CN109384330B - Carbon dioxide decalcification system and method suitable for gypsum neutralization process treatment post-treatment liquid - Google Patents
Carbon dioxide decalcification system and method suitable for gypsum neutralization process treatment post-treatment liquid Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 185
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 81
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 75
- 239000010440 gypsum Substances 0.000 title claims abstract description 72
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 72
- 238000006386 neutralization reaction Methods 0.000 title claims abstract description 63
- 230000008569 process Effects 0.000 title claims abstract description 41
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 88
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 44
- 235000019738 Limestone Nutrition 0.000 claims abstract description 40
- 239000006028 limestone Substances 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 39
- 239000008267 milk Substances 0.000 claims abstract description 36
- 210000004080 milk Anatomy 0.000 claims abstract description 36
- 235000013336 milk Nutrition 0.000 claims abstract description 36
- 239000002699 waste material Substances 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 239000000839 emulsion Substances 0.000 claims abstract description 24
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 23
- 238000005189 flocculation Methods 0.000 claims abstract description 21
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 20
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 20
- 239000004571 lime Substances 0.000 claims abstract description 20
- 230000016615 flocculation Effects 0.000 claims abstract description 19
- 238000005273 aeration Methods 0.000 claims abstract description 16
- 150000002505 iron Chemical class 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 239000008394 flocculating agent Substances 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims description 44
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 33
- 229910052791 calcium Inorganic materials 0.000 claims description 33
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 24
- 229910001385 heavy metal Inorganic materials 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000005276 aerator Methods 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 22
- 229910001424 calcium ion Inorganic materials 0.000 description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 20
- 150000002500 ions Chemical class 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 9
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 8
- 230000009471 action Effects 0.000 description 8
- 229910052785 arsenic Inorganic materials 0.000 description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 8
- -1 fluoride ions Chemical class 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910004261 CaF 2 Inorganic materials 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 2
- NVDORESINSWXKC-UHFFFAOYSA-N [Ca].O=C=O Chemical compound [Ca].O=C=O NVDORESINSWXKC-UHFFFAOYSA-N 0.000 description 2
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 description 2
- 229940103357 calcium arsenate Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 230000003993 interaction Effects 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
- 230000008719 thickening Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
- C02F5/06—Softening water by precipitation of the hardness using calcium compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a carbon dioxide decalcification system and a method suitable for a liquid after gypsum neutralization process treatment, wherein the system comprises the following steps: the gypsum reaction tank is provided with a limestone emulsion inlet, a waste acid inlet containing sulfuric acid, a carbon dioxide outlet, a gypsum outlet and a reacted liquid outlet; the neutralization reaction device is provided with a post-reaction liquid inlet, a lime milk inlet, an iron salt inlet, a precipitation outlet and a post-neutralization liquid outlet; an aeration reaction tank having a neutralized liquid inlet, a carbon dioxide inlet, and a mixed liquid outlet; the flocculation reaction tank is provided with a mixed liquid inlet, a flocculating agent inlet and a flocculated liquid outlet; the filtering device is provided with a flocculated liquid inlet, a filtered liquid outlet and a calcium carbonate outlet, and the calcium carbonate outlet is connected with the limestone emulsion inlet.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a carbon dioxide decalcification system and a method suitable for a liquid after gypsum neutralization process treatment.
Background
At present, most of acid-making wastewater generated by nonferrous smelting enterprises is treated by adopting a gypsum neutralization process, namely, limestone milk is utilized to neutralize waste acid to prepare gypsum, most of free acid and fluoride ions are removed, and lime milk and ferric salt are utilized to remove heavy metal ions in the wastewater. Even if the neutralized liquid obtained by the method meets the standard, the neutralized liquid needs to be recycled completely according to the national environmental protection requirement, and no matter the neutralized liquid is directly recycled or recycled after advanced treatment, calcium ions in the wastewater need to be removed to reduce the hardness of the wastewater, so that the damage of calcium scaling to subsequent equipment and pipelines is prevented. The existing method for removing calcium from wastewater mainly comprises a sodium carbonate method and a carbon dioxide method, wherein the former method has good calcium removing effect, but has high medicament cost, and the latter method generally adopts outsourced carbon dioxide as a calcium removing agent, and the medicament cost for treatment is 30% -40% of that of the former method, but needs to increase supporting equipment such as carbon dioxide storage, replacement, addition and the like. The traditional calcium removal process removes the calcium ions in the neutralized liquid, and the chemical cost of only carbon dioxide or sodium carbonate reaches 1-1.2 yuan and 2-2.3 yuan respectively according to the Ca concentration of the effluent of 250mg/L, and the higher chemical cost is the biggest limitation of the traditional wastewater calcium removal process at present.
