CN102974209B - Desulfurization synergist having scale inhibition performance, and preparation method thereof - Google Patents
Desulfurization synergist having scale inhibition performance, and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a desulfurization synergist having a scale inhibition performance and for a limestone-gypsum wet flue gas desulfurization system (FDG), and a preparation method thereof. The desulfurization synergist is characterized in that the desulfurization synergist is prepared by compounding 70-90% by mass of a hydroxyl carboxylate and an organic carboxylate, 9-28% by mass of a scale inhibitor, and 1-2% by mass of a fluorescent tracer, wherein a mass ratio of the hydroxyl carboxylate to the organic carboxylate is an arbitrary ratio. With the present invention, desulfurization efficiency can be significantly improved.
Description
Technical field
The present invention has desulfurization synergistic agent of scale-inhibiting properties and preparation method thereof for wet desulfurization of flue gas by limestone-gypsum method system (FDG).
Background technology
At present the electric power of China is mainly derived from coal-fired thermal power generation, and the SO2 producing because of fire coal more than 100,000 tons, is the pollution reducing atmospheric environment every year, and each high-power station has all adopted different modes to remove processing to the SO2 in boiler smoke.Wherein wet desulfurization of flue gas by limestone-gypsum method has that technical maturity, removal efficiency are high, strong adaptability, accessory substance gypsum can utilize and the advantage such as absorbent lime stone source is abundant, most widely used in all sulfur methods.At present, more than 80% power plant of China all carries out desulfurization processing by the method.
Although wet desulfurization of flue gas by limestone-gypsum method has above-mentioned plurality of advantages, also there is following shortcoming:
1) consumption of limestone amount is large, and lime stone utilization rate is on the low side.Ca/S when most of power plant actual motion is than between 1.03～1.10, the lime stone utilization rate space that improves.
2) desulphurization system energy consumption is large.The energy consumption of desulphurization system is mainly from many slurry circulating pumps, oxidation fan and booster fan.If a slurry circulating pump electric current is 70A, every day power consumption=70A × 6KV × 1.732 × 0.85 × 24h=14839.78KW, as the circulating pump of stopping transport, the electric weight of annual consumption saving is when in 1,000,000 yuan.
3) the easy fouling of system.Because the product after desulfurization is mainly CaSO4.2H2O and CaSO3.1/2H2O, be scale forming matter, make fouling be difficult to avoid.Every 1 month, shut down and need the phenomenon of scale removal all to have generation in many power plant because fouling causes.
4) the coal-fired sulfur content of the design of many power plant, 1.0～1.5%, designs coal-fired sulfur-bearing value low, and now corresponding desulfuration efficiency also can meet the demands.But when in coal supply anxiety, or for reducing costs while using the high tinpot coal of sulfur content, may cause SO2 discharge to exceed standard.
In patent before this, as mentioned in CN10574615A, by improving desulfuration efficiency with dialkyl group sulfonic acid succinate and small molecular alcohol, but dialkyl group sulfonic acid succinate foaminess is strong in actual use, can make slurries foam increase and cause overflow; In addition dialkyl group sulfonic acid succinate facile hydrolysis under acid and hot environment lost efficacy, and these 2 all can affect desulfurized effect.The absorbent using organic amine, phosphate and acylate as desulphurization denitration of mentioning in patent CN102068888A, is mainly that cost is too high, has also got rid of the actual conditions of power plant using lime stone as absorbent.
A kind of desulfurization synergistic agent that the present invention proposes has the performance that improves desulfuration efficiency and slow down desulphurization system fouling simultaneously, in patent in the past, is not also mentioned.
Summary of the invention
The object of the present invention is to provide a kind of can obviously improve desulfuration efficiency there is desulfurization synergistic agent of scale-inhibiting properties and preparation method thereof.
