CN117303536B - Coking wastewater liquid defluorinating agent and preparation method and application thereof - Google Patents
Coking wastewater liquid defluorinating agent and preparation method and application thereof Download PDFInfo
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- 238000004939 coking Methods 0.000 title claims abstract description 113
- 239000002351 wastewater Substances 0.000 title claims abstract description 103
- 239000007788 liquid Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 77
- 239000007864 aqueous solution Substances 0.000 claims abstract description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052567 struvite Inorganic materials 0.000 claims abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 25
- 239000011737 fluorine Substances 0.000 claims abstract description 25
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 claims abstract description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 17
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 16
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 16
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 15
- 238000006115 defluorination reaction Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 15
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 claims description 14
- 238000004090 dissolution Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- -1 fluoride ions Chemical class 0.000 abstract description 19
- 239000012535 impurity Substances 0.000 abstract description 4
- 229940126589 solid medicine Drugs 0.000 abstract description 3
- NNCOOIBIVIODKO-UHFFFAOYSA-N aluminum;hypochlorous acid Chemical compound [Al].ClO NNCOOIBIVIODKO-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910001424 calcium ion Inorganic materials 0.000 description 9
- 238000004062 sedimentation Methods 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- 239000010865 sewage Substances 0.000 description 7
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 6
- 229910001425 magnesium ion Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 101100500409 Caenorhabditis elegans dyf-5 gene Proteins 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 101100500407 Caenorhabditis elegans dyf-2 gene Proteins 0.000 description 1
- 101100274801 Caenorhabditis elegans dyf-3 gene Proteins 0.000 description 1
- 101100500408 Caenorhabditis elegans dyf-4 gene Proteins 0.000 description 1
- 101100500410 Caenorhabditis elegans dyf-7 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GFIKIVSYJDVOOZ-UHFFFAOYSA-L calcium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Ca+2].[O-]P([O-])(F)=O GFIKIVSYJDVOOZ-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 101150028810 dyf-1 gene Proteins 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2101/14—Fluorine or fluorine-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a coking wastewater liquid defluorinating agent, a preparation method and application thereof, and belongs to the technical field of coking wastewater treatment, wherein the coking wastewater liquid defluorinating agent is prepared by dissolving struvite by dilute sulfuric acid and then adding polymeric ferric sulfate to prepare solution A; mixing and heating an aluminum trichloride aqueous solution, an aluminum hydroxychloride aqueous solution and an aluminum sulfate aqueous solution, adding the solution A for reaction, and cooling to room temperature to obtain the coking wastewater liquid fluorine removing agent; the coking wastewater liquid defluorinating agent is used for treating fluoride ions in coking wastewater. The special coking wastewater liquid defluorination agent for coking wastewater, which is developed according to the characteristic of difficult treatment of coking wastewater, can be directly added into the coking wastewater for defluorination without a solid medicine dissolving link, and has the advantages of convenient addition, labor reduction, less mud production, low cost, high defluorination efficiency, no introduction of other impurities and the like.
Description
Technical Field
The invention relates to the technical field of coking wastewater treatment, in particular to a coking wastewater liquid defluorinating agent and a preparation method and application thereof.
Background
Coking wastewater is used as toxic organic wastewater which is difficult to degrade, and the treatment difficulty is always at a higher level in the field of sewage treatment. With the implementation of the national 'double carbon' target, the treatment of coking wastewater is increasingly developed towards reclaimed water recycling and zero emission. But the coking wastewater contains fluoride, which can scale on the reverse osmosis membrane in the treatment process, and has great harm to the reverse osmosis membrane. Therefore, the removal of fluoride from coking wastewater is particularly important. The development of the fluoride remover for removing fluoride in the coking wastewater with high efficiency and low cost can obviously promote the development of the coking wastewater treatment industry.
