CN115430395B - Method for circularly removing chloride ions in wastewater by using calcium aluminum stone material - Google Patents
Method for circularly removing chloride ions in wastewater by using calcium aluminum stone material Download PDFInfo
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- CN115430395B CN115430395B CN202211190881.9A CN202211190881A CN115430395B CN 115430395 B CN115430395 B CN 115430395B CN 202211190881 A CN202211190881 A CN 202211190881A CN 115430395 B CN115430395 B CN 115430395B
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 69
- 239000002351 wastewater Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 13
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 title claims description 10
- 239000004575 stone Substances 0.000 title description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- 239000000460 chlorine Substances 0.000 claims abstract description 69
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 67
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims description 37
- 239000011575 calcium Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 abstract description 23
- 239000003795 chemical substances by application Substances 0.000 abstract description 16
- 238000001035 drying Methods 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- -1 chlorine ions Chemical class 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 30
- 238000001556 precipitation Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000004064 recycling Methods 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 244000144972 livestock Species 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 244000144977 poultry Species 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910001647 dawsonite Inorganic materials 0.000 description 2
- 230000000382 dechlorinating effect Effects 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 1
- 102000007590 Calpain Human genes 0.000 description 1
- 108010032088 Calpain Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- QNFBKOHHLAWWTC-UHFFFAOYSA-N Fraxidin Chemical class C1=CC(=O)OC2=C1C=C(OC)C(OC)=C2O QNFBKOHHLAWWTC-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000282898 Sus scrofa Species 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a method for circularly removing chloride ions in wastewater by using a mayenite material, which is characterized in that the chlorine-containing wastewater is treated by using mayenite, the chlorine ions are removed by stirring reaction at a certain temperature, and a indissolvable chlorine-containing mayenite product, namely friedel salt, is obtained by solid-liquid separation. The friedel salt is treated with sodium hydroxide solution, and the hydroxide radical is exchanged with chloride ion to replace chloride ion in the friedel salt. And (3) obtaining a dechlorination product after solid-liquid separation, and drying and calcining to obtain the regenerated mayenite dechlorination agent. The mayenite chlorine removal agent has low raw material cost, simple preparation, cleanness and environmental protection, and can circularly remove chloride ions in wastewater.
Description
Technical Field
The invention belongs to the technical field of wastewater chloride ion treatment and resource utilization, and particularly relates to a method for circularly removing chloride ions in wastewater by using a calcium aluminum stone material.
Background
The high-concentration chloride ions in the wastewater have great harm, and the high-concentration chloride-containing wastewater is directly discharged into a river to cause natural ecological unbalance of a water body, so that the water quality is deteriorated, the production of fishery production and aquaculture is reduced, fresh water resources are damaged, and underground water and a drinking water source are polluted even when serious. In addition, chloride ions corrode steel pipelines, so that the durability of the pipelines is reduced, and the service life is shortened. When the concentration of chloride ions in water is too high, the chloride ions can cause harm to human and animals. When the concentration of chloride in drinking water of poultry and livestock reaches 1511mg/L, the chloride can cause harm to poultry, cattle, sheep and pig and livestock, and when the concentration of chloride in drinking water exceeds 4111mg/L, the poultry and livestock can die. The high concentration of chloride ions can also produce toxic effects on the biological treatment of wastewater. The high concentration of chloride ions damages the cell membrane of the microorganism and enzymes in the cell body mainly by the increased osmotic pressure of the environment, thereby damaging the physiological activities of the microorganism. The common chloride ion removing method at present mainly comprises chemical precipitation, membrane separation, adsorption, electrolysis, evaporative crystallization and the like. Among them, the calpain dechlorination method in the chemical precipitation method is also studied to a certain extent, because of the wide source of raw materials, low cost and high dechlorination efficiency. Blain Paul et al (mayinite-to-hydrocalumite transformation for the removal of chloride from salinized groundwater and the recycling potential of spent hydrocalumite for chromate removal, desalination,2121, 474, 114186) explored the feasibility of using a Mayenite phase to remove chloride ions from salted groundwater, and after treatment, the chloride ion concentration in wastewater was reduced to 631-491 mg/L. Kong Xiuqin et al (method for removing sulfate ions and chloride ions from wastewater by ultra-high lime aluminum method, CN 212111893226.9) discuss a method for removing sulfate ions and chloride ions from wastewater by ultra-high lime aluminum method. However, a great amount of fraxidin salts which are difficult to be absorbed are generated after the dechlorination reaction of the mayenite and the ultra-high lime aluminum method. The invention provides a method for circularly removing chloride ions in wastewater by using calcium aluminum material, which is characterized in that the friedel salt of a chlorine removal product is treated and then is continuously used as a chlorine removal agent, so that the circular chlorine removal is realized.
