CN105251335A - Limestone-gypsum wet flue gas desulfurization synergist and preparation method thereof - Google Patents
Limestone-gypsum wet flue gas desulfurization synergist and preparation method thereof Download PDFInfo
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- CN105251335A CN105251335A CN201410339096.4A CN201410339096A CN105251335A CN 105251335 A CN105251335 A CN 105251335A CN 201410339096 A CN201410339096 A CN 201410339096A CN 105251335 A CN105251335 A CN 105251335A
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Abstract
The present invention discloses a limestone-gypsum wet flue gas desulfurization synergist, which comprises, by weight, 70-90 parts of an organic acid salt, 5-20 parts of an organic anhydride, and 5-15 parts of a surfactant. According to the present invention, the type of the component of the desulfurization synergist is simplified while the obtained synergetic desulfurization effect is good; due to the excellent and stable desulfurization effect, under the same conditions, the used raw materials are less, the production cost of the enterprise is low, and the performance price ratio is high; and the sodium diacetate accounting for the absolute proportion in the desulfurization synergist components is the internationally-recognized efficient, safe and inexpensive food additive, and has characteristics of good safety and good environmental protection during the production process, the storage and transportation process, the use process and other processes.
Description
Technical field
The present invention relates to wet process of FGD field, particularly relate to a kind of wet desulfurization of flue gas by limestone-gypsum method synergist and preparation method thereof.
Background technology
Along with the emergence of China's economic, the international obligation that China fulfils in international community is heavier, particularly environmental protection pressure is more and more heavier, and country requires more and more higher to the reduction of discharging of thermoelectricity, and the design capacity of the existing desulfurizer of Chinese many power plant more and more can not meet the environmental requirement of country.Meanwhile, in recent years along with the continuous increase of fired power generating unit, the supply-demand relationship of coal market there occurs very large change, and due to the change of supply-demand relationship, causing thermal power plant to be burnt, coal is corresponding changes.China starts to go up flue gas desulfur device on a large scale from thermal power plant in 2005, because coal market was lower at that time, the coal sulfur-bearing of the desulfurizer therefore designed at that time is generally on the low side, now because the well sold and in short supply present coal sulfur of coal market is difficult to the demand meeting sulfur removal technology.
Wet desulfurization of flue gas by limestone-gypsum method technique because of its technology maturation, desulfuration efficiency high, absorbent abundance, cheap, byproduct the feature such as can to utilize and be widely adopted, become China's most widely used method of coal fired power plant flue gas desulfurization at present, account for total amount more than 80%.
Due to character and the technique restriction of lime stone itself, wet desulfurization of flue gas by limestone-gypsum method technique also exists that energy consumption is high, the easy fouling corrosion of system, GGH (GasGasHeater, flue gas heat-exchange unit) blocking, absorption tower slurries overflow, calcium sulfite the reasons such as oxidation is insufficient cause dehydration difficulty; Coal in power plant Quality Down calorific value is low, sulfur-bearing is high, and desulfuration efficiency does not reach design load, needs equipment dilatation, and the problem such as have high input.
Solve the problem, common way is application Desulfurization synergist.Conventional Desulfurization synergist divides organic type, inorganic type and compound three classes.Wherein compoundly can consider from many aspects to deal with problems and more concerned.Such as application number be CN201210101207.9 application discloses a kind of Limestone-gypsum Wet Flue Gas Desulfurization Process additive, the component of described sulfur-removing additives and the percentage by weight of each component are: adipic acid: 60-90%, magnesium sulfate: 2-10%, sodium carbonate: 4-20%, copper sulphate: 1-8%, manganese sulfate: 1-8%.
Also have application number be CN201210137526.5 application discloses a kind of wet desulfurization of flue gas by limestone-gypsum method additive, it is characterized in that, the component of described sulfur-removing additives and the weight percentage of each component are: adipic acid: 30-60%; Sodium carboxymethylcellulose: 30-50%; Sodium carbonate: 2-20%; Aluminum sulfate: 1-15%; Catalytic oxidant: 2-15%; Described catalytic oxidant is at least one in ferric sulfate, copper sulphate, manganese sulfate.
Component disclosed in above-mentioned patent document take adipic acid as main component, can improve lime stone rate of dissolution; Alkaline environment is caused to be conducive to SO with slaine again
2hydrolysis; Solve slurries overflow with the auxiliary agent such as pro-oxygenic agent, defoamer again and be oxidized the problems such as insufficient.But such scheme can find produce discrepancy between each link from structure analysis.Main because be that the component that participation is reacted is too many, and the more heterogeneous impact pind down mutually of component is larger, find optimal balance point difficulty.In addition, the interpolation of tradition organic acid (comprising adipic acid) can reduce limestone granularity, strengthens lime stone reactivity, but higher to dosing method, dosage and monitoring requirement, there will be and become large, the problem that efficiency declines along with extending pH fluctuation service time.Therefore the organic acid use such as adipic acid can cause the fluctuation of pH value, and unfavorable desulfurization is stable to be continued to carry out, and raw material addition must be caused to increase, the problems such as enterprise's production cost increase.
