CN107789965A - A kind of ammonia magnesium combination smoke desulfurization and the method for by-product guanite - Google Patents
A kind of ammonia magnesium combination smoke desulfurization and the method for by-product guanite Download PDFInfo
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- B01D53/34—Chemical or biological purification of waste gases
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Abstract
The invention discloses a kind of ammonia magnesium combination smoke desulfurization and the method for by-product guanite, and it includes A, sulfur-containing smoke gas and first carries out the ammonia process of desulfurization, obtains ammonium sulfate or liquid containing ammonium sulfate solution；B, the flue gas after processing of step A carries out magnesium processes desulfurization again, obtains magnesium sulfate or containing magnesium sulfate solution；C, the pH value that solution is adjusted after mixing the obtained magnesium sulfate of the obtained ammonium sulfate of step A or liquid containing ammonium sulfate solution, step B or the aqueous solution of containing magnesium sulfate solution and phosphorous acid group generates ammonium magnesium phosphate crystal.Further innovation and the development in conventional ammoniacal ammonium sulphate method desulfurization and magnesium sulfuric acid magnesium processes desulfurization technical foundation in the present invention, solve the problems, such as the conventional ammoniacal ammonium sulphate method desulfurization technology of tradition and magnesium sulfuric acid magnesium processes desulfurization technology, reduce by-product production cost, improve accessory substance economic value, and solve the problems, such as secondary pollution caused by the escaping of ammonia and aerosol simultaneously, reduce energy consumption.
Description
Technical field
The invention belongs to environmental technology field, and in particular to the side of a kind of ammonia-magnesium combination smoke desulfurization and by-product guanite
Method.
Background technology
The method of flue gas desulfurization has a variety of.Wherein limestone wet-process is the most commonly used, but this method needs to consume substantial amounts of stone
Lime stone and water, while substantial amounts of reluctant byproduct calcium sulfate is produced, so being basically applied to the flue gas of large power plant
Desulfurization.
Ammonia type flue gas desulfurizing technology is to remove SO as absorbent using ammonia2Deng the flue gases purification of pollutant.20 generation
Japan at the beginning of the seventies that records begins one's study ammonia flue gas desulfurization technique technology with the country such as Italy, and in succession successful, but because
For the problems such as aerosol, its application receives certain limitation in tail gas after operating cost, burn into purification.Into 20th century 90
In the age, with reasons such as the continuous development of ammonia synthesizing industry, technological progresses, ammonia type flue gas desulfurizing technology applies rapid increase.
Ammonia type flue gas desulfurizing technology has the characteristics of not available for other many flue gas desulfurization technique techniques.At present, ammonia is a kind of be easy to get
Good alkaline absorbent, from absorption mechanism, alkaline absorbent absorbs the SO in flue gas2It is acid-base neutralization reaction, absorbs
Agent alkalescence is stronger, and infiltration rate is faster, and the alkalescence of ammonia is better than calcium-base absorbing agent；And from absorption mechanism, calcium-base absorbing agent
Absorb SO2It is gas-solid reaction, reaction speed is slow, and reaction is incomplete, and absorbent utilization rate is low, it is necessary to which larger energy is inhaled
Receive liquid mist, circulation etc. and improve absorbent utilization rate；And ammonia type flue gas desulfurizing absorption of technology SO2It is that gas-liquid or gas-gas are reacted, instead
Answer speed fast, the reaction of absorbent ammonia is complete, and absorbent utilization rate is high, can accomplish very high desulfuration efficiency, absorbing liquid atomization, follow
The process energy consumption such as ring is low, and equipment volume is small.At present, the ammonia process of desulfurization is occupied an leading position in flue gas desulfurization industry, its byproduct
Mainly ammonium sulfate, ammonium sulfate can take out the cost of compensation part of smoke desulfurization, ammonia type flue gas desulfurizing technology is compared
Other technologies have certain economy.But being continuously increased with ammonia ammonium sulphate process flue gas desulfurization device, ammonium sulfate
Apparent availability is increasing, and selling price unavoidably declines so that the economy of ammonia ammonium sulphate process flue gas desulfurization device
Gradually lose.The problem of ammonia ammonium sulphate process flue gas desulfurization device is also faced with is that the synthesis ammonia of high value is converted into low value
Ammonium sulfate product, enterprise operation cost are too high.
At present, domestic ammonia desulfurizing process is directed to the difference of accessory substance ammonium sulfate crystallization mode, can be divided into saturation knot in tower
Brilliant technique and the outer evaporative crystallization technique of tower.The outer evaporative crystallization technique of tower has desulphurization system is more reliable, sulphur ammonium crystallization outward appearance is good etc.
Advantage, but its investment is big, high energy consumption, operation are uneconomical.Simultaneously with the flue gas desulfurization technique phase such as lime stone, sodium hydroxide and magnesium processes
Compare, ammonia type flue gas desulfurizing also has the secondary pollution of the gentle colloidal sol of raw material the escaping of ammonia:
1) the escaping of ammonia：The ammonia escaped in flue gas depends on the concentration with absorbing liquid sulfite ammonium.
2) aerosol：Many ammonia ammonium sulphate process flue gas desulfurization device chimney row white cigarettes are fairly obvious, and plume hangover is very long.
Some is up to several kilometers.It is the main reason for western developed country abandons developing him that ammonia type flue gas desulfurizing, which produces aerosol,.
The so-called aerosol of our meanings, is the glue that the fine particle of liquid or solid disperses and formed in the sky air that suspends
Body dispersion.The formation of aerosol particle mainly passes through two kinds of approach in ammonia type flue gas desulfurizing：
1. in ammonia process of desulfurization liquid, do not taken off in ammoniacal liquor volatilization the effusion gaseous ammonia, with flue gas of the flue gas entrained with of chimney discharge
The sulfur dioxide removed generates the components such as ammonium sulfite, ammonium bisulfite, ammonium sulfate by gas phase reaction and forms aerosol.This gas
Colloidal sol composition is decided by moisture and oxygen amount in ratio, flue-gas temperature and the flue gas of sulfur dioxide in flue gas/ammonia, two in flue gas
Sulfur oxide and the more aerosols of ammonia form more serious.