Disclosure of Invention
Aiming at the problems that chloride ions in the wastewater are difficult to remove and the rear end products are difficult to recycle, the method for circularly removing the chloride ions in the wastewater by using the calcium aluminum material is provided. The method provided by the invention is clean and environment-friendly, is simple and convenient to operate, has low raw material cost, realizes the recycling of the mayenite, and greatly avoids the generation of a large amount of chlorine removal product sludge.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the invention provides a method for circularly removing chloride ions in wastewater by using a calcium aluminum material, which comprises the following steps:
adding the mayenite into the wastewater containing chloride ions, stirring and reacting to remove the chloride ions, and obtaining a dechlorinated product, and after alkaline washing and calcination, obtaining the mayenite for cyclic dechlorination. And continuously removing chloride ions in the wastewater by the obtained mayenite according to the steps, so that the aim of circularly removing chloride from the mayenite material is fulfilled.
Further, the mayenite is prepared by the following method: calcium oxide and aluminum oxide were mixed according to Ca: the mole ratio of Al is 1-1.3: 1 are evenly mixed and calcined for 1.5 to 2 hours at 1211 to 2111 ℃ to obtain the mayenite. Wherein, the content of Ca is slightly excessive so as to be beneficial to the adjustment of the pH value in the dechlorination reaction of the mayenite and supplement the consumption of Ca; in the calcining temperature range, the mayenite material with higher relative content of mayenite can be obtained.
Further, the content of chloride ions in the wastewater is 1111-51111 mg/L.
Further, the mass ratio of the mayenite to the chlorine in the wastewater chloride is 11-25:1.
Further, the stirring reaction temperature is 25-121 ℃, and the stirring time is 31-61 min.
Further, the alkaline washing is performed by using sodium hydroxide solution. The concentration of sodium hydroxide is 1-6 mol/L, and the solid-liquid ratio of the chlorine removal product and the sodium hydroxide solution is 1-11:11.
Further, the calcination temperature is 211-811 ℃, and the calcination time is 1-24 h. During calcination, if the temperature is too low, the mayenite purity is lowered; the calcining temperature is too high, the energy consumption is increased, the production cost is too high, and the industrial preparation is not facilitated.
Compared with the prior art, the invention has the following beneficial effects:
the method of the invention uses the mayenite material to efficiently treat chloride ions in the wastewater, and obtains the recyclable mayenite dechlorinating agent. The principle of removing chloride ions in the wastewater by the mayenite is that hydroxide and chloride ions are exchanged to form indissolvable chlorine-containing mayenite products, namely Friedel salt, and the product is subjected to alkali washing, water washing and calcining to obtain the recyclable mayenite dechlorinating agent. The principle of obtaining the recyclable mayenite is that hydroxide in alkaline washing liquid is exchanged with chloride ions to replace chloride ions in dechlorinated products, and the obtained dechlorinated products can be calcined to obtain the mayenite Dan Chulv agent, wherein the partial reaction formula is as follows:
4Ca(OH) 2 +2Al(OH) 3 ＝Ca 4 Al 2 (OH) 14
4Ca(OH) 2 +2Al(OH) 3 +2Cl - ＝Ca 4 Al 2 (OH) 12 Cl 2 +2OH -
Ca 4 Al 2 (OH) 12 Cl 2 +2OH - ＝Ca 4 Al 2 (OH) 14 +2Cl -
the Ca obtained 4 Al 2 (OH) 14 The dechlorinated product can be continuously formed into mayenite after being calcined, otherwise, the dechlorination effect is poor. While the alkali washing liquid has sodium hydroxide with certain concentration remained, the alkali washing liquid can be recycled, and high-purity sodium chloride crystals are obtained through evaporation and crystallization after multiple uses and enrichment.