For achieving the above object, the technical solution adopted in the present invention is: a kind of desulfurization synergistic agent with scale-inhibiting properties, it is characterized in that it is by hydroxycarboxylate and organic carboxylate (having increase desulfuration efficiency), and antisludging agent (having Synergistic), and fluorescent tracer is composite forms (scale inhibition of taking into account desulfurization synergistic and desulphurization system); The shared mass percent of each raw material is: hydroxycarboxylate and organic carboxylate 70～90%, antisludging agent 9～28%, fluorescent tracer 1～2%; Wherein, between hydroxycarboxylate and organic carboxylate, mass ratio is any proportioning.
Described hydroxycarboxylate comprises the mixing of any one or any two or more (containing two kinds) in trisodium citrate, 2 hydroxy propanoic acid sodium, sodium itaconate, hydroxysuccinic acid disodium or suberic acid sodium etc., and any two above (containing two kinds) is any proportioning while mixing.
Described organic carboxylate comprises the mixing of any one or any two or more (containing two kinds) in sodium formate, sodium acetate, sulfo group sodium propionate, sodium sulfo-succinate, Sodium glutarate, hexanedioic acid sodium, sodium acetate, sodium succinate etc., and any two above (containing two kinds) is any proportioning while mixing.
Described antisludging agent comprises lignosulfonates, polyepoxysuccinic acid salt, polyacrylic acid, carboxylate-sulfonate-nonionic terpolymer 3100, acrylic acid-2-acrylamide-2-methyl propane sulfonic copolymer A A/AMPS sodium salt, and ATMP four sodium ATMPNa
4, HEDP four sodium HEDPNa
4, 2-phosphonic acids butane-1,2,4-tricarboxylic acids, four sodium PBTCANa
4in the mixing of any one or any two or more (containing two kinds), any two above (containing two kinds) is any proportioning while mixing.
Wherein lignosulfonates are wood-fibred papermaking accessory substance, and polyepoxysuccinic acid salt, polyacrylic acid, carboxylate-sulfonate-nonionic terpolymer 3100 and acrylic acid-2-acrylamide-2-methyl propane sulfonic copolymer A A/AMPS molecular weight are 2000～4000.
Fluorescent tracer is water-soluble, and the fluorescent tracer of variable concentrations produces the fluorescence of respective intensities under 385nm wavelength laser irradiates.The raw materials used powdery solid that is above.
The preparation method of the above-mentioned desulfurization synergistic agent with scale-inhibiting properties, is characterized in that it comprises the steps:
1) the shared mass percent of each raw material is: hydroxycarboxylate and organic carboxylate 70～90%, and antisludging agent 9～28%, fluorescent tracer 1～2%, chooses hydroxycarboxylate and organic carboxylate, antisludging agent, fluorescent tracer, for subsequent use; Wherein, between hydroxycarboxylate and organic carboxylate, mass ratio is any proportioning;
2) hydroxycarboxylate and organic carboxylate, antisludging agent, and fluorescent tracer mix and blend 1～2 hour, obtain having the desulfurization synergistic agent of scale-inhibiting properties.
The present invention is for Wet Fgd By Limestone.This working concentration with the desulfurization synergistic agent of scale-inhibiting properties is 300～1200PPM, according to system status and former flue gas SO
2concentration determine.
This using method of desulfurization synergistic agent with scale-inhibiting properties is as follows:
1) calculate the volume of slurries in tower by the actual height of slurries in desulfurizing tower diameter and slurry pool, according to the working concentration of desulfurization synergistic agent, calculate the weight of required desulfurization synergistic agent;
2) the desulfurization synergistic agent of aequum is divided and is added for 2～4 times in desulfurizing tower melt pit in batches, often add a collection of, stir within 5～10 minutes, make it dissolve after squeezed in desulfurizing tower by melt pit elevator pump;
3) desulfurization synergistic agent in use has certain loss, and its concentration can record by the amount that detects fluorescent tracer, then supplements the medicament of respective amount according to synergist concentration in slurries.
