CN114517300B - Method for synthesizing water treatment agent by utilizing sulfuric acid waste liquid - Google Patents
Method for synthesizing water treatment agent by utilizing sulfuric acid waste liquid Download PDFInfo
- Publication number
- CN114517300B CN114517300B CN202210145720.1A CN202210145720A CN114517300B CN 114517300 B CN114517300 B CN 114517300B CN 202210145720 A CN202210145720 A CN 202210145720A CN 114517300 B CN114517300 B CN 114517300B
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- waste liquid
- acid waste
- water treatment
- treatment agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000007788 liquid Substances 0.000 title claims abstract description 80
- 239000002699 waste material Substances 0.000 title claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 30
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 230000006698 induction Effects 0.000 claims description 5
- 238000007747 plating Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 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 abstract description 25
- 229910000360 iron(III) sulfate Inorganic materials 0.000 abstract description 25
- 239000000047 product Substances 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 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 abstract description 9
- 239000007795 chemical reaction product Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 9
- 238000007792 addition Methods 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- -1 ferric iron ions Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/046—Alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to the technical field of recycling of sulfuric acid waste liquid, in particular to a method for synthesizing a water treatment agent by utilizing sulfuric acid waste liquid. Which comprises the following steps: using iron or/and aluminum as an anode, using an inert electrode as a cathode, and electrolyzing the sulfuric acid waste liquid to obtain electrolytic product liquid; stirring the electrolytic solution, and heating the electrolytic solution to 90-110 ℃ for reaction to obtain the water treatment agent. In the application, the mode of the electrolytic sulfuric acid waste liquid is adopted, so that the continuous preparation of the polymeric ferric sulfate or the polymeric aluminum sulfate is realized, the reaction product is not required to be frequently transferred in the preparation process, and the production efficiency is higher.
Description
Technical Field
The invention relates to the technical field of recycling of sulfuric acid waste liquid, in particular to a method for synthesizing a water treatment agent by utilizing sulfuric acid waste liquid.
Background
The annual water consumption in the world is over 1 trillion tons, about 80% of the water is industrial water, along with the continuous improvement of living standard, the demand of human beings for water is continuously increased, the sewage is also continuously increased, and the water treatment agent is mainly used for treating production and living water and sewage, so that the water is recycled, and has quite important significance for saving water, energy, saving materials and protecting environment.
The coagulating sedimentation is an important technical link in the flow of the water treatment process, the flocculating agent belongs to one of water treatment agents, and the flocculating agent commonly used at present comprises polymeric ferric sulfate, polymeric aluminum sulfate and the like. The polymeric ferric sulfate is an inorganic high-molecular coagulant with excellent performance, the morphological character is light yellow amorphous powdery solid, the polymeric ferric sulfate is extremely easy to dissolve in water, and 10 percent (mass) of aqueous solution is reddish brown transparent solution and has hygroscopicity. Polymeric ferric sulfate is widely used for purifying drinking water, industrial water, various industrial waste water, municipal sewage, sludge dewatering and the like. The polyaluminium sulfate is a compound high molecular polymer, has huge molecular structure and strong adsorption capacity, and has better water purifying effect than all traditional inorganic water purifying agents. The floccule formed after the raw water is added is large, the sedimentation speed is high, the activity is high, and the filterability is good. And has strong adaptability to various raw water and little influence on the PH value of water (PH value is 4-11). The purification effect is remarkable no matter the turbidity of raw water or the concentration of pollutants in waste water. The dosage is less, the corrosion to equipment and pipelines is less, the operation is convenient, the dosage is less, and the purification cost is low.
In the production process of the polymeric ferric sulfate and the polymeric aluminum sulfate, sulfuric acid is an indispensable reaction component, and if the two water treatment agents can be prepared through sulfuric acid waste liquid, the reutilization of the sulfuric acid waste liquid can be realized.
