CN105621640B - A kind of flue gas desulfurization antisludging agent - Google Patents
A kind of flue gas desulfurization antisludging agent Download PDFInfo
- Publication number
- CN105621640B CN105621640B CN201610006778.2A CN201610006778A CN105621640B CN 105621640 B CN105621640 B CN 105621640B CN 201610006778 A CN201610006778 A CN 201610006778A CN 105621640 B CN105621640 B CN 105621640B
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- Prior art keywords
- flue gas
- gas desulfurization
- solution
- antisludging agent
- ammonium persulfate
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
- C02F5/125—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen combined with inorganic substances
-
- 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
- B01D53/508—Sulfur oxides by treating the gases with solids
-
- 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
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/606—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
A kind of flue gas desulfurization antisludging agent, it is prepared by the following method, is specifically：After maleic anhydride monomer is completely dissolved with deionized water, mixed with allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether monomer, be then copolymerized and form in the presence of initiator ammonium persulfate.The present invention is to be used as additive addition in the desulfurization slurry used in limestone-gypsum wet desulfuration system, and the scale inhibition effect in flue gas desulfurization course complies fully with requirement.It is environmentally friendly because of not phosphorous, the eutrophication without causing surrounding water of the invention compared with existing organic additive.Compared with some slant acidity flue gas desulfurization antisludging agents, because partial neutral of the present invention is without corroding desulfurizer pipeline, and then desulfurizer service life can be extended.
Description
Technical field
The present invention relates to the antisludging agent that fouling is prevented in flue gas desulfurization course.
Background technology
To reduce and preventing sulfur dioxide (SO2) pollution to air, will be to cigarette that it is excluded in thermal power plant
Gas carries out desulfurization process.The method of flue gas desulfurization (FGD) is a lot, wherein with limestone-gypsum wet flue gas desulfurization technology application
At most, it has technology maturation, is applicable the advantages that coal is wide, desulfurization degree is high, desulfurizing agent wide material sources.Simply, no matter that is a kind of
Fume desulphurization method, it can all generate some calcium sulfate (CaSO to some extent in corresponding desulfurizing tower4) precipitation --- fouling.This
The resistance of system operation is increased, causes desulfuration efficiency to decline.When layer of scale reaches certain thickness and come off, also often can
Injure the nozzle and corrosion-proof lining in desulfurizing tower by a crashing object, system is resulted even in when situation is serious to be run.Then, people develop again
The various flue gas desulfurization antisludging agents for reducing and preventing fouling are gone out.In Limestone-gypsum Wet Flue Gas Desulfurization Process system, flue gas desulfurization resistance
Dirty agent is that it is broadly divided into as additive addition in the desulfurization slurry (lime stone, gypsum mixed serum) used in the method
Inorganic additive and the class of organic additive two.Wherein, scale inhibition effect is preferable, so using it is more be organic additive.However,
Because these organic additives are mostly organic phosphoric acid, organic polyphosphoric acid or organic polyphosphate, such as ATMP
(ATMP), 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP), 2- phosphates -1,2,4- butane tricarboxylates (PBTCA) etc., so, to flue gas
In the failure desulfurization slurry more to be swapped out after progress desulfurization process, also just contain many phosphorus compounds.Not only to the de- of failure
Sulphur slurries carry out harmless treatment and bring difficulty, moreover, once appearance handles not thorough and arrived surrounding by rain drop erosion again
In water body, the eutrophication of water body can result in --- still cause pollution to environment.
The content of the invention
Harmless treatment is carried out it is an object of the present invention to provide a kind of desulfurization slurry to failure to be easier, and will not
The flue gas desulfurization antisludging agent polluted to environment.