Summary of the invention
In order to solve the problems of the prior art, the object of the invention is a kind of simple, effectively, economical, safety, sweetening process of can optimizing, improve the wet desulfurization of flue gas by limestone-gypsum method synergist of the desulfurization performance of FGD (fluegasdesulphuration, flue gas desulfurization) system.This wet desulfurization of flue gas by limestone-gypsum method synergist can adapt to the coal of various sulfur content, reduces the energy loss of flue gas desulphurization system, brings good economic and social benefit to power plant.
For achieving the above object, the present invention by the following technical solutions: a kind of wet desulfurization of flue gas by limestone-gypsum method synergist, the component of this Desulfurization synergist and the weight portion of corresponding component as follows:
Acylate 70-90 weight portion;
Organic acid anhydride 5-20 weight portion;
Surfactant 5-15 weight portion.
Preferred version, described acylate is sodium Diacetate; Described organic acid anhydride is maleic anhydride; Described surfactant is polysiloxanes.
Further preferred version, described sodium Diacetate is 70 weight portions, and described maleic anhydride is 5 weight portions; Described surfactant is polysiloxanes is 5 weight portions.
Further preferred version, described sodium Diacetate is 90 weight portions, and described maleic anhydride is 20 weight portions; Described surfactant is polysiloxanes is 15 weight portions.
Described sodium Diacetate can also be 80 weight portions, and described maleic anhydride is 15 weight portions; Described surfactant is polysiloxanes is 10 weight portions.
Described sodium Diacetate is 80 weight portions, and described maleic anhydride is 10 weight portions; Described surfactant is polysiloxanes is 10 weight portions.
Another object of the present invention is to provide a kind of method preparing wet desulfurization of flue gas by limestone-gypsum method synergist, after it is weighed according to the component of above-mentioned wet desulfurization of flue gas by limestone-gypsum method synergist and weight, adding reactor is at normal temperatures and pressures stirred well to evenly, namely can obtain Desulfurization synergist.
Synergist of the present invention has catalysed oxidn to calcium sulfite, makes lime stone slurry sulfite radical content between 0.07%--0.2%, meets the national regulation value requirement lower than 0.3%.Synergist has removing effect to desulphurization system Central Plains attachment, has certain scavenging action to the dirt that original system generates.The utilization rate of lime stone can be improved, after adding synergist, limestone utilization 0.1%--1.1% can be improved.On the good basis of ature of coal (coal-fired sulfur content is less than 0.8%), use synergist can stop a serum recycle pump operation, reach good energy-saving and cost-reducing effect.Synergist has good pH value buffer capacity to lime stone slurry, can slow down local ph in desulfurizing tower and rise or decline change, be conducive to alleviating incrustation or corrosion.Found by the experiment of three of us's moon, system incrustation phenomenon alleviates, and does not occur etching problem.
Desulfurization synergist surface of the present invention has activity in sum, can catalytic oxidation, can promote the direct reaction of SO2, accelerate the dissolving of CaCO3, promote that CaCO3 rapid oxidation becomes CaCO3, the precipitation of strengthening CaSO4, reduce liquid-gas ratio, reduce calcium sulfur ratio, reduce the evaporation of moisture.When smoke inlet SO2 concentration increases, during higher than design load, in the reaction tank of absorption tower, pH value reduces, need larger Ca/S than time, when absorption tower reaction tank volume does not need to expand, CaCO3 can rapid solution, increases calcium ion concentration, keep plasm PH value in normal range (NR), have certain cushioning effect to pH value.After usual use Desulfurization synergist, desulfuration efficiency can improve about 5% ~ 8%.
Detailed description of the invention
Embodiment 1, at normal temperatures and pressures, take acylate (sodium Diacetate 70 kilograms), organic acid anhydride (maleic anhydride 5 kilograms) and surfactant (polysiloxanes is 5 kilograms) to add in reactor and be stirred to evenly, i.e. a kind of wet desulfurization of flue gas by limestone-gypsum method synergist of obtained the present invention.In production process, because powder is many, the protection flying powder should be noted.Meanwhile, during this wet desulfurization of flue gas by limestone-gypsum method synergist accumulating, shady and cool ventilation place should be placed in, avoid high temperature and forbid outdoor storage.