2. desulfurization drop is carried out by high-temperature flue gas after ammonia absorption sulfur dioxide in flue gas, because evaporation separates out Asia
Ammonium sulfate solids crystallize to form aerosol.
Discharge ammonia in flue gas forms the decomposition that important channel is the ammonium sulfite of desulphurization reaction generation, sulfurous with sulfur dioxide
Sour ammonium be decomposed into ammonia and sulfur dioxide temperature to be typically larger than 70 DEG C under conditions of could carry out：Simultaneously in the alkaline environment Central Asia
Ammonium sulfate also easily decomposes.
The absorption liquid carried by flue gas, containing ammonium sulfite, when discharging flue-gas temperature and being less than 30 DEG C, ammonium sulfite by
It is small in solubility, the ammonium sulfite crystal of 0.07-0.7 microns is easily generated, it is molten in the presence of gas is formed with superfines micron level
Glue.
Magnesium processes desulfurization technology is a kind of ripe flue gas desulfurization technique, there is very more application achievements all over the world,
Individual project more than 100 wherein is applied in Japan, the power station 95% of TaiWan, China is to use magnesium oxide method, in addition in the U.S., moral
The ground such as state have all been applied, and have had the achievement of application in China some areas at present.
Its feature and technical advantage are：Sufficient raw, desulfuration efficiency are high, investment cost is few, it is reliable, without secondary
Pollution, subsequent treatment are more perfect, solve the problems, such as secondary pollution.The shortcomings of large-scale wet method are turn avoid simultaneously, because
This magnesia FGD technology is progressively more widely used, and just has been to be concerned by more and more people.Magnesium processes desulfurization technology is not
Foot part：Using method is abandoned, accessory substance magnesium sulfate wastes desulfurization absorbing liquid；Desulfurization absorbing liquid uses epsom salt processed,
Preparation process is relative complex, can good height；The method that desulfurization absorbing liquid uses Sulphuric acid, is limited by desulphurization system scale, to cigarette
The dust removal requirement of gas is high, it is difficult to good overall economic efficiency is obtained, cost hardly possible and Large sulfuric acid competition among enterprises；Accessory substance is difficult in a word
The problem of effectively to utilize, constrains the development of the method.
The content of the invention
The invention aims to solve the above problems, there is provided a kind of ammonia-magnesium combination smoke body desulfurization and by-product birds droppings
The method of stone, the shortcomings that overcoming ammonia process and magnesium method flue gas desulphurization technology, make full use of ammonia process and magnesium method flue gas desulphurization technique
The advantages of technology, form new combination smoke desulphurization technological process.In conventional ammonia ammonium sulphate process desulfurization and magnesium-sulphur in the present invention
Further innovation and development, solves the conventional ammonia ammonium sulphate process desulfurization technology of tradition and magnesium-sulfuric acid in sour magnesium processes desulfurization technical foundation
The problem of magnesium processes desulfurization technology, by-product production cost is reduced, improve accessory substance economic value, and it is gentle to solve the escaping of ammonia simultaneously
Secondary pollution problem caused by colloidal sol, reduce energy consumption.
The purpose of the present invention can be reached by following measures：
A kind of ammonia-magnesium combination smoke desulfurization and the method for by-product guanite, it comprises the following steps：
A, sulfur-containing smoke gas first carries out the ammonia process of desulfurization, obtains ammonium sulfate or liquid containing ammonium sulfate solution；
B, the flue gas after processing of step A carries out magnesium processes desulfurization again, obtains magnesium sulfate or containing magnesium sulfate solution；
C, by the obtained magnesium sulfate of the obtained ammonium sulfate of step A or liquid containing ammonium sulfate solution, step B or containing magnesium sulfate solution with
And the pH value generation ammonium magnesium phosphate crystal of solution is adjusted after the aqueous solution mixing of phosphorous acid group.
This method utilizes ammonia or ammoniacal liquor suitable for the production process of flue gas desulfurization producing ammonium sulfate byproduct and sulfuric acid magnesium compound
And magnesium hydroxide is the sulfur dioxide in absorbent absorption flue gas, and ammonium sulfate and sulfuric acid magnesium compound is prepared, removes it
In solid impurity after, with phosphoric acid or phosphate solution or phosphoric acid or phosphatic waste water and ammonia-magnesium combination smoke desulfurization
Accessory substance mixes in proportion, and struvite crystals are made, and is sold after drying as outside high-quality compound fertilizer.
Guanite molecular formula is Mg (NH4) PO46H2O, is orthorhombic system, is excellent nitrogenous-phosphatic manure, molten in water
Solution degree very little, is easily crystallized out from water, and struvite crystals are made in this law, is sold after drying as outside high-quality compound fertilizer.
In step C, in the solution for generating ammonium magnesium phosphate crystal, the mol ratio of Mg elements and P element is 1~2：1 scope
It is interior and be 1：1, the mol ratio of N element and P element is 1~2：In the range of 1 and it is not 1：1.In step C, in crystallization process
Crystal seed is added, the crystal seed is selected from graininess quartz sand or graininess guanite.
The solution of the present invention mainly includes A) ammonia process of desulfurization, B) magnesium processes desulfurization and C) three steps of guanite are prepared, below
These three steps are elaborated：
Step A:
A kind of step A preferable scheme is：The sulfur-containing smoke gas of removing dust first carries out absorbing instead with ammoniacal liquor in absorption tower
Should, reaction be absorbed liquid part or all in absorption tower or outside absorption tower be oxidized, obtain ammonium sulfate or sulfur acid
Ammonium salt solution.