Detailed Description
The invention is further described below in connection with specific embodiments. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
(1) Chlorine-containing wastewater with the chloride ion concentration of 11111mg/L is removed:
calcium oxide and aluminum oxide were mixed according to Ca: the molar ratio of Al is 1:1 are evenly mixed and calcined for 2 hours at 1211 ℃ to obtain the mayenite. Aiming at wastewater with the chloride ion content of 11111mg/L, the mayenite is added according to the mass ratio of 11:1 of the mayenite to the chlorine in the wastewater, the mixture is stirred for 61min at 25 ℃ to carry out precipitation reaction, solid-liquid separation is carried out after the reaction is finished, and the chloride ion content of the liquid part is measured.
The chlorine removal efficiency of the wastewater of this example was 55.5%.
(2) The obtained dechlorination product treatment method and the cyclic dechlorination performance:
adding 1L of 2mol/L sodium hydroxide solution into the chlorine removal product for alkali washing, wherein the solid-liquid ratio of the chlorine removal product (drying mass) to the sodium hydroxide solution is 1:11. And (3) carrying out solid-liquid separation after alkaline washing, continuously recycling the obtained regenerated liquid, washing a solid product for 1-3 times, carrying out solid-liquid separation, drying solid powder, and calcining the solid powder in a muffle furnace at 211 ℃ for 24 hours to obtain the mayenite chlorine removal agent.
Aiming at the wastewater with the chloride ion content of 11111mg/L, adding the mayenite according to the mass ratio of the mayenite to the chlorine in the wastewater of 11:1, stirring for 61min at 25 ℃ to perform precipitation reaction, performing solid-liquid separation after the reaction is finished, measuring the chloride ion content of a liquid part, continuously performing the alkaline washing and calcination treatment on the obtained chlorine scavenger product, obtaining the mayenite Dan Chulv agent again, and continuously performing chlorine removal on the wastewater. This cycle was run 6 times and the results are shown in the following table. The reason why the cyclic chlorine removal efficiency is slightly lowered is due to the consumption of mayenite. In order to ensure better circulation efficiency, the chlorine removal product and sodium hydroxide are fully reacted during alkaline washing. The concentration of sodium hydroxide and the reaction time of alkaline washing are key parameters.
Example 2
(1) Chlorine-containing wastewater with the chlorine ion concentration of 21391mg/L is removed:
calcium oxide and aluminum oxide were mixed according to Ca: al molar ratio is 1.2:1 are evenly mixed and calcined at 2111 ℃ for 1.5 hours to obtain the mayenite. Aiming at the wastewater with the chloride ion content of 21391mg/L, the dawsonite is added according to the mass ratio of the dawsonite to the chlorine in the wastewater of 15:1, the mixture is stirred for 31min at 121 ℃ to carry out precipitation reaction, solid-liquid separation is carried out after the reaction is finished, the chloride ion content of the liquid part is measured,
the chlorine removal efficiency of the industrial chlorine-containing wastewater of the embodiment is 74.3 percent.