Containing sodium Diacetate, maleic anhydride and polysiloxanes in this Desulfurization synergist.Sweetening process is optimized by simple, effective, the most economic, safe method, to improve FGD (fluegasdesulphuration, flue gas desulfurization) desulfurization performance of system, the coal of various sulfur content can be adapted to, reduce system capacity loss, bring good economic and social benefit to power plant.
Wherein sodium Diacetate links by short hydrogen bond the molecular compound CH3COONa.CH3COOH.xH2O that acetic acid and sodium acetate form, owing to being the link of short hydrogen bond, be comparatively easily decomposed into acetic acid and sodium acetate CH3COONa.CH3COOH.xH2O<=>CH3CO ONa+CH3COOH+xH2O.Sodium acetate can dissociate into sodium ion and acetic acid.Enough acetic acid can ensure that desulfurizing tower PH is stabilized in 5.4-5.7 optimum value, impels lime stone (calcium carbonate) rate of dissolution improve and guarantee that SO3 and Ca fully reacts.Meanwhile, sodium ion generation NaOH creation alkaline environment, improves SO2 and hydrate generates H2SO4 ability, and absorbs free hydrogen in a large number, to ensure that the fully oxidized smooth dehydration of calcium sulfite generates conforming articls level gypsum.
In Limestone/Gypsum-based Wet Process Flue Gas Desulfuration, maleic anhydride is hydrolyzed to obtain maleic acid, and supplementing and desulphurization reaction initator and reaction intermediate as sodium Diacetate, effectively can regulate, stablize pH value.
In Limestone/Gypsum-based Wet Process Flue Gas Desulfuration, polysiloxanes is as surfactant, the participation slurries of desulphurization reaction and the surface tension of water are regulated, effectively expands the reaction specific area of oxysulfide and water and calcic slurries, most important to raising desulfuration efficiency; In addition, foam can be suppressed excessively to generate and cause slurries overflow, also increase slurries calcium particle dispersion and rheological characteristic simultaneously, prevent scaling from blocking.
The reasonable integration of the present invention characteristic of component, drop to minimum, but each component can obtain very good coordinated desulfurization effect by component material kind.Meanwhile, because superior stable effect makes injected volume less, production cost is low, and cost performance is good.Internationally recognized efficient, safe, inexpensive food additives as the sodium Diacetate accounting for absolute share in Desulfurization synergist component; Polysiloxanes is also belong to the important source material that can be used for cosmetics.Therefore desulfurizing agent of the present invention is all very good in the security of whole production, accumulating, use procedure, the feature of environmental protection.
Embodiment 2, at normal temperatures and pressures, takes sodium Diacetate 90 kilograms, maleic anhydride 20 kilograms and polysiloxanes and is 15 kilograms and adds in reactor and be stirred to evenly, be i.e. a kind of wet desulfurization of flue gas by limestone-gypsum method synergist of obtained the present invention.
Embodiment 3, at normal temperatures and pressures, takes sodium Diacetate 80 kilograms, maleic anhydride 15 kilograms and polysiloxanes and is 10 kilograms and adds in reactor and be stirred to evenly, be i.e. a kind of wet desulfurization of flue gas by limestone-gypsum method synergist of obtained the present invention.
Embodiment 4, at normal temperatures and pressures, takes sodium Diacetate 80 kilograms, maleic anhydride 10 kilograms and polysiloxanes and is 10 kilograms and adds in reactor and be stirred to evenly, be i.e. a kind of wet desulfurization of flue gas by limestone-gypsum method synergist of obtained the present invention.
Embodiment 5, at normal temperatures and pressures, takes sodium Diacetate 70-90 kilogram, maleic anhydride 5-20 kilogram and polysiloxanes is 5-15 kilogram and adds in reactor and be stirred to evenly, be i.e. a kind of wet desulfurization of flue gas by limestone-gypsum method synergist of obtained the present invention.
Embodiment 6, in order to the effect of this Desulfurization synergist of further experiment, the 1# unit that we are selected in certain power plant 600WM has carried out desulfurization.The desulphurization system situation of this power plant is: Desulfurization tower slurry capacity is 1100 ~ 1300; Have 3 slurry circulating pumps, the internal circulating load of every platform is 6000 ~ 7500, and the electric current of circulating pump is between 55 ~ 85 amperes; System does not have spare circulating pump, when there is equipment fault, cannot ensure that desulphurization system is normally run.
When not using Desulfurization synergist of the present invention, when the sulfur content of coal is 0.8% time, the content of sulfur dioxide of desulfurizing tower import at about 1600 milligrams/cubic metre, 3 slurry circulating pump standard-sized sheets, record desulfurizer outlet content of sulfur dioxide be greater than 300 milligrams/cubic metre; When the sulfur content of coal is 1.25%, the content of sulfur dioxide of corresponding desulfurizing tower import 2800 milligrams/cubic metre, 3 slurry circulating pump standard-sized sheets, the content of sulfur dioxide recording desulfurizer outlet is greater than 400 milligrams/cubic metre.