The desulfurization synergistic agent that the present invention has scale-inhibiting properties has certain scale inhibition and dispersion performance, in the process of desulfurization, there is the dirty formation of good prevention, have and extend dirty scavenging period, greatly reduce the labour intensity of cleaning, owing to having added suitable dirt dispersion agent, make dirty form that variation occur, easily rinse and come off, extended the service life of chimney.There is the performance that improves desulfuration efficiency and slow down desulphurization system fouling simultaneously.
This desulfurization synergistic agent is added in desulfurizing tower slurries by finite concentration, can improve desulfuration efficiency 5～15%, and at the bottom of can slowing down desulfurizer mist eliminator, tower and the fouling of exhaust pass.The agent of this desulfurization synergistic is nontoxic, is easy to biodegradation, convenient for production, uses desulfurization synergistic agent of the present invention to have good economic benefit and environmental benefit.
The present invention has following beneficial effect:
1, the desulfurization synergistic agent (product) originally with scale-inhibiting properties is joined in means of flue gas desulfurization of power plant absorption tower, can effectively improve the desulfuration efficiency to flue gas, reduce SO
2discharge and the pollution to environment.
2, in actual motion, if coal-fired sulfur content, absorption tower inlet flue gas SO
2concentration is all in scope of design, and the desulfuration efficiency on absorption tower is greater than 90%, outlet flue gas SO
2when concentration meets discharging standards, just can, by adding desulfurization synergistic agent, realize one to two slurry circulating pump of stopping transport, reach the effect of saving electricity consumption.
If when the desulfuration efficiency on the 3 on-the-spot fire coals that use sulfur content higher (matter time inexpensive), absorption tower is on the low side again, by adding desulfurization synergistic agent, can realize the qualified discharge of smoke desulfurization efficiency, reduce the coal-fired expense of purchasing (valency of fine quality is high) that sulfur content is lower.
4, desulfurization synergistic agent can not cause damage to means of flue gas desulfurization of power plant tower and pipe-line system thereof after use, desulfurization synergistic agent simultaneously has good peptizaiton to calcium carbonate, calcium sulfite and calcium sulphate crystal, can slow down equipment, tube wall and spray nozzle encrustation situation and occur, pipeline and equipment periodic maintenance intervals time are extended greatly.
5, use after desulfurization synergistic agent, can make lime stone fully dissolve and conversion, the calcium carbonate content in output gypsum is significantly reduced, can effectively save amount of lime, effectively improve gypsum qualitt, and the balance of system is played a positive role.
6, because of 1 ~ 2 circulating pump of stopping transport, thus the maintenance cost of having saved circulating pump.
Brief description of the drawings
Fig. 1 is Wet Fgd By Limestone artwork involved in the present invention.
Detailed description of the invention
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.The present invention is raw materials used all to be bought and obtains from market.
embodiment 1
Have a desulfurization synergistic agent for scale-inhibiting properties, it forms by following raw material is composite,
The shared mass percent of raw material is:
Trisodium citrate 50%,
Sodium acetate 22%,
Sodium lignin sulfonate 5%,
Polyepoxy sodium succinate 8%,
Sodium Polyacrylate 7%,
ATMP (ATMP) 7%,
Fluorescent tracer 1%.
The preparation method of the above-mentioned desulfurization synergistic agent with scale-inhibiting properties, by above-mentioned raw materials mix and blend 1～2 hour, obtains having the desulfurization synergistic agent of scale-inhibiting properties.
embodiment 2
Have a desulfurization synergistic agent for scale-inhibiting properties, it forms by following raw material is composite,
The shared mass percent of raw material is:
2 hydroxy propanoic acid sodium 35%,
Sodium formate 45%,
Sodium lignin sulfonate 3%,
Polyepoxy sodium succinate 8%,
Sodium Polyacrylate 7%,
Fluorescent tracer 2%.