The obtained dechlorination product treatment method and the cyclic dechlorination performance:
adding 1L of 3mol/L sodium hydroxide solution into the chlorine removal product for alkali washing, wherein the solid-to-liquid ratio of the chlorine removal product (drying mass) to the sodium hydroxide solution is 5:11. And (3) carrying out solid-liquid separation after alkaline washing, continuously recycling the obtained regenerated liquid, washing a solid product with water for 1-3 times, carrying out solid-liquid separation, drying solid powder, and calcining the solid powder in a muffle furnace at 311 ℃ for 18 hours to obtain the mayenite chlorine removal agent.
Aiming at the wastewater with the chloride ion content of 21391mg/L, adding the mayenite according to the mass ratio of 15:1 of the mayenite to the chlorine in the wastewater, stirring for 31min at 121 ℃ to perform precipitation reaction, performing solid-liquid separation after the reaction is finished, measuring the chloride ion content of the liquid part, continuously performing the alkaline washing and calcination treatment on the obtained chlorine remover product, obtaining the mayenite Dan Chulv agent again, and continuously performing chlorine removal on the wastewater. This was cycled 9 times.
| Number of cycles | Efficiency of chlorine removal |
| 1 time | 74.3％ |
| 2 times | 69.7％ |
| 3 times | 68.5％ |
| 4 times | 66.9％ |
| 5 times | 66.2％ |
| 6 times | 67.4％ |
| 7 times | 65.1％ |
| 8 times | 64.6％ |
| 9 times | 65.5％ |
Example 3
(1) Chlorine-containing wastewater with the chloride ion concentration of 39321mg/L is removed:
calcium oxide and aluminum oxide were mixed according to Ca: al molar ratio is 1.3:1 are evenly mixed and calcined for 1.5 hours at 1711 ℃ to obtain the mayenite. Aiming at the wastewater with the chloride ion content of 39321mg/L, the mayenite is added according to the mass ratio of 21:1 of the mayenite to the chlorine in the wastewater, the mixture is stirred for 45min at the temperature of 51 ℃ to carry out precipitation reaction, solid-liquid separation is carried out after the reaction is finished, and the chloride ion content of the liquid part is measured.
The chlorine removal efficiency of the wastewater of this example was 88.6%.
(2) The obtained dechlorination product treatment method and the cyclic dechlorination performance:
adding 1L of 4mol/L sodium hydroxide solution into the chlorine removal product for alkali washing, wherein the solid-to-liquid ratio of the chlorine removal product (drying mass) to the sodium hydroxide solution is 7:11. And (3) carrying out solid-liquid separation after alkaline washing, continuously recycling the obtained regenerated liquid, washing a solid product with water for 1-3 times, carrying out solid-liquid separation, drying solid powder, and calcining the dried solid powder in a muffle furnace at 511 ℃ for 4 hours to obtain the mayenite chlorine removal agent.
Aiming at the wastewater with the chloride ion content of 39321mg/L, adding the mayenite according to the mass ratio of 21:1 of the mayenite to chlorine in the wastewater, stirring for 45min at the temperature of 51 ℃ to perform precipitation reaction, performing solid-liquid separation after the reaction is finished, measuring the chloride ion content of a liquid part, continuously performing the alkaline washing and calcination treatment on the obtained chlorine remover product to obtain a calcium aluminum Dan Chulv agent again, and continuously performing chlorine removal on the wastewater. This cycle was operated 11 times.
| Number of cycles | Efficiency of chlorine removal |
| 1 time | 88.6％ |
| 2 times | 89.8％ |
| 3 times | 86.3％ |
| 4 times | 88.5％ |
| 5 times | 87.8％ |
| 6 times | 87.6％ |
| 7 times | 86.5％ |
| 8 times | 87.1％ |
| 9 times | 85.8％ |
| 11 times | 86.2％ |
Example 4
(1) Chlorine-containing wastewater with the chloride ion concentration of 51111mg/L is removed:
calcium oxide and aluminum oxide were mixed according to Ca: al molar ratio is 1.1:1 are evenly mixed and calcined for 1h at 1511 ℃ to obtain the mayenite. Aiming at the wastewater with the chloride ion content of 51111mg/L, the mayenite is added according to the mass ratio of 25:1 of the mayenite to the chlorine in the wastewater, the mixture is stirred for 35min at 91 ℃ for precipitation reaction, solid-liquid separation is carried out after the reaction is finished, the chloride ion content of the liquid part is measured, 21ml of 5mol/L sodium hydroxide solution is added into the solid product for alkaline washing, water washing is carried out after the alkaline washing, and the recyclable mayenite material is obtained after calcination for 2h at 511 ℃.
