CN204933227U - The equipment of a kind of Waste Hydrogen Fluoride Gas improvement and recycling - Google Patents
The equipment of a kind of Waste Hydrogen Fluoride Gas improvement and recycling Download PDFInfo
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- CN204933227U CN204933227U CN201520534007.1U CN201520534007U CN204933227U CN 204933227 U CN204933227 U CN 204933227U CN 201520534007 U CN201520534007 U CN 201520534007U CN 204933227 U CN204933227 U CN 204933227U
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- hydrogen fluoride
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- fluoride gas
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Abstract
The utility model discloses the equipment of the improvement of a kind of brand-new Waste Hydrogen Fluoride Gas and recycling, it is characterized in that, comprise blower fan, spray column, header tank, crystallization reactor and centrifuge, the outlet of described blower fan is connected with spray column, be connected with header tank bottom described spray column, be connected bottom described header tank by pump with spray column top, described pump is also connected with crystallization reactor, described crystallization reactor is connected with centrifuge, and described centrifuge is connected with header tank.
Description
Technical field
The utility model relates to field of industrial production, particularly relates to improvement and the recycling of Waste Hydrogen Fluoride Gas produced in the industrial production, belongs to environment protection treating field.
Background technology
Hydrogen fluoride gas is a kind of extremely strong corrosive agent, has severe toxicity.It is colourless gas, in atmosphere, as long as will produce the taste of stimulation more than 3ppm.HF is the toxic gas with strong and stimulating smell and severe corrosive, they to the harm of people than SO
2large about 20 times of gas.Fluoride gas comprises hydrogen fluoride (HF), ocratation (SiF
4), silicofluoric acid (H
2siF
6) etc., be the atmosphere pollution very strong to crop toxicity, wherein hydrogen fluoride is the fluoride that discharge capacity is maximum, toxicity is the strongest.Waste gas containing fluoride, to the harm of human body, has direct stimulus to the sense organ to injure, and also have the accumulation in body to poison, the fluorine as invaded human body about has 50% to deposit in tooth, bone.High-concentration fluorine-contained gas has stimulation damaging action to the respiratory tract of people and ocular delivery, can cause bronchitis, pneumonia, pulmonary edema, vomit, suffer from abdominal pain, gastrointestinal distress or the CNS intoxication symptom such as diarrhoea time serious, even makes people's death by suffocation.Produce fluorine and compound thereof sick to fluorine caused by practitioner, listed China's " occupational disease catalogue " in, belong to one of legal 56 kinds of occupational poisoning illness.Therefore, country is to Exposed fluorine and fluoride restricted property regulation: in workplace air, contained the highest of HF allows that mass concentration is 2mg/m
3(by F).
The diffusion of waste gas containing fluoride, transfer, comprise the sedimentation be mixed in acid rain, the pollution to air, water body, soil can be formed, and to the corrosion of building, equipment and the destruction etc. of ozone layer, also animals and plants are worked the mischief, actuatable thing death, plant necrosis when fluoride pollution is serious.Therefore, the waste gas containing fluoride that industrial production produces must purify qualified could discharge.
Hydrogen fluoride gas mainly comes from the industries such as chemical industry, metallurgy, building materials, thermoelectricity, electrolysis, factory containing fluorine in all use ores all can discharge fluoride, to the calcining at high temperature of fluorine-containing ore, melting or chemical reaction process, for example can discharge HF gas with sulfuric acid decomposition ground phosphate rock, HF discharges SiF with the silicon dioxde reaction in rock phosphate in powder again
4gas.Therefore, electrolytic aluminium factory, cement plant, thermal power plant, phosphoric acid and phosphate fertilizer plant etc. are the main sources of waste gas containing fluoride.Refer to table 1.