Thus, the existing technology for treating wastewater needs to be further improved.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. It is therefore an object of the present invention to provide a carbon dioxide decalcification system and method suitable for use with post-gypsum neutralization process fluids. The system saves the cost of the calcium remover, saves the cost of the gypsum neutralization process, has stable operation, and can save 80-85% of treatment cost and 85-90% of operation cost compared with the traditional process.
In one aspect, the invention provides a carbon dioxide decalcification system for use with a post-gypsum neutralization process treatment fluid, the system comprising, in accordance with an embodiment of the invention:
the gypsum reaction tank is provided with a limestone emulsion inlet, a sulfuric acid-containing waste acid inlet, a carbon dioxide outlet, a gypsum outlet and a post-reaction liquid outlet, and is suitable for carrying out neutralization reaction on the limestone emulsion and the sulfuric acid-containing waste acid so as to obtain carbon dioxide, gypsum and a post-reaction liquid;
the neutralization reaction device is provided with a post-reaction liquid inlet, a lime milk inlet, an iron salt inlet, a precipitation outlet and a post-neutralization liquid outlet, wherein the post-reaction liquid inlet is connected with the post-reaction liquid outlet and is suitable for carrying out a neutralization reaction on the post-reaction liquid, the lime milk and the iron salt so as to obtain a post-neutralization liquid and a precipitate containing calcium sulfate and heavy metal hydroxide;
the aeration reaction tank is provided with a neutralized liquid inlet, a carbon dioxide inlet and a mixed liquid outlet, wherein the neutralized liquid inlet is connected with the neutralized liquid outlet, and the carbon dioxide inlet is connected with the carbon dioxide outlet and is suitable for mixing the neutralized liquid and the carbon dioxide so as to obtain a mixed liquid;
the flocculation reaction tank is provided with a mixed liquid inlet, a flocculating agent inlet and a flocculated liquid outlet, wherein the mixed liquid inlet is connected with the mixed liquid outlet and is suitable for mixing the mixed liquid with the flocculating agent for flocculation treatment so as to obtain flocculated liquid;
the filtering device is provided with a flocculated liquid inlet, a filtered liquid outlet and a calcium carbonate outlet, the flocculated liquid inlet is connected with the flocculated liquid outlet, the calcium carbonate outlet is connected with the limestone emulsion inlet and is suitable for filtering the flocculated liquid so as to obtain filtered liquid and calcium carbonate, and the calcium carbonate is returned to the gypsum reaction tank to be used as limestone emulsion.
According to the carbon dioxide calcium removing system suitable for the liquid after the gypsum neutralization process treatment, limestone milk is firstly utilized to treat sulfuric acid-containing waste acid, most of free acid and fluoride ions in the sulfuric acid-containing waste acid are removed to obtain carbon dioxide, gypsum and reacted liquid, then lime milk, ferric salt and the reacted liquid are utilized to react, calcium sulfate and heavy metal ions in the reacted liquid are removed to obtain neutralized liquid, then carbon dioxide generated in the front is used as a calcium removing agent to act on the neutralized liquid, and after aeration, flocculation and filtration, calcium ions in the neutralized liquid are removed in the form of calcium carbonate, so that the filtered liquid which can be recycled or discharged is obtained, and the obtained calcium carbonate can be used as limestone milk for a gypsum reaction tank. Compared with the prior art, the system saves the cost of the calcium remover, the cost of the gypsum neutralization process, and has stable operation, and can save 80-85% of treatment cost and 85-90% of operation cost.
In addition, the carbon dioxide decalcification system applicable to the treated liquid of the gypsum neutralization process according to the above embodiment of the present invention may have the following additional technical features:
in some embodiments of the invention, the aeration reaction tank is an inflatable aerator, and an inflatable suspension machine is disposed within the inflatable aerator. Thereby, the utilization rate of carbon dioxide and the yield of calcium carbonate are improved.
In some embodiments of the invention, the filtration device is a suspended filler filter. Thus, the filter efficiency of the filter device is improved and the blockage is avoided.
