CN108355479B - Fluorine-containing gas purifying and recycling system and fluorine-containing gas defluorination method - Google Patents
Fluorine-containing gas purifying and recycling system and fluorine-containing gas defluorination method Download PDFInfo
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- CN108355479B CN108355479B CN201810355281.0A CN201810355281A CN108355479B CN 108355479 B CN108355479 B CN 108355479B CN 201810355281 A CN201810355281 A CN 201810355281A CN 108355479 B CN108355479 B CN 108355479B
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- 239000011737 fluorine Substances 0.000 title claims abstract description 135
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 135
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 25
- 238000004064 recycling Methods 0.000 title description 15
- 239000007921 spray Substances 0.000 claims abstract description 78
- -1 rare earth fluoride Chemical class 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 55
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 54
- 238000011084 recovery Methods 0.000 claims abstract description 27
- 238000000746 purification Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000012295 chemical reaction liquid Substances 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 52
- 239000011550 stock solution Substances 0.000 abstract description 16
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 67
- 238000012546 transfer Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 239000002516 radical scavenger Substances 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 6
- 229910052629 lepidolite Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 5
- 229960001633 lanthanum carbonate Drugs 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 208000002064 Dental Plaque Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010023232 Joint swelling Diseases 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RUYHESZEGBRDBD-UHFFFAOYSA-H [Pm+3].[Pm+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O Chemical compound [Pm+3].[Pm+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O RUYHESZEGBRDBD-UHFFFAOYSA-H 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- QGXMZGYYAAPYRV-UHFFFAOYSA-H dysprosium(3+);tricarbonate Chemical compound [Dy+3].[Dy+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QGXMZGYYAAPYRV-UHFFFAOYSA-H 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- AKFFNTKRAYWFRN-UHFFFAOYSA-N ethyl 5-(trifluoromethyl)-1h-pyrazole-3-carboxylate Chemical compound CCOC(=O)C=1C=C(C(F)(F)F)NN=1 AKFFNTKRAYWFRN-UHFFFAOYSA-N 0.000 description 1
- SULCVUWEGVSCPF-UHFFFAOYSA-L europium(2+);carbonate Chemical compound [Eu+2].[O-]C([O-])=O SULCVUWEGVSCPF-UHFFFAOYSA-L 0.000 description 1
- 239000004459 forage Substances 0.000 description 1
- RQXZRSYWGRRGCD-UHFFFAOYSA-H gadolinium(3+);tricarbonate Chemical compound [Gd+3].[Gd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O RQXZRSYWGRRGCD-UHFFFAOYSA-H 0.000 description 1
- FZKKGPOEHOOXQE-UHFFFAOYSA-H holmium(3+);tricarbonate Chemical compound [Ho+3].[Ho+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O FZKKGPOEHOOXQE-UHFFFAOYSA-H 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- UMTLFFUVLKOSNA-UHFFFAOYSA-H lutetium(3+);tricarbonate Chemical compound [Lu+3].[Lu+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O UMTLFFUVLKOSNA-UHFFFAOYSA-H 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- UTWHRPIUNFLOBE-UHFFFAOYSA-H neodymium(3+);tricarbonate Chemical compound [Nd+3].[Nd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O UTWHRPIUNFLOBE-UHFFFAOYSA-H 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- XIRHLBQGEYXJKG-UHFFFAOYSA-H praseodymium(3+);tricarbonate Chemical compound [Pr+3].[Pr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XIRHLBQGEYXJKG-UHFFFAOYSA-H 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- QCZFMLDHLOYOQJ-UHFFFAOYSA-H samarium(3+);tricarbonate Chemical compound [Sm+3].[Sm+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QCZFMLDHLOYOQJ-UHFFFAOYSA-H 0.000 description 1
- NYMLCLICEBTBKR-UHFFFAOYSA-H scandium(3+);tricarbonate Chemical compound [Sc+3].[Sc+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NYMLCLICEBTBKR-UHFFFAOYSA-H 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- LMEHHJBYKPTNLM-UHFFFAOYSA-H terbium(3+);tricarbonate Chemical compound [Tb+3].[Tb+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O LMEHHJBYKPTNLM-UHFFFAOYSA-H 0.000 description 1