In commercial Application, technical process is usually：After the dedusting attracted through boiler induced-draft fan (or desulphurization devices)
Flue gas enters ammonia desulphurization absorption tower after water or the circulation washing of ammonia absorbing liquid are cooled to below 70 DEG C, and absorption tower can be single
Tower or multitower.Reaction generation (NH4)2SO3-NH4HSO3-H2O absorption liquid system, ammonia addition is controlled, makes absorbing liquid
The mol ratio of ammonia and ammonium sulfite is 1 in body：0.9~1.1, preferably 1：1 or so.In ammonia sweetening process, solution temperature (absorbs
The temperature of reaction) control is at 40~60 DEG C, and preferably 40~45 DEG C, the pH value for controlling absorbing liquid is 5.0~6.3, optimal pH control
System is 5.6 or so.The mass concentration of ammoniacal liquor is 3~28%；Air or oxygen is passed through when absorbing liquid oxidation to be aoxidized, and is aoxidized
The pH value of journey is 4.5~6.5.
Reaction principle is divided to following two steps to carry out：
(1) with the SO in the aqueous solution2And NH3Reaction based on absorption process, using ammonia by the SO in waste gas2Removing,
Obtain (NH4)2SO3-NH4HSO3-H2O absorption liquid system, carry out heat chemistry absorption process：
2NH4OH+SO2←→(NH4)2SO3+H2O (1)
SO2+(NH4)2SO3+H2O←→2NH4HSO3 (2)
NH4OH+NH4HSO3←→(NH4)2SO3+H2O (3)
Ionization equilibrium be present in inferior sulfate radical and bisulfite：
H++SO3 2-←→HSO3 - (4)
In ammonia desulfurization absorption process, formed (NH4)2SO3-NH4HSO3-H2O absorption liquid system, in the absorption liquid system
NH4HSO3To SO2Without absorbability, in the solution (NH4)2SO3To SO2With good absorbability, it is in ammonia process
Main absorber.Because of NH in the solution4HSO3To SO2Without absorbability, so NH in solution4HSO3Reach certain dense
, it is necessary to take measures to handle when spending, ammonia ammonium sulphate process flue gas desulphurization system, using air oxidation and the controlling measurement of ammonia is added
NH in absorbent solution4HSO3Concentration, ammonia, the molar concentration rate of ammonium sulfite pass through the pH value of solution and reacted in absorbent solution.Institute
So that the control of ammonia ammonium sulphate process flue gas desulfurization course absorbing liquid pH value is extremely important.
(2) an ammonium sulfite part for generation recycles as absorbent again, and another part is in absorption tower or absorbs
Ammonium sulfate is oxidized in oxidation trough (or pond) outside tower.To improve oxidation efficiency, stirring, interior setting static mixing can be used
Device, force the measures such as outer circulation.
And the air oxidation that ammonium sulfite, bisulfite ammonium salt solution are blasted is mended ammonia and adjusted into ammonium sulfate, ammonium bisulfate solution
PH value is saved, neutralizes acid salt NH4HSO4, generate ammonium sulfate.
Using air to ammonium sulfite, ammonium bisulfite aoxidize, this process be by caused by flue gas desulfurization absorbing reaction not
Ammonium sulfate of the stable intermediate product sulfite oxidation into stabilization.Main oxidation reaction is represented simply as：
2NH4HSO3+O2→2NH4HSO4 (1)
2(NH4)2SO3+O2→2(NH4)2SO4 (2)
Discharge system absorbing liquid ammonium bisulfite content is typically much higher than sulfurous acid caused by ammonia ammonium sulphate process flue gas desulfurization
Ammonium content, so ammonia ammonium sulphate process flue gas desulfurization absorbs the mainly reaction (1) that liquid oxidation occurs.The easy oxygen of ammonium bisulfite
Change, oxidation reaction can occurs at normal temperatures, and temperature rise, oxidation reaction is accelerated.The heat of control ammonia type flue gas desulfurizing process,
Water balance, make the temperature control of the flue gas discharge ammonia process of desulfurization between 40~60 DEG C.
Ammonia regulation pH value is mended, neutralizes acid salt NH4HSO4, generate ammonium sulfate：
NH4HSO4+NH4OH→(NH4)2SO4+H2O (3)
Because the flue gas after ammonia type flue gas desulfurizing enters magnesium method flue gas desulphurization system, therefore the discharge cigarette of ammonia type flue gas desulfurizing
Gas is washed with water, to reduce the SO discharged in flue gas without using water washing at the discharge flue gas of magnesium method flue gas desulphurization2With ammonia with
And salt.
Oxidation gained ammonium sulfate send step C.
The scheme that can be selected is to send ammonium sulfate obtained by partial oxidation to ammonium sulfate crystallization device, produce solid sulfur
Sour ammonium, ammonium sulfate obtained by partial oxidation send step C.
The ammonia escaped in flue gas depends on the concentration with absorbing liquid sulfite ammonium.In absorption process, (NH is formed4)2SO3-
NH4HSO3-H2O absorption liquid system, NH in the absorption liquid system4HSO3To SO2Without absorbability, (NH in the solution4)2SO3To SO2With good absorbability, it is the main absorber in ammonia process.Ammoniacal liquor is to SO2Assimilation effect it is poor, when
Ammonia in absorbing liquid：Ammonium sulfite=1:During 1 (mol ratio) concentration, assimilation effect is best.Because of NH in the solution4HSO3To SO2Do not have
There is absorbability, so NH in solution4HSO3, it is necessary to take measures to handle when reaching finite concentration, ammonia ammonium sulphate process flue gas takes off
Sulphur system, using air oxidation and add NH in the controlling measurement absorbent solution of ammonia4HSO3Concentration, ammonia, sulfurous acid in absorbent solution
The molar concentration rate of ammonium is reacted by the pH value of solution.So the control of ammonia ammonium sulphate process flue gas desulfurization course absorbing liquid pH value is non-
It is often important.
Step B:
Flue gas after ammonia desulfurization absorption carries out next step magnesium sweetening process, and with general industry magnesia powder, (purity is about
85%~90%) curing slurries make absorbent, with the SO in flue gas2Reaction generation magnesium sulfite, magnesium sulfite further aoxidize,
Generate magnesium sulfate.