In still another aspect, the present invention provides a method for removing calcium from carbon dioxide, which is applied to a post-treatment liquid of a gypsum neutralization process, using the above-mentioned system for removing calcium from carbon dioxide, and according to an embodiment of the present invention, the method comprises:
(1) Limestone emulsion and waste acid containing sulfuric acid are supplied to the gypsum reaction tank for neutralization reaction so as to obtain carbon dioxide, gypsum and reacted liquid;
(2) Lime milk, ferric salt and the reacted liquid are supplied to the neutralization reaction device for neutralization reaction so as to obtain precipitation and neutralized liquid;
(3) Supplying the neutralized liquid and the carbon dioxide to the aeration reaction tank for mixing so as to obtain a mixed liquid;
(4) Feeding a flocculating agent and the mixed liquid into the flocculation reaction tank for flocculation reaction so as to obtain flocculated liquid;
(5) And (2) feeding the flocculated liquid into the filtering device for filtering treatment so as to obtain filtered liquid and calcium carbonate, and returning the calcium carbonate to the gypsum reaction tank in the step (1) for use as limestone emulsion.
According to the method for removing calcium by using carbon dioxide, which is suitable for the liquid after the treatment of the gypsum neutralization process, firstly, limestone milk is utilized to treat sulfuric acid-containing waste acid, most of free acid and fluoride ions in the sulfuric acid-containing waste acid are removed, carbon dioxide, gypsum and reacted liquid are obtained, then lime milk, ferric salt and the reacted liquid are utilized to react, calcium sulfate and heavy metal ions in the reacted liquid are removed, neutralized liquid is obtained, then, carbon dioxide generated in the front is used as a calcium removing agent to act on the neutralized liquid, and after aeration, flocculation and filtration, calcium ions in the neutralized liquid are removed in the form of calcium carbonate, so that the filtered liquid which can be recycled or discharged is obtained, and the obtained calcium carbonate can be used as limestone milk for a gypsum reaction tank. Compared with the prior art, the method saves the cost of the calcium remover, saves the cost of the gypsum neutralization process, has stable operation, and can save 80-85% of treatment cost and 85-90% of operation cost.
In addition, the method for removing calcium by carbon dioxide, which is applicable to the liquid after the gypsum neutralization process treatment, according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the invention, in step (1), the pH of the post-reaction solution is from 2.5 to 3. Thereby facilitating the removal of free acid and fluoride ions from the spent acid containing sulfuric acid.
In some embodiments of the invention, in step (2), the pH of the neutralized liquid is 10.5 to 11. Thereby being beneficial to removing calcium sulfate and heavy metal ions in the reacted liquid.
In some embodiments of the invention, in step (3), the flow rate of carbon dioxide is 1.1 to 1.3 times the theoretical required amount. Thereby facilitating the removal of calcium ions from the neutralized liquid.
In some embodiments of the invention, in step (3), the pH of the neutralized liquid is 11-12. Thereby, calcium ions in the neutralized liquid can be further removed.
In some embodiments of the invention, in step (3), the pH of the mixed liquor is 7.5-8. Thereby, calcium ions in the neutralized liquid can be further removed.
In some embodiments of the invention, in step (4), the flocculant is polyacrylamide. Thereby, calcium ions in the neutralized liquid can be further removed.
In some embodiments of the invention, in step (4), the flocculant is added in an amount of 2-4mg per liter of the post-mix liquid. Thereby, calcium ions in the neutralized liquid can be further removed.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic diagram of a carbon dioxide decalcification system suitable for use with a post-gypsum neutralization process treatment fluid in accordance with one embodiment of the present invention;
FIG. 2 is a schematic flow diagram of a method for removing calcium from carbon dioxide suitable for use in the post-gypsum neutralization process treatment fluid in accordance with one embodiment of the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In one aspect of the present invention, there is provided a carbon dioxide decalcification system for use with a post-gypsum neutralization process treatment fluid, according to an embodiment of the present invention, and referring to FIG. 1, the system comprises: gypsum reaction tank 100, neutralization reaction apparatus 200, aeration reaction tank 300, flocculation reaction tank 400, and filtration apparatus 500.