- ZXOGQNPNWAUSGY-UHFFFAOYSA-H thulium(3+);tricarbonate Chemical compound [Tm+3].[Tm+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O ZXOGQNPNWAUSGY-UHFFFAOYSA-H 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- JCDQGOSXWGXOQQ-UHFFFAOYSA-H ytterbium(3+);tricarbonate Chemical compound [Yb+3].[Yb+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O JCDQGOSXWGXOQQ-UHFFFAOYSA-H 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/253—Halides
- C01F17/265—Fluorides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The utility model provides a fluorine-containing gas purification recovery system, including the second stock solution storehouse that connects gradually, the second spray column, first stock solution storehouse, first spray column, hydrocyclone and vacuum belt filter press, and vacuum belt filter press is connected with the second stock solution storehouse, first spray column is connected with the second spray column, hydrocyclone is connected with first stock solution storehouse, can carry out twice adsorption defluorination to fluorine-containing gas, the defluorination agent solution concentration in the second spray column is high, after the secondary defluorination, the secondary purification gas can discharge up to standard, reacted solution homoenergetic is recycled through this system, the recovery separates out rare earth fluoride product and excessive rare earth carbonate salt, rare earth fluoride product has better economic value, can sell out the product, and excessive rare earth carbonate salt then continues to circulate in great fluorine-containing gas purification recovery system, have great environmental protection meaning.
Description
Technical Field
The invention relates to the field of gas purification, in particular to a fluorine-containing gas purification and recovery system and a fluorine-containing gas defluorination method.
Background
Lepidolite is one of the main raw materials for extracting rare metal lithium. Lepidolite often contains rubidium and cesium, and is also an important raw material for extracting these rare metals. Lepidolite chemical composition K (Li, al) 2.5-3[ Si 3.5-3Al 0.5-1O10]The analysis data prove that all the mica containing lithium elements contains a certain amount of fluorine elements. The higher the lithium-containing element, the higher the fluorine element content. In typical lepidolite concentrates, the fluorine content is generally between 5% and 8% (mass fraction). Most of these fluorine elements exist in the form of alkali metal fluoride in minerals, so that fluorine-containing gas is generated as a by-product during lepidolite processing, fluorine is an accumulated poison, plant leaves and pastures can absorb fluorine, and after eating the polluted forage, the joint swelling is caused,Osteoporosis and even paralysis. Excessive fluorine intake by human body can interfere with enzyme activity, destroy calcium and phosphorus metabolic balance, and cause fluoripathy with symptoms of dental plaque, joint deformation, etc., so that fluorine-containing gas is required to be treated and reaches emission standard. At present, the treatment of lepidolite roasting fluorine-containing waste gas mainly adopts a calcium salt method, and the calcium salt mainly comprises CaO and CaCl 2 、Ca(OH) 2 And the like, calcium fluoride precipitates are formed by adding chemicals mainly containing calcium salts. The method has the advantages of simplicity, convenient treatment and low cost, but the lime has low solution degree, can only be added in the form of emulsion, and the CaF is produced 2 The precipitate is coated with Ca (OH) 2 The surface of the particles was coated with Ca (OH) 2 Cannot be fully utilized, resulting in large lime usage. The fluorine content in the treated wastewater can only be reduced to 20-50 mg/L generally, and cannot reach the first-level standard specified in the integrated wastewater discharge standard, and the wastewater has the defects of slow sedimentation, difficult dehydration, long period for treating large-flow discharge and inadaptability to continuous treatment and continuous discharge. The calcium salt method cannot lead the fluorine-containing gas to reach the emission standard, the treated solid product is calcium fluoride, and the economic value of the calcium fluoride is low.
Disclosure of Invention
The invention aims to solve the technical problem of providing a fluorine-containing gas purifying and recycling system and a fluorine-containing gas defluorination method.