The preparation method of the above-mentioned desulfurization synergistic agent with scale-inhibiting properties, by above-mentioned raw materials mix and blend 1～2 hour (carrying out in powder mixing stirrer), obtains having the desulfurization synergistic agent of scale-inhibiting properties.
embodiment 3
Have a desulfurization synergistic agent for scale-inhibiting properties, it forms by following raw material is composite,
The shared mass percent of raw material is:
Sodium glutarate 25%,
Hexanedioic acid sodium 35%,
Hydroxysuccinic acid disodium 28%,
Carboxylate-sulfonate-nonionic terpolymer 3,100 6%,
Acrylic acid-2-acrylamide-2-methyl propane sulfonic copolymer A A/AMPS 4%,
Fluorescent tracer 2%.
The preparation method of the above-mentioned desulfurization synergistic agent with scale-inhibiting properties, by above-mentioned raw materials mix and blend 1～2 hour (carrying out in powder mixing stirrer), obtains having the desulfurization synergistic agent of scale-inhibiting properties.
embodiment 4
Have a desulfurization synergistic agent for scale-inhibiting properties, it forms by following raw material is composite,
The shared mass percent of raw material is:
Hexanedioic acid sodium 50%,
Sodium acetate 13%,
Hydroxysuccinic acid disodium 20%,
Polyepoxy sodium succinate 8%,
Sodium Polyacrylate 7%,
Fluorescent tracer 2%.
The preparation method of the above-mentioned desulfurization synergistic agent with scale-inhibiting properties, by above-mentioned raw materials mix and blend 1～2 hour (carrying out in powder mixing stirrer), obtains having the desulfurization synergistic agent of scale-inhibiting properties.
The using method of the desulfurization synergistic agent with scale-inhibiting properties of embodiment 1, embodiment 2, embodiment 3, embodiment 4 is as follows:
1) calculate the volume of slurries in tower by the actual height of slurries in desulfurizing tower diameter and slurry pool, according to the working concentration of desulfurization synergistic agent, calculate the weight of required desulfurization synergistic agent;
2) the desulfurization synergistic agent of aequum is divided and is added for 2～4 times in desulfurizing tower melt pit in batches, often add a collection of, stir within 5～10 minutes, make it dissolve after squeezed in desulfurizing tower by melt pit elevator pump;
3) desulfurization synergistic agent in use has certain loss, and its concentration can record by the amount that detects fluorescent tracer, then supplements the medicament of respective amount according to synergist concentration in slurries.
The synergist of above-described embodiment 1, embodiment 2, embodiment 3, embodiment 4 is added in desulfurizing tower slurries by concentration 0,300,600,1000PPM, and the desulfuration efficiency of experimental record is as shown in table 1 below:
Table 1
| Synergist concentration | 0PPM | 300PPM | 600PPM | 1000PPM |
| Embodiment 1 desulfuration efficiency | 89.3% | 92.4% | 94.3% | 96.2% |
| Embodiment 2 desulfuration efficiencies | 89.3% | 92.7% | 94.6% | 96.1% |
| Embodiment 3 desulfuration efficiencies | 89.3% | 92.9% | 94.7% | 96.2% |
| Embodiment 4 desulfuration efficiencies | 89.3% | 93.0% | 94.8% | 96.3% |
In table 1, data show: add desulfurization synergistic agent can obviously improve desulfuration efficiency, and the larger desulfuration efficiency of concentration is higher.
The synergist of above-described embodiment 1, embodiment 2, embodiment 3, embodiment 4 is added in desulfurizing tower slurries by concentration 0,300,600,1000PPM, record is carried out to the dirty layer thickness at the bottom of tower and the same position of demister in 1 month in interval, and experimental data is as shown in table 2 below:
Table 2
In table 1, data show: add obviously relieving system fouling of desulfurization synergistic agent, and concentration to slow down more greatly the effect of fouling better.