One such method disclosed in the publication CN105948210a for producing polymeric ferric sulfate from industrial waste acid and scrap iron comprises the steps of: taking waste acid and waste iron as raw materials to react to obtain ferrous iron; adding waste iron powder, water and 50% waste sulfuric acid into a soaking tank according to the weight ratio of 1:1-2.5:2-2.5, stirring uniformly, soaking, and stirring once every half an hour to obtain ferrous iron solution comprising ferrous sulfate and ferric sulfate; performing oxidation reaction by taking potassium chlorate as an oxidant to obtain ferric iron; adding oxidant potassium chlorate into the obtained ferrous iron solution at the temperature of 40-60 ℃ in a mass ratio of 0.2-0.3, and reacting for 2-3 hours to obtain a ferric iron solution; carrying out hydrolysis reaction; continuously introducing water vapor into the obtained ferric iron solution, and raising the temperature to 90-110 ℃ to enable ferric iron ions and hydroxyl ions to be combined with each other to generate hydrolysis reaction; the polymerization process from oligomer to polymer yields polymeric ferric sulfate. One such method disclosed in publication No. CN104773748A for preparing low-iron polyaluminum sulfate from an aluminum-containing spent sulfuric acid mother liquor comprises the steps of: adding aluminum-containing waste sulfuric acid mother liquor into a pretreatment reaction kettle, adding a heavy metal capturing agent, and performing filter pressing separation to obtain a reaction liquid I; mixing industrial sulfuric acid and calcium aluminate powder according to a certain proportion for reaction to obtain a reaction solution II; and (3) carrying out alkalization polymerization reaction on the reaction liquid I and the reaction liquid II at a certain temperature, adding a stabilizing agent, continuing the polymerization reaction, carrying out filter pressing separation, and cooling to obtain a liquid low-iron polyaluminium sulfate product.
It can be seen that in the existing process for producing polymeric ferric sulfate and aluminum sulfate by using sulfuric acid waste liquid, the preparation process is generally in an intermittent operation mode, and the defects of auxiliary operations such as loading and unloading, difficulty in stabilizing product quality, complex operation, low yield and the like exist.
Disclosure of Invention
The invention aims to solve the problems and provides a water treatment agent synthesized by utilizing sulfuric acid waste liquid and a continuous production method.
The technical scheme for solving the problem is that the invention provides a method for synthesizing a water treatment agent by utilizing sulfuric acid waste liquid, which comprises the following steps: using iron or/and aluminum as an anode, using an inert electrode as a cathode, and electrolyzing the sulfuric acid waste liquid to obtain electrolytic product liquid; stirring the electrolytic solution, and heating the electrolytic solution to 90-110 ℃ for reaction to obtain the water treatment agent.
Wherein, the inert electrode can be selected arbitrarily, and the inert electrode comprises one or more of a graphite electrode and a Pt electrode as a preferable mode of the invention.
In this application, creatively adopts the mode of electrolysis sulfuric acid waste liquid to prepare polymeric ferric sulfate or polymeric aluminum sulfate in succession, through designing an electrolysis trough that has heating device and agitating unit, can accomplish whole reaction, need not frequent transfer reaction product, production efficiency is higher.
The principle of producing polymeric ferric sulfate by using the electrolytic sulfuric acid waste liquid is as follows: during electrolysis, the iron or aluminum of the anode undergoes oxidation: fe-2e - = Fe 2+ ，Al - 3e - = Al 3+ The method comprises the steps of carrying out a first treatment on the surface of the The cathode undergoes a reduction reaction: 2H (H) 2 O + 2e - = 2OH - + H 2 。
In common knowledge, it is often considered that the electrolysis of dilute sulfuric acid is equivalent to the electrolysis of water, and in fact, the conclusion is that the electrolysis of dilute sulfuric acid is problematicThe volume ratio of oxyhydrogen is often much greater than 2:1, indicating that side reactions occur in addition to electrolysis of water. The sulfuric acid waste liquid electrolysis process is as follows: h 2 SO 4 = H + + HSO 4- The method comprises the steps of carrying out a first treatment on the surface of the But bisulfate ion HSO 4- Is not complete, K.apprxeq.10 -2 The HSO with higher concentration exists in the solution 4- Negatively charged HSO after power-on 4- Is easily moved to the anode where side reactions may occur: 2HSO 4- - 2e = H 2 S 2 O 8 (peroxodisulfuric acid); h 2 S 2 O 8 Slow hydrolysis in solution near the anode: h 2 S 2 O 8 + H 2 O = H 2 SO 5 (Per-sulfuric acid) +H 2 SO 4 ，H 2 SO 5 + H 2 O = H 2 + H 2 O 2 . Whereas in an acidic solution H 2 O 2 Has quite stability and can exist in solution for a long time.
