CN105688633B - One kind being used for coal burning flue gas desulfurization agent - Google Patents
One kind being used for coal burning flue gas desulfurization agent Download PDFInfo
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- CN105688633B CN105688633B CN201610041785.6A CN201610041785A CN105688633B CN 105688633 B CN105688633 B CN 105688633B CN 201610041785 A CN201610041785 A CN 201610041785A CN 105688633 B CN105688633 B CN 105688633B
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- agent
- flue gas
- gas desulfurization
- chloride
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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
-
- 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
- B01D53/68—Halogens or halogen compounds
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
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- 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
- B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2047—Hydrofluoric acid
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- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
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- Treating Waste Gases (AREA)
Abstract
The invention discloses one kind being used for coal burning flue gas desulfurization agent, belongs to environmental protection technical field.The desulfurizing agent is using magnesium chloride as matrix, it is aided with calcium chloride or/and zinc chloride simultaneously, it is scattered in formation A agent in polyvinyl alcohol water solution, and surfactant is added into sodium hydrate aqueous solution and forms B agent, A agent and the isometric hybrid reaction of B agent are prepared into coal burning flue gas desulfurization agent.Coal burning flue gas desulfurization agent particle of the present invention is small, large specific surface area, cost are relatively low, to SO2There is significant removing to act on, and its production prepares and application does not generate secondary pollution, is good for the environment and waste utilization.
Description
Technical field
The invention belongs to environmental protection technical fields, and in particular to one kind being used for coal burning flue gas desulfurization agent.
Background technology
China is one using coal as the country of main energy sources, every year because the sulfur dioxide that fire coal is discharged reaches more than 2000
Ten thousand tons, serious atmosphere pollution is caused, significant impact is generated to China environmental protection and economic development.Wet process of FGD skill
Art be in the world large-scale commercial applications apply, it is most effective control sulfur dioxide pollution sulfur method.Wet process of FGD category
In the scope of chemical absorbing, basic principle be the alkaline desulfurizing agent of liquid and sulfur dioxide in flue gas that acid-base neutralization occurs is anti-
It answers, to remove the sulfur dioxide in flue gas.The process of chemical absorbing is by two process groups of physical absorption process and chemical reaction
At.It is dissolved in the liquid phase by the active component in absorption gas when reaching a certain concentration, proceeds by chemical reaction.Work as chemistry
It is the limit of MODEL OF CHEMICAL ABSORPTION PROCESS by the consumption of absorption gas when reaction reaches balance.In MODEL OF CHEMICAL ABSORPTION PROCESS, absorbed
The vapor-liquid equilibrium relationship of gas not only obeys phase equilibrium relationship, but also obeys chemical balance relationship.
Wet desulfurizing process mainly has：(1) Wet Limestone/gypsum desulfurization technology, the advantage of this process is that technology at
It is ripe, desulfuration efficiency is high, up to 90% or more, absorbent is of low cost, and waste residue can be used as gypsum to recycle, the disadvantage is that equipment is easily long-pending
Dirt is blocked, corrodes and is worn, it is difficult to long-period stable operation, and by-product is almost without purposes.(2) dual alkali scrubbing FGD process,
The advantage of this process is that desulfuration efficiency is high, system is easy, small investment；System is less scaling, blocks；Liquid-gas ratio low (generally 1.8
~2:1 or so), power consumption is few, operating cost is low；Absorption tower is using spray void tower, and resistance is small, reliable for operation, the disadvantage is that technique
Complexity, maturity is not high, the difficult life of sodium sulfate byproduct.(3) ammonia type flue gas desulfurizing, the advantage of this process is that desulfuration efficiency is high,
It can keep that desulfuration efficiency 95%~99%, low energy consumption, reaction rate is fast, absorbent utilization rate is high, the disadvantage is that absorbent cost
It is high.
Absorption for sulfur dioxide in flue gas, magnesia absorption process are also one of the application process of current extensive concern,
Its basic principle is that magnesia is added in absorption tower to make itself and the exhaust gas counter current contacting containing sulfur dioxide, generates magnesium sulfite.