While not adding desulfurization synergistic agent as certain power plant, desulfuration efficiency is 92～93%, and A, B, C, the operation of D platform slurry circulating pump altogether, adds synergist 1000PPM of the present invention from high to low, stops C pump or D pump, and service data is as follows:
Stop 1 circulating pump, desulfuration efficiency is still significantly improved, simultaneously the amount of saving energy:
The voltage of C pump and D pump is 6KV, and electric current is respectively 65A and 70A:
Stop D pump and save electric weight=65A × 6KV × 1.732 × 0.85 × 24h=13779.79KW every day
Stop C pump and save electric weight=70A × 6KV × 1.732 × 0.85 × 24h=14839.78KW every day
Add synergist 1000PPM of the present invention, in the situation that stopping D pump, the quality of dehydrated gypsum is as following table 3:
Table 3
From table 3, data can be found: CaCO3 (lime stone) content in gypsum reduces, and CaCO3 (lime stone) utilization rate increases; Attached water reduces, and gypsum qualitt improves.
embodiment 5
Have a desulfurization synergistic agent for scale-inhibiting properties, it forms by following raw material is composite,
The shared mass percent of raw material is:
Sodium itaconate 50%,
Suberic acid sodium 13%,
Sulfo group sodium propionate 7%,
Sodium lignin sulfonate 28%,
Fluorescent tracer 2%.
embodiment 6
Have a desulfurization synergistic agent for scale-inhibiting properties, it forms by following raw material is composite,
The shared mass percent of raw material is:
Trisodium citrate 50%,
Sodium succinate 40%,
Polyepoxy sodium succinate 9%,
Fluorescent tracer 1%.
The preparation method of the above-mentioned desulfurization synergistic agent with scale-inhibiting properties, by above-mentioned raw materials mix and blend 1～2 hour, obtains having the desulfurization synergistic agent of scale-inhibiting properties.
The using method of the desulfurization synergistic agent with scale-inhibiting properties of embodiment 5, embodiment 6 is as follows:
1) calculate the volume of slurries in tower by the actual height of slurries in desulfurizing tower diameter and slurry pool, according to the working concentration of desulfurization synergistic agent, calculate the weight of required desulfurization synergistic agent;
2) the desulfurization synergistic agent of aequum is divided and is added for 2～4 times in desulfurizing tower melt pit in batches, often add a collection of, stir within 5～10 minutes, make it dissolve after squeezed in desulfurizing tower by melt pit elevator pump;
3) desulfurization synergistic agent in use has certain loss, and its concentration can record by the amount that detects fluorescent tracer, then supplements the medicament of respective amount according to synergist concentration in slurries.
The synergist of above-described embodiment 5, embodiment 6 is added in desulfurizing tower slurries by concentration 0,300,600,1000PPM, and the desulfuration efficiency of experimental record is as shown in table 4 below:
Table 4
| Synergist concentration | 0PPM | 300PPM | 600PPM | 1000PPM |
| Embodiment 5 desulfuration efficiencies | 89.3% | 92.4% | 94.3% | 96.2% |
| Embodiment 6 desulfuration efficiencies | 89.3% | 92.7% | 94.6% | 96.7% |
In table 4, data show: add desulfurization synergistic agent can obviously improve desulfuration efficiency, and the larger desulfuration efficiency of concentration is higher.
Each raw material that the present invention is cited, and the bound of the each raw material of the present invention, interval value, and bound, the interval value of technological parameter (as time etc.) can realize the present invention, do not enumerate embodiment at this.