The chlorine removal efficiency of the wastewater of this example was 86.7%.
(2) The obtained dechlorination product treatment method and the cyclic dechlorination performance:
adding 1L of 5mol/L sodium hydroxide solution into the chlorine removal product for alkali washing, wherein the solid-liquid ratio of the chlorine removal product (drying mass) to the sodium hydroxide solution is 11:11. And (3) carrying out solid-liquid separation after alkali washing, continuously recycling the obtained regenerated liquid, washing a solid product for 1-3 times, carrying out solid-liquid separation, drying solid powder, and calcining for 1h at 811 ℃ in a muffle furnace to obtain the mayenite chlorine removal agent.
Aiming at the wastewater with the chloride ion content of 51111mg/L, the mayenite is added according to the mass ratio of 25:1 of the mayenite to the chlorine in the wastewater, the precipitation reaction is carried out by stirring for 35min at 91 ℃, the solid-liquid separation is carried out after the reaction is finished, the chloride ion content of the liquid part is measured, the obtained chlorine remover product is continuously subjected to the alkaline washing and the calcination treatment, the calcium aluminum Dan Chulv agent is obtained again, and the chlorine removal of the wastewater is continuously carried out. This cycle was operated 5 times.
| Number of cycles | Efficiency of chlorine removal |
| 1 time | 96.7％ |
| 2 times | 95.7％ |
| 3 times | 95.2％ |
| 4 times | 94.3％ |
| 5 times | 96.4％ |
Example 5
(1) Chlorine-containing wastewater with the chloride ion concentration of 51111mg/L is removed:
calcium oxide and aluminum oxide were mixed according to Ca: al molar ratio is 1.1:1 are evenly mixed and calcined for 1h at 1511 ℃ to obtain the mayenite. Aiming at the wastewater with the chloride ion content of 51111mg/L, the mayenite is added according to the mass ratio of 25:1 of the mayenite to the chlorine in the wastewater, the mixture is stirred for 35min at 91 ℃ for precipitation reaction, solid-liquid separation is carried out after the reaction is finished, the chloride ion content of the liquid part is measured, 21ml of 1.5mol/L sodium hydroxide solution is added into the solid product for alkaline washing, water washing is carried out after the alkaline washing, and the recyclable mayenite material is obtained after calcination for 2h at 511 ℃.
The chlorine removal efficiency of the wastewater of this example was 86.7%.
(2) The treatment method and the cyclic chlorine removal performance (11 times of sodium hydroxide concentration) of the obtained chlorine removal product are as follows:
adding 1L of 1.5mol/L sodium hydroxide solution into the chlorine removal product for alkali washing, wherein the solid-to-liquid ratio of the chlorine removal product (drying mass) to the sodium hydroxide solution is 11:11. And (3) carrying out solid-liquid separation after alkali washing, continuously recycling the obtained regenerated liquid, washing a solid product for 1-3 times, carrying out solid-liquid separation, drying solid powder, and calcining for 1h at 811 ℃ in a muffle furnace to obtain the mayenite chlorine removal agent.