Based on the above electrolytic process, fe is generated 2+ Or/and Al 3+ 、H 2 O 2 At H 2 O 2 Under the action of Fe 2+ Can be oxidized into Fe quickly 3+ . To ensure Fe 2+ Preferably, the electrolyte is heated to 50-70 ℃ for reaction, stirred, and then heated to 90-110 ℃ for reaction. At 50-70 ℃ to make Fe 2+ And (5) fully oxidizing. Preferably, the electrolytic solution is heated to 50-70 ℃ for reaction for 2-3h.
Then, the application agitates the electrolytic solution to stir Fe of the anode 3+ And OH of cathode - Mixing together, heating to 90-110 ℃, and carrying out hydrolytic polymerization reaction: fe (Fe) 3+ + SO 4 2- + OH － → [Fe 2 (OH) n (SO 4 ) 3-n/2 ] m . Similarly, al 3+ + SO 4 2- + OH － → [Al 2 (OH) n (SO 4 ) 3-n/2 ] m The obtained polymeric ferric sulfate or/and polymeric aluminum sulfate water treatment agent is obtained.
Wherein the stirring speed is not required to be excessively high, and is preferably 10-20r/min. The hydrolysis polymerization time is not too short or too long, and is preferably heated to 90-110 ℃ for reaction for 3-5h.
The above reaction is more pronounced as the sulfuric acid concentration is higher. Preferably, the sulfuric acid waste liquid is concentrated to a sulfuric acid concentration of 50-70% before electrolysis.
Under the condition of higher sulfuric acid concentration, when hydrolysis polymerization reaction is carried out subsequently, OH － May be insufficient to increase OH － Preferably, the electrolytic solution is introduced with water and heated to 90-110 ℃ for reaction.
From the above process, it can be seen that the electrode of the anode and the sulfuric acid waste liquid are continuously consumed, the consumption of the anode can be solved by adopting a large-scale electrode, and in order to maintain acidity and reaction continuity in the electrolytic tank, the sulfuric acid waste liquid is divided into a plurality of groups as the preference of the invention, one group of sulfuric acid waste liquid is firstly taken for electrolysis, and one group of sulfuric acid waste liquid is added after 30-60min of electrolysis.
When the electrolysis is finished, the electrolysis liquid is obtained by the yellow-green mark in the electrolysis tank. Generally in the range of 800-1200A/m 2 After electrolysis for 12-20 hours, the current density is 800-1200A/m when the electrolysis is performed 2 The electrolysis time is 12-20h.
In addition, in order to increase the polymerization degree of the polymeric ferric sulfate/aluminum prepared in the present application, it is preferable in the present invention that the obtained product is cured for 20 to 30 hours after heating to 90 to 110 ℃ for reaction. Ripening is a common operation in chemical industry, i.e., the reaction product is left to stand at a soak temperature for a period of time to allow for adequate reaction.
In the application, the polymeric ferric sulfate and the polymeric aluminum sulfate can be obtained respectively by adopting different anodes, and the polymeric ferric sulfate aluminum can be obtained by taking iron and aluminum as the anodes together, so that the polymeric ferric sulfate aluminum has the characteristics of the polymeric aluminum and the polymeric iron, overcomes the defects of low settling speed of aluminum salt, high concentration of residual aluminum and higher chromaticity of ferric salt effluent, and has the advantages of stable performance and formationLarge floc, fast settling speed, wide application range, small dosage and good mixing effect. Since it is difficult to produce polymeric ferric sulfate when aluminum has a higher activity than iron and both are present, it is preferable to use a composite material in which aluminum is coated with iron when iron and aluminum are used together as an anode in the present invention. Such a composite material may be produced by electroplating, and as a preferred aspect of the present invention, the iron-clad aluminum composite material is produced by: after removing the oxide film on the surface of the aluminum piece, sending the aluminum piece into a plating bath, and carrying out alternating current and direct current alternating current plating; during electroplating, the electrolyte is ferrous chloride acid water solution with the direct current density of 15-25A/dm 2 The alternating current density is 6-8A/dm 2 。
In addition, in order to improve the water treatment effect of the prepared polymeric ferric sulfate and polymeric aluminum sulfate, the product obtained by hydrolytic polymerization can be magnetized, and the product is magnetized for 2-5min under the magnetic induction intensity of 15-25mT after being heated to 90-110 ℃ for reaction as the preferential choice of the invention.