According to an embodiment of the present invention, the gypsum reaction tank 100 has a limestone milk inlet 101, a sulfuric acid-containing waste acid inlet 102, a carbon dioxide outlet 103, a gypsum outlet 104, and a post-reaction liquid outlet 105, and is adapted to neutralize limestone milk with sulfuric acid-containing waste acid to obtain carbon dioxide, gypsum, and a post-reaction liquid. Specifically, the sulfuric acid-containing waste acid is acid-making waste water generated by nonferrous smelting enterprises, and the main components comprise: sulfuric acid, hydrofluoric acid, arsenic, and heavy metal ions. Under the action of limestone emulsion, sulfuric acid and hydrofluoric acid in sulfuric acid-containing waste acid react with calcium carbonate to produce calcium sulfate (gypsum) and calcium fluoride precipitate respectively, so that most of free acid and fluoride ions in sulfuric acid-containing waste acid can be removed, carbon dioxide can be obtained, and main components of reaction liquid obtained after the reaction are small amount of sulfuric acid and hydrofluoric acid, and arsenic and heavy metal ions. The chemical reactions mainly occurring in the gypsum reaction tank are:
CaCO 3 +H 2 SO 4 ＝CaSO 4 ↓+CO 2 ↑+H 2 O (1)
CaCO 3 +2HF＝CaF 2 ↓+CO 2 ↑+H 2 O (2)
according to one embodiment of the invention, the pH of the post-reaction solution may be 2.5-3. The inventor finds that the pH value of the liquid after the reaction depends on the mixing mass ratio of limestone emulsion and sulfuric acid-containing waste acid, if the content of the limestone emulsion is too high, the pH value of the liquid after the reaction is increased, the content of heavy metal ions in gypsum is increased, and the quality of the gypsum is reduced; if the content of limestone emulsion is too low, the aim of removing waste acid cannot be achieved, the gypsum yield is reduced, and the neutralization treatment cost is increased. Therefore, the pH value of the reacted liquid is controlled in the range disclosed by the invention, so that the quality and the yield of gypsum can be improved, and the cost of neutralization treatment can be reduced.
According to an embodiment of the invention, the neutralization reaction apparatus 200 has a post-reaction liquid inlet 201, a lime milk inlet 202, an iron salt inlet 203, a precipitation outlet 204 and a post-neutralization liquid outlet 205, the post-reaction liquid inlet 201 being connected to the post-reaction liquid outlet 105 and being adapted to carry out a neutralization reaction of the post-reaction liquid with lime milk, iron salt so as to obtain a post-neutralization liquid and a precipitate containing calcium sulfate and heavy metal hydroxide. Specifically, the main components of the reaction solution comprise a small amount of sulfuric acid, hydrofluoric acid, arsenic and heavy metal ions, and the sulfuric acid, the hydrofluoric acid, the arsenic and most of the heavy metal ions in the reaction solution are removed in a precipitation form under the action of lime milk and ferric salt. After the reaction is finished, the obtained precipitate mainly comprises calcium sulfate, metal hydroxide precipitate, calcium arsenate, calcium fluoride and the like. The chemical reaction formula mainly comprises:
H 2 SO 4 +Ca(OH) 2 ＝CaSO 4 ·2H 2 O↓ (3)
CuSO 4 +Ca(OH) 2 +2H 2 O＝Cu(OH) 2 ↓+CaSO 4 ·2H 2 O (4)
ZnSO 4 +Ca(OH) 2 +2H 2 O＝Fe(OH) 2 ↓+CaSO 4 ·2H 2 O (5)
2H 3 AsO 4 +3Ca(OH) 2 ＝Ca 3 (AsO 4 ) 2 ↓+3H 2 O (6)
2HF+Ca(OH) 2 ＝CaF 2 ↓+2H 2 O (7)
according to one embodiment of the invention, the pH value of the neutralized liquid is 10.5-11, and the inventor finds that the pH value of the neutralized liquid is determined by the mixing mass ratio of the reacted liquid, lime milk and ferric salt, wherein the adding amount of the ferric salt is according to the iron-arsenic ratio 1: (4-10), and the ratio is too high or too low, which leads to the effluent not reaching the standard and increases the neutralization treatment cost.
According to an embodiment of the present invention, the aeration reaction tank 300 has a post-neutralization liquid inlet 301, a carbon dioxide inlet 302 and a post-mixing liquid outlet 303, the post-neutralization liquid inlet 301 being connected to the post-neutralization liquid outlet 205, the carbon dioxide inlet 302 being connected to the carbon dioxide outlet 103 and being adapted to mix the post-neutralization liquid with carbon dioxide so as to obtain a mixed post-liquid. Specifically, under the action of carbon dioxide, calcium ions in the neutralized liquid are converted into calcium carbonate, so that the calcium ions in the neutralized liquid can be removed, and the carbon dioxide comes from a gypsum reaction tank, so that the medicament cost of a calcium removing agent (carbon dioxide or sodium carbonate) is saved.