The source of table 1 fluorinated hydrogen waste gas
| Source categories | Production process or factory's classification | Release fluoride or fluoro-gas |
| Rock phosphate in powder | Phosphoric acid, phosphate fertilizer, phosphorus production | HF, SiF4 (a large amount of gas) |
| Ice crystal | Aluminum Electrolysis Production | Smoking gas containing fluorine |
| Fluorite | Fluorine contained chemicals is processed; Steel-making | Waste gas containing fluoride |
| Fluorine-containing ore (soil, coal) | Pottery, cement, glass, thermoelectricity, synthesis ammonia plant | Waste gas containing fluoride or flue dust |
For the process of hydrogen fluoride gas, prior art mainly utilizes water absorption method, alkali absorb method, adsorption cleaning method.Utilize water absorption method directly to form hydrofluoric acid solution, hydrofluoric acid is a kind of strong acid, therefore serious to the corrosivity of equipment.Alkali liquor absorption mainly utilizes NaOH, ammoniacal liquor isogonic akaline liquid absorbs hydrogen fluoride gas, after absorbing, solution becomes fluorine-containing salt compounds, therefore the corrosivity of equipment is reduced, but absorbing liquid becomes high-salt wastewater, mainly evaporative crystallization is adopted to the process of high-salt wastewater, the cost of evaporative crystallization is very high, and enterprise generally cannot bear.Adsorption cleaning method mainly utilizes the materials such as active carbon, aluminium oxide, diatomite to adsorb, the specific area of sorbing material is mainly utilized to adsorb, this technology can only process hydrogen fluoride concentration gas on the low side, and the hydrogen fluoride gas for high concentration is ineffective by reach capacity very soon.
Summary of the invention
The utility model content, for the problem such as equipment corrosion, spray liquid secondary pollution, hydrogen fluoride concentration limit value of existing hydrofluoric treatment technology, discloses the method for the improvement of a kind of brand-new hydrogen fluoride gas and recycling.Mainly comprise following step:
(1) utilize blower fan hydrogen fluoride gas to be carried out collection to concentrate, fan outlet is linked into the spray column containing lithium hydroxide absorbing liquid, carries out the spray-absorption of Waste Hydrogen Fluoride Gas;
(2) utilize lithium hydroxide absorbing liquid fully to be absorbed by hydrogen fluoride gas, the reaction of generation is: HF+LiOH → LiF+H
2o, the pH of monitoring spray-absorption liquid is to reacting completely;
(3) the spray-absorption liquid will reacted completely, adds lithium hydroxide solid, and stir, utilize common-ion effect to be separated out by lithium fluoride, Separation of Solid and Liquid, solid reclaims, and liquid returns in step (1) again and recycles.
Preferably, in step (1), the initial pH of lithium hydroxide absorbing liquid is 11-14.
Preferably, the pH of the middle absorbing liquid of step (2) is in 5-9 scope and reacts completely.
Preferably, in step (3), the amount adding solid lithium hydroxide is 10-100g/L.
The utility model also relates to the equipment of the improvement of a kind of Waste Hydrogen Fluoride Gas and recycling, comprise blower fan, spray column, header tank, crystallization reactor and centrifuge, the outlet of described blower fan is connected with spray column, header tank is connected with bottom described spray column, be connected with spray column top by pump bottom described header tank, described pump is also connected with crystallization reactor, and described crystallization reactor is connected with centrifuge, and the rejection filter liquid of described centrifuge is connected with header tank.
PH analyzer is provided with in described spray column.
PH analyzer is provided with in described header tank.
PH analyzer is provided with in described crystallization reactor.
Creationary improvement and the application technology as the second resource disclosing a kind of hydrogen fluoride gas of the utility model, the utility model has the following advantages:
(1) hydrogen fluoride gas assimilation effect significantly improves.Waste Hydrogen Fluoride Gas is a kind of acid waste gas, and absorbing liquid remains strong basicity state, and the absorption for hydrogen fluoride gas significantly improves, and greatly reduces the content of hydrogen fluoride gas in air.