The invention has the beneficial effects that:
in the application, the mode of the electrolytic sulfuric acid waste liquid is adopted, so that the continuous preparation of the polymeric ferric sulfate or the polymeric aluminum sulfate is realized, the reaction product is not required to be frequently transferred in the preparation process, and the production efficiency is higher.
Detailed Description
The following is a specific embodiment of the present invention and further describes the technical solution of the present invention, but the present invention is not limited to these examples.
Example 1
A method for synthesizing a water treatment agent by utilizing sulfuric acid waste liquid comprises the following steps:
an electrolytic cell is prepared, a heating device is arranged at the bottom of the electrolytic cell, a stirring device is arranged at the top of the electrolytic cell, iron is used as an anode, and graphite is used as a cathode.
Directly putting the sulfuric acid waste liquid into an electrolytic tank, and controlling the current density to be 1000A/m 2 And (5) carrying out electrolysis for 15h to obtain an electrolysis product liquid.
Stopping power supply, starting the stirring device, stirring the electrolytic production liquid in the electrolytic tank at a speed of 15r/min for 5min, and stopping stirring. And controlling the heating device to work to heat the electrolytic production liquid to 100 ℃ for 4 hours to obtain the polymeric ferric sulfate water treatment agent.
Example 2
This embodiment is substantially the same as embodiment 1, except that:
and heating and concentrating the sulfuric acid waste liquid at high temperature by adopting a graphite tube heater until the sulfuric acid concentration is 60%, and then throwing the concentrated sulfuric acid waste liquid into an electrolytic tank for electrolysis.
Example 3
This embodiment is substantially the same as embodiment 1, except that:
the sulfuric acid waste liquid was equally divided into 20 parts. Firstly, taking one part of the mixture to be put into an electrolytic tank, and controlling the current density to be 1000A/m 2 Carrying out electrolysis for 45min, then adding a part of concentrated sulfuric acid waste liquid, and continuing the electrolysis; after 45min of electrolysis, adding a part of concentrated sulfuric acid waste liquid; repeating the steps until the addition of 20 parts of concentrated sulfuric acid waste liquid is completed, continuing to electrolyze for 45min, and completing the electrolysis for 15h to obtain an electrolysis product liquid.
Example 4
This embodiment is substantially the same as embodiment 1, except that:
after the power-on is stopped, the heating device is started first, and the electrolytic solution in the electrolytic tank is heated to 60 ℃ for 2.5h. Then the stirring device is started, and the electrolytic production liquid in the electrolytic tank is stirred at the speed of 15r/min for 5min, and then the stirring is stopped.
Example 5
This embodiment is substantially the same as embodiment 1, except that:
after stopping stirring, water accounting for 5% of the electrolytic solution is added into the electrolytic tank, and the heating device is controlled to work so as to heat the electrolytic solution to 100 ℃ for reaction for 4 hours.
Example 6
This embodiment is substantially the same as embodiment 1, except that:
and heating the electrolytic solution to 100 ℃ for reaction for 4 hours, taking a tank cover to cover the notch of the electrolytic tank, keeping the temperature at 60 ℃, and standing for 24 hours.
Example 7
This embodiment is substantially the same as embodiment 1, except that:
and heating to 100 ℃ to react for 4 hours to obtain a product, and magnetizing the product for 3 minutes under the magnetic induction of 20mT to obtain the magnetized polymeric ferric sulfate water treatment agent.
Example 8
This embodiment is substantially the same as embodiment 1, except that:
aluminum was used as the anode.
Example 9
This embodiment is substantially the same as embodiment 1, except that:
iron-coated aluminum composite material is used as an anode.
The iron-coated aluminum composite material is prepared by the following steps: sequentially performing alkali washing, boiling water washing and 30% hydrochloric acid soaking treatment on the aluminum piece for 30s, and removing an oxide film on the surface of the aluminum piece; then the aluminum piece is sent into a plating tank with electrolyte being ferrous chloride acidic aqueous solution, and firstly 6-8A/dm is led in 2 Alternating current is then superimposed at 20A/dm 2 Electroplating until the thickness of the iron is one fifth of the diameter of the aluminum part, and then taking out the composite part for flushing.
Example 10
A method for synthesizing a water treatment agent by utilizing sulfuric acid waste liquid comprises the following steps:
an electrolytic cell is prepared, a heating device is arranged at the bottom of the electrolytic cell, a stirring device is arranged at the top of the electrolytic cell, iron is used as an anode, and graphite is used as a cathode.