According to an embodiment of the present invention, the aeration reaction tank is not particularly limited, and a person skilled in the art may select according to actual needs, and according to an embodiment of the present invention, the aeration reaction tank may be an inflatable aerator, and an inflatable suspension machine is provided inside the inflatable aerator. The inventor finds that compared with the traditional perforation aeration process, the utilization rate of carbon dioxide and the conversion efficiency of calcium ions in the neutralized liquid into calcium carbonate can be obviously improved by adopting an inflatable aerator.
According to still another embodiment of the present invention, the flow rate of carbon dioxide is not particularly limited, and may be selected according to actual needs by those skilled in the art, and according to a specific embodiment of the present invention, the flow rate of carbon dioxide may be 1.1 to 1.3 times the theoretical required amount. The inventor finds that if the flow rate of the carbon dioxide is too high, the waste of the carbon dioxide is caused, and if the flow rate of the carbon dioxide is too low, the amount of calcium ions converted into calcium carbonate in the neutralized liquid is reduced, so that the hard removal requirement on the neutralized liquid is not facilitated, and the yield of the calcium carbonate obtained later and the quality of the filtered liquid are affected.
According to still another embodiment of the present invention, the pH of the mixed solution is not particularly limited, and may be selected according to actual needs by those skilled in the art, and according to one embodiment of the present invention, the pH of the mixed solution may be 7.5 to 8. The inventor finds that if the pH value of the mixed liquid is too high, the calcium removal effect is not good; if the pH of the mixed solution is too low, the dissolution will occur, which is not conducive to removing calcium ions in the neutralized solution.
According to an embodiment of the present invention, flocculation reaction tank 400 has a post-mixing liquid inlet 401, a flocculant inlet 402, and a post-flocculation liquid outlet 403, and post-mixing liquid inlet 401 is connected to post-mixing liquid outlet 303 and is adapted to mix the post-mixing liquid with a flocculant for flocculation treatment so as to obtain a post-flocculation liquid. Therefore, under the action of the flocculant, calcium carbonate generated in the mixed liquid is flocculated and precipitated, which is beneficial to the subsequent filtration and separation.
The specific type of flocculant according to one embodiment of the present invention is not particularly limited, and may be selected according to actual needs by those skilled in the art, and according to one embodiment of the present invention, the flocculant may be polyacrylamide. Thus, the produced calcium carbonate can be accumulated, and the subsequent filtering and separating treatment is facilitated.
According to still another embodiment of the present invention, the addition amount of the flocculant is not particularly limited, and may be selected according to actual needs by those skilled in the art, and according to one embodiment of the present invention, the addition amount of the flocculant is 2-4mg per liter of the mixed liquid. The inventors found that if the addition amount of the flocculant is too low, flocculation effect is affected, which is unfavorable for removing calcium in the neutralized liquid, whereas if the addition amount of the flocculant is too high, the treatment cost is increased, which is unfavorable for the economy of the whole process.
According to an embodiment of the invention, the filter device 500 has a flocculated liquor inlet 501, a filtered liquor outlet 502 and a calcium carbonate outlet 503, the flocculated liquor inlet 501 being connected to the flocculated liquor outlet 403 and the calcium carbonate outlet 503 being connected to the limestone milk inlet 101 and being adapted to filter the flocculated liquor to obtain filtered liquor and calcium carbonate and to return the calcium carbonate to the gypsum reaction tank for use as limestone milk. Therefore, the hard removal treatment of the neutralized liquid can be realized, the obtained filtered liquid can be directly recycled or discharged, and the obtained calcium carbonate can be used as limestone emulsion for a gypsum reaction tank, so that the economy of the whole process is improved. Compared with the traditional calcium removal process, namely, the calcium removal agent adopts sodium carbonate or outsourced carbon dioxide, the process for reducing the concentration of calcium ions in the neutralized liquid from 800mg/L to 250mg/L can respectively save 2-2.3 yuan/ton and 1-1.2 yuan/ton, meanwhile, the process can save 85% -90% of operation cost, and the whole process is stable in operation.
The filtering device according to an embodiment of the present invention is not particularly limited, and may be selected according to actual needs by those skilled in the art, and according to a specific embodiment of the present invention, the filtering device may be a suspended filler filter. The inventor finds that compared with the traditional thickening tank or other filtering devices, the suspended filler filter can improve the solid-liquid separation efficiency and the separation precision and avoid the phenomenon of scaling and blocking.