Claims (3)
1. there is a desulfurization synergistic agent for scale-inhibiting properties, it is characterized in that it is by hydroxycarboxylate and organic carboxylate, and antisludging agent, and fluorescent tracer is composite forms; The shared mass percent of each raw material is: hydroxycarboxylate and organic carboxylate 70～90%, antisludging agent 9～28%, fluorescent tracer 1～2%; Wherein, between hydroxycarboxylate and organic carboxylate, mass ratio is any proportioning;
Described hydroxycarboxylate comprises the mixing of any one or any two or more in trisodium citrate, 2 hydroxy propanoic acid sodium, sodium itaconate, hydroxysuccinic acid disodium or suberic acid sodium, when any two above mixing, is any proportioning;
Described organic carboxylate comprises the mixing of any one or any two or more in sodium formate, sodium acetate, sulfo group sodium propionate, sodium sulfo-succinate, Sodium glutarate, hexanedioic acid sodium, sodium acetate, sodium succinate, when any two above mixing, is any proportioning.
2. a kind of desulfurization synergistic agent with scale-inhibiting properties according to claim 1, it is characterized in that, described antisludging agent comprises the sodium salt of lignosulfonates, polyepoxysuccinic acid salt, polyacrylic acid, carboxylate-sulfonate-nonionic terpolymer 3100, acrylic acid-2-acrylamide-2-methyl propane sulfonic copolymer A A/AMPS, and ATMP four sodium, HEDP four sodium, 2-phosphonic acids butane-1,2, the mixing of any one or any two or more in 4-tricarboxylic acids four sodium is any proportioning when any two above mixing.
3. the preparation method of the desulfurization synergistic agent with scale-inhibiting properties as claimed in claim 1, is characterized in that it comprises the steps:
1) the shared mass percent of each raw material is: hydroxycarboxylate and organic carboxylate 70～90%, and antisludging agent 9～28%, fluorescent tracer 1～2%, chooses hydroxycarboxylate and organic carboxylate, antisludging agent, fluorescent tracer, for subsequent use; Wherein, between hydroxycarboxylate and organic carboxylate, mass ratio is any proportioning;
Described hydroxycarboxylate comprises the mixing of any one or any two or more in trisodium citrate, 2 hydroxy propanoic acid sodium, sodium itaconate, hydroxysuccinic acid disodium or suberic acid sodium, when any two above mixing, is any proportioning;
Described organic carboxylate comprises the mixing of any one or any two or more in sodium formate, sodium acetate, sulfo group sodium propionate, sodium sulfo-succinate, Sodium glutarate, hexanedioic acid sodium, sodium acetate, sodium succinate, when any two above mixing, is any proportioning;
2) hydroxycarboxylate and organic carboxylate, antisludging agent, and fluorescent tracer mix and blend 1～2 hour, obtain having the desulfurization synergistic agent of scale-inhibiting properties.
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| CN103432894A (en) * | 2013-08-30 | 2013-12-11 | 杨子江 | Synergist for assisting wet-process desulphurization of thermal power plant, and application method of synergist |
| CN105854511A (en) * | 2016-05-24 | 2016-08-17 | 南京华电节能环保设备有限公司 | Exhaust gas sulphur removal agent |
| CN107138030A (en) * | 2017-06-08 | 2017-09-08 | 北京可林维尔化工有限公司 | Wet desulfurization system synergy scale inhibition heavy metals removal agent and preparation method thereof |
| CN107213775A (en) * | 2017-06-14 | 2017-09-29 | 昆明理工大学 | A kind of dispersion stabilizer for flotation tailing slurries desulfurization |
| CN108905591A (en) * | 2018-06-29 | 2018-11-30 | 南通乐尔环保科技有限公司 | A kind of efficient wet flue gas desulfurization synergist |
| CN110624364A (en) * | 2019-09-12 | 2019-12-31 | 中国石油化工股份有限公司 | Organic absorbent for removing sulfur dioxide in mixed gas and preparation method |
| CN114788987B (en) * | 2021-05-26 | 2023-11-10 | 上海未来企业股份有限公司 | Synergist with high desulfurization efficiency and obvious energy-saving effect and preparation method thereof |
| CN116688744B (en) * | 2023-08-02 | 2023-10-31 | 杭州尚善若水环保科技有限公司 | Mixed medicament for improving fluidity of lime slurry |
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