CN107497270A - The method of ammonia calcium combined desulfurization - Google Patents
The method of ammonia calcium combined desulfurization Download PDFInfo
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- CN107497270A CN107497270A CN201710298536.XA CN201710298536A CN107497270A CN 107497270 A CN107497270 A CN 107497270A CN 201710298536 A CN201710298536 A CN 201710298536A CN 107497270 A CN107497270 A CN 107497270A
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- desulfurization
- tower
- ammonia
- calcium
- mixed solution
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/48—Sulfites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Inorganic Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The method of ammonia calcium combined desulfurization, the present invention include a kind of new technological flow of coal-burning boiler tail flue gas desulfurization, and the main inventive scheme of the technique is：Tail gas desulphurizing system sets desulfurizing tower, absorbed in tower using low concentration ammonium sulfurous, ammonium sulfate, calcium chloride mixed solution, mixed solution after desulfurization uses carbide slurry (PVC accessory substances outside tower, principal component Ca (OH) 2) causticization regeneration, ammonia after regeneration is dissolved in recycling in mixed solution, CaSO4 (gypsum) and CaSO3 (calcium sulfite) desulfurization Precipitation, the solid material of precipitation and utilization is further processed.
Description
Technical field：The method of ammonia calcium combined desulfurization is applied to the tail gas desulfurization field of coal-burning boiler.
Background technology：The tail gas desulfurization of domestic common coal-burning boiler uses ammonia desulfurizing process at present, but ammonia process takes off
Sulphur technique is common, and there are the following problems：
1st, chimney tailing problem, due to the limitation of process system, aerosol phenomenon turns into ammonia method desulfurizing system to be difficult to
Solve the problems, such as.
2nd, the corrosion problems of ammonia method desulfurizing system, because the ammonia process of desulfurization is strong acid weak base system, process stream corrosion is tight
Weight, equipment corrosion, which has become, restricts the persistent ailment that ammonia method desulfurizing system is run steadily in the long term.
The content of the invention：
Summary：The present invention includes a kind of new technology of coal-burning boiler tail flue gas desulfurization, the main inventive scheme of the technique
It is：Tail gas desulphurizing system sets ammonia calcium combined desulfurization tower, is mixed in tower using low concentration ammonium sulfite, ammonium sulfate, calcium chloride molten
Liquid absorbs, and the mixed solution after desulfurization uses carbide slurry (PVC accessory substances, principal component Ca (OH) outside tower2) causticization regeneration, regeneration
Ammonia afterwards is dissolved in recycling in mixed solution, CaSO4(gypsum) and CaSO3(calcium sulfite) desulfurization Precipitation, precipitation
Utilization is further processed in solid material.
The process program of invention：
First, low concentration ammonium sulfurous, ammonium sulfate, the density domination of calcium chloride mixed solution arrive in 1050 gram per liters in desulfurizing tower
1200 gram per liters or so, wherein entering the control of tower ammonia density 1% to 5% or so.Taken off using low concentration desulfurization mixed solution
Sulphur absorbs.
Research data shows, causes main three big reasons of aerosol phenomenon to be in ammonia method desulfurizing system：Flue gas flow rate mistake
Hurry up, desulfurization mixed solution excessive concentration, desulfurization mixed solution temperature it is too high.
In ammonia method desulfurizing system operation, aerosol production rate increases and increased with doctor solution concentration；This mainly due to
The higher desulfurization drop of desulfurization agent concentration easily evaporates precipitation aerosol particles；Meanwhile desulfurization agent concentration it is higher when, be advantageous to gaseous state
Ammonia volatilizees effusion from doctor solution, increases ammonia density in gas phase, the aerosol amount with the sulfur dioxide reaction generation in flue gas
Increase.
Here is an experiment：Oversaturated ammonium sulfate and in the solution mix suitable quantity of water be configured to 20% sulfuric acid
Ammonium is as doctor solution, and aerosol production result is as shown in Figure 1.
From the point of view of the actual operating mode of desulphurization system, the liquid-tight height of spending of desulfurizing tower entoplasm is the pass for causing aerosol phenomenon
Key reason, in desulfurizing tower under the operation of slurries high density crystallization processes, concentration of slurry can more and more higher, in the environment of high velocity smoke
Substantial amounts of aerosol, and extremely difficult removing after aerosol generation can be produced, even if long time can be also present by having arrived in air.