The technical scheme for realizing the goal of the invention is such a flue gas desulfurization antisludging agent, it prepare by the following method and
Into its step is：
1. in reaction vessel, maleic anhydride monomer is completely dissolved with deionized water；Sodium hydroxide solution is added dropwise afterwards,
So that its pH value is adjusted between 4.0~5.0；
2. it is 3.0 according to the mass ratio of maleic anhydride monomer and allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether monomer
~4.0 ratio, allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether monomer is added into step 1. in resulting solution, and stir
Uniformly；
3. continue whipping step 2. resulting solution, and it is molten to interior gradually dropwise addition ammonium persulfate after being warming up to 60~80 DEG C
Liquid；Wherein, the mass percent concentration of ammonium persulfate solution is 1.0~1.4%, maleic anhydride monomer: ammonium persulfate solution=
0.7Kg: 1L, total time for adding is controlled between 1~1.5h；It is incubated 3~5h under 60~80 DEG C of water bath conditions again afterwards；
4. after question response terminates, being cooled to room temperature, separated out and precipitated with methanol layer, filtered, dry and grind, to obtain powder
The flue gas desulfurization antisludging agent of shape；Powder diameter is not more than 0.15mm.
From scheme as can be seen that in the flue gas desulfurization antisludging agent of the present invention, not phosphorous or phosphorus compound, therefore,
After being added to as additive in the desulfurization slurry of Limestone-gypsum Wet Flue Gas Desulfurization Process system, finally it is being replaced mistake
It is also impossible in effect desulfurization slurry containing phosphorus or phosphorus compound.So, relatively easily harmless treatment can not only fail
Desulfurization slurry, but also any worry of eutrophication is not caused to surrounding water, so, compared with prior art,
The present invention is a kind of flue gas desulfurization antisludging agent not polluted the environment substantially.Checking shows, flue gas desulfurization antisludging agent of the invention
Scale inhibition effect in flue gas desulfurization course is also fully consistent with requiring.It can also be seen that the flue gas desulfurization of the present invention from scheme
Antisludging agent partial neutral, compared with some slant acidity flue gas desulfurization antisludging agents, it will not also corrode desulfurizer pipeline, Jin Erneng
The advantages of extending desulfurizer service life.In addition, it can also be seen that the present invention also has technological process when preparing from scheme
Simply, the advantages of product quality is easily controlled.
With reference to embodiment, the invention will be further described.
Embodiment
A kind of flue gas desulfurization antisludging agent, it is prepared by the following method, and its step is：
1. in reaction vessel, maleic anhydride monomer is completely dissolved with deionized water；Sodium hydroxide is added dropwise afterwards
(NaOH) solution, by the regulation of its pH value between 4.0~5.0；
Maleic anhydride in this step is maleic anhydride, must after being completely dissolved with deionized water
To maleic acid, therefore, the dosage of deionized water is defined by that whole maleic anhydrides can be changed into maleic acid.By
The course of reaction that structural formula represents is as follows：
It is to ensure that subsequent step smoothly enters with purpose and effect of the sodium hydroxide solution regulation pH value between 4.0~5.0
Go and obtain as far as possible more flue gas desulfurization antisludging agents.Obviously, the concentration of sodium hydroxide solution using can guarantee that smoothly regulation pH value as
Standard, generally take 2mol/L.
2. it is 3.0 according to the mass ratio of maleic anhydride monomer and allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether monomer
~4.0 ratio, allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether monomer is added into step 1. resulting solution (maleic two
Acid solution) in, and stir；
3. continuing whipping step 2. resulting solution, and ammonium persulfate is gradually added dropwise to interior after being warming up to 60~80 DEG C
[(NH4)2S2O8] solution；Wherein, the mass percent concentration of ammonium persulfate solution is 1.0~1.4%, maleic anhydride monomer: mistake
Ammonium sulfate=0.7Kg: 1L, total time for adding are controlled between 1~1.5h；Afterwards again under 60~80 DEG C of water bath conditions
It is incubated 3~5h；
4. after question response terminates, being cooled to room temperature, separated out and precipitated with methanol layer, filtered, dry and grind, to obtain powder
The flue gas desulfurization antisludging agent of shape；Powder diameter is not more than 0.15mm.
Above-mentioned steps are 2., it is clear that are to make both well mixed.Step 3. in ammonium persulfate solution be initiator,
It can ensure that the polymerisation between maleic acid and allyloxy Nonylphenoxy propyl alcohol APEO obtains after adding it
To realize.4. gained is precipitated step, is the flue gas desulfurization antisludging agent of the present invention, and ammonium persulfate and unreacted is washed away through filtering
Monomer, after drying, grinding, just it is possibly realized the product of actual use.