A kind of preferable scheme of this step is：Still the flue gas of sulfur-bearing uses desulfurizing agent Mg (OH) after processing of step A2
Desulfurization process is carried out in magnesium processes absorption tower and obtains magnesium sulfite, some or all of magnesium sulfite is in or beyond magnesium processes absorption tower
Portion is oxidized, and obtains magnesium sulfate or containing magnesium sulfate solution.
In oxidizing process, a kind of preferable scheme is：Magnesium sulfite is passed through air or oxygen when aoxidizing and aoxidized, oxygen
Caused SO during change2Return in magnesium processes absorption tower and carry out desulfurization process；Or phosphoric acid is further added in oxidizing process
Hydrogen diamino is with caused SO in assist absorption oxidizing process2, the flue gas after further recycling step A ammonia type flue gas desulfurizings enters
Ammonia, the ammonium sulfate etc. of the entrainment of magnesium method flue gas desulphurization system produce the material of aerosol.
The magnesium processes that the present invention is said, desulfurizing agent refer to Mg (OH)2, it is specifically as follows fine ore or hydroxide containing magnesia
Magnesium, i.e. magnesium oxide method and hydroxide magnesium processes.Wherein desulfurizing agent Mg (OH)2Obtained after being mixed by MgO with hot water, can also be straight
Connect and Mg (OH) is added into magnesium processes absorption tower2。
Magnesium processes desulfurization reaction mechanism：
The desulphurization mechanism of magnesia is similar to the desulphurization mechanism of calcium oxide, is all basic anhydride and water reaction generation hydrogen-oxygen
Compound, then with sulfur dioxide be dissolved in water generation sulfurous acid solution carry out acid-base neutralization reaction.
Reaction principle is divided to following two steps to carry out：
(1) with the SO in the aqueous solution2With Mg (OH)2Reaction based on absorption process, utilize Mg (OH)2By in waste gas
SO2Removing, carry out heat chemistry absorption process：
Mg(OH)2+SO2+5H2O←→Mg SO3.6H2O↓ (1)
Mg SO3+SO2+H2O←→Mg(HSO3)2↓ (2)
Mg(HSO3)2+Mg(OH)2+10H2O←→2Mg SO3.6H2O↓ (3)
In absorbing liquid, there is ionization equilibrium in inferior sulfate radical and bisulfite：
H++SO3 2-←→HSO3 - (4)
A magnesium sulfite part for generation recycles as absorbent again, and another part is in absorption tower or outside absorption tower
Oxidation trough (or pond) in be oxidised with air to magnesium sulfate.
To improve oxidation efficiency, stirring, interior setting static mixer can be used, force the measures such as outer circulation.
(2) magnesium sulfite, magnesium bisulfite are aoxidized using air.Main oxidation reaction is represented simply as：
Mg(HSO3)2+1/2O2+6H2O→MgSO4·7H2O↓ (1)
2Mg SO3+1/2O2+7H2O→MgSO4·7H2O↓+SO2↑ (2)
SO caused by oxidizing process2Sulphite is changed into absorbing liquid reaction and remove in absorption tower.
In magnesium sweetening process, solution temperature control is at 45~50 DEG C, and solution ph control range is 6.0~6.8, Optimal pH
Value control is 6.3 or so.Magnesium sulfite reaction condition in absorption tower：Solution temperature control is at 45~50 DEG C, solution pH value control
Scope processed is 6.0~6.8, and optimal pH is controlled 6.3 or so.
Reaction condition when magnesium sulfite is oxidized outside absorption tower, solution temperature control is at 45~50 DEG C, solution ph
Control range is 6.3~6.5, and optimal pH is controlled 6.3 or so.
Flue gas after magnesium processes desulfurization, it is washed with water, demisting is discharged after reaching environmental protection standard requirement.
Magnesium sulfate, Adlerika or the magnesium desulfurization absorbing liquid of oxidation gained all send step C.
Step C：
This step is to prepare guanite.
A kind of scheme of this step is：The sulfur acid that ammonium sulfate or liquid containing ammonium sulfate solution that step A is obtained, step B are obtained
The aqueous solution of magnesium solution and phosphorous acid group mixes in struvite crystallization reactor, and the pH value for adding acid or alkali regulation solution is entered
Row crystallization, generation ammonium magnesium phosphate (MgNH4PO46H2O, are commonly called as：Guanite) crystal；
In a kind of simple scheme, ammonium sulfate and Adlerika that step A and step B come, the water with phosphorous acid group
Solution mixes in proportion, and course of reaction adds the pH value of acid-base accommodation control solution.Generate the ammonium magnesium phosphate of indissoluble
(MgNH4PO46H2O, it is commonly called as：Guanite) crystal.
Guanite is a kind of extremely complex crystalline compounds.The change of pH value has very big shadow to its reaction of formation in water
Ring, with the change of pH value, the NH in water4 +、Mg2+And PO4 3-Concentration constantly changes, when the activity product of these three ions has exceeded phosphorus
During solubility product constant (Ksp) of sour ammonium magnesium, then solution supersaturation precipitates.The activity of these three ions depends on system
Solvable Mg, N and phosphatic concentration in pH value and solution.
Utilize PO4 3-、Mg2+、NH4+The complex reaction of three, generate stable sediment, production composite fertilizer guanite.Should
React for ionic, reaction rate is fast, can quickly handle desulfurization absorbing liquid.The phosphate radical for preparing guanite reactor outlet contains
After amount is down to below 30mg/L, reacted waste water is handled into waste plant.
The main chemical reactions occurred during guanite is formed are as follows：
Mg++NH4 ++P04 3-+6H2O--MgNH4PO4·6H2O↓ (1)
Mg2++NH4 ++HPO4 -+6H2O----MgNH4PO4·6H2O↓+H+ (2)
Mg2++NH4 ++H2PO4 -+6H2O-----MgNH4PO4·6H2O↓+2H+ (3)
This method has that reaction rate is fast, simple operation and other advantages.The guanite precipitation of generation contains the kind such as nitrogen, phosphorus, magnesium
Nutrient, it is a kind of good slow-release fertilizer.Therefore the desulfurizing agent ammonia, the recycling of magnesium that ammonia flue gas desulfurization technique uses can be realized
Reuse.
