CN101766954B - Composite type organic inhibitor for magnesia method desulfuration by-product recovery - Google Patents
Composite type organic inhibitor for magnesia method desulfuration by-product recovery Download PDFInfo
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- CN101766954B CN101766954B CN2010101205585A CN201010120558A CN101766954B CN 101766954 B CN101766954 B CN 101766954B CN 2010101205585 A CN2010101205585 A CN 2010101205585A CN 201010120558 A CN201010120558 A CN 201010120558A CN 101766954 B CN101766954 B CN 101766954B
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- organic inhibitor
- ethanol
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Abstract
The invention discloses a composite type organic inhibitor for magnesia desulfuration by-product recovery, a preparation method and application thereof, belonging to the technical field of flue gas desulfurization; the composite type organic inhibitor is formed by dissolving ascorbic acid, phenol and ethanol, the mole ratio of the ascorbic acid, the phenol and the ethanol is (1-10):1:1, the ascorbic acid, phenol and ethanol are added in a desulfuration liquid holding-up groove, so as to lead the amount-of-substance concentration of ascorbic acid, the phenol and the ethanol to be 2.67*10-6-2.67*10-3mol.L-1, 2.67*10-6-2.67*10-4mol.L-1 and 2.67*10-6-2.67*10-4mol.L-1 sequentially. In the invention, by reducing the oxidizing reaction rate of magnesium sulfite and improving the content of the magnesium sulfite in magnesium sulfite by-products, the desulfuration by-products can be convenient for recovery, the process is simplified and the energy consumption of the by-product recovery is reduced.
Description
Technical field
The invention belongs to the flue gas desulfurization technique field, particularly a kind of composite type organic inhibitor that is used for the magnesia desulfuration by-product recovery.
Background technology
The existing abroad ripe application of magnesium oxide method sulfur removal technology, but still be in the ground zero stage in China, be mainly used in the smoke pollution control of middle-size and small-size Industrial Boiler at present.Its basic principle is to be absorbent with magnesian hydration solution, absorbs the accessory substance magnesium sulfite that generates indissoluble after the sulfur in smoke, or after further oxidation, generates and be prone to molten magnesium sulfate.This technology still can be kept under low liquid-gas ratio (about 3-5) condition and be higher than 95% desulfuration efficiency, has small investment, takes up an area of characteristics such as little, stable, efficient, therefore in recent years in China's development rapidly.
The recovery of magnesia desulfuration by-product can be carried out through dual mode, i.e. oxidation absorption method and method of reproduction.Wherein, method of reproduction need suppress the oxidation of magnesium sulfite in sweetening process, and through filter type the magnesium sulfite of collecting is calcined back generation magnesia and sulfur dioxide under 350～400 ℃ of conditions.Magnesia can recycle as desulfurization absorbent once more, and sulfur dioxide is the raw material of preparation sulfuric acid.But owing to contain 6% the oxygen of having an appointment in the practical sulphur removal flue gas, and in separation of by-products, transportation and storage process, magnesium sulfite unavoidably can contact concurrent first portion oxidation with air, thus increased the energy consumption of calcination process greatly.
Existing research shows that the factor that influences sulfite oxidation speed has a lot, comprises pH, partial pressure of oxygen, ion concentration of inferior sulfate radical, temperature etc.But in actual process, still lack the method for effectively slowing down the magnesium sulfite oxidation, main cause is to adjust the continous-stable operation that above-mentioned parameter can influence system, and effect is limited, thereby operability is not strong.Comparatively speaking; Adding inhibitor can be under the prerequisite that does not influence desulphurization system balance and stability; Reduce the oxidizing reaction rate of magnesium sulfite effectively, after filtering separation, can obtain the magnesium sulfite solid of higher degree again, thereby be convenient to the recycling of desulfurizing byproduct.
The research that at present sulphite is suppressed oxidation also seldom, once the someone attempted using the oxidation reaction process that material such as sodium thiosulfate slows down magnesium sulfite, but actual effect is not good.The present invention is on the basis of a large amount of relevant magnesium sulfite oxidation reaction kinetics experiment of having carried out; Optimal inhibition agent and proportioning thereof have been obtained to the magnesium sulfite oxidation; Can under the prerequisite that adds the minute quantity inhibitor, make the magnesium sulfite oxidation rate be reduced to 1/5～1/2 when additive-free, thereby have application promise in clinical practice.
Summary of the invention
The purpose of this invention is to provide a kind of composite type organic inhibitor that magnesia desulfuration by-product reclaims that is used for.
A kind of composite type organic inhibitor that is used for the magnesia desulfuration by-product recovery; It is characterized in that said composite type organic inhibitor is to mix ascorbic acid, phenol and ethanol are soluble in water; Wherein, the mol ratio of ascorbic acid, phenol and ethanol is (1～10): 1: 1.