Carrying out desulfurization absorption less than the low concentration desulfurization ammonium sulfate slurries of 1200 gram per liters using density has following benefit：
A, the whole absorbent capacity on absorption tower is improved, passes through operative practice and theoretical research, the operation of low concentration desulfurization slurry
Operating mode is to SO2Absorbability be higher than high concentration operating condition.
B, equipment attrition is reduced, the slurries of low concentration are free of the crystallization of graininess, belong to normal fluid liquid, so as to
Avoid, because the crystallization of fluid inclusion granule is to a series of infringements caused by equipment, pipeline etc., reducing equipment attrition, reducing production dimension
Protect cost, the service life of extension device.
The 2nd, settling tank and causticization regenerated reactor are set, launch a certain proportion of carbide slag in the solution, pass through carbide slag and sulphur
Sour ammonium, ammonium sulfite carry out causticizing reaction, utilize Ca (OH)2Strong basicity, regeneration output NH3 be dissolved in mixed solution, precipitate
Separate out CaSO4(gypsum) and CaSO3(calcium sulfite).
The process chemistry reacts：
(NH3)2SO4+Ca(OH)2=CaSO1↓+2NH3
(NH3)2SO3+Ca(OH)2=CaSO3↓+2NH3
Pass through CaSO caused by precipitation4(gypsum) CaSO3(calcium sulfite) carries out desulfurization precipitation, while CaSO4(gypsum)
CaSO3(calcium sulfite) possesses porous characterization of adsorption, and it is heavy that the complex compound that can fail to understand fractions in slurries adsorbs
Form sediment.
The schematic diagram of accompanying drawing 1 is shown in ammonia calcium combined desulfurization technological process：
Simultaneously because the course of reaction can produce substantial amounts of NH3, reclaim this part NH3, and by the causticizing reaction of desulfurization slurry
Supernatant (is rich in substantial amounts of NH3) return to absorption tower and be continuing with, control back into tower NH3Concentration 3% or so.Recovery
NH3Operating cost can be saved, according to NH per ton3About 2000 yuan of calculating, every 4 tons or so carbide slags (about 200 yuan of totle drilling cost) can
To reclaim about 1 ton of liquid ammonia solution, about 1800 yuan of value is created in recovery.
It is expected that effect, under the low concentration slurries operating mode of absorption tower, from the point of view of early stage operating experience, desulfurized effect is with respect to mesh
Before improve, entrance so2 concentration be less than 1000PPM under conditions of can solve the problem that aerosol, thiamines rain, dense smoke etc. are asked
Topic.
3rd, using oxidizing sulfur dioxide technique in the conventional ammonia process of desulfurization at present and lime stone flue gas desulfurization technique is changed, stop
With oxidative system, the power consumption of desulphurization system is reduced, it is energy-saving.
Because the present invention is using CaSO3 (calcium sulfite) progress desulfurization precipitation techniques, the use of conventional desulfurization system is changed
SO4 2+Crystallize (gypsum or ammonium sulfate) process program, it is no longer necessary to carry out oxidizing sulfur dioxide technique, not reproduction ammonium sulfate.System
The relevant device of stoppage in transit oxidative system and ammonium sulfate system in system, including oxidation fan, oxidation cycle pump, crystallization pump, dry system
A series of equipment such as system.
It is expected that the coal burning boiler of power station of every 500 tphs of evaporation capacity, annual about 4,000,000 KW that economize on electricity, convert into and save mark
About 1300 tons of coal, reduces cost about 2,000,000.
After the transformation of ammonia-calcium combined desulfurization is implemented, there will be following benefit：
1st, operating cost is greatly lowered, if production control is proper, operation operation is ripe, will no longer consume finished fluid
Ammonia；It is expected that nearly 5000 tons of liquefied ammonia can be saved every year, it is annual about 8000 tons that urea production capacity can be increased.
2nd, the amount of coming into operation of desulfuration in furnace carbide slag can be optimized, improve the utilization ratio of carbide slag.
3rd, by depositing reservoir regeneration cycle, the temperature of desulphurization system can be reduced, beneficial to the Effec-tive Function of desulphurization system.
4th, oxidative system etc. is disabled, desulphurization system is often covered and disables the auxiliary devices such as oxidation fan, economize on electricity about 4,000,000 KW every year, often
Year power cost saving about 2,000,000.
Brief description of the drawings
Fig. 1：Oversaturated ammonium sulfate and in the solution mix suitable quantity of water be configured to 20% ammonium sulfate as desulfurization
Liquid, aerosol production result.
Fig. 2：Ammonia calcium combined desulfurization technological process..