According to the carbon dioxide calcium removing system suitable for the liquid after the gypsum neutralization process treatment, limestone milk is firstly utilized to treat sulfuric acid-containing waste acid, most of free acid and fluoride ions in the sulfuric acid-containing waste acid are removed to obtain carbon dioxide, gypsum and reacted liquid, then lime milk, ferric salt and the reacted liquid are utilized to react, calcium sulfate and heavy metal ions in the reacted liquid are removed to obtain neutralized liquid, then carbon dioxide generated in the front is used as a calcium removing agent to act on the neutralized liquid, and after aeration, flocculation and filtration, calcium ions in the neutralized liquid are removed in the form of calcium carbonate, so that the filtered liquid which can be recycled or discharged is obtained, and the obtained calcium carbonate can be used as limestone milk for a gypsum reaction tank. Compared with the prior art, the system saves the cost of the calcium remover, the cost of the gypsum neutralization process, and has stable operation, and can save 80-85% of treatment cost and 85-90% of operation cost.
In still another aspect of the present invention, the present invention proposes a method for removing calcium from carbon dioxide, which is applied to a post-gypsum neutralization process liquid, using the above-mentioned carbon dioxide removal system applied to a post-gypsum neutralization process liquid, according to an embodiment of the present invention, referring to fig. 2, the method comprises:
s100: the limestone emulsion and the waste acid containing sulfuric acid are subjected to neutralization reaction
In this step, limestone emulsion and sulfuric acid-containing waste acid are subjected to a neutralization reaction to obtain carbon dioxide, gypsum and a post-reaction liquid. Specifically, the sulfuric acid-containing waste acid is acid-making waste water generated by nonferrous smelting enterprises, and the main components comprise: sulfuric acid, hydrofluoric acid, arsenic, and heavy metal ions. Under the action of limestone emulsion, sulfuric acid and hydrofluoric acid in sulfuric acid-containing waste acid react with calcium carbonate to produce calcium sulfate (gypsum) and calcium fluoride precipitate respectively, so that most of free acid and fluoride ions in sulfuric acid-containing waste acid can be removed, carbon dioxide can be obtained, and main components of reaction liquid obtained after the reaction are small amount of sulfuric acid and hydrofluoric acid, and arsenic and heavy metal ions. The chemical reactions mainly occurring in the gypsum reaction tank are:
CaCO 3 +H 2 SO 4 ＝CaSO 4 ↓+CO 2 ↑+H 2 O (1)
CaCO 3 +2HF＝CaF 2 ↓+CO 2 ↑+H 2 O (2)
according to one embodiment of the invention, the pH of the post-reaction solution may be 2.5-3. The inventor finds that the pH value of the liquid after the reaction depends on the mixing mass ratio of limestone emulsion and sulfuric acid-containing waste acid, if the content of the limestone emulsion is too high, the pH value of the liquid after the reaction is increased, the content of heavy metal ions in gypsum is increased, and the quality of the gypsum is reduced; if the content of limestone emulsion is too low, the aim of removing waste acid cannot be achieved, the gypsum yield is reduced, and the neutralization treatment cost is increased. Therefore, the pH value of the reacted liquid is controlled in the range disclosed by the invention, so that the quality and the yield of gypsum can be improved, and the cost of neutralization treatment can be reduced.
S200: lime milk, ferric salt and the reacted liquid are subjected to neutralization reaction
In this step, lime milk, iron salt and the post-reaction liquid are subjected to neutralization reaction to obtain a precipitated and post-neutralization liquid. Specifically, the main components of the reaction solution comprise a small amount of sulfuric acid, hydrofluoric acid, arsenic and heavy metal ions, and the sulfuric acid, the hydrofluoric acid, the arsenic and most of the heavy metal ions in the reaction solution are removed in a precipitation form under the action of lime milk and ferric salt. After the reaction is finished, the obtained precipitate mainly comprises calcium sulfate, metal hydroxide precipitate, calcium arsenate, calcium fluoride and the like. The chemical reaction formula mainly comprises:
H 2 SO 4 +Ca(OH) 2 ＝CaSO 4 ·2H 2 O↓ (3)
CuSO 4 +Ca(OH) 2 +2H 2 O＝Cu(OH) 2 ↓+CaSO 4 ·2H 2 O (4)
ZnSO 4 +Ca(OH) 2 +2H 2 O＝Fe(OH) 2 ↓+CaSO 4 ·2H 2 O (5)
2H 3 AsO 4 +3Ca(OH) 2 ＝Ca 3 (AsO 4 ) 2 ↓+3H 2 O (6)
2HF+Ca(OH) 2 ＝CaF 2 ↓+2H 2 O (7)
according to one embodiment of the invention, the pH value of the neutralized liquid is 10.5-11, and the inventor finds that the pH value of the neutralized liquid is determined by the mixing mass ratio of the reacted liquid, lime milk and ferric salt, wherein the adding amount of the ferric salt is according to the iron-arsenic ratio 1: (4-10), and the ratio is too high or too low, which leads to the effluent not reaching the standard and increases the neutralization treatment cost.