Currently, there are few fluorine scavengers dedicated to the fluorine removal of coking wastewater in the market, and the liquid fluorine scavengers of coking wastewater are less. The liquid fluorine removing agent can reduce the solid medicine dissolving link, so that the labor intensity of workers is reduced, and the medicine addition is more stable, so that the cost can be effectively reduced by using the liquid fluorine removing agent. In the coking wastewater defluorination process, the conventional industrial wastewater solid or liquid defluorination agent used in the market has unsatisfactory defluorination effect, and the conventional solid or liquid defluorination agent has the problems of poor defluorination effect, large dosage, large introduced other impurities, large mud production amount, loose generated mud, difficult sedimentation and the like, and seriously influences the process of the subsequent treatment process. Therefore, development of a novel liquid defluorinating agent special for coking wastewater is needed.
Disclosure of Invention
Aiming at the problems that the existing fluorine removing agent is poor in fluorine removing effect, large in dosage, large in mud yield, inconvenient to add and the like when being used for coking wastewater, the invention provides a coking wastewater liquid fluorine removing agent and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the coking wastewater liquid defluorination agent comprises the following raw materials in parts by weight:
5-18 parts of polymeric ferric sulfate, 10-35 parts of aluminum trichloride aqueous solution, 10-35 parts of aluminum chlorohydrate aqueous solution, 15-28 parts of aluminum sulfate aqueous solution, 3-15 parts of struvite and 9-45 parts of dilute sulfuric acid.
Further, the concentration of the aluminum trichloride aqueous solution is 22-24wt%, the concentration of the aluminum hydroxychloride aqueous solution is 49-51wt%, and the concentration of the aluminum sulfate aqueous solution is 24-26wt%.
Further, the concentration of the dilute sulfuric acid is 28-32wt%.
The preparation method of the coking wastewater liquid defluorinating agent comprises the following steps:
s1, adding dilute sulfuric acid into struvite, heating for dissolution, and then adding polymeric ferric sulfate for dissolution to obtain a solution A;
and S2, taking an aluminum trichloride aqueous solution, an aluminum hydroxychloride aqueous solution and an aluminum sulfate aqueous solution, fully mixing, heating, then adding the solution A for reaction, and cooling to room temperature to obtain the coking wastewater liquid fluorine removing agent.
In step S1, the dissolution temperature is 50-65 ℃.
In step S2, the reaction temperature is 70-80 ℃ and the reaction time is more than 1 h.
Further, in the step S1, the particle size of struvite is less than or equal to 0.075mm.
The application of the coking wastewater liquid defluorinating agent in the coking wastewater treatment process is that the coking wastewater liquid defluorinating agent is added into coking wastewater to be treated, stirred for reaction, and then added with cationic polyacrylamide aqueous solution flocculating agent for precipitation.
Further, the ratio relation between the consumption of the coking wastewater liquid defluorinating agent and the coking wastewater to be treated is 2-15 g:1L.
Further, after adding the coking wastewater liquid defluorinating agent into the coking wastewater to be treated and before adding the cationic polyacrylamide aqueous solution flocculant, stirring for 20-25 min, and then measuring the pH value;
if the pH value is lower than 6, adding alkali to adjust the pH value to 6-7;
after the cationic polyacrylamide aqueous solution flocculant is added, the precipitation time is more than 2 hours.