The above-mentioned composite type organic inhibitor that is used for the magnesia desulfuration by-product recovery; It is characterized in that its preparation method is following: take by weighing ascorbic acid, phenol and ethanol in molar ratio; Under 40～50 ℃ of conditions that it is soluble in water; And be stirring and evenly mixing under 4.5～8.5 the condition in the pH value, obtain composite type organic inhibitor.
The above-mentioned composite type organic inhibitor that is used for the magnesia desulfuration by-product recovery; It is characterized in that its application process is following: composite type organic inhibitor is joined desulfurization hold in the liquid bath, make ascorbic acid, phenol and the ethanol amount of substance concentration in desulfurization slurry be followed successively by 2.67 * 10
-6～2.67 * 10
-3MolL
-1, 2.67 * 10
-6～2.67 * 10
-4MolL
-1, 2.67 * 10
-6～2.67 * 10
-4MolL
-1
Sulfur in smoke and magnesium hydroxide slurry reaction add composite type organic inhibitor in the gained desulfurization slurry, play the effect of effective inhibition magnesium sulfite oxidizing reaction rate.
Proof procedure is: get a certain amount of inhibitor and be added to desulfurization and hold in the liquid bath; Every certain interval of time is measured the concentration of holding sulfate radical in the liquid bath; Represent the oxidizing reaction rate of magnesium sulfite can get the reaction rate of magnesium sulfite under rejection condition with sulfate radical growing amount in the unit interval.Experimental result at breadboard mini-system shows, behind the adding inhibitor, can suppress the oxidation of magnesium sulfite effectively, 1/5～1/2 the when oxidation rate of magnesium sulfite is additive-free.
Beneficial effect of the present invention is: inhibitor of the present invention is through reducing the oxidizing reaction rate of magnesium sulfite; Thereby the content of magnesium sulfite in the raising desulfurizing byproduct; Be convenient to desulfurizing byproduct is recycled, and simplified technology, reduced the energy consumption of by-product recovery.Compare with prior art, the present invention has following advantage:
(1) common being easy to get of inhibitor raw material of the present invention, the preparation process is simple, and operating condition is easily understood.
(2) inhibition effect of the present invention is remarkable, and behind the adding inhibitor, 1/5～1/2 the when oxidation rate of magnesium sulfite is additive-free can effectively be applied to the recovery of magnesium oxide method sulfur removal technology accessory substance.
(3) use of the present invention can not have a negative impact to desulphurization system, can not reduce the reactivity of absorbent behind the adding inhibitor.
(4) composite type organic inhibitor activity of the present invention is low, and consumption is little, and toxicity is little, can produce the secondary pollution problem hardly.
Description of drawings
Fig. 1 is that sulfate radical generates concentration over time among the different embodiment.
The specific embodiment
In order to be illustrated more clearly in the present invention, enumerate following examples, but it there is not any restriction to scope of the present invention.
The preparation and the use of embodiment 1 inhibitor of the present invention
Take by weighing ascorbic acid (C
6H
8O
6) 1.88kg, ethanol (C
2H
5OH) 0.62L, phenol (C
6H
5OH) 1.0kg is dissolved in 0.5m under 40 ℃ of conditions
3In the deionized water, it is about 7.0 to regulate the pH value with hydrochloric acid and ammoniacal liquor, and stirring and evenly mixing is processed composite type organic inhibitor (in the composite type organic inhibitor of present embodiment gained, the mol ratio of ascorbic acid, phenol and ethanol is 1: 1: 1).
In the sweetening process, magnesium hydroxide slurry and sulfur in smoke reaction, gained desulfurization slurry (the desulfurization slurry main component is magnesium sulfite, magnesium sulfate) gets into desulfurization and holds liquid bath, gets above-mentioned composite type organic inhibitor 0.5m
3, joining desulfurization and hold in the liquid bath, the reaction solution cumulative volume is 200m
3, ascorbic acid, phenol and the ethanol amount of substance concentration in desulfurization slurry is 5.33 * 10
-5MolL
-1, 2/5 when recording magnesium sulfite oxidation rate under the rejection condition and being about the unrestraint condition.
The preparation and the use of embodiment 2 inhibitor of the present invention
Take by weighing ascorbic acid (C
6H
8O
6) 4.70kg, ethanol (C
2H
5OH) 1.54L, phenol (C
6H
5OH) 2.51kg is dissolved in 0.5m under 40 ℃ of conditions
3In the deionized water, it is about 6.5 to regulate the pH value with hydrochloric acid and ammoniacal liquor, and stirring and evenly mixing is processed composite type organic inhibitor (in the composite type organic inhibitor of present embodiment gained, the mol ratio of ascorbic acid, phenol and ethanol is 1: 1: 1).