And heating and concentrating the sulfuric acid waste liquid at high temperature by adopting a graphite tube heater until the sulfuric acid concentration is 60%, and dividing the concentrated sulfuric acid waste liquid into 20 parts averagely. Firstly, taking one part of the mixture to be put into an electrolytic tank, and controlling the current density to be 1000A/m 2 Carrying out electrolysis for 45min, then adding a part of concentrated sulfuric acid waste liquid, and continuing the electrolysis; after 45min of electrolysis, adding a part of concentrated sulfuric acid waste liquid; repeating the steps until the addition of 20 parts of concentrated sulfuric acid waste liquid is completed, continuing to electrolyze for 45min, and completing the electrolysis for 900min to obtain the electrolysisAnd (5) producing liquid.
Stopping power supply, starting the heating device, and heating the electrolytic solution in the electrolytic tank to 60 ℃ for 2.5h. Then the stirring device is started, and the electrolytic production liquid in the electrolytic tank is stirred at the speed of 15r/min for 5min, and then the stirring is stopped. And then adding water with the mass accounting for 5 percent of the mass of the electrolytic liquid into the electrolytic tank, and controlling the heating device to work so as to heat the electrolytic liquid to 100 ℃ for reaction for 4 hours, thus obtaining a reaction product. The cell cover is covered on the notch of the electrolytic cell, the temperature is kept at 60 ℃, and the cell cover is kept stand for 24 hours.
Example 11
A method for synthesizing a water treatment agent by utilizing sulfuric acid waste liquid comprises the following steps:
an electrolytic cell is prepared, a heating device is arranged at the bottom of the electrolytic cell, a stirring device is arranged at the top of the electrolytic cell, iron is used as an anode, and graphite is used as a cathode.
And (3) heating and concentrating the sulfuric acid waste liquid at high temperature by adopting a graphite tube heater until the sulfuric acid concentration is 50%, and dividing the concentrated sulfuric acid waste liquid into 36 parts averagely. Firstly, taking one part of the mixture to be put into an electrolytic tank, and controlling the current density to be 800A/m 2 Carrying out electrolysis for 20min, then adding a part of concentrated sulfuric acid waste liquid, and continuing the electrolysis; after electrolysis for 20min, adding a part of concentrated sulfuric acid waste liquid; repeating the steps until the addition of 20 parts of concentrated sulfuric acid waste liquid is completed, continuing to electrolyze for 20min, and completing the electrolysis for 12h to obtain an electrolysis product liquid.
Stopping power supply, starting the heating device, and heating the electrolytic solution in the electrolytic tank to 50 ℃ for 2h. Then the stirring device is started, the electrolytic production liquid in the electrolytic tank is stirred at the speed of 10r/min for 10min, and then the stirring is stopped. And then adding water with the mass accounting for 1 percent of the mass of the electrolytic solution into the electrolytic tank, and controlling the heating device to work so as to heat the electrolytic solution to 90 ℃ for reaction for 3 hours, thus obtaining a reaction product. The cell cover is covered on the notch of the electrolytic cell, the temperature is kept at 40 ℃, and the cell cover stands for 20h. And standing for 20h to obtain a product, and magnetizing the product for 2min under 15mT magnetic induction intensity to obtain the polymeric ferric sulfate water treatment agent.
Example 12
A method for synthesizing a water treatment agent by utilizing sulfuric acid waste liquid comprises the following steps:
an electrolytic cell is prepared, a heating device is arranged at the bottom of the electrolytic cell, a stirring device is arranged at the top of the electrolytic cell, iron is used as an anode, and graphite is used as a cathode.
And heating and concentrating the sulfuric acid waste liquid at high temperature by adopting a graphite tube heater until the sulfuric acid concentration is 70%, and dividing the concentrated sulfuric acid waste liquid into 20 parts averagely. Firstly, taking one part of the mixture to be put into an electrolytic tank, and controlling the current density to be 1200A/m 2 Carrying out electrolysis for 60min, then adding a part of concentrated sulfuric acid waste liquid, and continuing the electrolysis; after electrolysis for 60min, adding a part of concentrated sulfuric acid waste liquid; repeating the steps until the addition of 20 parts of concentrated sulfuric acid waste liquid is completed, continuing to electrolyze for 60 minutes, and completing the electrolysis for 20 hours to obtain an electrolysis product liquid.