After using Desulfurization synergist of the present invention, even if stop a slush pump, no matter the sulfur content of coal is 1.25% at 0.8% or the sulfur content of coal, and the content of sulfur dioxide that we record desulfurizer outlet is all less than 100 milligrams/cubic metre.Even if therefore we draw and we used sulphur coal, when 3 circulating pump standard-sized sheets, still can ensure that desulfuration efficiency is more than 90%, reduce lime consumption and gypsum moisture content, realize environmental requirement.
Embodiment 7, we have also carried out sulfur-removing additives experiment in Chalco Lanzhou power plant for self-supply of branch company.Experimental method is: under the same conditions, first record the desulfurization situation data of not adding wet desulfurization of flue gas by limestone-gypsum method system before synergist of the present invention, 300 kilograms of Desulfurization synergist of the present invention are added first again to wet desulfurization of flue gas by limestone-gypsum method system, add 50 kilograms of Desulfurization synergist of the present invention every day more afterwards, then repetitive measurement desulphurization system entrance so2 concentration and gateway S02 concentration contrast.
The detailed data that obtains of test is as following table in fact:
Show by experiment, when entrance sulfur dioxide concentration is 2000 milligrams of every standard cubic meters, after adding Desulfurization synergist of the present invention, the desulfurization degree of wet desulfurization of flue gas by limestone-gypsum method system about 6% can be improved.
Claims (7)
1. a wet desulfurization of flue gas by limestone-gypsum method synergist, is characterized in that: the component of described Desulfurization synergist and the weight portion of corresponding component as follows:
Acylate 70-90 weight portion;
Organic acid anhydride 5-20 weight portion;
Surfactant 5-15 weight portion.
2. a kind of wet desulfurization of flue gas by limestone-gypsum method synergist as claimed in claim 1, is characterized in that: described acylate is sodium Diacetate; Described organic acid anhydride is maleic anhydride; Described surfactant is polysiloxanes.
3. a kind of wet desulfurization of flue gas by limestone-gypsum method synergist as claimed in claim 2, it is characterized in that: described sodium Diacetate is 70 weight portions, described maleic anhydride is 5 weight portions; Described surfactant is polysiloxanes is 5 weight portions.
4. a kind of wet desulfurization of flue gas by limestone-gypsum method synergist as claimed in claim 2, it is characterized in that: described sodium Diacetate is 90 weight portions, described maleic anhydride is 20 weight portions; Described surfactant is polysiloxanes is 15 weight portions.
5. a kind of wet desulfurization of flue gas by limestone-gypsum method synergist as claimed in claim 2, it is characterized in that: described sodium Diacetate is 80 weight portions, described maleic anhydride is 15 weight portions; Described surfactant is polysiloxanes is 10 weight portions.
6. a kind of wet desulfurization of flue gas by limestone-gypsum method synergist as claimed in claim 2, it is characterized in that: described sodium Diacetate is 80 weight portions, described maleic anhydride is 10 weight portions; Described surfactant is polysiloxanes is 10 weight portions.
7. prepare the method for wet desulfurization of flue gas by limestone-gypsum method synergist for one kind, it is characterized in that: after it is weighed according to the component of the wet desulfurization of flue gas by limestone-gypsum method synergist of one of claim 1 to 6 and weight, adding reactor is at normal temperatures and pressures stirred well to evenly, i.e. this Desulfurization synergist obtained.
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| CN106039977A (en) * | 2016-07-25 | 2016-10-26 | 合肥天翔环境工程有限公司 | Limestone-gypsum wet flue gas desulfurization additive and preparation method thereof |
| CN107754564A (en) * | 2017-11-04 | 2018-03-06 | 李景春 | Medicine Factory waste gas purification treatment fluid |
| CN108114587A (en) * | 2017-12-31 | 2018-06-05 | 华电高科环保技术有限公司 | The Desulfurization synergist of wet process of FGD |
| CN108905591A (en) * | 2018-06-29 | 2018-11-30 | 南通乐尔环保科技有限公司 | A kind of efficient wet flue gas desulfurization synergist |
| CN112892177A (en) * | 2021-01-15 | 2021-06-04 | 河北梓烨化工有限公司 | Desulfurization synergist and preparation method thereof |
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| CN106039977A (en) * | 2016-07-25 | 2016-10-26 | 合肥天翔环境工程有限公司 | Limestone-gypsum wet flue gas desulfurization additive and preparation method thereof |
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| CN108905591A (en) * | 2018-06-29 | 2018-11-30 | 南通乐尔环保科技有限公司 | A kind of efficient wet flue gas desulfurization synergist |
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Application publication date: 20160120 |