The coking wastewater liquid defluorinating agent and the preparation method and application thereof have the beneficial effects that:
the special coking wastewater liquid defluorinating agent for coking wastewater, which is developed according to the characteristic of difficult treatment of coking wastewater, can be directly added into the coking wastewater for defluorination without a solid medicine dissolving link, and has the advantages of convenient addition, labor reduction, less mud production, low cost, high defluorination efficiency, no introduction of other impurities and the like;
the fluorine removing agent mainly relies on the combined action of a plurality of high aluminum-containing medicaments, wherein the complexation of aluminum to fluoride ions is the main fluorine removing effect;
the struvite main component adopted by the inventionIs magnesium ammonium phosphate with a chemical formula of Mg (NH) 4 )PO 4 ·6H 2 O, which is soluble in dilute sulfuric acid to produce free magnesium ions and phosphate ions; in the subsequent defluorination process, magnesium ions can form magnesium fluoride precipitates with fluorine ions in water, and phosphate radicals can form calcium fluorophosphate (Ca 5 (PO 4 ) 3 F) Precipitating;
magnesium ammonium phosphate (commonly known as struvite) in the defluorinating agent provides a defluorinating promoting effect in the defluorinating process, and as a part of the defluorinating agent, phosphate ions and magnesium ions are generated through acid dissolution; meanwhile, as the solubility of the calcium fluophosphate is far smaller than that of the calcium fluoride at normal temperature, when the calcium ions and the fluorine ions form a precipitate and reach the condition of balancing ionization, namely under the condition that the calcium ions and the fluorine ions coexist in coking wastewater, the phosphate radical in the added defluorinating agent can further jointly generate the calcium fluophosphate precipitate by the calcium ions and the fluorine ions;
meanwhile, although the solubility of magnesium fluoride is larger than that of calcium fluoride, the concentration of calcium ions in coking wastewater is generally within 100mg/L, most of calcium ions and fluorine ions exist in ion states, under the action of other component medicaments of the fluorine removal agent, the fluorine ions are mainly enriched together by virtue of complexation to form a complex state, and the existence of magnesium ions and calcium ions can promote the removal of fluorine, and the magnesium ions and the calcium ions cooperate with each other; when the enrichment of the fluoride ions reaches a certain state, as the calcium ions in the water are relatively less, and the calcium ions are insufficient to completely precipitate the fluoride ions, the magnesium ions and the redundant fluoride ions can further generate precipitation, so that fluoride is further removed;
the coking wastewater liquid defluorinating agent contains aluminum hydroxide chloride, wherein the aluminum hydroxide chloride is an inorganic high molecular compound, can be polymerized through hydroxyl bridging, has a large number of hydroxyl groups in molecules, and has a strong bridging adsorption function; the aqueous aluminum chlorohydrate solution contains high aluminum content (23% Al) 2 O 3 ) And basicity (83-90%), in the process of treating coking wastewater, fluoride ions and aluminum ions in the water are complexed through complexation, and then are bridged through hydroxyl groups to form macromolecular adsorption coagulation, and are further precipitated to sludgeIn (a) and (b);
the coking wastewater liquid defluorinating agent contains polymeric ferric sulfate, wherein the polymeric ferric sulfate is a polyhydroxy and polynuclear complex inorganic high molecular polymer, generates a large amount of polymeric ferric complex ions after being dissolved in water, electrically neutralizes colloid particles of suspended matters in water, simultaneously has the coagulation effects of adsorption and bridging, and makes particles flocculate into large particles so as to accelerate particle sedimentation, and can complex and adsorb fluorine ions in the process;
according to the invention, fluoride ions in coking wastewater can be effectively complexed to form a complex by adding an appropriate amount of aluminum trichloride aqueous solution and aluminum sulfate aqueous solution, and the complex is precipitated into sludge through coagulating sedimentation;
the coking wastewater liquid defluorinating agent can reduce fluoride in coking wastewater from more than 100mg/L to less than 10mg/L by selecting proper raw material types and dosage, can stably reduce fluoride to less than 1mg/L by controlling dosage according to different effluent index requirements, can simultaneously remove other pollutants such as chromaticity, COD, metal ions, heterocyclic compounds and the like in the coking wastewater, does not increase the hardness of the coking wastewater in the defluorination process, and can reduce burden for deep treatment of the coking wastewater;
the coking wastewater liquid defluorinating agent can effectively remove impurities such as metal ions, heterocyclic compounds and the like which interfere with defluorination of the defluorinating agent in coking wastewater, thereby improving the defluorinating efficiency and reducing the dosage.