Embodiment：Ammonia method desulfurizing system is transformed, mixed in tower using low concentration ammonium sulfurous, ammonium sulfate, calcium chloride
The density domination of solution is closed in 1050 gram per liters to 1200 gram per liters or so, wherein it is left 1% to 5% to enter the control of tower ammonia density
It is right.Desulfurization absorption is carried out using low concentration desulfurization mixed solution.Settling tank and causticization regenerated reactor are set outside tower, launched in the solution
A certain proportion of carbide slag, causticizing reaction is carried out by carbide slag and ammonium sulfate, ammonium sulfite, utilized Ca (OH)2Strong basicity,
Regenerate output NH3It is dissolved in mixed solution, Precipitation CaSO4(gypsum) and CaSO3(calcium sulfite).
Claims (6)
1. tail gas desulphurizing system sets ammonia calcium combined desulfurization tower, mixed in tower using low concentration ammonium sulfurous, ammonium sulfate, calcium chloride molten
Liquid absorbs.Absorptivity is improved using low concentration solution and reduces the characteristic of aerosol generation, improves the operational efficiency of desulphurization system.
2. the mixed solution after desulfurization uses carbide slurry (PVC accessory substances, principal component Ca (OH) outside tower2) causticization regeneration, after regeneration
Ammonia be dissolved in recovery in mixed solution return ammonia calcium combined desulfurization tower recycle, CaSO4(gypsum) and CaSO3(calcium sulfite) is de-
Utilization is further processed in sulphur Precipitation, the solid material of precipitation.
3. changing oxidizing sulfur dioxide technique in the conventional ammonia process of desulfurization at present and lime stone flue gas desulfurization technique, oxidation system is disabled
System, reduces the power consumption of desulphurization system, energy-saving.It is expected that the coal burning boiler of power station of every 500 tphs of evaporation capacity, per the Spring Festival holidays
About 4,000,000 KW of electricity, convert into and save about 1300 tons of coal of mark, reduce cost about 2,000,000.
4.CaSO4(gypsum) and CaSO3(calcium sulfite) desulfurization Precipitation technique, produce the CaSO of high-purity3(sulfurous acid
Calcium).Improve the value of byproduct.
5. nodeless mesh technique in tower, ammonia calcium combined desulfurization tower is interior to use low concentration ammonium sulfurous, ammonium sulfate, calcium chloride mixed solution,
Not in tower, the solid material such as generation crystallization, avoids the blockage problem of shower nozzle, pipeline, extends the service life of pump, carry
The operational efficiency of high system.
6. neutral or weakly alkaline solution operation process：Low concentration ammonium sulfurous, ammonium sulfate, calcium chloride are used in ammonia calcium combined desulfurization tower
Mixed solution, and oxidative system is disabled, the SO of highly acid is reduced in solution4 2+Generation, mixed solution PH controls in desulfurizing tower
Neutral or alkalescent scope (pH value is controlled between 6.5 to 8.5), the corrosivity of system is reduced, extends system metal material
Service life.
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| CN201710298536.XA CN107497270A (en) | 2017-04-28 | 2017-04-28 | The method of ammonia calcium combined desulfurization |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110787604A (en) * | 2019-11-29 | 2020-02-14 | 湖南绿脉环保科技有限公司 | Comprehensive treatment method of sulfur-containing waste flue gas and carbide slag |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194176A (en) * | 1997-03-21 | 1998-09-30 | 沈阳环境科学研究所 | New technology for absorbing and eliminating sulfur dioxide in smoke chemically |
| CN102485325A (en) * | 2011-04-19 | 2012-06-06 | 安徽理工大学 | Flue gas desulphurization technology with ammonium sulfate-calcium hydroxide slurry method |
-
2017
- 2017-04-28 CN CN201710298536.XA patent/CN107497270A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194176A (en) * | 1997-03-21 | 1998-09-30 | 沈阳环境科学研究所 | New technology for absorbing and eliminating sulfur dioxide in smoke chemically |
| CN102485325A (en) * | 2011-04-19 | 2012-06-06 | 安徽理工大学 | Flue gas desulphurization technology with ammonium sulfate-calcium hydroxide slurry method |
Non-Patent Citations (2)
| Title |
|---|
| 李建新主编: "《燃烧污染物控制技术》", 31 December 2012, 中国电力出版社 * |
| 詹益兴主编: "《现代化工小商品制法大全 第1集》", 31 August 1999, 湖南大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110787604A (en) * | 2019-11-29 | 2020-02-14 | 湖南绿脉环保科技有限公司 | Comprehensive treatment method of sulfur-containing waste flue gas and carbide slag |
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