A kind of detailed process is that ammonia desulfurization absorbing liquid and magnesium desulfurization absorbing liquid are sent into struvite crystallization by pump and reacted
Device, phosphate is added in struvite crystallization reactor, add the pH value of acid or alkali regulation course of reaction.
The aqueous solution of phosphorous acid group in the present invention is formulated with water by phosphoric acid or phosphate or is phosphoric acid
The waste water of salt.Crystallization temperature is 25~35 DEG C, preferably 30 DEG C or so.
Acid and ammoniacal liquor reaction generation ammonium hydrogen phosphate and DAP, DAP are good desulfurizing agents, therefore can be with
DAP is added in magnesium method flue gas desulphurization outer circulation oxidation trough, discharged with assist absorption magnesium sulfite oxidizing process
SO2.Ammonia, the ammonium sulfate that can also be carried secretly in recycling step A tail gas.Because in magnesium method flue gas desulphurization system, in desulfurization temperature and
Under the conditions of acid-base value, ammonium phosphate magnesium salts is generated, send step C to recycle.
Based on the complexity of struvite crystallization process, struvite crystallization reactor need to meet following reaction condition：
(1) crystallization reaction process pH value：When pH value is higher, the magnesium salts of addition is easier generation Mg under strongly alkaline conditions
(OH)2Precipitation, reduces Mg in solution2+Concentration, thus be unfavorable for the recovery of nitrogen and phosphorus；
When pH value is relatively low, solution is in acidity.H+Concentration is larger, as can be seen that will be unfavorable for reacting from reaction mechanism
Carried out to positive direction.The sediment rate of settling is slower after pH value is more than 10.0, and gained precipitation is more loose, there is more floccule.
Now the residual quantity of ammonia nitrogen can raise.This is probably to generate Mg later there occurs side reaction more than 10.0 due to pH value3
(PO4)2、Mg(OH)2Deng accessory substance, it is unfavorable for the recovery of ammonia nitrogen in absorbing liquid.
PH value has ammonia nitrogen residual quantity relatively low in higher phosphorus utilization and solution in the range of 8.5~10.5.pH
Be worth for 9.5 when solution in the mass concentration of residual nitrogen also obtain minimum value.
(2) Mg, N, P mol ratio：When the recovery desulfurization of the guanite precipitation method absorbs the ammonia nitrogen and magnesium in liquid, its ammonia nitrogen and magnesium
Organic efficiency and asynchronous.According to recovery ammonia nitrogen and the specific purposes of magnesium, MgNH is generated4PO4Crystal, theoretical n (Mg)：n
(N)：N (P)=1：1：L, but it is too high and bring secondary dirt due to prevent from reclaiming ammonia nitrogen and phosphorus concentration in the waste water after guanite
Dye.N (Mg) under normal circumstances：N (P) is more than 1, and n (N)：N (P) is more than 1, and specific Mg, N, P mol ratio is because of solution ph, anti-
Answer the different and different of condition etc.；In a kind of scheme, in the solution for generating ammonium magnesium phosphate crystal, Mg elements and P element
Mol ratio 1~2：In the range of 1 and it is not 1：1, preferably 1.5~1.1：1, more preferably 1.3~1.2：1, N element and P element
Mol ratio 1~2：In the range of 1 and it is not 1：1, preferably 1.2~1.01：1, more preferably 1.1~1.02：1；
(3) add crystal seed in crystallization reactor, crystal seed can use it is of the prior art it is a variety of being capable of institute in the method
The actual seed crystal of application, in a kind of preferred scheme, crystal seed is selected from graininess quartz sand or graininess guanite, particularly particle
The quartz sand of shape, it can promote crystallization process and make reacted MgNH4PO4It is attached to quartz sand precipitation, easy cleaning.
Further, the following condition of struvite crystallization reactor can also be controlled：
(4) water come out from crystallization reactor top, can will contain MgNH by sand filter4PO4Short grained devolatilization
After be discharged into wastewater treatment equipment.
(5) it is attached to MgNH on quartz sand4PO4Bead is sent to after bead collecting box is dried from crystallization reactor bottom and packed.
The precipitated product of the crystallized reaction generation of this step can be used as high-grade phosphorus ore or slow-release fertilizer, have higher
Economic value.
In the prior art, the byproduct that ammonia type flue gas desulfurizing is generally prepared is ammonium sulfate, the byproduct that magnesium processes are generally prepared
It is epsom salt, as being sold outside fertilizer, secondary valence value is not high, and ammonium sulfate, magnesium sulfate evaporative crystallization need to consume largely
Heat, processing cost is of a relatively high, and byproduct recovery cost is big.Ammonia type flue gas desulfurizing technology is used alone often by the escaping of ammonia and tail
Plumage problem, secondary pollution can be caused, using the advantage of two kinds of technologies, new flue gas desulfurization by-product guanite provided by the invention
Method, in addition to the efficiently single phosphorus magnesium compound fertilizer guanite of by-product, the escaping of ammonia that can also effectively solve ammonia type flue gas desulfurizing is gentle
Secondary pollution problem caused by colloidal sol, reduce energy consumption.The flue gas desulfurization new technology that this law is combined using ammonia process and magnesium processes, from strict
Control ammonia-magnesium method flue gas desulphurization condition etc. essentially eliminates the condition of ammonia mist formation, and it is gentle economically to solve ammonia damage, the escaping of ammonia
Colloidal sol problem, and change into efficient compound nitrogen phosphate fertilizer guanite by liquid is absorbed caused by combined method.