The technical scheme for solving the technical problems is as follows: the utility model provides a fluorine-containing gas purification recovery system, includes first stock solution storehouse, first spray column, second stock solution storehouse, second spray column, hydrocyclone and vacuum belt filter press, the second stock solution storehouse the second spray column the first stock solution storehouse first spray column the hydrocyclone with vacuum belt filter press connects gradually, just vacuum belt filter press with the second stock solution storehouse is connected, first spray column is connected with the second spray column, the hydrocyclone with first stock solution storehouse is connected.
Further, the device also comprises a defluorinating agent bin, and the defluorinating agent bin is connected with the second liquid storage bin.
Further, the device also comprises a slurry discharge pump, and the first spray tower is connected with the hydrocyclone through the slurry discharge pump.
Further, a PH tester is arranged in the first spray tower.
Further, the second spray tower is provided with a PH meter.
A fluorine-containing gas defluorination method comprising a recovery system for the fluorine-containing gas comprising:
the raw material providing step: providing a fluorine-containing gas;
preparing a fluorine removing agent solution: preparing a fluorine removing agent solution comprising rare earth carbonate, and respectively adding the fluorine removing agent solution into the first liquid storage bin and the second liquid storage bin;
primary defluorination: introducing fluorine-containing gas into a first spray tower, conveying a fluorine removing agent solution of a first liquid storage bin to the first spray tower, and primarily removing fluorine from the fluorine-containing gas to obtain primary purified gas and a first reaction liquid;
and (3) a secondary defluorination step: conveying the primary purified gas from the first spray tower to the second spray tower, conveying the fluorine removing agent solution of the second liquid storage bin to the second spray tower, performing secondary fluorine removal on the primary purified gas to obtain secondary purified gas and second reaction liquid, and outputting the secondary purified gas from the second spray tower;
a first reaction liquid recovery step: conveying the first reaction liquid from a first spray tower to a hydrocyclone for separation to obtain water and slurry, conveying the water to a first liquid storage bin, conveying the slurry to a vacuum belt filter press for solid-liquid separation to obtain rare earth fluoride and a recovery liquid, outputting the rare earth fluoride, and conveying the recovery liquid to a second liquid storage bin; and
and a second reaction liquid recovery step: and conveying the second reaction liquid to the first liquid storage bin.
Further, the PH value of the defluorinating agent solution in the first liquid storage bin is 7-9.
Further, the PH value of the defluorinating agent solution in the second liquid storage bin is 5-8.
Further, the concentration of rare earth carbonate of the fluorine removing agent solution in the second liquid storage bin is 50-100 g/L.
Further, the fluorine removing agent solution is prepared by mixing rare earth carbonate and water.
The beneficial effects of the invention are as follows: through fluorine-containing gas purification recovery system, can carry out twice adsorption fluorine removal to fluorine-containing gas, the fluorine-removing agent solution concentration in the second spray column is high, and after the secondary removes fluorine, the secondary purification gas can discharge up to standard, and the solution of reaction can both be recycled through this system, and the recovery separates out rare earth fluoride product and excessive rare earth carbonate, and rare earth fluoride product has better economic value, can sell the product, and excessive rare earth carbonate then continues to circulate in fluorine-containing gas purification recovery system, has great environmental protection meaning, and fluorine-containing gas's fluorine removal method has following advantage: (1) the obtained rare earth fluoride product has higher economic value as a byproduct of the reaction, and can be sold to obtain a certain sales profit; (2) the rare earth carbonate is fully utilized, the materials can be recycled, after the secondary defluorination step, the unreacted and complete rare earth carbonate is recycled to the first spray tower for continuous use, and after the reaction of the rare earth carbonate in the first spray tower is finished, the byproduct rare earth fluoride is obtained through operations such as separation, filtration and the like, and the separation liquid is repeatedly utilized; (3) when the fluorine-containing gas purifying and recycling system is used, the fluorine-containing gas purifying and recycling system is in a circulating connection state, and after the fluorine-containing gas is input, only the timing is controlled to add the fluorine-removing agent solution into the second liquid storage bin, discharge the rare earth fluoride and discharge the standard-reaching gas, so that the continuous treatment and continuous discharge conditions can be realized.