Its chemical equation is as follows：
It absorbs：MgO+SO2=MgSO3
Oxidation：2MgSO3+O2=2MgSO4
MgO activity is stronger, is Ca (OH)2630 times, while in desulfurizing byproduct, MgSO3Solubility be about CaSO3
630 times, system sulfite root activity is high, therefore, can greatly improve and absorb SO2Efficiency.It is anti-for magnesia FGD
It answers, when import sulfur dioxide concentration is 1100~1300mg/m3, system pH be 5~6, maximum liquid-gas ratio is 8~11:1L/m3,
Desulfurization general efficiency can reach 93.4%, but due in milk of magnesia magnesia be in suspension form, need be stirred continuously
It is lower to be susceptible to the problems such as slurry is uneven, desulfurization effect fluctuates, and liquid-gas ratio is higher with absorption system is pumped into,
Doctor solution consumption is bigger.
Magnesium oxide slurry absorption process is one of the application process of current extensive concern, compared with magnesium oxide method desulfurizing agent,
Magnesium oxide slurry is stablized relatively, and granular size is controllable, and especially nanometric magnesium hydroxide is since particle is small, anti-with sulfur dioxide
Should it is fast, sulfur dioxide abjection effect is good and attracts attention.
Invention content
Technical problem to be solved by the present invention lies in overcoming the problems, such as that existing desulfurizing agent exists, provide it is a kind of it is nontoxic, at
The coal burning flue gas desulfurization agent that this is low, dosage is few, desulfuration efficiency is high.
Technical solution is used by solving above-mentioned technical problem：Magnesium chloride and calcium chloride or/and zinc chloride are added and steamed
In distilled water, polyvinyl alcohol is added under stiring, stirs evenly, obtains A agent, the matter of calcium chloride or zinc chloride and magnesium chloride in A agent
Amount is than being 1:1~4 or calcium chloride and zinc chloride gross mass and magnesium chloride mass ratio be 1:1~4, and magnesium chloride in A agent
It is 15%~20% with the total mass concentration of calcium chloride or/and zinc chloride；The sodium hydroxide for being 10%~20% to mass fraction
Surfactant is added in aqueous solution, stirs evenly, obtains B agent；It is 1 by volume by A agent and B agent:1 mixing, is stirred to react
15~30 minutes, obtain coal burning flue gas desulfurization agent.
The mass ratio of preferably calcium chloride or zinc chloride and magnesium chloride is 1 in above-mentioned A agent:3~4 or calcium chloride and chlorine
The mass ratio of the gross mass and magnesium chloride of changing zinc is 1:3~4.
The mass concentration of preferred polyvinyl alcohol is 0.1%~0.4%, the wherein average mark of polyvinyl alcohol in above-mentioned A agent
Son amount is 800~1000.
The mass concentration of preferred surfactant is 0.1%~0.4% in above-mentioned B agent, wherein the surface-active
Agent is lauryl sodium sulfate or alpha-olefin sodium sulfonate.
The application method of fume desulfurizing agent of the present invention is：Boiler original flue gas is down to through primary dedusting and dust concentration
100mg/m3Below, after flue gas is 90 DEG C or so, into the desulfurization workspace being made of three-level absorption plant, with desulphurizer mixing
And misty liquid droplets are formed, wherein import sulfur dioxide concentration is 1300~2500mg/m3, system pH be 6, liquid-gas ratio be 1~
2:1L/m3, the SO in flue gas2, generate salt after the harmful substances such as HCl, HF and reactive desulfurizing agent and effectively removed.
Inventive desulfurization agent is in polymer polyethylene alcohol, Surfactant SDS or alpha-olefin sodium sulfonate
In the presence of, by magnesium chloride, calcium chloride or/and zinc chloride and sodium hydroxide complex hydroxide lotion obtained by the reaction, wherein
The presence of polymer, surfactant can control the reaction rate between substance, the in addition variation of particle surface properties, so as to get
Complex hydroxide lotion in solid particle small (hundreds of nanometers), good dispersion, surface area be big, strong (stationary phase reaches stability
To 12h or more), mass transfer effect it is good, it is good that fast, desulfurization effect is reacted with sulfur dioxide.
Beneficial effects of the present invention are as follows：
(1) coal burning flue gas desulfurization agent of the present invention does not have toxicity, can be in the fields extensive use such as flue gas desulfurization.
(2) surface tension of coal burning flue gas desulfurization agent of the present invention is low, makes gas be easy to form minute bubbles, effectively increases
Big gas-liquid specific surface area, improves mass transfer rate, makes desulfuration efficiency up to 99.4% or more.