Detailed Description
The following description of the technical solution in the embodiments of the present invention is clear and complete. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
The coking wastewater liquid defluorinating agent comprises the following components in percentage by weight:
the raw materials for preparing the active ingredients of the coking wastewater liquid defluorinating agent comprise the following components in parts by weight: 5-18 parts of polymeric ferric sulfate, 10-35 parts of aluminum trichloride aqueous solution with the concentration of 22-24 wt%, 10-35 parts of aluminum hydroxychloride aqueous solution with the concentration of 49-51 wt%, 15-28 parts of aluminum sulfate aqueous solution with the concentration of 24-26 wt%, 3-15 parts of struvite and 9-45 parts of dilute sulfuric acid with the concentration of 28-32 wt%.
The preparation method of the coking wastewater liquid defluorinating agent comprises the following steps:
s1, grinding struvite, sieving with a screen mesh with more than 200 meshes to obtain struvite with the particle size less than or equal to 0.075 mm;
diluting concentrated sulfuric acid with deionized water to obtain dilute sulfuric acid;
adding ground and sieved struvite into dilute sulfuric acid, heating to 50-65 ℃, maintaining the temperature of 50-65 ℃ and stirring to fully dissolve the struvite, then adding polymeric ferric sulfate, maintaining the temperature of 50-65 ℃ and stirring again to fully dissolve the polymeric ferric sulfate, thus obtaining solution A;
and S2, sequentially adding an aluminum trichloride aqueous solution, an aluminum hydroxychloride aqueous solution and an aluminum sulfate aqueous solution into a reaction kettle, stirring and fully mixing, heating to 70-80 ℃, then adding the solution A, maintaining the temperature of 70-80 ℃ and stirring and reacting for more than 1h, and finally cooling to room temperature to obtain the coking wastewater liquid defluorinating agent.
The coking wastewater liquid defluorinating agent of the invention has the application process that:
adding the coking wastewater liquid fluorine removal agent into the coking wastewater to be treated, adding 2-15 g of the coking wastewater liquid fluorine removal agent into each 1L of coking wastewater to be treated according to the proportion, fully stirring for 20-25 min, measuring the pH value, and adding liquid alkali to adjust the pH value to 6-7 if the pH value is lower than 6; then adding a cationic polyacrylamide aqueous solution flocculant, and carrying out precipitation for more than 2 hours.
Example 1 preparation method of coking wastewater liquid defluorinating agent
S1, grinding struvite, and sieving with a 200-mesh screen to obtain struvite with the particle size of 0.075 mm;
adding 15kg of ground and sieved struvite into 30wt% dilute sulfuric acid, heating to 60 ℃, stirring to fully dissolve the struvite, adding 5kg of polymeric ferric sulfate, and stirring again to fully dissolve the polymeric ferric sulfate to obtain a solution A;
s2, sequentially adding 10kg of aluminum trichloride aqueous solution with the concentration of 23wt%, 20kg of aluminum chlorohydrate aqueous solution with the concentration of 50wt% and 15kg of aluminum sulfate aqueous solution with the concentration of 25wt% into a reaction kettle, stirring and fully mixing, heating to 75 ℃, then adding the solution A, maintaining the temperature of 75 ℃ and stirring for reacting for 1h, and finally cooling to room temperature to obtain the coking wastewater liquid defluorinating agent, namely YF1.
Example 2-5 preparation method of coking wastewater liquid defluorinating agent
Examples 2 to 5 are respectively a preparation method of coking wastewater liquid defluorinating agent, and the steps are basically the same as example 1, except that part of parameters are different, and the specific details are shown in table 1:
table 1 list of parameters in examples 2-5
The content of the other parts of embodiments 2 to 5 is the same as that of embodiment 1, and will not be described here again.
Comparative examples 1 to 11
Comparative examples 1 to 10 are comparative tests of the preparation process of the liquid defluorinating agent for coking wastewater in example 1, and differ only in that:
in comparative example 1, the amount of struvite is 1kg, the amounts of other raw materials and the technological parameters are unchanged, and the obtained coking wastewater liquid defluorinating agent is marked as DYF1.