Drawings
FIG. 1 is a schematic diagram of an embodiment of an apparatus connection of a fluorine-containing gas purification recovery system;
FIG. 2 is a schematic process flow diagram of a fluorine-containing gas purification recovery system and a fluorine-containing gas defluorination method according to one embodiment;
FIG. 3 is a process flow diagram of a method for fluorine removal of fluorine-containing gas in accordance with one embodiment.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
As shown in fig. 1, in one embodiment, a fluorine-containing gas purification recovery system includes a first liquid storage bin 100, a first spray tower 200, a second liquid storage bin 300, a second spray tower 400, a hydrocyclone 500, and a vacuum belt filter press 600, wherein the second liquid storage bin 300, the second spray tower 400, the first liquid storage bin 100, the first spray tower 200, the hydrocyclone 500, and the vacuum belt filter press 600 are sequentially connected, and the vacuum belt filter press 600 is connected with the second liquid storage bin 300, the first spray tower 200 is connected with the second spray tower 400, and the hydrocyclone 500 is connected with the first liquid storage bin 100. The fluorine-containing gas purifying and recycling system can adsorb and remove fluorine for two times, the rare earth fluoride product and excessive rare earth carbonate are separated during recycling, the rare earth fluoride product has better economic value, the product can be sold, and the excessive rare earth carbonate can be continuously recycled in the fluorine-containing gas purifying and recycling system, so that the fluorine-containing gas purifying and recycling system has an environment-friendly effect.
For the convenience understanding this scheme, specifically, first spray column has first air inlet, first department gas port, first inlet and first liquid outlet, the second spray column has second air inlet, second gas outlet, second inlet and second liquid outlet, fluorine-containing gas purifies recovery system includes gas-supply pipe, first transfer line, second transfer line, third transfer line and fourth transfer line, first spray column pass through the gas-supply pipe with the second spray column is connected, just first gas outlet passes through the gas-supply pipe with the second air inlet intercommunication, first stock solution storehouse passes through first transfer line with first spray column is connected, just the inside of first stock solution storehouse passes through first transfer line with first inlet intercommunication, first spray column passes through the second transfer line with the hydrocyclone is connected, just first liquid outlet passes through the second transfer line with the inside intercommunication of hydrocyclone, the second stock solution storehouse passes through the gas-supply pipe with the second transfer line with the second stock solution storehouse passes through the second transfer line and the second spray column passes through the second transfer line and the second stock solution storehouse passes through the second transfer line and the second spray column passes through the second stock solution storehouse and the second liquid storehouse passes through the second liquid storehouse and the second liquid storehouse is connected. In this way, material transport between the devices can be achieved.
To facilitate the transfer of the fluorine removal agent solution to the second reservoir 300, facilitate a continuous supply, and reduce labor, in one embodiment, a fluorine removal agent silo 700 is also included, the fluorine removal agent silo 700 being connected to the second reservoir 300. In this way, the prepared fluorine removal agent solution can be supplied to the fluorine removal agent bin 700 at one time, and the solution of the fluorine removal agent bin 700 can be slowly conveyed to the second liquid storage bin 300, so that the flow of pouring the fluorine removal agent solution is not required to be controlled manually, the effects of safety and labor saving are achieved, and meanwhile, the fluorine removal agent bin 700 can continuously supply the fluorine removal agent solution to the second liquid storage bin 300, and continuous supply is achieved. In order to achieve better effect, the flow rate of the fluorine removal agent storage bin 700 to the second liquid storage bin 300 can be controlled by using a known means, so that the effects of saving manpower and continuously supplying are achieved. For example, to achieve flow control, a three-phase microcomputer time-controlled switch is used to operate a liquid pump to achieve the function of delivering the fluorine scavenger solution at regular time and quantity. Of course, other well-known means with the same effect exist to realize the flow control, and the description of this embodiment is not repeated.