The course of reaction of the step of being represented by structural formula 3. is as follows：
In the structural formula of flue gas desulfurization antisludging agent,
The present invention has passed through the verification experimental verification done in laboratory, and the result is shown in proof list.
The preparation method (step) of flue gas desulfurization antisludging agent is identical with above-mentioned embodiment.Evaluation of antisludging performance, press
Enter according to People's Republic of China's oil and gas industry standard SY/T5673-93 " scale inhibitor for oilfield method of evaluating performance "
OK --- reason is to there is no special professional standard at present to the performance evaluation of flue gas desulfurization resist dirt agent, so using " oil field
With scale preventative method of evaluating performance " come to the present invention carry out scale inhibitor performance evaluation.
Specific method is：Simulation fouling is prepared first (generates CaSO4Precipitation) two kinds of solution --- solution A and B are molten
CaCl of liquid --- the solution A by mass concentration for 7.50g/L NaCl (sodium chloride) and 11.10g/L2·2H2O (two water chlorinations
Calcium) mix, Na of the B solution by mass concentration for 7.50g/L NaCl and 10.66g/L2SO4(sodium sulphate) mixes.
Wherein, the CaCl in solution A2·2H2Na in O and B solution2SO4Mol ratio be 1: 1, NaCl has been to dilute in two kinds of solution
The medium of effect, but the proportional quantity Ying Yineng in solution A accesses the mass concentration of calcium ion and is defined for 11.1g/L, it is molten in B
To guarantee comparatively fast to generate CaSO in liquid4(it can generally be used and identical proportional quantity in solution A) for degree.Then, it incite somebody to action this
The antisludging agent of invention is configured to the scale inhibition agent solution that mass percent concentration is 0.5%.
Using the method for contrast test during checking.
Add experiment, the continuous mode of antisludging agent of the present invention as follows：
50mL solution A and 50mL B solution are taken respectively in 2 beakers, and 0.2g resistances are separately added into two beakers
Dirty agent solution, and being sufficiently mixed, then the constant temperature 0.5h in 70 DEG C of water bath with thermostatic control；After the solution in two beakers is mixed again
The constant temperature 25h again in 70 DEG C of waters bath with thermostatic control；Cooling, filtering are taken out afterwards.During measure, take 1mL filtrates to add and filled 50mL steamings
Mixed in the bottle of distilled water, using GB7476-1987《Water quality calcium catalyst EDTA titrations》Specified in method, determine calcium ion
Mass concentration.
In no tests and measurements for adding antisludging agent of the present invention, in addition to antisludging agent this operation is added without, remaining examination
Test and continuous mode all same.
Finally, according to equation below, scale inhibition performance is calculated：
In formula：E --- scale inhibition performance (%)；
C2--- add after antisludging agent calcium ion mass concentration (g/L) in mixed solution；
C1--- calcium ion mass concentration (g/L) in mixed solution not plus before antisludging agent；
C0--- the half of calcium ion mass concentration in solution A.
Proof list
(note：Maleic anhydride monomer and allyloxy Nonylphenoxy third during in table 2. " monomer weight ratio " represents step
The mass ratio of alcohol polyoxyethylene ether monomer；" ammonium persulfate solution concentration " be step 3. in ammonium persulfate solution quality percentage
The abbreviation of specific concentration；" time for adding " refer to step 3. it is middle be added dropwise ammonium persulfate solution total time；" it is added dropwise and insulation is warm
Degree " ties up to the step 3. temperature that is incubated under water bath condition after the middle warming temperature being added dropwise before ammonium persulfate solution and completion of dropwise addition
Degree.)
As can be seen that the antisludging agent of the present invention has higher scale inhibition performance from proof list, even scale inhibition performance is 85.1%
(checking example 7), also fully meet and be actually needed.In addition, not phosphorous or phosphorus compound in antisludging agent of the invention, because
This, its really a kind of desulfurization slurry to failure carries out harmless treatment and is easier, and environment will not be polluted, and
The higher flue gas desulfurization antisludging agent of scale inhibition performance.