Beneficial effects of the present invention：
1) present invention is the innovation in conventional ammonia ammonium sulphate process desulfurization and magnesium-sulfuric acid magnesium processes desulfurization technical foundation and hair
Exhibition, with reference to ammonia and magnesium to the absorbability of sulfur dioxide and the advantage of process optimization, and strictly control ammonia-magnesium method flue gas desulphurization
Condition etc., each process is kept optimal electrochemical conditions, essentially eliminate the condition of ammonia mist formation, cost-effectively solve
There is the secondary pollution problem such as tail feathers in ammonia-ammonium sulfate method flue gas desulfurization ammonia damage, the escaping of ammonia and flue gas；
2) ammonia and magnesium resource in the technology recovered flue gas desulfurizing agent, height is changed into by liquid is absorbed caused by combined method
The compound nitrogen phosphate fertilizer guanite of effect, increase the high-grade recycling of accessory substance, turn waste into wealth, can be carried with the treatment of wastes with processes of wastes against one another
The economic benefit of high flue gas desulfurization；
3) technology recovery accessory substance no longer needs ammonia ammonium sulphate process desulfurization and magnesium-sulfuric acid magnesium processes desulfurization technology using steaming
The method recovery ammonium sulfate or magnesium sulfate, energy consumption of hair water removal Crystallization Separation significantly reduce.
Brief description of the drawings
Fig. 1 is a kind of method process flow diagram of ammonia magnesium method flue gas desulphurization of the present invention；
In figure, prepared by 1-ammoniacal liquor；2-ammonia type flue gas desulfurizing；3-magnesium method flue gas desulphurization；4—Mg(OH)2Prepare；5-system
Standby guanite；6-ammonia；7-water；8-ammoniacal liquor；9-contain SO2Flue gas；10-through ammonia flue gas after desulfurization；11—Mg(OH)2Solution；
12-MgO powder；13-hot water；14-after magnesium desulfurization MgSO4Solution；15-after ammonia desulfurization (NH4)2SO4Solution；16-bird
Coprolite；17-sewage disposal；18-desulphurization system discharges flue gas；19-air；20-acid or alkali；21-phosphoric acid or phosphate
Liquid；22-gravel.
Embodiment
The method of the present invention is described further below in conjunction with drawings and examples.
The method technological process of the ammonia magnesium method flue gas desulphurization of the present invention is as shown in Figure 1：Ammonia (6) compares as requested with water (7)
Example, is configured to finite concentration ammoniacal liquor (8), for ammonia type flue gas desulfurizing (2).Containing SO2Prepared first with ammoniacal liquor after flue gas (9) dedusting
(1) ammoniacal liquor prepared by step reacts in absorption tower, carries out ammonia type flue gas desulfurizing (2).Ammonia type flue gas desulfurizing process, in flue gas
SO2Generation NH is reacted with ammonia4HSO3(NH4)2SO3, by controlling absorbing liquid pH value 5.0-6.3,40-60 DEG C of temperature is absorbed, is inhaled
It is 1 to receive the mol ratio of ammonia and ammonium sulfite in liquid：1 or so；A part of absorbing liquid can be exported in absorption process to be aoxidized, and also may be used
Directly aoxidized in absorption tower.Air (19) oxidation, oxidizing process pH value 4.5-6.5, by sulfurous acid are blasted in absorbing liquid
Ammonium is oxidized to ammonium sulfate, (the NH after ammonia desulfurization4)2SO4Solution goes to prepare guanite (5).The temperature adjusting of flue gas after processing is extremely
40-60 DEG C, it is prepared to enter into next step.
Flue gas (10) after ammonia type flue gas desulfurizing, still containing a certain amount of SO2And ammonia, and sulfate is entrained with, enter
Next step magnesium method flue gas desulphurization (3).The desulfurizing agent Mg (OH) of magnesium method flue gas desulphurization (3)2Solution is by Mg (OH)2Prepare (4) step
There is provided, after being mixed with MgO powder (12) with hot water (13), Mg (OH) should be generated2.It is remaining in magnesium method flue gas desulphurization (3) process, flue gas
Under SO2Continue and Mg (OH)2Reaction generation MgSO3.6H2O and Mg2H(SO3)3, in magnesium sweetening process, solution temperature control exists
45~50 DEG C, solution ph control range is 6.0~6.8, and optimal pH is controlled 6.3 or so.Magnesium sulfite is in absorption tower
Reaction condition：Solution temperature control is at 45~50 DEG C, and solution ph control range is 6.0~6.8, and optimal pH is controlled 6.3
Left and right.
Reaction condition when magnesium sulfite is oxidized outside absorption tower, solution temperature control is at 45~50 DEG C, solution ph
Control range is 6.3~6.5, and optimal pH is controlled 6.3 or so.
The scheme that can be selected is：Acid and ammoniacal liquor reaction generation ammonium hydrogen phosphate and DAP, DAP are good
Good desulfurizing agent, therefore DAP can be added in magnesium method flue gas desulphurization outer circulation oxidation trough, with assist absorption sulfurous acid
The SO that magnesium oxidizing process discharges2.Ammonia, the ammonium sulfate that can also be carried secretly in recycling step A tail gas.Because in magnesium method flue gas desulphurization system
In system, under the conditions of desulfurization temperature and acid-base value, ammonium phosphate magnesium salts is generated, send step C to recycle.
Magnesium sulfite, the magnesium bisulfite obtained using air to desulfurization carries out oxidation generation MgSO4·7H2O.Aoxidized
SO caused by journey2Sulphite is changed into absorbing liquid reaction and remove in absorption tower.Flue gas after magnesium method flue gas desulphurization,
Discharged after washing, demisting require up to environmental protection standard.
Contain MgSO after magnesium method flue gas desulphurization4Solution goes to prepare guanite (5).(the NH after ammonia type flue gas desulfurizing4)2SO4
Solution (15), the MgSO after magnesium method flue gas desulphurization4Solution, acid or alkali (20), phosphoric acid or phosphatic liquid (21), equipped with
Carry out preparing guanite (5) in the crystallization reactor of gravel (22), control ph is in the range of 8.5-10.5, under normal circumstances instead
Temperature is answered at 30 DEG C or so, n (Mg)：N (P) is more than 1, and n (N)：N (P) is more than 1, and specific Mg, N, P mol ratio is because of pH value of solution
Value, reaction condition etc. it is different and different.Prepare the course of reaction of guanite (5), NH4 +, Mg2+, PO4 3-Formed
MgNH4PO4·6H2O crystal is guanite.