In order to enable better transportation of the mixed liquor in the first spray tower 200 to the hydrocyclone 500, in one embodiment, a slurry pump 800 is further included, and the first spray tower 200 is connected to the hydrocyclone 500 through the slurry pump 800. Because the rare earth fluoride content in the first spray tower 200 is higher than that in the second spray tower 400, and the rare earth fluoride is colloidal in the solution, the slurry pump 800 can be used for better conveying the mixed liquid in the first spray tower 200, so that the pipeline is prevented from being blocked, and the conveying speed of the mixed liquid is accelerated.
The inventors have found in practice that the mixed liquor in the first spray tower 200 has an optimum PH range for the recovered mixed liquor when recovered, and that in order to better monitor the PH of the mixed liquor in the first spray tower 200, in one embodiment, a PH meter is provided in the first spray tower 200. In this way, the PH of the mixed liquor in the first spray tower 200 can be measured, allowing for better monitoring of the PH of the solution in the first spray tower 200.
The inventors have found in practice that the mixed liquor in the second spray tower 400 is recovered with an optimum PH range for recovering the mixed liquor, and that in order to better monitor the PH of the mixed liquor in the second spray tower 400, in one embodiment, the second spray tower 400 is provided with a PH meter. In this way, the PH of the mixed liquor in the second spray tower 400 can be measured, allowing for better monitoring of the PH of the solution in the second spray tower 400.
As shown in fig. 1, 2 and 3, in one embodiment, there is provided a fluorine-containing gas defluorination method including a recovery system of the fluorine-containing gas, comprising the steps of:
the raw material providing step: providing a fluorine-containing gas.
Preparing a fluorine removing agent solution: a fluorine scavenger solution including rare earth carbonate is prepared and is added to the first and second reservoirs 100 and 300, respectively.
Primary defluorination: introducing fluorine-containing gas into a first spray tower 200, conveying the fluorine-removing agent solution of the first liquid storage bin 100 to the first spray tower 200, and primarily removing fluorine from the fluorine-containing gas to obtain primary purified gas and a first reaction solution, wherein the reaction is HF+ReCO 3 →ReF 3 +H 2 O, i.e., in this step, the fluorine-containing gas is HF (hydrogen fluoride) gas, and the first reaction liquid contains ReF3 (rare earth fluoride), a small amount of rare earth carbonate salt and water.
And (3) a secondary defluorination step: the primary purified gas is conveyed from the first spray tower 200 to the second spray tower 400, the defluorinating agent solution of the second liquid storage bin 300 is conveyed to the second spray tower 400, the primary purified gas is subjected to secondary defluorination to obtain secondary purified gas and second reaction liquid, and the secondary purified gas is output from the second spray tower 400, wherein the reaction is still HF+ReCO 3 →ReF 3 +H 2 O, in this step, HF (hydrogen fluoride) molecules are reactedThe fluorine scavenger solution is fully absorbed.
A first reaction liquid recovery step: the first reaction liquid is conveyed from the first spray tower 200 to the hydrocyclone 500 for separation to obtain water and slurry, the water is conveyed to the first liquid storage bin 100, the slurry is conveyed to the vacuum belt filter press 600 for solid-liquid separation to obtain rare earth fluoride and recovered liquid, the rare earth fluoride is output, and the recovered liquid is conveyed to the second liquid storage bin 300. In this step, the first reaction liquid, that is, the mixed solution of the ReF3 (rare earth fluoride), a small amount of rare earth carbonate, and water, which is produced in the primary defluorination step, is separated. The hydrocyclone separates out water and slurry, the slurry is composed of rare earth fluoride, a small amount of rare earth carbonate and a small amount of water, the vacuum belt filter press carries out solid-liquid separation, so that the solid rare earth fluoride is separated, namely, a small amount of rare earth carbonate and a small amount of water are left in the recovery liquid, and after separation, the recovery liquid is conveyed to a second liquid storage bin.
And a second reaction liquid recovery step: the second reaction solution is transferred to the first reservoir 100.