(2) lithium salts is fluoridized in recovery.In the utility model, hydrogen fluoride and lithium hydroxide react and generate lithium fluoride, and the solubility of lithium fluoride is very little, be 1.6g/L under normal temperature, and the solubility under lithium hydroxide normal temperature is 126g/L, in absorbing liquid again after supplemental hydrogen lithia, according to the principle of common-ion effect, LiF Crystals can be separated out.
(3) huge economic benefit is obtained.An engineering that must implement of strengthen environmental protection during hydrogen fluoride gas process, needs to drop into a large amount of financial resources.But the utility model technology not only can be reduced to zero through environmental protection cost, can also obtain huge economic benefit.The cost of lithium hydroxide is 45000 yuan/ton, and the price of lithium fluoride is 100000-120000 yuan/ton, drops into lithium hydroxide and reclaims the price difference that lithium fluoride can obtain 60000 yuan per ton.The utility model is creative to be changed Environmental Inputs in order to the project of getting a profit, significant.
Accompanying drawing explanation
Fig. 1 is the pilot plant test flow chart of method described in the utility model;
Fig. 2 is the schematic diagram of the equipment of Waste Hydrogen Fluoride Gas improvement and recycling;
Wherein: 1 blower fan, 2 spray columns, 3 header tanks, 4 crystallization reactors, 5 centrifuges, 6 pumps.
Detailed description of the invention
embodiment 1 lithium fluoride separates out pilot plant test
1.1
materials and methods
1.1.1 experimental design
Experiment is carried out in the laboratory of Nanjing Ge Luote environmental project limited company.In the lab because cannot there be the generation of Waste Hydrogen Fluoride Gas, therefore we have prepared the lithium fluoride mother liquor of variable concentrations according to the solubility of lithium fluoride, then when adding lithium hydroxide solid, observe crystal precipitation state and crystal precipitation quality.The solubility of lithium hydroxide and lithium fluoride is as shown in table 2, and experimental program is as shown in table 3.
The solubility table (unit: g/100ml) of table 2LiOH and LiF
| 10℃ | 20℃ | 30℃ | 40℃ | 50℃ | 60℃ | 70℃ | 80℃ | 90℃ | 100℃ | |
| LiOH | 12.7 | 12.8 | 12.9 | 13.0 | 13.3 | 13.8 | -- | 15.3 | -- | 17.5 |
| LiF | -- | 0.16 | -- | -- | -- | -- | -- | -- | -- | -- |
Table 3 experimental program
1.1.2 Sequencing and analysis
Experiment equipment: pH analyzer, electronic balance, magnetic stirring apparatus, beaker, filter paper
Testing index: pH, adopts pH analyzer to measure; The amount of lithium fluoride: emperor's balance weighs; Lithium hydroxide addition: electronic balance weighing; Crystal separates out quality: electronic balance weighing;
1.1.3 data analysis
WordOffice2003 software and Excel software is adopted to carry out analytic statistics to experimental data.
results and analysis
In experimentation, have recorded the quality of crystal precipitation state after at every turn adding lithium hydroxide and crystallize out, experimental data is as shown in table 4.
Table 4 experimental result data
As can be seen from table 3 data, when the concentration of lithium fluoride is higher, more easily separate out LiF Crystals when adding lithium hydroxide, when lithium fluoride concentration one timing, the amount of the lithium hydroxide added increases, and its lixiviate quality separated out is also more.Its reason is due to common-ion effect, and when two kinds of salt containing same ion are water-soluble, their solubility all can reduce, but the solubility of lithium hydroxide comparatively lithium fluoride is compared, its solubility is much larger, and when lithium fluoride is close to sub-saturated state, can lithium fluoride be separated out, instead of lithium hydroxide.Therefore, in the solution of lithium fluoride, when adding lithium hydroxide solid, have LiF Crystals and separate out.As can be seen from the data, lithium fluoride concentration, when being greater than 1.0g/L, adds 20-50g lithium hydroxide, it is best that its LiF Crystals separates out effect, therefore, in pilot scale and engineering mimoir, control the concentration of lithium fluoride at more than 1.0g/L, then add lithium hydroxide solid.
