CN102989260A - Sulfuric acid mist elimination method - Google Patents
Sulfuric acid mist elimination method Download PDFInfo
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- CN102989260A CN102989260A CN2012105194786A CN201210519478A CN102989260A CN 102989260 A CN102989260 A CN 102989260A CN 2012105194786 A CN2012105194786 A CN 2012105194786A CN 201210519478 A CN201210519478 A CN 201210519478A CN 102989260 A CN102989260 A CN 102989260A
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- sulfuric acid
- acid mist
- flyash
- cao
- modification
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Abstract
The embodiment of the invention discloses a sulfuric acid mist elimination method. The method comprises the following steps of absorbing the sulfuric acid mist by adopting solid waste coal ash; and further carrying out alkaline activation and modification on the coal ash by adopting NaOH or CaO as a modifying agent so as to improve the adsorption performance of the coal ash. According to the sulfuric acid mist elimination method, not only is the cost low, but also the adsorptive property is good, an the secondary pollution can be avoided, so that the management problem of the sulfuric acid mist in a lead-acid storage battery plant is solved, and the treatment problem of industrial waste material coal ash is also solved.
Description
Technical field
The present invention relates to the Sour gas disposal technical field, relate in particular to a kind of removing method of sulfuric acid mist.
Background technology
At present, in electrochmical power source, lead-acid accumulator has the electromotive force height, capacitance is large, the life-span is long, the environment for use temperature range is wide, is applicable to the advantages such as heavy-current discharge.But in lead-acid accumulator production process, the electrolyte sulfuric acid temperature remains on 60 ℃, and sulfuric acid molecule wherein can the part evaporation enter air, forms acid mist with airborne hydrogenesis; Chemical reaction can occur in formation process on the other hand, produces hydrogen and oxygen, forms bubble floating explosion behind the liquid level, and sulfuric acid is taken out of with the droplet form.
The sulfuric acid mist of above-mentioned generation is the material between flue gas and water smoke, has stronger corrosivity, if do not processed, can be to personnel's skin, the mucous membrane in the workplace, and respiratory tracts etc. cause very big harm; The Long Term Contact sulfuric acid mist also can exert an influence to the circulatory system, digestive system, internal system, nervous system; Sulfuric acid mist also can corrode plant and equipment and precision instrument simultaneously.
In the prior art there being much the processing method of sulfuric acid mist, mainly contains static demist method, liquid absorption method, filtration method, cladding process, solid absorption method etc.Wherein the technology of static demist method is comparatively ripe, and sulfuric acid mist is had good assimilation effect, and absorptivity can reach more than 90%, but cost is higher, volume is large; Liquid absorption method has the advantages such as good absorbing effect, equipment investment are low, but has water consumption, problems such as power consumption is large, operating cost is high, equipment corrosion, secondary pollution and preventing freeze in winter; Filtration method has facility compact, easy to operate, the advantage such as recover materials is pure and running cost is lower, but have that filter area is less, filtration velocity should not be excessively high etc. problem; Cladding process is simple, is convenient to grasp, but is subjected to the restriction of process conditions, and effect was not good enough when acid strength was too high; The cost of solid absorption method is low, stable, the non-secondary pollution of generation product, but the general adsorbent capacity that adopts is limited, and assimilation effect is undesirable.
Summary of the invention
The removing method that the purpose of this invention is to provide a kind of sulfuric acid mist, the method not only price is cheap, and absorption property is good, can not bring secondary pollution, namely solve the governing problem of lead-acid accumulator factory sulfuric acid mist, solved again the processing problem of industrial waste flyash.
A kind of removing method of sulfuric acid mist, described method comprises:
Adopt solid waste coal ash that sulfuric acid mist is absorbed;
And further adopt NaOH or CaO as modifier described flyash to be carried out the alkaline activation modification, to improve the absorption property of described flyash.
When with described NaOH during as modifier, the concentration of described NaOH is 3mol/L, and temperature is 120 ℃, and solid-to-liquid ratio is 1:10, and the packing material size of modified coal ash is 3mm, and modification time is 5h.