(3) coal burning flue gas desulfurization agent of the present invention is at low cost, can be 1~2 for sweetening process liquid-gas ratio:1L/m3, greatly
Doctor solution consumption has been saved greatly, has reduced the workload of subsequent processing, acidity load is high, and energy consumption is few, good economy performance.
Specific implementation mode
With reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities
Apply example.
Embodiment 1
400g magnesium chlorides and 100g calcium chloride are added in 1992.5g distilled water, 7.5g mean molecules are added under stiring
Amount is 800 polyvinyl alcohol, stirs evenly, obtains 2500g A agent；The sodium hydroxide water for being 15% to 2497.5g mass fractions
2.5g lauryl sodium sulfate is added in solution, stirs evenly, obtains 2500g B agent.Volume is pressed into A agent and B agent with metering pump
Than being 1:1 is pumped into blending tank, is stirred to react 30 minutes, obtains coal burning flue gas desulfurization agent, average grain diameter 470nm.
Embodiment 2
375g magnesium chlorides and 125g zinc chloride are added in 1997.5g distilled water, 2.5g mean molecules are added under stiring
Amount is 1000 polyvinyl alcohol, stirs evenly, obtains 2500g A agent；The sodium hydroxide water for being 20% to 2492.5g mass fractions
7.5g lauryl sodium sulfate is added in solution, stirs evenly, obtains 2500g B agent.Volume is pressed into A agent and B agent with metering pump
Than being 1:1 is pumped into blending tank, is stirred to react 25 minutes, obtains coal burning flue gas desulfurization agent, average grain diameter 560nm.
Embodiment 3
225g magnesium chlorides and 75g zinc chloride are added in 1694g distilled water, 6g average molecular weight is added under stiring is
1000 polyvinyl alcohol, stirs evenly, and obtains 2000g A agent；In the sodium hydrate aqueous solution for being 20% to 1996g mass fractions
4g alpha-olefin sodium sulfonates are added, stirs evenly, obtains 2000g B agent.By A agent and B agent it is 1 by volume with metering pump:1 is pumped into
It in blending tank, is stirred to react 15 minutes, obtains coal burning flue gas desulfurization agent, average grain diameter 630nm.
Embodiment 4
225g magnesium chlorides and 75g calcium chloride are added in 1692g distilled water, 8g average molecular weight is added under stiring is
1000 polyvinyl alcohol, stirs evenly, and obtains 2000g A agent；In the sodium hydrate aqueous solution for being 20% to 1994g mass fractions
6g lauryl sodium sulfate is added, stirs evenly, obtains 2000g B agent.By A agent and B agent it is 1 by volume with metering pump:1 pump
Enter in blending tank, be stirred to react 10 minutes, obtains coal burning flue gas desulfurization agent, average grain diameter 490nm.
Embodiment 5
400g magnesium chlorides and 100g calcium chloride are added in 1995g distilled water, 5g average molecular weight is added under stiring is
800 polyvinyl alcohol, stirs evenly, and obtains 2500g A agent；In the sodium hydrate aqueous solution for being 20% to 2495g mass fractions
5g lauryl sodium sulfate is added, stirs evenly, obtains 2500g B agent.By A agent and B agent it is 1 by volume with metering pump:1 pump
Enter in blending tank, be stirred to react 20 minutes, obtains coal burning flue gas desulfurization agent, average grain diameter 580nm.
Embodiment 6
400g magnesium chlorides and 50g calcium chloride, 50g zinc chloride are added in 1990g distilled water, it is flat that 10g is added under stiring
The polyvinyl alcohol that average molecular weight is 800, stirs evenly, obtains 2500g A agent；The hydroxide for being 20% to 2490g mass fractions
10g lauryl sodium sulfate is added in sodium water solution, stirs evenly, obtains 2500g B agent.Body is pressed into A agent and B agent with metering pump
Product is than being 1:1 is pumped into blending tank, is stirred to react 10 minutes, obtains coal burning flue gas desulfurization agent, average grain diameter is
610nm。
In order to prove that beneficial effects of the present invention, inventor use the coal burning flue gas desulfurization of the embodiment of the present invention 1~5
Agent carries out boiler flue gas desulfurization, and the specific method is as follows：
Boiler original flue gas is after primary dedusting and dust concentration is down to 100mg/m3Below, flue gas be 90 DEG C after, by
The desulfurization workspace of three-level absorption plant composition, and desulphurizer mixing and forms misty liquid droplets, wherein import sulfur dioxide concentration
For 2000mg/m3, system pH be 6, liquid-gas ratio 1:1L/m3, outlet sulfur dioxide concentration is tested, the de- of sulfur dioxide is calculated
Sulphur efficiency the results are shown in Table 1.