Stopping power supply, starting the heating device, and heating the electrolytic solution in the electrolytic tank to 70 ℃ for 3h. Then the stirring device is started, and the electrolytic production liquid in the electrolytic tank is stirred at the speed of 20r/min for 3min, and then the stirring is stopped. And then adding water with the mass accounting for 10 percent of the mass of the electrolytic liquid into the electrolytic tank, and controlling the heating device to work so as to heat the electrolytic liquid to 110 ℃ for reaction for 5 hours, thus obtaining a reaction product. The cell cover is covered on the notch of the electrolytic cell, the temperature is kept at 70 ℃, and the cell cover is kept stand for 30 hours. And standing for 30 hours to obtain a product, and magnetizing the product for 5 minutes under the magnetic induction of 25mT to obtain the polymeric ferric sulfate water treatment agent.
Comparative example 1
Polymeric ferric sulfate was prepared according to the method disclosed in the publication No. CN105948210A, using the same amount of iron and sulfuric acid waste as used in the present application as reactants.
Flocculation detection
The domestic sewage was equally divided into 14 parts, 13 parts of the water treatment agents prepared in examples and comparative examples were added at 30mg/L, respectively, and 1 part was a blank group, to obtain 14 parts of samples. Each sample was stirred at a rotation speed of 150r/min for 2min, then stirred at a speed of 50r/min for 10min, and then left to stand for 20min, the supernatant below the liquid level of 4cm was removed, turbidity was measured by a Hash 2100Q nephelometer, COD was measured by a potassium dichromate method, and the detection results were as shown in Table 1 below.
Table 1.
As can be seen from Table 1, the water treatment agent prepared by the method has good flocculation effect, and the flocculation effect is even slightly better than that of the prior art, which indicates that the method has the characteristics of continuous production and high production efficiency, and has the characteristic of good product flocculation effect.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (6)
1. A method for synthesizing a water treatment agent by utilizing sulfuric acid waste liquid is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the steps of using iron as an anode or using a composite material of iron coated with aluminum as an anode, using an inert electrode as a cathode, and electrolyzing sulfuric acid waste liquid to obtain electrolytic solution, wherein H is arranged near the anode 2 O 2 And Fe (Fe) 2+ OH is arranged near the cathode - ；
Heating the electrolytic solution to 50-70 ℃ for 2-3H, and reacting in H 2 O 2 Under the action of Fe 2+ Is rapidly oxidized into Fe 3+ ；
Stirring again to stir Fe of anode 3+ And OH of cathode - Mixing together; then heating to 90-110 ℃ for reaction for 3-5h, and carrying out hydrolytic polymerization reaction; curing the obtained product for 20-30h; and (3) magnetizing the obtained product for 2-5min under 15-25mT magnetic induction intensity to obtain the water treatment agent.
2. The method for synthesizing a water treatment agent by using sulfuric acid waste liquid according to claim 1, wherein the method comprises the following steps: when in electrolysis, the current density is 800-1200A/m 2 The electrolysis time is 12-20h.
3. The method for synthesizing a water treatment agent by using sulfuric acid waste liquid according to claim 1, wherein the method comprises the following steps: dividing the sulfuric acid waste liquid into a plurality of groups, firstly taking one group of sulfuric acid waste liquid for electrolysis, and then adding one group of sulfuric acid waste liquid after 30-60min of electrolysis.
4. The method for synthesizing a water treatment agent by using sulfuric acid waste liquid according to claim 1, wherein the method comprises the following steps: and concentrating the sulfuric acid waste liquid until the sulfuric acid concentration is 50-70% before electrolysis.
5. The method for synthesizing a water treatment agent by using sulfuric acid waste liquid according to claim 1, wherein the method comprises the following steps: the inert electrode comprises one or more of a graphite electrode and a Pt electrode.