When with described CaO during as modifier, described flyash and CaO mass ratio are 15, and the temperature of described CaO is 120 ℃, and solid-to-liquid ratio is 1:10, and the packing material size of modified coal ash is 3mm, modification time 5h.
Described method also comprises: when adopting NaOH or CaO as modifier described flyash to be carried out the alkaline activation modification, add polyvinyl alcohol and sodium carbonate.
Described flyash comes from the various coal-burning boilers of each factory.
As seen from the above technical solution provided by the invention, described method adopts solid waste coal ash that sulfuric acid mist is absorbed; And further adopt NaOH or CaO as modifier described flyash to be carried out the alkaline activation modification, to improve the absorption property of described flyash.The method not only price is cheap, and absorption property is good, can not bring secondary pollution, has namely solved the governing problem of lead-acid accumulator factory sulfuric acid mist, has solved again the processing problem of industrial waste flyash.
Description of drawings
In order to be illustrated more clearly in the technical scheme of the embodiment of the invention, the accompanying drawing of required use was done to introduce simply during the below will describe embodiment, apparently, accompanying drawing in the following describes only is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite of not paying creative work, can also obtain other accompanying drawings according to these accompanying drawings.
The flow chart of the sulfuric acid mist removing method that Fig. 1 provides for the embodiment of the invention;
Fig. 2 be after the modification that the embodiment of the invention gives an actual example flyash to the clearance comparing result schematic diagram of sulfuric acid mist.
The specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on embodiments of the invention, those of ordinary skills belong to protection scope of the present invention not making the every other embodiment that obtains under the creative work prerequisite.
Flyash described in the embodiment of the invention is the solid waste that produces in the coal-fired process, its forming process is that at first coal dust is injected in the coal furnace, some gasification temperatures are lower in the coal dust composition effusion, combustion heating, make coal dust have some holes, further become the porous carbon granules.Along with the rising of temperature, the organic compound combustion in the coal dust, the kaolin kinetics is SiO
2And Al
2O
3, iron sulfide is decomposed into Fe
2O
3By the time after the carbon in the coal dust divided whole all burnts, particle namely became porous vitreum, and coal ash has just become flyash, can collect from flue gas and obtain flyash.
Because flyash has porous, the characteristics that specific area is large, so good absorption property is arranged, mainly contain physical absorption and chemisorbed, also comprise the effects such as ion-exchange absorption, Electrostatic Absorption, flocculation absorption, precipitation and filtration, the embodiment of the invention is exactly to utilize the flyash after the modification to adsorb sulfuric acid mist.Below in conjunction with accompanying drawing the embodiment of the invention is described in further detail, is illustrated in figure 1 as the flow chart of the sulfuric acid mist removing method that the embodiment of the invention provides, described method comprises:
Step 11: adopt solid waste coal ash that sulfuric acid mist is absorbed;
In the specific implementation, the described flyash of the embodiment of the invention can come from the various coal-burning boilers of each factory.
Step 12: further adopt NaOH or CaO as modifier described flyash to be carried out the alkaline activation modification, to improve the absorption property of described flyash.
In this step, when using different modifier to carry out the alkaline activation modification, NaOH NaOH has respectively different best modified conditions with calcium oxide CaO:
When using described NaOH as modifier, the concentration of described NaOH is 3mol/L, and temperature is 120 ℃, and solid-to-liquid ratio is 1:10, and the packing material size of modified coal ash is 3mm, and modification time is 5h.
When using described CaO as modifier, described flyash and CaO mass ratio are 15, and the temperature of described CaO is 120 ℃, and solid-to-liquid ratio is 1:10, and the packing material size of modified coal ash is 3mm, modification time 5h.
In addition, described method also comprises:
When adopting NaOH or CaO as modifier described flyash to be carried out the alkaline activation modification, can also add polyvinyl alcohol and sodium carbonate, wherein the effect of polyvinyl alcohol is: binding agent makes the well moulding of flyash filler; And the effect of sodium carbonate is: alkali-activator, the silicate glass network structure in the flyash is had direct destruction, and can discharge inner soluble SiO
2And Al
2O
3Make the particle porous that becomes, volume increases, and specific area increases.