conclusion
Can draw in the crystallization experiment carrying out lithium fluoride, in the sub-saturated solution of lithium fluoride, supplement a certain amount of lithium hydroxide, successfully LiF Crystals can be separated out, reclaim lithium fluoride.Meanwhile, spray liquid becomes the undersaturated strong alkali solution of lithium fluoride, can continue to recycle, and absorbs Waste Hydrogen Fluoride Gas.
the pilot experiment that embodiment 2 Waste Hydrogen Fluoride Gas absorbs
2.1
materials and methods
2.1.1 experimental design
Experiment is carried out in the laboratory of Nanjing Ge Luote environmental project limited company.After carrying out laboratory lab scale, carried out the design of testing pilot scale, its flow chart as shown in Figure 1.
As shown in Figure 2, build pilot-plant according to flow process, facility is made up of blower fan 1, spray column 2, pH analyzer, header tank 3, crystallization reactor 4, centrifuge 5 and pump 6 etc.Concrete connected mode is: the outlet of blower fan 1 is connected with spray column 2, header tank 3 is connected with bottom described spray column 2, be connected with spray column 2 top by pump 6 bottom described header tank 3, described pump 6 is also connected with crystallization reactor 4, described crystallization reactor 4 is connected with centrifuge 5, and described centrifuge 5 is connected with header tank 3.PH analyzer is equipped with in described spray column 2, header tank 3 and crystallization reactor.
Experiment is carried out at normal temperatures, and temperature is about 25 degrees Celsius, and experiment is mainly divided into three steps:
Step one: preparation lithium hydroxide spray liquid, initial concentration is 10g/L, pH is 13.62, and the volume of spray liquid is 50L; Utilize blower fan 1 hydrogen fluoride gas to be carried out collection to concentrate, blower fan 1 outlet is linked into the spray column 2 of circulated sprinkling lithium hydroxide absorbing liquid, carries out the spray-absorption of Waste Hydrogen Fluoride Gas;
Step 2: utilize lithium hydroxide absorbing liquid fully to be absorbed by hydrogen fluoride gas, the reaction of generation is: HF+LiOH → LiF+H
2o.The pH change of on-line monitoring spray-absorption liquid, until when spray-absorption liquid pH is for pH shown in table 5, spray liquid is entered header tank 3, after stopping spray-absorption, spray-absorption liquid in header tank 3 is entered crystallization reactor 4, in crystallization reactor 4, supplements 2.5kg lithium hydroxide solid in every 50L spray liquid, stir, after the temperature cooling of solution, send into centrifuge 5 and carry out Separation of Solid and Liquid;
Step 3: pilot scale adopts precipitation+centrifugal pattern when Separation of Solid and Liquid, finally obtains lithium fluoride solid, centrifugal go out liquid continue reuse, form circulation, make spray liquid " zero-emission ".
sequencing and analysis
Experiment equipment: pH analyzer, electronic balance, header tank, blower fan etc.
Testing index: pH, adopts pH analyzer to measure; The amount of lithium fluoride: emperor's balance weighs; Lithium hydroxide addition: electronic balance weighing; Crystal separates out quality: electronic balance weighing;
2.1.3 data analysis
WordOffice2003 software and Excel software is adopted to carry out analytic statistics to experimental data.
results and analysis
Its experimental data is as shown in table 5.