1 desulfuration efficiency test result of table
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Desulfuration efficiency (%) | 99.5 | 99.6 | 99.7 | 99.6 | 99.4 | 99.7 |
By table 1 as it can be seen that the desulfuration efficiency of coal burning flue gas desulfurization agent of the present invention can reach 99.4% or more.
Claims (4)
1. a kind of preparation method for coal burning flue gas desulfurization agent, it is characterised in that：By magnesium chloride and calcium chloride or/and chlorine
Change zinc to be added in distilled water, polyvinyl alcohol be added under stiring, stirs evenly, obtains A agent, in A agent calcium chloride or zinc chloride with
The mass ratio of magnesium chloride is 1:1~4 or calcium chloride and zinc chloride gross mass and magnesium chloride mass ratio be 1:1~4, and A
Magnesium chloride and the total mass concentration of calcium chloride or/and zinc chloride are 15%~20% in agent；The hydrogen for being 10%~20% to mass fraction
Surfactant is added in aqueous solution of sodium oxide, stirs evenly, obtains B agent；It is 1 by volume by A agent and B agent:1 mixing, is stirred
It mixes reaction 15~30 minutes, obtains coal burning flue gas desulfurization agent；
The average molecular weight of above-mentioned polyvinyl alcohol is 800~1000；The surfactant be lauryl sodium sulfate or
Alpha-olefin sodium sulfonate.
2. the preparation method according to claim 1 for coal burning flue gas desulfurization agent, it is characterised in that：The A
The mass ratio of calcium chloride or zinc chloride and magnesium chloride is 1 in agent:3~4 or calcium chloride and zinc chloride gross mass and magnesium chloride
Mass ratio be 1:3~4.
3. the preparation method according to claim 1 or 2 for coal burning flue gas desulfurization agent, it is characterised in that：It is described
A agent in polyvinyl alcohol mass concentration be 0.1%~0.4%.
4. according to claim 1 or 2 be used for coal burning flue gas desulfurization agent preparation method, it is characterised in that：The B
The mass concentration of surfactant is 0.1%~0.4% in agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610041785.6A CN105688633B (en) | 2016-01-22 | 2016-01-22 | One kind being used for coal burning flue gas desulfurization agent |
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| CN201610041785.6A CN105688633B (en) | 2016-01-22 | 2016-01-22 | One kind being used for coal burning flue gas desulfurization agent |
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| Publication Number | Publication Date |
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| CN105688633A CN105688633A (en) | 2016-06-22 |
| CN105688633B true CN105688633B (en) | 2018-08-31 |
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| CN108479327B (en) * | 2018-03-22 | 2020-12-11 | 北京阳光欣禾科技有限公司 | Desulfurization and denitrification composite material and production process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920159A (en) * | 2010-09-10 | 2010-12-22 | 北京金源化学集团有限公司 | Method for removing and reclaiming sulfur dioxide from gas by low power consumption renewable absorbent |
| CN103084056A (en) * | 2011-10-31 | 2013-05-08 | 三菱重工业株式会社 | Flue Gas Desulfurization |
| CN103910367A (en) * | 2013-01-06 | 2014-07-09 | 北京化工大学 | Method for preparing transparent magnesium hydroxide liquid phase dispersion |
| CN104759194A (en) * | 2015-03-20 | 2015-07-08 | 金隆铜业有限公司 | Flue gas desulphurization method |
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2016
- 2016-01-22 CN CN201610041785.6A patent/CN105688633B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920159A (en) * | 2010-09-10 | 2010-12-22 | 北京金源化学集团有限公司 | Method for removing and reclaiming sulfur dioxide from gas by low power consumption renewable absorbent |
| CN103084056A (en) * | 2011-10-31 | 2013-05-08 | 三菱重工业株式会社 | Flue Gas Desulfurization |
| CN103910367A (en) * | 2013-01-06 | 2014-07-09 | 北京化工大学 | Method for preparing transparent magnesium hydroxide liquid phase dispersion |
| CN104759194A (en) * | 2015-03-20 | 2015-07-08 | 金隆铜业有限公司 | Flue gas desulphurization method |
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