In the sweetening process, magnesium hydroxide slurry and sulfur in smoke reaction, gained desulfurization slurry (the desulfurization slurry main component is magnesium sulfite, magnesium sulfate) gets into desulfurization and holds liquid bath, gets above-mentioned composite type organic inhibitor 0.5m
3, joining desulfurization and hold in the liquid bath, the reaction solution cumulative volume is 200m
3, ascorbic acid, phenol and the ethanol amount of substance concentration in desulfurization slurry is 1.33 * 10
-4MolL
-1, 1/4 when recording magnesium sulfite oxidation rate under the rejection condition and being about the unrestraint condition.
The preparation and the use of embodiment 3 inhibitor of the present invention
Take by weighing ascorbic acid (C
6H
8O
6) 23.5kg, ethanol (C
2H
5OH) 3.75L, phenol (C
6H
5OH) 6.25kg is dissolved in 2.5m under 40 ℃ of conditions
3In the deionized water, it is about 6.5 to regulate the pH value with hydrochloric acid and ammoniacal liquor, and stirring and evenly mixing is processed composite type organic inhibitor (in the composite type organic inhibitor of present embodiment gained, the mol ratio of ascorbic acid, phenol and ethanol is 2: 1: 1).
In the sweetening process, magnesium hydroxide slurry and sulfur in smoke reaction, gained desulfurization slurry (the desulfurization slurry main component is magnesium sulfite, magnesium sulfate) gets into desulfurization and holds liquid bath, measures above-mentioned composite type organic inhibitor 2.0m
3, joining desulfurization and hold in the liquid bath, the reaction solution cumulative volume is 200m
3, ascorbic acid, phenol and the ethanol amount of substance concentration in desulfurization slurry is respectively 5.33 * 10
-4MolL
-1, 2.66 * 10
-4MolL
-1, 2.66 * 10
-4MolL
-1, 1/5 when recording magnesium sulfite oxidation rate under the rejection condition and being about the unrestraint condition.
The experimental result of the foregoing description is as shown in Figure 1; Among Fig. 1, under the case 0 expression unrestraint agent existence condition, desulfurization holds that magnesium sulfate concentration in the liquid bath internal reaction solution increases in time and situation about increasing; Its slope is also promptly represented the oxidizing reaction rate of magnesium sulfite; Case 1～3 represents the oxidation rate of magnesium sulfite under embodiment 1～3 condition respectively, and slope of a curve is big more, shows that the oxidation rate of magnesium sulfite is fast more.
Claims (3)
1. one kind is used for the composite type organic inhibitor that magnesia desulfuration by-product reclaims; It is characterized in that said composite type organic inhibitor is to mix ascorbic acid, phenol and ethanol are soluble in water; Wherein, the mol ratio of ascorbic acid, phenol and ethanol is (1～10): 1: 1.
2. a kind of composite type organic inhibitor that magnesia desulfuration by-product reclaims that is used for according to claim 1; It is characterized in that its preparation method is following: take by weighing ascorbic acid, phenol and ethanol in molar ratio; Under 40～50 ℃ of conditions that it is soluble in water; And be stirring and evenly mixing under 4.5～8.5 the condition in the pH value, obtain composite type organic inhibitor.
3. a kind of composite type organic inhibitor that magnesia desulfuration by-product reclaims that is used for according to claim 1; It is characterized in that its application process is following: composite type organic inhibitor is joined desulfurization hold in the liquid bath, make ascorbic acid, phenol and the ethanol amount of substance concentration in desulfurization slurry be followed successively by 2.67 * 10
-6～2.67 * 10
-3MolL
-1, 2.67 * 10
-6～2.67 * 10
-4MolL
-1, 2.67 * 10
-6～2.67 * 10
-4MolL
-1
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101205585A CN101766954B (en) | 2010-03-08 | 2010-03-08 | Composite type organic inhibitor for magnesia method desulfuration by-product recovery |
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|---|---|---|---|
| CN2010101205585A CN101766954B (en) | 2010-03-08 | 2010-03-08 | Composite type organic inhibitor for magnesia method desulfuration by-product recovery |
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|---|---|
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| CN101766954B true CN101766954B (en) | 2012-03-28 |
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| CN102188887B (en) * | 2011-04-07 | 2013-01-30 | 华北电力大学（保定） | Composite inhibitor for recovering by-products generated during desulphurization by sodium alkali method as well as preparation and application thereof |
| CN110787601B (en) * | 2018-08-01 | 2021-11-30 | 中国石油天然气股份有限公司 | Heat-stable salt inhibitor for desulfurization system and solvent for removing sulfur dioxide |
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| JPS57194089A (en) * | 1981-05-26 | 1982-11-29 | Showa Denko Kk | Treatment of aqueous solution containing chromium |
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