnel; Continue stirring reaction 120min, decompression vacuum pumping removes solvent and obtains white solid and be polyacrylic acid, pulverizes.
2) under 0～5 ℃, 18.00g polyacrylic acid and 100ml deionized water are put into the 250ml there-necked flask, stirring and dissolving slowly drips the 28.75g TMG, stirs 60～90min, promptly gets polyacrylic acid TMG aqueous solutions of polymers.
3) in polyacrylic acid TMG aqueous solutions of polymers, add 1.00g hydroquinones anti-oxidant under the room temperature, the 0.50g basic copper carbonate, the 1.00g silicone defoaming agent promptly gets polyacrylic acid TMG aqueous solutions of polymers desulfurizing agent.
Based on the polyacrylic acid TMG aqueous solutions of polymers desulfurizing agent of embodiment 2 gained to the sulfur dioxide cigarette of three kinds of variable concentrations and contain CO
2Concentration is that 10% flue gas is handled, and its result is as shown in table 2.
Table 2
Can know that by table 2 utilize the polyacrylic acid TMG aqueous solutions of polymers desulfurizing agent of the embodiment of the invention that the sulfur dioxide flue gas of any concentration is handled, desulfuration efficiency all can reach more than 99.00%.
Embodiment 3
1) solvent 100ml, 3.00g initator are put into a 250ml there-necked flask; Start stirring, slowly be warming up to 120 ℃, take by weighing 20.00g acrylic acid; Slowly be added drop-wise in the there-necked flask with separatory funnel; Continue stirring reaction 120min, decompression vacuum pumping removes solvent and obtains white solid and be polyacrylic acid, pulverizes.
2) under 0～5 ℃, 18.00g polyacrylic acid and 100ml deionized water are put into the 250ml there-necked flask, stirring and dissolving slowly drips the 28.75g TMG, stirs 60～90min, promptly gets polyacrylic acid TMG aqueous solutions of polymers.
3) in polyacrylic acid TMG aqueous solutions of polymers, add 1.00g hydroquinones anti-oxidant under the room temperature, the 0.50g basic copper carbonate, the 1.00g silicone defoaming agent promptly gets polyacrylic acid TMG aqueous solutions of polymers desulfurizing agent.
Based on the polyacrylic acid TMG aqueous solutions of polymers desulfurizing agent of embodiment 3 gained to the sulfur dioxide cigarette of three kinds of variable concentrations and contain CO
2Concentration is that 10% flue gas is handled, and its result is as shown in table 1.
Table 3
Can know that by table 3 utilize the polyacrylic acid TMG aqueous solutions of polymers desulfurizing agent of the embodiment of the invention that the sulfur dioxide flue gas of any concentration is handled, desulfuration efficiency all can reach more than 99.20%.
Embodiment 4
1) solvent 100ml, 3.00g initator are put into a 250ml there-necked flask; Start stirring, slowly be warming up to 120 ℃, take by weighing 20.00g acrylic acid; Slowly be added drop-wise in the there-necked flask with separatory funnel; Continue stirring reaction 120min, decompression vacuum pumping removes solvent and obtains white solid and be polyacrylic acid, pulverizes.
2) under 0～5 ℃, 18.00g polyacrylic acid and 100ml deionized water are put into the 250ml there-necked flask, stirring and dissolving slowly drips the 28.75g TMG, stirs 60～90min, promptly gets polyacrylic acid TMG aqueous solutions of polymers.
3) in polyacrylic acid TMG aqueous solutions of polymers, add 0.50g hydroquinones anti-oxidant under the room temperature, the 0.5g basic copper carbonate, the 0.50g silicone defoaming agent promptly gets polyacrylic acid TMG aqueous solutions of polymers desulfurizing agent.
Based on the polyacrylic acid TMG aqueous solutions of polymers desulfurizing agent of embodiment 4 gained to the sulfur dioxide cigarette of three kinds of variable concentrations and contain CO
2Concentration is that 10% flue gas is handled, and its result is as shown in table 4.
Table 4
Table 4 presentation of results, the polyacrylic acid TMG aqueous solution desulfurizing agent of the present invention's preparation is to the sulfur dioxide of any concentration even at high CO
2The flue gas of concentration is handled, and desulfuration efficiency all can reach more than 99.10%.
Claims (5)
1. the invention provides a kind of preparation method who contains the aqueous solution desulfurizing agent of polyacrylic acid TMG, it is characterized in that: component (mass fraction) is:
2. among the aqueous solution desulfurizing agent preparation method of polyacrylic acid TMG polymer according to claim 1, described anti-oxidant can be any of hydroquinones, tannic acid and sodium thiosulfate.
3. the aqueous solution desulfurizing agent preparation method of polyacrylic acid TMG polymer according to claim 1, what described corrosion inhibiter can be for basic copper carbonate, potassium antimony tartrate is any.
4. among the aqueous solution desulfurizing agent preparation method of polyacrylic acid TMG polymer according to claim 1, described antifoaming agent can be for silicone based antifoaming agent, also can be mineral oil defoaming agent.
5. a kind of method for preparing above-mentioned polyacrylic acid TMG aqueous solutions of polymers desulfurizing agent according to claim 1 is characterized in that: may further comprise the steps:
(1) with solvent; Initator adds and to have stirring, reflux condenser, temperature and take into account in the there-necked flask of nitrogen conduit, opens and stirs, and is warming up to 120～140 ℃; Slow dropwise addition of acrylic acid; Dropwise and continue insulation reaction 90～120min, decompression distillation removes solvent then, pulverizes to be the polyacrylic acid that low molecular weight narrow distributes.
(2) under 0～5 ℃, a certain proportion of polyacrylic acid and TMG are stirred neutralization in the aqueous solution, stir 60～90min, form polyacrylic acid TMG aqueous solutions of polymers.
(3) at room temperature in polyacrylic acid TMG aqueous solutions of polymers, adding an amount of anti-oxidant, corrosion inhibiter, antifoaming agent stirs and promptly obtains containing the aqueous solution desulfurizing agent of polyacrylic acid TMG polymer.
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Cited By (3)
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| CN105169921A (en) * | 2015-10-14 | 2015-12-23 | 神华集团有限责任公司 | Composition for flue gas desulfurization and denitrification treatment, flue gas desulfurization and denitrification treatment device and flue gas desulfurization and denitrification treatment method |
| CN109603428A (en) * | 2019-01-09 | 2019-04-12 | 江苏蓝电环保股份有限公司 | SO is recycled from flue gas2Solvent |
| CN111888924A (en) * | 2020-07-29 | 2020-11-06 | 和县明生环保材料有限责任公司 | Baking-free brick tunnel kiln desulfurization cleaning agent and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105169921A (en) * | 2015-10-14 | 2015-12-23 | 神华集团有限责任公司 | Composition for flue gas desulfurization and denitrification treatment, flue gas desulfurization and denitrification treatment device and flue gas desulfurization and denitrification treatment method |
| CN109603428A (en) * | 2019-01-09 | 2019-04-12 | 江苏蓝电环保股份有限公司 | SO is recycled from flue gas2Solvent |
| CN111888924A (en) * | 2020-07-29 | 2020-11-06 | 和县明生环保材料有限责任公司 | Baking-free brick tunnel kiln desulfurization cleaning agent and preparation method thereof |
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Application publication date: 20120912 |