In comparative example 2, the amount of struvite is 20kg, the amounts of other raw materials and the technological parameters are unchanged, and the obtained coking wastewater liquid defluorinating agent is marked as DYF2.
The amount of 20wt% aqueous aluminum chlorohydrate solution in comparative example 3 was 5kg, and the amount of other raw materials and the process parameters were unchanged, and the obtained coking wastewater liquid fluorine-removing agent was designated as DYF3.
The dosage of the 30wt percent aqueous solution of aluminum chlorohydrate in comparative example 4 is 40kg, the dosage of other raw materials and the technological parameters are unchanged, and the obtained coking wastewater liquid defluorinating agent is marked as DYF4.
The amount of aluminum trichloride aqueous solution with the concentration of 30wt% in comparative example 5 was 5kg, and the amount of other raw materials and the process parameters were unchanged, and the obtained coking wastewater liquid defluorinating agent was marked as DYF5.
The amount of 55wt% aqueous aluminum trichloride solution in comparative example 6 was 40kg, and the amounts of other raw materials and the process parameters were unchanged, and the obtained coking wastewater liquid fluorine-removing agent was designated as DYF5.
The amount of the aqueous aluminum sulfate solution with the concentration of 20wt% in comparative example 7 was 5kg, and the amount of other raw materials and the process parameters were unchanged, and the obtained coking wastewater liquid defluorinating agent was marked as DYF7.
The amount of the aluminum sulfate aqueous solution with the concentration of 30wt% in comparative example 8 was 35kg, and the amount of other raw materials and the process parameters were unchanged, and the obtained coking wastewater liquid defluorinating agent was designated as DY8.
The dosage of polymeric ferric sulfate in comparative example 9 is 1kg, the dosage of other raw materials and the technological parameters are unchanged, and the obtained coking wastewater liquid defluorinating agent is marked as DYF9.
The dosage of polymeric ferric sulfate in comparative example 10 is 25kg, the dosage of other raw materials and the technological parameters are unchanged, and the obtained coking wastewater liquid defluorinating agent is marked as DYF10.
Comparative example 11 preparation of coking wastewater liquid defluorinating agent DY11, the specific steps include:
s1, grinding struvite, and sieving with a 200-mesh screen to obtain struvite with the particle size of 0.075 mm;
adding 15kg of ground and sieved struvite into 30wt% dilute sulfuric acid, heating to 60 ℃, stirring to fully dissolve the struvite, adding 5kg of polymeric ferric sulfate, and stirring again to fully dissolve the polymeric ferric sulfate to obtain a solution A;
s2, adding 2.3kg of aluminum trichloride, 10kg of aluminum chlorohydrate and 3.75kg of aluminum sulfate into 28.95L of deionized water (which is completely consistent with the raw material consumption of 10kg of aluminum trichloride aqueous solution with the concentration of 23wt%, 20kg of aluminum chlorohydrate aqueous solution with the concentration of 50wt% and 15kg of aluminum sulfate aqueous solution with the concentration of 25wt% in example 1), stirring and fully mixing for dissolution (the dissolution effect is not ideal, insoluble substances exist), heating to 75 ℃, then adding the solution A, maintaining the temperature of 75 ℃ for stirring and reacting for 1h, and finally cooling to room temperature to obtain the coking wastewater liquid defluorinating agent, namely DYF11.
Example 6 application of coking wastewater liquid defluorinating agent
Coking wastewater liquid defluorinating agents YF 1-YF 5 and DYF 1-DYF 11 prepared in examples 1-5 and comparative examples 1-11 are respectively treated for biochemical secondary sedimentation water (namely coking wastewater to be treated) of a coking plant sewage station, and the specific steps are as follows:
taking 1L of biochemical secondary sedimentation water of sewage stations of different coking plants, respectively adding coking wastewater liquid defluorinating agents YF 1-YF 5 and DYF 1-DYF 11, fully stirring for 20min, measuring the pH value, and if the pH value is lower than 6, adding liquid caustic soda (generally adopting 32wt% sodium hydroxide as liquid caustic soda) to adjust the pH value to 6-7; then adding a cationic polyacrylamide aqueous solution flocculant, precipitating for 2 hours, and taking supernatant to detect the concentration of fluoride ions.