S300: mixing the neutralized liquid with carbon dioxide
In this step, the neutralized liquid and carbon dioxide are mixed to obtain a mixed liquid. Specifically, under the action of carbon dioxide, calcium ions in the neutralized liquid are converted into calcium carbonate, so that the calcium ions in the neutralized liquid can be removed, and the carbon dioxide comes from a gypsum reaction tank, so that the medicament cost of a calcium removing agent (carbon dioxide or sodium carbonate) is saved.
The flow rate of carbon dioxide according to one embodiment of the present invention is not particularly limited, and may be selected according to actual needs by those skilled in the art, and according to one embodiment of the present invention, the flow rate of carbon dioxide may be 1.1 to 1.3 times the theoretical required amount. The inventor finds that if the flow rate of the carbon dioxide is too high, the waste of the carbon dioxide is caused, and if the flow rate of the carbon dioxide is too low, the amount of calcium ions converted into calcium carbonate in the neutralized liquid is reduced, so that the hard removal requirement on the neutralized liquid is not facilitated, and the yield of the calcium carbonate obtained later and the quality of the filtered liquid are affected.
According to still another embodiment of the present invention, the pH of the mixed solution is not particularly limited, and may be selected according to actual needs by those skilled in the art, and according to one embodiment of the present invention, the pH of the mixed solution may be 7.5 to 8. The inventor finds that if the pH value of the mixed liquid is too high, the calcium removal effect is not good; if the pH of the mixed solution is too low, the dissolution will occur, which is not conducive to removing calcium ions in the neutralized solution.
S400: flocculating the flocculant and the mixed solution
In this step, a flocculation reaction is performed on the flocculant and the mixed liquid so as to obtain a flocculated liquid. Therefore, under the action of the flocculant, calcium carbonate generated in the mixed liquid is flocculated and precipitated, which is beneficial to the subsequent filtration and separation.
The specific type of flocculant according to one embodiment of the present invention is not particularly limited, and may be selected according to actual needs by those skilled in the art, and according to one embodiment of the present invention, the flocculant may be polyacrylamide. Thus, the produced calcium carbonate can be accumulated, and the subsequent filtering and separating treatment is facilitated.
According to still another embodiment of the present invention, the addition amount of the flocculant is not particularly limited, and may be selected according to actual needs by those skilled in the art, and according to one embodiment of the present invention, the addition amount of the flocculant is 2-4mg per liter of the mixed liquid. The inventors found that if the addition amount of the flocculant is too low, flocculation effect is affected, which is unfavorable for removing calcium in the neutralized liquid, whereas if the addition amount of the flocculant is too high, the treatment cost is increased, which is unfavorable for the economy of the whole process.
S500: filtering the flocculated liquid
In this step, the flocculated liquid is subjected to filtration treatment to obtain a filtered liquid and calcium carbonate, and the calcium carbonate is returned to S100 for use as limestone milk. Therefore, the hard removal treatment of the neutralized liquid can be realized, the obtained filtered liquid can be directly recycled or discharged, and the obtained calcium carbonate can be used as limestone emulsion for a gypsum reaction tank, so that the economy of the whole process is improved. Compared with the traditional calcium removal process, namely, the calcium removal agent adopts sodium carbonate or outsourced carbon dioxide, the process for reducing the concentration of calcium ions in the neutralized liquid from 800mg/L to 250mg/L can respectively save 2-2.3 yuan/ton and 1-1.2 yuan/ton, meanwhile, the process can save 85% -90% of operation cost, and the whole process is stable in operation.