By combining the fluorine-containing gas purifying and recycling system and adopting the fluorine-containing gas defluorination method, the following beneficial effects can be achieved: (1) the obtained rare earth fluoride product has higher economic value as a byproduct of the reaction, and can be sold to obtain a certain sales profit; (2) fully utilizing rare earth carbonate, recycling the materials, recycling the unreacted and complete rare earth carbonate after the secondary defluorination step, recycling the unreacted and complete rare earth carbonate to the first spray tower 200 for continuous use, and obtaining a byproduct rare earth fluoride through operations such as separation, filtration and the like after the reaction of the rare earth carbonate in the first spray tower 200 is finished, and repeatedly utilizing the separation liquid; (3) when the fluorine-containing gas purifying and recycling system is used, the fluorine-containing gas purifying and recycling system is in a circulating connection state, and after the fluorine-containing gas is input, the fluorine-removing agent solution is only required to be added into the second liquid storage bin 300 at a controlled timing, the rare earth fluoride is discharged, and the standard gas is discharged, so that the continuous treatment and continuous discharge conditions can be realized.
The PH of the fluorine-removing agent solution may affect the fluorine-removing efficiency of the fluorine-containing gas, when the second reaction solution and water are mixed into the first liquid storage bin 100, the PH of the fluorine-removing agent solution in the first liquid storage bin 100 may be changed, and in the practical process, it is found that the fluorine-removing agent solution may increase the reaction rate of fluorine ions within a certain range, so that the PH of the fluorine-removing agent solution in the first liquid storage bin 100 may be finely adjusted to achieve a better fluorine-removing effect, in one embodiment, the PH of the fluorine-removing agent solution in the first liquid storage bin 100 is 7-9, and when the concentration of the fluorine-removing agent solution in the first liquid storage bin 100 is adjusted, the PH is controlled to be 7-9, which may well achieve the effect of primary fluorine removal, and significantly increase the fluorine-removing efficiency.
The PH of the fluorine-removing agent solution affects the fluorine removal effect of the fluorine-containing gas, and in practice, the fluorine-removing agent solution is found to react more fully with fluorine ions within a certain range, so that the fluorine ions of the fluorine-containing gas react fully, and in one embodiment, the PH of the fluorine-removing agent solution in the second liquid storage bin 300 is 5-8. The fluorine removing agent solution with the pH value of 5-8 can well adsorb a small amount of fluorine ions in fluorine-containing gas, so that a trace amount of fluorine ions can fully react with the fluorine removing agent solution, and further the fluorine removal of the fluorine-containing solution is more complete.
The concentration of rare earth carbonate in the fluorine-removing agent solution affects the fluorine-removing effect of the fluorine-containing gas, and in practice, the concentration of the fluorine-removing agent solution is found to be within a certain range, so that the fluorine-removing agent solution can more sufficiently and quickly adsorb fluorine ions of the fluorine-containing gas, and in one embodiment, the concentration of the rare earth carbonate in the fluorine-removing agent solution in the second liquid storage bin 300 is 50-100 g/L. When the rare earth carbonate is kept at 50-100 g/L, the absorption of fluorine ions is quicker, and the reaction of fluorine ions and rare earth carbonate is more sufficient.
A fluorine scavenger solution is provided, which in one embodiment is provided by mixing a rare earth carbonate salt with water. Specifically, the fluorine removing agent solution is prepared by mixing one or more of lanthanum carbonate, cerium carbonate, praseodymium carbonate, neodymium carbonate, promethium carbonate, samarium carbonate, europium carbonate, gadolinium carbonate, terbium carbonate, dysprosium carbonate, holmium carbonate, erbium carbonate, thulium carbonate, ytterbium carbonate, lutetium carbonate, yttrium carbonate and scandium carbonate with water. One or more of the rare earth carbonates are dissolved in water to prepare a fluorine removing agent solution, so that the fluorine removing effect on fluorine-containing gas is realized.
In one embodiment, a fluorine scavenger is provided, which consists of the following substances in parts by weight: lanthanum carbonate 0.2-0.4, and pure water in balance.