Granular quartz sand is added in crystallization reactor, promotes crystallization process and makes reacted MgNH4PO4Attachment
Precipitated in quartz sand, easy cleaning；
The water come out from crystallization reactor top, will contain MgNH by sand filter4PO4It is discharged into after short grained devolatilization
Sewage disposal (17).
It is attached to MgNH on quartz sand4PO4Bead is sent to after bead collecting box is dried from crystallization reactor and packed, and makees ammonia phosphorus
Sold outside composite fertilizer.
Embodiment 1
Exemplified by handling 220t/h boiler smokes, its exhaust gas volumn 270000Nm3/ h (operating mode exhaust gas volumn 398600m3/ h), enter
125 DEG C of flue-gas temperature of mouth, inlet flue gas SO2Concentration 2000mg/Nm3, with the ammonia absorption of 5% (wt) concentration, absorbing liquid pH value
5.0-6.3,40-60 DEG C of temperature is absorbed, oxidizing process pH value 4.5-6.5, the amount of caused ammonium sulfate is 322.99kg/h
(24468.8mol/h), the molal quantity of nitrogen is 4894mol/h, SO2Removal efficiency about 29%.
Contain SO after ammonia type flue gas desulfurizing2Flue gas enters magnesium method flue gas desulphurization device, with Mg (OH)2As desulfurizing agent
Absorb, SO2Removal efficiency is about the 69% of total amount.Two step sweetening processes add up to SO2Removal efficiency is the 98% of total amount, caused sulphur
Sour magnesium amount 698.625kg/h (5821.88mol/h), Mg molal quantity is 5821.88mol/h.
Struvite crystallization reactor pH value is controlled to have higher tp removal rate and relatively low in the range of 8.5-10.5
Ammonia nitrogen residual quantity.The mass concentration of residual phosphorus reaches minimum value when pH value is 9.5, is 12.98mg/L, corresponding phosphorus utilization reaches
It is 99.76% to maximum.Now the mass concentration of residual nitrogen also obtains minimum value in water, is 201.80mg/L.
Phosphate radical is provided with sodium phosphate, the amount of sodium phosphate is 4663mol/h (890.633kg/h), is 9.5, n in pH value
(Mg)： n(N)：N (P)=1.25：1.05：L, stir speed (S.S.) are 200r/min or so.20min is reacted, precipitates 20min conditions
Under, for phosphorus utilization up to 99.96%, the residual quantity of phosphorus is 2.20mg/L, and the rise of ammonia nitrogen concentration in waste water will not be caused and
Bring secondary pollution.
Granular quartz sand, reacted MgNH are added in crystallization reactor4PO4It is attached to quartz sand precipitation.
The water come out from crystallization reactor top, will contain MgNH by sand filter4PO4It is discharged into after short grained devolatilization
Waste water biochemical treatment device.
It is attached to MgNH on quartz sand4PO4Bead is sent to after bead collecting box is dried from crystallization reactor bottom and packed, and does
Contain MgNH in solid after dry4PO4Amount be about 637.29kg/h.
The technique water washing flue gas of the absorption tower upper supplementary of magnesium method flue gas desulphurization.Flue gas removes by folded plate demister and electricity
In day with fog heel row amplification air.Go out the adsorption tower smoke temperature 50 C of magnesium method flue gas desulphurization, exiting flue gas SO2The mg/ of concentration≤80
Nm3, desulfuration efficiency >=98%,.The average ＜ 30mg/m of dust content are discharged after desulfurizer3, the average ＜ of amount of ammonia slip
0.2kg/h。
Embodiment 2
Exemplified by handling 220t/h boiler smokes, its exhaust gas volumn 270000Nm3/ h (operating mode exhaust gas volumn 398600m3/ h), enter
125 DEG C of flue-gas temperature of mouth, inlet flue gas SO2Concentration 2000mg/Nm3, with the ammonia absorption of 5% (wt) concentration, absorbing liquid pH value
5.0-6.3,40-60 DEG C of temperature is absorbed, oxidizing process pH value 4.5-6.5, the amount of caused ammonium sulfate is 322.99kg/h
(24468.8mol/h), the molal quantity of nitrogen is 4894mol/h, SO2Removal efficiency about 29%.
Contain SO after ammonia type flue gas desulfurizing2Flue gas enters magnesium method flue gas desulphurization device, with Mg (OH)2As desulfurizing agent
Absorb, SO2Removal efficiency is about the 69% of total amount.Two step sweetening processes add up to SO2Removal efficiency is the 98% of total amount, caused sulphur
Sour magnesium amount 698.625kg/h (5821.88mol/h), Mg molal quantity is 5821.88mol/h.
Struvite crystallization reactor pH value is controlled to have higher tp removal rate and relatively low in the range of 8.5-10.5
Ammonia nitrogen residual quantity.The mass concentration of residual phosphorus reaches minimum value when pH value is 9.5, is 12.98mg/L, corresponding phosphorus utilization reaches
It is 99.76% to maximum.Now the mass concentration of residual nitrogen also obtains minimum value in water, is 201.80mg/L.
The waste water of liquid handling phosphoric acid ammonium dihydrogen is absorbed with above flue gas desulfurization, magnesium method flue gas desulphurization is such as absorbed into liquid
Exhaust, Mg molal quantity is 5821.88mol/h, is 9.5, n (Mg) in pH value：n(N)：N (P)=1.25：1.05：Under l
Reaction, ammonium dihydrogen phosphate provide phosphate radical 4657.504mol/h, and ammonium dihydrogen phosphate provides ammonium root 4657.504mol/h, insufficient
The absorbing liquid of ammonium root part ammonia type flue gas desulfurizing, the ammonium root amount that the absorbing liquid of ammonia type flue gas desulfurizing provides is 1164.376
mol/h.Stir speed (S.S.) is 200r/min or so.20min is reacted, under the conditions of precipitating 20min, the phosphorus rate taken off in waste water is reachable
99.96%, the residual quantity of phosphorus is 2.20mg/L, and will not cause the rise of ammonia nitrogen concentration in waste water and bring secondary pollution.