Table 5 pilot experiment data
| Sequence number | pH | Crystal separates out quality g | Add spray liquid pH after alkali |
| Initial spray liquid | 13.62 | - | - |
| Spray liquid 1 | 9.03 | 35.6 | 13.70 |
| Spray liquid 2 | 8.11 | 42.4 | 13.42 |
| Spray liquid 3 | 7.06 | 59.7 | 13.11 |
| Spray liquid 4 | 6.22 | 72.5 | 13.02 |
| Spray liquid 5 | 5.61 | 76.3 | 12.56 |
As can be seen from the data in table 4, along with the pH of spray liquid is lower, the LiF Crystals of separating out after supplemental hydrogen lithia is more.Because the hydrogen fluoride gas that pH lower explanation spray liquid absorbs is more, its lithium fluoride generated is more, therefore when after the lithium hydroxide adding certain mass, can separate out more crystal.Spray liquid is after supplemental hydrogen lithia, and pH value of solution is strong basicity, can not reduce, and achieve the zero-emission of spray liquid, achieve the unification of environmental benefit and economic benefit in the process that spray liquid recycles to the assimilation effect of hydrogen fluoride gas.
From embodiment 1 and 2, creationary improvement and the application technology as the second resource developing a kind of hydrogen fluoride gas of this research, its characteristic is: (1) absorbing liquid remains strong basicity state, and hydrogen fluoride gas assimilation effect significantly improves; (2) reclaim and fluoridize lithium salts, in absorbing liquid again after supplemental hydrogen lithia, according to the principle of common-ion effect, separate out LiF Crystals; (3) obtain huge economic benefit, according to the price difference of lithium hydroxide and lithium fluoride, huge economic benefit can be obtained; (4) zero-emission of spray liquid, spray liquid after adding lithium hydroxide, according to common-ion effect, can separate out LiF Crystals in spray, the lithium fluoride therefore in spray liquid is undersaturated condition, and highly basic state, therefore can recycle, realize the zero-emission of spray liquid.
Claims (4)
1. the equipment of a Waste Hydrogen Fluoride Gas improvement and recycling, it is characterized in that, comprise blower fan, spray column, header tank, crystallization reactor and centrifuge, the outlet of described blower fan is connected with spray column, be connected with header tank bottom described spray column, be connected bottom described header tank by pump with spray column top, described pump is also connected with crystallization reactor, described crystallization reactor is connected with centrifuge, and described centrifuge is connected with header tank.
2. the equipment of a kind of Waste Hydrogen Fluoride Gas improvement according to claim 1 and recycling, is characterized in that, be provided with pH analyzer in described spray column.
3. the equipment of a kind of Waste Hydrogen Fluoride Gas improvement according to claim 1 and recycling, is characterized in that, be provided with pH analyzer in described header tank.
4. the equipment of a kind of Waste Hydrogen Fluoride Gas improvement according to claim 1 and recycling, is characterized in that, be provided with pH analyzer in described crystallization reactor.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201520534007.1U CN204933227U (en) | 2015-07-22 | 2015-07-22 | The equipment of a kind of Waste Hydrogen Fluoride Gas improvement and recycling |
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|---|---|---|---|
| CN201520534007.1U CN204933227U (en) | 2015-07-22 | 2015-07-22 | The equipment of a kind of Waste Hydrogen Fluoride Gas improvement and recycling |
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|---|---|
| CN204933227U true CN204933227U (en) | 2016-01-06 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971609A (en) * | 2015-07-22 | 2015-10-14 | 南京格洛特环境工程股份有限公司 | Hydrogen fluoride waste gas control and recycling method and equipment |
| CN108654347A (en) * | 2018-04-17 | 2018-10-16 | 江苏金石稀土有限公司 | A kind of method that fluoride system electrolysis rare earth waste gas recovery utilizes |
-
2015
- 2015-07-22 CN CN201520534007.1U patent/CN204933227U/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971609A (en) * | 2015-07-22 | 2015-10-14 | 南京格洛特环境工程股份有限公司 | Hydrogen fluoride waste gas control and recycling method and equipment |
| CN108654347A (en) * | 2018-04-17 | 2018-10-16 | 江苏金石稀土有限公司 | A kind of method that fluoride system electrolysis rare earth waste gas recovery utilizes |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160106 Termination date: 20170722 |