In one embodiment, a fluorine scavenger is provided, which consists of the following substances in parts by weight: lanthanum carbonate 0.1-0.2, cerium carbonate 0.1-0.2, and pure water in balance.
In one embodiment, a fluorine scavenger is provided, which consists of the following substances in parts by weight: 0.2 to 0.4 percent of lanthanum carbonate, 0.03 to 0.05 percent of polyacrylamide and the balance of pure water.
In one embodiment, a fluorine scavenger is provided, which consists of the following substances in parts by weight: lanthanum carbonate 0.34-0.36, polyacrylamide 0.038-0.042, and pure water in balance.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A fluorine removal method for a fluorine-containing gas, comprising:
providing a fluorine-containing gas purification recovery system comprising: the hydraulic cyclone device comprises a first liquid storage bin, a first spray tower, a second liquid storage bin, a second spray tower, a hydraulic cyclone and a vacuum belt filter press, wherein the second liquid storage bin, the second spray tower, the first liquid storage bin, the first spray tower, the hydraulic cyclone and the vacuum belt filter press are sequentially connected, the vacuum belt filter press is connected with the second liquid storage bin, the first spray tower is connected with the second spray tower, and the hydraulic cyclone is connected with the first liquid storage bin;
the raw material providing step: providing a fluorine-containing gas;
preparing a fluorine removing agent solution: preparing a fluorine removing agent solution comprising rare earth carbonate, and respectively adding the fluorine removing agent solution into the first liquid storage bin and the second liquid storage bin;
primary defluorination: introducing fluorine-containing gas into a first spray tower, conveying a fluorine removing agent solution of a first liquid storage bin to the first spray tower, and primarily removing fluorine from the fluorine-containing gas to obtain primary purified gas and a first reaction liquid;
and (3) a secondary defluorination step: conveying the primary purified gas from the first spray tower to the second spray tower, conveying the fluorine removing agent solution of the second liquid storage bin to the second spray tower, performing secondary fluorine removal on the primary purified gas to obtain secondary purified gas and second reaction liquid, and outputting the secondary purified gas from the second spray tower;
a first reaction liquid recovery step: conveying the first reaction liquid from a first spray tower to a hydrocyclone for separation to obtain water and slurry, conveying the water to a first liquid storage bin, conveying the slurry to a vacuum belt filter press for solid-liquid separation to obtain rare earth fluoride and a recovery liquid, outputting the rare earth fluoride, and conveying the recovery liquid to a second liquid storage bin; and
and a second reaction liquid recovery step: and conveying the second reaction liquid to the first liquid storage bin.
2. The fluorine-containing gas defluorination method according to claim 1, further comprising a defluorination agent bin connected to the second liquid storage bin.
3. The fluorine-containing gas defluorination method according to claim 1, further comprising a slurry discharge pump, wherein the first spray tower is connected with the hydrocyclone through the slurry discharge pump.
4. The fluorine-containing gas defluorination method according to claim 1, wherein a PH measuring instrument is provided in the first spray tower.
5. The fluorine-containing gas defluorination method according to claim 1, wherein the second spray tower is provided with a PH meter.
6. The fluorine-containing gas defluorination method according to claim 1, wherein the PH of the defluorination agent solution in the first liquid storage bin is 7-9.
7. The fluorine-containing gas defluorination method according to claim 1, wherein the PH value of the defluorination agent solution in the second liquid storage bin is 5-8.
8. The fluorine-containing gas defluorination method according to claim 1, wherein the concentration of rare earth carbonate of the defluorination agent solution in the second liquid storage bin is 50-100 g/L.