According to the method for removing calcium by using carbon dioxide, which is suitable for the liquid after the treatment of the gypsum neutralization process, firstly, limestone milk is utilized to treat sulfuric acid-containing waste acid, most of free acid and fluoride ions in the sulfuric acid-containing waste acid are removed, carbon dioxide, gypsum and reacted liquid are obtained, then lime milk, ferric salt and the reacted liquid are utilized to react, calcium sulfate and heavy metal ions in the reacted liquid are removed, neutralized liquid is obtained, then, carbon dioxide generated in the front is used as a calcium removing agent to act on the neutralized liquid, and after aeration, flocculation and filtration, calcium ions in the neutralized liquid are removed in the form of calcium carbonate, so that the filtered liquid which can be recycled or discharged is obtained, and the obtained calcium carbonate can be used as limestone milk for a gypsum reaction tank. Compared with the prior art, the method saves the cost of the calcium remover, saves the cost of the gypsum neutralization process, has stable operation, and can save 80-85% of treatment cost and 85-90% of operation cost.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A method for removing calcium from carbon dioxide suitable for use in a post-gypsum neutralization process treatment fluid, the method being practiced using a system comprising:
the gypsum reaction tank is provided with a limestone emulsion inlet, a sulfuric acid-containing waste acid inlet, a carbon dioxide outlet, a gypsum outlet and a post-reaction liquid outlet, and is suitable for carrying out neutralization reaction on the limestone emulsion and the sulfuric acid-containing waste acid so as to obtain carbon dioxide, gypsum and a post-reaction liquid;
the neutralization reaction device is provided with a post-reaction liquid inlet, a lime milk inlet, an iron salt inlet, a precipitation outlet and a post-neutralization liquid outlet, wherein the post-reaction liquid inlet is connected with the post-reaction liquid outlet and is suitable for carrying out a neutralization reaction on the post-reaction liquid, the lime milk and the iron salt so as to obtain a post-neutralization liquid and a precipitate containing calcium sulfate and heavy metal hydroxide;
the aeration reaction tank is provided with a neutralized liquid inlet, a carbon dioxide inlet and a mixed liquid outlet, wherein the neutralized liquid inlet is connected with the neutralized liquid outlet, and the carbon dioxide inlet is connected with the carbon dioxide outlet and is suitable for mixing the neutralized liquid and the carbon dioxide so as to obtain a mixed liquid;
the flocculation reaction tank is provided with a mixed liquid inlet, a flocculating agent inlet and a flocculated liquid outlet, wherein the mixed liquid inlet is connected with the mixed liquid outlet and is suitable for mixing the mixed liquid with the flocculating agent for flocculation treatment so as to obtain flocculated liquid;
the filtering device is provided with a flocculated liquid inlet, a filtered liquid outlet and a calcium carbonate outlet, the flocculated liquid inlet is connected with the flocculated liquid outlet, the calcium carbonate outlet is connected with the limestone milk inlet and is suitable for filtering the flocculated liquid so as to obtain filtered liquid and calcium carbonate, and the calcium carbonate is returned to the gypsum reaction tank to be used as the limestone milk;
the method comprises the following steps:
(1) Limestone emulsion and waste acid containing sulfuric acid are supplied to the gypsum reaction tank for neutralization reaction so as to obtain carbon dioxide, gypsum and reacted liquid;
(2) Lime milk, ferric salt and the reacted liquid are supplied to the neutralization reaction device for neutralization reaction so as to obtain precipitation and neutralized liquid;
(3) Supplying the neutralized liquid and the carbon dioxide to the aeration reaction tank for mixing so as to obtain a mixed liquid;
(4) Feeding a flocculating agent and the mixed liquid into the flocculation reaction tank for flocculation reaction so as to obtain flocculated liquid;
(5) And (2) feeding the flocculated liquid into the filtering device for filtering treatment so as to obtain filtered liquid and calcium carbonate, and returning the calcium carbonate to the gypsum reaction tank in the step (1) for use as limestone emulsion.
2. The method of claim 1, wherein the aeration reaction tank is an inflatable aerator and an inflatable suspension machine is disposed within the inflatable aerator.
3. The method of claim 1 or 2, wherein the filtration device is a suspended filler filter.
4. The method according to claim 1, wherein in step (1), the pH of the post-reaction solution is 2.5 to 3.
5. The method according to claim 1, wherein in step (2), the pH of the neutralized liquid is 10.5 to 11.
6. The method according to claim 1, wherein in step (3), the flow rate of the carbon dioxide is 1.1 to 1.3 times the theoretical required amount.
7. The method according to claim 6, wherein in step (3), the pH of the neutralized liquid is 11 to 12.
8. The method according to claim 7, wherein in step (3), the pH of the mixed solution is 7.5 to 8.
9. The method of claim 1, wherein in step (4), the flocculant is polyacrylamide.
10. The method according to claim 9, wherein in step (4), the flocculant is added in an amount of 2-4mg per liter of the post-mixing liquid.
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