In addition, in specific implementation, above-mentioned alkaline matter as modifier can replace with other kin alkali.
The below comes the process of above-mentioned elimination sulfuric acid mist method is described with concrete example:
Present embodiment is by carrying out the sulfuric acid mist waste gas that modification comes Adsorption of Lead acid accumulator factory to produce to the flyash after the burning in the coal-burning boiler, simultaneously in view of the little problem of raw material Powder ash adsorption capacity, further flyash is carried out modification, change its surface or architectural characteristic, its reactivity is strengthened, improve the adsorption capacity of flyash.
With NaOH and two kinds of modifier of CaO for instance, present embodiment adopts NaOH and these two kinds of alkaline matters of CaO as main modifier flyash to be carried out the alkaline activation modification, adds simultaneously polyvinyl alcohol and sodium carbonate.The different modifier of above-mentioned employing has different modified conditions, specifically can pass through BET surface area method of testing, the test result of X-ray diffraction (XRD) method of testing and SEM sem test method obtains best modified condition, and the best modified condition that records in the embodiment of the invention is respectively:
NaOH modification method: the concentration of NaOH is 3mol/L, and temperature is 120 ℃, and solid-to-liquid ratio is 1:10, and the modified coal ash packing material size is 3mm, and modification time is 5h.
CaO modification method: flyash and CaO mass ratio are 15, and modification temperature is 120 ℃, and solid-to-liquid ratio is 1:10, and the packing material size of modified coal ash is 3mm, modification time 5h.
The below by various test modes to above-mentioned modification after the performance of flyash describe, still adopt two kinds of alkaline modifier of NaOH and CaO, then under its best modified condition, flyash is carried out modification respectively.
At first adopt SEM sem test method to detect, measure preliminary treatment before detection: after the solid absorbent after the modification was ground, behind the oven dry 24h, the sample that takes a morsel was fixed, metal spraying in baking oven, surveys ESEM.Scheme as can be known by the SEM that observes them:
After the modification of NaOH modification method, the destruction that causes crystal phase structure, the vitreum of fly ash grain generates novel substance, and particle diminishes, and porosity increases greatly, thereby has enlarged specific area.
Flyash Electronic Speculum figure after the modification of CaO modification method just can see clearly under 30,000 times of pixels, and with comparing before the modification, surface texture is destroyed, and surface roughness obviously increases, and it is many that fold becomes, and it is many that hole becomes, and particle diameter has diminished.As seen flyash is by the CaO modification, and the duct of flyash has obtained fully getting through, and it is large that specific area becomes, and surface energy has also improved.
Then detecting by BET surface area method of testing, before detection, carrying out Measurement preprocessing: after the solid absorbent after the modification is ground, in vacuum drying oven, behind the oven dry 24h, getting the 0.2000g sample and measure.Use the specific area instrument to measure the specific area of Adsorbent modification front and back, analyze the variation of modification front and back specific area:
The specific area of former flyash is 2.4215m
2/ g:
The specific area of flyash is 28.6912m after the NaOH modification
2/ g is with respect to former flyash 2.4215m
2The specific area of/g, the flyash specific area has approximately increased by 11.85 times after the modification;
The specific area of flyash is 32.8695m after the CaO modification
2/ g is with respect to former flyash 2.4215m
2The specific area of/g, the flyash specific area has approximately increased by 13.57 times after the modification.
Last experiment of adsorbing again sulfuric acid mist, sampling detect flyash after the modification to the clearance of sulfuric acid mist, comparing result as shown in Figure 2, as shown in Figure 2:
Former flyash can only reach 81.8% to the clearance of acid mist is the highest, and along with the time changes rapidly and reduces, has dropped to below 10% when 8h;
And the flyash of CaO modification obviously improves the adsorption effect of acid mist, and the highest clearance can reach 99%, and minimum (when soak time reaches 12h) also has more than 60%;
Through the flyash after the NaOH modification to the clearance of acid mist also much larger than former flyash, the clearance of sulfuric acid mist has been up to 98.5%, minimum (when soak time reaches 12h) also has 57%.