9. The fluorine-containing gas defluorination method according to claim 1, wherein the defluorination agent solution is prepared by mixing rare earth carbonate with water.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0431351A1 (en) * | 1989-12-07 | 1991-06-12 | MAN Nutzfahrzeuge Aktiengesellschaft | Method and apparatus of removing fluorine and anorganic fluorine compounds from gases |
| JP2008195592A (en) * | 2007-02-15 | 2008-08-28 | Stella Chemifa Corp | Process for recovering hydrogen chloride |
| CN101274151A (en) * | 2007-12-12 | 2008-10-01 | 杭州蓝星新材料技术有限公司 | Waste gas treatment method in on-line production of float low-emission glass and device thereof |
| CN102247708A (en) * | 2011-07-19 | 2011-11-23 | 北京北科环境工程有限公司 | Process for treating tail gas of rare earth mineral powder and concentrated sulphuric acid roasting process |
| CN103143235A (en) * | 2013-02-28 | 2013-06-12 | 包头稀土研究院 | Method for treating tail gas during production process for rare-earth metals and alloys |
| CN203139858U (en) * | 2013-03-18 | 2013-08-21 | 赣州嘉通新材料有限公司 | Novel rare-earth metal electrolytic cleaning device |
| CN103638775A (en) * | 2013-12-09 | 2014-03-19 | 深圳市芭田生态工程股份有限公司 | Treatment method of water vapor containing fluoride ammonia |
| CN103739048A (en) * | 2013-11-13 | 2014-04-23 | 南京格洛特环境工程股份有限公司 | Defluorination medicine and preparation method thereof |
| 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 |
| CN105107358A (en) * | 2015-08-31 | 2015-12-02 | 赣州嘉通新材料有限公司 | Rare earth metal smelting tail gas recovery device and method |
| CN205269384U (en) * | 2015-12-24 | 2016-06-01 | 上海皓清环保工程有限公司 | Utilize device of hydrogen fluoride in dynamic wave desorption tail gas |
| CN208212887U (en) * | 2018-04-19 | 2018-12-11 | 广东璞睿泰科环保科技有限公司 | A kind of fluoro-gas purification-recovery system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211035B (en) * | 2013-06-04 | 2016-08-31 | 四川玖长科技有限公司 | From the kiln discharge flue gas of kiln-process phosphoric acid technique, aquation inhales phosphorus and the method reclaiming fluorine |
-
2018
- 2018-04-19 CN CN201810355281.0A patent/CN108355479B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0431351A1 (en) * | 1989-12-07 | 1991-06-12 | MAN Nutzfahrzeuge Aktiengesellschaft | Method and apparatus of removing fluorine and anorganic fluorine compounds from gases |
| JP2008195592A (en) * | 2007-02-15 | 2008-08-28 | Stella Chemifa Corp | Process for recovering hydrogen chloride |
| CN101274151A (en) * | 2007-12-12 | 2008-10-01 | 杭州蓝星新材料技术有限公司 | Waste gas treatment method in on-line production of float low-emission glass and device thereof |
| CN102247708A (en) * | 2011-07-19 | 2011-11-23 | 北京北科环境工程有限公司 | Process for treating tail gas of rare earth mineral powder and concentrated sulphuric acid roasting process |
| CN103143235A (en) * | 2013-02-28 | 2013-06-12 | 包头稀土研究院 | Method for treating tail gas during production process for rare-earth metals and alloys |
| CN203139858U (en) * | 2013-03-18 | 2013-08-21 | 赣州嘉通新材料有限公司 | Novel rare-earth metal electrolytic cleaning device |
| CN103739048A (en) * | 2013-11-13 | 2014-04-23 | 南京格洛特环境工程股份有限公司 | Defluorination medicine and preparation method thereof |
| CN103638775A (en) * | 2013-12-09 | 2014-03-19 | 深圳市芭田生态工程股份有限公司 | Treatment method of water vapor containing fluoride ammonia |
| 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 |
| CN105107358A (en) * | 2015-08-31 | 2015-12-02 | 赣州嘉通新材料有限公司 | Rare earth metal smelting tail gas recovery device and method |
| CN205269384U (en) * | 2015-12-24 | 2016-06-01 | 上海皓清环保工程有限公司 | Utilize device of hydrogen fluoride in dynamic wave desorption tail gas |
| CN208212887U (en) * | 2018-04-19 | 2018-12-11 | 广东璞睿泰科环保科技有限公司 | A kind of fluoro-gas purification-recovery system |
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