Aiming at the wastewater with the chloride ion content of 51111mg/L, the mayenite is added according to the mass ratio of 25:1 of the mayenite to the chlorine in the wastewater, the precipitation reaction is carried out by stirring for 35min at 91 ℃, the solid-liquid separation is carried out after the reaction is finished, the chloride ion content of the liquid part is measured, the obtained chlorine remover product is continuously subjected to the alkaline washing and the calcination treatment, the calcium aluminum Dan Chulv agent is obtained again, and the chlorine removal of the wastewater is continuously carried out. This cycle was operated 5 times.
| Number of cycles | Efficiency of chlorine removal |
| 1 time | 96.7％ |
| 2 times | 61.6％ |
| 3 times | 55.3％ |
| 4 times | 47.5％ |
| 5 times | 38.8％ |
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (7)
1. A method for circularly removing chloride ions in wastewater by using a calcium aluminum material, which is characterized by comprising the following steps:
adding mayenite into wastewater containing chloride ions, stirring and reacting to remove chloride ions, and performing alkali washing and calcination on the obtained dechlorinated product to obtain mayenite for cyclic dechlorination;
the alkaline washing is performed by sodium hydroxide solution;
the concentration of the sodium hydroxide is 1-6 mol/L, and the solid-liquid ratio of the chlorine removal product to the sodium hydroxide solution is 1-10:10;
the calcination temperature is 200-800 ℃ and the calcination time is 1-24 h.
2. The method according to claim 1, characterized in that the mayenite is prepared by: and (3) uniformly mixing the calcium oxide and the aluminum oxide, and calcining to obtain the mayenite.
3. The method according to claim 2, wherein Ca in the calcium oxide and aluminum oxide: the mole ratio of Al is 1-1.3: 1.
4. the method according to claim 2, wherein the calcination is carried out at a temperature of 1200 to 2000 ℃ for a time of 0.5 to 2 hours.
5. The method according to claim 1, wherein the content of chloride ions in the wastewater is 1000-50000 mg/L.
6. The method according to claim 1, characterized in that the mass ratio of mayenite to chlorine in the wastewater chloride is 10-25:1.
7. The method according to claim 1, wherein the stirring reaction temperature is 25 to 120 ℃ and the stirring time is 30 to 60 minutes.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674515A (en) * | 2012-05-18 | 2012-09-19 | 上海大学 | Method for regulating, controlling and forming hydrotalcite-like compound deep treatment leachate tail water |
| CN102730813A (en) * | 2012-07-31 | 2012-10-17 | 北京盖雅技术中心有限公司 | Efficient cation/anion remover and preparation method thereof |
| CN104396949A (en) * | 2014-11-17 | 2015-03-11 | 江苏隆昌化工有限公司 | Method for structural reconstruction of hydrated aluminum chloroaluminate to synthesize pesticide controlled release agent |
| CN107973362A (en) * | 2017-12-22 | 2018-05-01 | 中国地质大学（武汉） | A kind of method and device for removing removing fluorine in water and arsenate at the same time based on hydrocalumite |
-
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- 2022-09-28 CN CN202211190881.9A patent/CN115430395B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674515A (en) * | 2012-05-18 | 2012-09-19 | 上海大学 | Method for regulating, controlling and forming hydrotalcite-like compound deep treatment leachate tail water |
| CN102730813A (en) * | 2012-07-31 | 2012-10-17 | 北京盖雅技术中心有限公司 | Efficient cation/anion remover and preparation method thereof |
| CN104396949A (en) * | 2014-11-17 | 2015-03-11 | 江苏隆昌化工有限公司 | Method for structural reconstruction of hydrated aluminum chloroaluminate to synthesize pesticide controlled release agent |
| CN107973362A (en) * | 2017-12-22 | 2018-05-01 | 中国地质大学（武汉） | A kind of method and device for removing removing fluorine in water and arsenate at the same time based on hydrocalumite |
Non-Patent Citations (2)
| Title |
|---|
| Mayenite-to-hydrocalumite transformation for the removal of chloride from salinized groundwater and the recycling potential of spent hydrocalumite for chromate removal;Blain Paul, et al;Desalination;第474卷;第2页右栏第2段至第3页左栏第5段 * |
| 欧育湘，等.稳定剂.国防工业出版社,2011,第312-315页. * |
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