By above result as can be known, flyash after CaO and NaOH modification to the removal effect of acid mist all clearly, Powder ash adsorption effect after the CaO modification is slightly high, this may be interpreted as, remove after CaO and the flyash reaction and increased active site, increased outside porosity and the specific area, also had part with Ca (OH)
2Form enter flyash inside, also increased the clearance of sulfuric acid mist and effective adsorption time.
In sum, the method that the embodiment of the invention provides not only price is cheap, and absorption property is good, can not bring secondary pollution, has namely solved the governing problem of lead-acid accumulator factory sulfuric acid mist, has solved again the processing problem of industrial waste flyash.
The above; only for the better specific embodiment of the present invention, but protection scope of the present invention is not limited to this, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (5)
1. the removing method of a sulfuric acid mist is characterized in that, described method comprises:
Adopt solid waste coal ash that sulfuric acid mist is absorbed;
And further adopt NaOH or CaO as modifier described flyash to be carried out the alkaline activation modification, to improve the absorption property of described flyash.
2. the removing method of sulfuric acid mist as claimed in claim 1 is characterized in that, when with described NaOH during as modifier, the concentration of described NaOH is 3mol/L, and temperature is 120 ℃, and solid-to-liquid ratio is 1:10, and the packing material size of modified coal ash is 3mm, and modification time is 5h.
3. the removing method of sulfuric acid mist as claimed in claim 1 is characterized in that, when with described CaO during as modifier, described flyash and CaO mass ratio are 15, and the temperature of described CaO is 120 ℃, and solid-to-liquid ratio is 1:10, the packing material size of modified coal ash is 3mm, modification time 5h.
4. the removing method of sulfuric acid mist as claimed in claim 1 is characterized in that described method also comprises:
When adopting NaOH or CaO as modifier described flyash to be carried out the alkaline activation modification, add polyvinyl alcohol and sodium carbonate.
5. the removing method of sulfuric acid mist as claimed in claim 1 is characterized in that described flyash comes from the various coal-burning boilers of each factory.
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| CN2012105194786A CN102989260A (en) | 2012-12-05 | 2012-12-05 | Sulfuric acid mist elimination method |
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| CN2012105194786A CN102989260A (en) | 2012-12-05 | 2012-12-05 | Sulfuric acid mist elimination method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107246413A (en) * | 2017-05-25 | 2017-10-13 | 合肥皖化电泵有限公司 | A kind of stove water pump radiator structure filter disc |
| CN107583417A (en) * | 2017-08-31 | 2018-01-16 | 沈阳三聚凯特催化剂有限公司 | A kind of normal temperature gas phase antichlor and preparation method and application |
| CN111111421A (en) * | 2019-12-16 | 2020-05-08 | 山东电力工程咨询院有限公司 | Device and method for improving utilization rate of absorbent in sulfur trioxide removal process |
-
2012
- 2012-12-05 CN CN2012105194786A patent/CN102989260A/en active Pending
Non-Patent Citations (2)
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| 方瑜 等: "碱法改性粉煤灰处理铅酸蓄电池厂硫酸雾试验研究", 《2011中国功能材料科技与产业高层论坛论文集》 * |
| 王小云 等: "改性粉煤灰在酸雾治理方面的研究", 《环境工程学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107246413A (en) * | 2017-05-25 | 2017-10-13 | 合肥皖化电泵有限公司 | A kind of stove water pump radiator structure filter disc |
| CN107583417A (en) * | 2017-08-31 | 2018-01-16 | 沈阳三聚凯特催化剂有限公司 | A kind of normal temperature gas phase antichlor and preparation method and application |
| CN107583417B (en) * | 2017-08-31 | 2019-12-24 | 沈阳三聚凯特催化剂有限公司 | Normal-temperature gas-phase dechlorinating agent and preparation method and application thereof |
| CN111111421A (en) * | 2019-12-16 | 2020-05-08 | 山东电力工程咨询院有限公司 | Device and method for improving utilization rate of absorbent in sulfur trioxide removal process |
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Application publication date: 20130327 |