Claims (1)
1. a kind of flue gas desulfurization antisludging agent, it is characterised in that it is prepared by the following method, and its step is：
1. in reaction vessel, maleic anhydride monomer is completely dissolved with deionized water；Then sodium hydroxide solution is added dropwise, with
It is degree between 4.0~5.0 by the regulation of its pH value；
2. according to the mass ratio of maleic anhydride monomer and allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether monomer for 3.0~
4.0 ratio, allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether monomer is added into step 1. in resulting solution, and stirred equal
It is even；
3. continuing whipping step 2. resulting solution, and ammonium persulfate solution is gradually added dropwise to interior after being warming up to 60~80 DEG C；Its
In, the mass percent concentration of ammonium persulfate solution is 1.0~1.4%, maleic anhydride monomer: ammonium persulfate solution=0.7Kg:
1L, total time for adding are controlled between 1~1.5h；It is incubated 3~5h under 60~80 DEG C of water bath conditions again afterwards；
4. after question response terminates, being cooled to room temperature, separated out and precipitated with methanol layer, filtered, dry and grind, it is powdered to obtain
Flue gas desulfurization antisludging agent；Powder diameter is not more than 0.15 mm.
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| CN201610006778.2A CN105621640B (en) | 2016-01-06 | 2016-01-06 | A kind of flue gas desulfurization antisludging agent |
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| CN201610006778.2A CN105621640B (en) | 2016-01-06 | 2016-01-06 | A kind of flue gas desulfurization antisludging agent |
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| CN105621640B true CN105621640B (en) | 2018-02-09 |
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| CN107754563A (en) * | 2017-11-01 | 2018-03-06 | 安徽鼎隆重工科技有限公司 | The special fume treatment liquid of hot chamber machine |
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| WO1995003342A1 (en) * | 1993-07-20 | 1995-02-02 | Nippon Shokubai Co., Ltd. | Maleic copolymer, process for producing the same and use thereof |
| CN101665287A (en) * | 2008-09-05 | 2010-03-10 | 华东电力试验研究院有限公司 | Scale inhibitor |
| CN101805068A (en) * | 2010-04-16 | 2010-08-18 | 常州市科威精细化工有限公司 | Scale inhibition dispersing agent and preparation method thereof |
| CN102284237A (en) * | 2010-06-21 | 2011-12-21 | 中国石油化工股份有限公司 | Method for inhibiting scaling in double alkali method flue gas desulfurization process |
| CN103288226A (en) * | 2013-05-07 | 2013-09-11 | 明增安 | Desulfurization tower slurry scale inhibitor |
| CN103833150A (en) * | 2014-02-21 | 2014-06-04 | 常州科威天使环保科技有限公司 | Dirt dispersion agent for circulating cooling water system and preparation method of dirt dispersion agent |
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2016
- 2016-01-06 CN CN201610006778.2A patent/CN105621640B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995003342A1 (en) * | 1993-07-20 | 1995-02-02 | Nippon Shokubai Co., Ltd. | Maleic copolymer, process for producing the same and use thereof |
| CN101665287A (en) * | 2008-09-05 | 2010-03-10 | 华东电力试验研究院有限公司 | Scale inhibitor |
| CN101805068A (en) * | 2010-04-16 | 2010-08-18 | 常州市科威精细化工有限公司 | Scale inhibition dispersing agent and preparation method thereof |
| CN102284237A (en) * | 2010-06-21 | 2011-12-21 | 中国石油化工股份有限公司 | Method for inhibiting scaling in double alkali method flue gas desulfurization process |
| CN103288226A (en) * | 2013-05-07 | 2013-09-11 | 明增安 | Desulfurization tower slurry scale inhibitor |
| CN103833150A (en) * | 2014-02-21 | 2014-06-04 | 常州科威天使环保科技有限公司 | Dirt dispersion agent for circulating cooling water system and preparation method of dirt dispersion agent |
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