Granular quartz sand, reacted MgNH are added in crystallization reactor4PO4It is attached to quartz sand precipitation.
The water come out from crystallization reactor top, will contain MgNH by sand filter4PO4It is discharged into after short grained devolatilization
Waste water biochemical treatment device.
It is attached to MgNH on quartz sand4PO4Bead is sent to after bead collecting box is dried from crystallization reactor bottom and packed, and does
Contain MgNH in solid after dry4PO4Amount be about 797.59kg/h.
The technique water washing flue gas of the absorption tower upper supplementary of magnesium method flue gas desulphurization.Flue gas passes through folded plate demister and/or electricity
In demister heel row amplification air.Go out the adsorption tower smoke temperature 50 C of magnesium method flue gas desulphurization, exiting flue gas SO2Concentration≤
80mg/Nm3, desulfuration efficiency >=98%.The average ＜ 30mg/m of dust content are discharged after desulfurizer3, the average ＜ of amount of ammonia slip
0.2kg/h。
Comparative example 1
Exemplified by handling 220t/h boiler smokes, its exhaust gas volumn 270000Nm3/ h (operating mode exhaust gas volumn 398600m3/ h), enter
125 DEG C of flue-gas temperature of mouth, inlet flue gas SO2Concentration 2000mg/Nm3, with the ammonia absorption of 5% (wt) concentration, absorbing liquid pH value
5.0-6.3, absorb 40-60 DEG C of temperature, oxidizing process pH value 4.5-6.5, SO2Removal efficiency about 95%.Exiting flue gas SO2Concentration≤
100mg/Nm3, export ammonia density≤100mg/Nm3, exiting flue gas carrying droplet 75mg/Nm3, produce sulphur ammonium (38%) about
2873kg/h, evaporation and concentration need quantity of steam about 3.1t/h, obtain ammonium sulfate solids 1058kg/h, amount of ammonia slip is average>2kg/
h。
Although the present invention is described and illustrated here by some or some particular arrangements, but its purpose and limit is not lain in
The details is made, because may have various modifications and structure change in the range of patent requirements, without departing from spirit.
Part that the present invention does not relate to is same as the prior art or can be realized using prior art.
Claims (9)
1. a kind of ammonia-magnesium combination smoke desulfurization and the method for by-product guanite, it is characterised in that comprise the following steps：
A, sulfur-containing smoke gas first carries out the ammonia process of desulfurization, obtains ammonium sulfate or liquid containing ammonium sulfate solution；
B, the flue gas after processing of step A carries out magnesium processes desulfurization again, obtains magnesium sulfate or containing magnesium sulfate solution；
C, by the obtained magnesium sulfate of the obtained ammonium sulfate of step A or liquid containing ammonium sulfate solution, step B or containing magnesium sulfate solution and contain
The pH value generation ammonium magnesium phosphate crystal of solution is adjusted after the aqueous solution mixing of phosphate radical.
2. according to the method for claim 1, it is characterised in that in step, the sulfur-containing smoke gas of removing dust first exists with ammoniacal liquor
Carrying out absorbing reaction in absorption tower, be absorbed part or all of liquid of reaction is oxidized in absorption tower or outside absorption tower,
Obtain ammonium sulfate or liquid containing ammonium sulfate solution.
3. according to the method for claim 2, it is characterised in that in step, the temperature of absorbing reaction is 40~60 DEG C, excellent
40~45 DEG C are selected, absorbing reaction generation (NH4)2SO3-NH4HSO3-H2The mol ratio of O absorbing liquid, wherein ammonia and ammonium sulfite is
1：0.9~1.1, preferably 1：1；The pH value for controlling absorbing liquid is 5.0~6.3, preferably 5.6；The mass concentration of ammoniacal liquor be 3~
28%；Air or oxygen is passed through when absorbing liquid oxidation to be aoxidized, the pH value of oxidizing process is 4.5~6.5；Through processing of step A
The temperature adjusting of flue gas afterwards is to 45-60 DEG C.
4. according to the method for claim 1, it is characterised in that in stepb, the flue gas of still sulfur-bearing is adopted after processing of step A
With desulfurizing agent Mg (OH)2Desulfurization process is carried out in magnesium processes absorption tower and obtains magnesium sulfite, some or all of magnesium sulfite
It is oxidized on magnesium processes in or beyond the absorption tower, obtains magnesium sulfate or containing magnesium sulfate solution.
5. according to the method for claim 4, it is characterised in that in stepb, the desulfurizing agent Mg (OH)2By MgO and hot water
Obtained after mixing, or Mg (OH) is directly added into magnesium processes absorption tower2；Temperature is 45~50 DEG C in desulfurization process, desulfurization
Reacting solution pH value in journey is 6.0~6.8, preferably 6.3.
6. according to the method for claim 4, it is characterised in that in stepb, magnesium sulfite is passed through air or oxygen when aoxidizing
Gas is aoxidized, caused SO in oxidizing process2Return in magnesium processes absorption tower and carry out desulfurization process；Or add in oxidizing process
Enter DAP with caused SO in assist absorption oxidizing process2。
7. according to the method for claim 1, it is characterised in that in step C, the scope of the pH value is 8.5-10.5；Institute
The aqueous solution for stating phosphorous acid group is formulated by phosphoric acid or phosphate with water；The phosphate is selected from ammonium phosphate, sodium phosphate or phosphorus
Sour potassium；Crystallization temperature is 25~35 DEG C, preferably 30 DEG C.
8. according to the method for claim 7, it is characterised in that in step C, in the solution for generating ammonium magnesium phosphate crystal, Mg
The mol ratio of element and P element is 1~2：In the range of 1 and it is not 1：1, preferably 1.5~1.1：1, more preferably 1.3~1.2：1, N
The mol ratio of element and P element is 1~2：In the range of 1 and it is not 1：1, preferably 1.2~1.01：1, more preferably 1.1~1.02：1.
9. according to the method for claim 7, it is characterised in that in step C, crystal seed, the crystal seed are added in crystallization process
Selected from graininess quartz sand or graininess guanite.
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