The treatment results of biochemical secondary sedimentation water in the sewage station of the coking plant A are shown in Table 2:
table 2 list of effects of liquid defluorinating agent for coking wastewater
The treatment results of the biochemical secondary sedimentation water of the sewage station of the coking plant B are shown in Table 3:
TABLE 3 coking wastewater liquid defluorinating agent Effect list
The treatment results of the biochemical secondary sedimentation water of the sewage station of the coking plant C are shown in Table 4:
table 4 shows the effects of the liquid defluorinating agent for coking wastewater
The biochemical secondary sedimentation water of the sewage station of the coking plant D adopts coking wastewater liquid defluorinating agent YF1 with different addition amounts to remove fluorine, and the specific treatment results are shown in Table 5:
TABLE 5 coking wastewater liquid defluorinating agent Effect list
As can be seen from tables 2-5, the coking wastewater liquid defluorinating agent can effectively remove fluoride ions in coking wastewater, has a defluorinating effect of more than 90.82%, can effectively reduce COD content, and simultaneously avoids hardness increase.
It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (9)
1. The coking wastewater liquid defluorination agent is characterized by comprising the following raw materials in parts by weight:
5-18 parts of polymeric ferric sulfate, 10-35 parts of aluminum trichloride aqueous solution, 10-35 parts of aluminum chlorohydrate aqueous solution, 15-28 parts of aluminum sulfate aqueous solution, 3-15 parts of struvite and 9-45 parts of dilute sulfuric acid;
the concentration of the aluminum trichloride aqueous solution is 22-24wt%, the concentration of the aluminum hydroxychloride aqueous solution is 49-51wt%, and the concentration of the aluminum sulfate aqueous solution is 24-26wt%.
2. The coking wastewater liquid defluorinating agent according to claim 1, wherein the concentration of the dilute sulfuric acid is 28-32wt%.
3. A method for preparing the coking wastewater liquid defluorinating agent as claimed in claim 1 or 2, wherein the preparation method comprises the following steps:
s1, adding dilute sulfuric acid into struvite, heating for dissolution, and then adding polymeric ferric sulfate for dissolution to obtain a solution A;
and S2, taking an aluminum trichloride aqueous solution, an aluminum hydroxychloride aqueous solution and an aluminum sulfate aqueous solution, fully mixing, heating, then adding the solution A for reaction, and cooling to room temperature to obtain the coking wastewater liquid fluorine removing agent.
4. The method for preparing a coking wastewater liquid defluorinating agent according to claim 3, wherein in the step S1, the dissolution temperature is 50-65 ℃.
5. The method for producing a liquid defluorinating agent for coking wastewater according to claim 3 or 4, wherein in the step S2, the reaction temperature is 70-80 ℃ and the reaction time is 1h or more.
6. The method for producing a liquid defluorinating agent for coking wastewater according to claim 3 or 4, wherein the particle size of struvite in step S1 is not more than 0.075mm.
7. Use of the coking wastewater liquid defluorinating agent according to claim 1 or 2 in a coking wastewater treatment process, wherein the use is to add the coking wastewater liquid defluorinating agent to coking wastewater to be treated, stir and react, then add a cationic flocculant to precipitate.
8. The use of claim 7, wherein the ratio of the amount of the coking wastewater liquid defluorinating agent to the coking wastewater to be treated is 2-15 g:1L.
9. The use according to claim 7 or 8, characterized in that,
adding the coking wastewater liquid defluorinating agent into the coking wastewater to be treated, stirring for 20-25 min before adding the cationic flocculant, and measuring the pH value;
if the pH value is lower than 6, adding alkali to adjust the pH value to 6-7;
after the cationic flocculant is added, the precipitation time is more than 2 hours.
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