6. The method for synthesizing a water treatment agent by using sulfuric acid waste liquid according to claim 1, wherein the method comprises the following steps: the iron-coated aluminum composite material is prepared by the following steps: after removing the oxide film on the surface of the aluminum piece, sending the aluminum piece into a plating bath, and carrying out alternating current and direct current alternating current plating; during electroplating, the electrolyte is ferrous chloride acid water solution with the direct current density of 15-25A/dm 2 The alternating current density is 6-8A/dm 2 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210145720.1A CN114517300B (en) | 2022-02-17 | 2022-02-17 | Method for synthesizing water treatment agent by utilizing sulfuric acid waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210145720.1A CN114517300B (en) | 2022-02-17 | 2022-02-17 | Method for synthesizing water treatment agent by utilizing sulfuric acid waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114517300A CN114517300A (en) | 2022-05-20 |
| CN114517300B true CN114517300B (en) | 2024-03-19 |
Family
ID=81599219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210145720.1A Active CN114517300B (en) | 2022-02-17 | 2022-02-17 | Method for synthesizing water treatment agent by utilizing sulfuric acid waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114517300B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4943478B1 (en) * | 1970-12-28 | 1974-11-21 | ||
| CN1177653A (en) * | 1997-06-20 | 1998-04-01 | 中国科学院生态环境研究中心 | Electrochemical synthesis of polymerized aluminum chloride |
| CN102051630A (en) * | 2010-12-25 | 2011-05-11 | 浙江工业大学 | Method for preparing superfine iron phosphate through electrolytic method |
| CN105948210A (en) * | 2016-07-11 | 2016-09-21 | 哈尔滨辰能工大环保科技股份有限公司 | Method for producing polymeric ferric sulfate from raw materials industrial waste acid and scrap iron |
| CN106191900A (en) * | 2016-06-29 | 2016-12-07 | 合肥工业大学 | A kind of device and method preparing high basicity bodied ferric sulfate |
| CN108503167A (en) * | 2018-03-30 | 2018-09-07 | 江苏宝钢精密钢丝有限公司 | A method of utilizing iron and steel pickling waste liquid synthesizing new water purification agent |
-
2022
- 2022-02-17 CN CN202210145720.1A patent/CN114517300B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4943478B1 (en) * | 1970-12-28 | 1974-11-21 | ||
| CN1177653A (en) * | 1997-06-20 | 1998-04-01 | 中国科学院生态环境研究中心 | Electrochemical synthesis of polymerized aluminum chloride |
| CN102051630A (en) * | 2010-12-25 | 2011-05-11 | 浙江工业大学 | Method for preparing superfine iron phosphate through electrolytic method |
| CN106191900A (en) * | 2016-06-29 | 2016-12-07 | 合肥工业大学 | A kind of device and method preparing high basicity bodied ferric sulfate |
| CN105948210A (en) * | 2016-07-11 | 2016-09-21 | 哈尔滨辰能工大环保科技股份有限公司 | Method for producing polymeric ferric sulfate from raw materials industrial waste acid and scrap iron |
| CN108503167A (en) * | 2018-03-30 | 2018-09-07 | 江苏宝钢精密钢丝有限公司 | A method of utilizing iron and steel pickling waste liquid synthesizing new water purification agent |
Non-Patent Citations (2)
| Title |
|---|
| 李家珍.李家珍.《燃料、染色工业废水处理》.北京：化学工业出版社,1997, * |
| 铝板电絮凝去除水体中镍离子的研究;杨波 等;《深圳大学学报理工版》;第103页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114517300A (en) | 2022-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108585146B (en) | Preparation method of titanium-containing composite ferric polysulfate flocculant | |
| CN104944400A (en) | Technology for preparing iron phosphate through hydrolytic method | |
| CN103896464B (en) | A kind of trade effluent materializing strategy agent and application thereof | |
| CN105948210A (en) | Method for producing polymeric ferric sulfate from raw materials industrial waste acid and scrap iron | |
| CN108193251B (en) | System and method for recovering nickel-tin salt coloring and medium-temperature hole sealing agent in aluminum processing | |
| CN104478050A (en) | Preparation method and application of modified polyferric sulfate for treating industrial wastewater | |
| CN109133293B (en) | Preparation process of polymeric ferric sulfate crystal for wastewater treatment | |
| CN110902898A (en) | Device and method for removing nitrogen and phosphorus in sewage by magnesium anode electrodialysis method | |
| CN107381892A (en) | A kind of handling process of high-concentration ammonia nitrogenous wastewater | |
| CN105293839B (en) | A kind of processing method of fluorescent brightener CBS waste water low boiler cut | |
| CN104876200A (en) | Method for recycling phosphorus resource from electroless nickel plating wastewater | |
| CN112811646B (en) | Method for treating wastewater with high fluorine ions, high COD (chemical oxygen demand) and high chroma | |
| CN102241448B (en) | Comprehensive utilization method of sodium sulfate wastewater | |
| CN114517300B (en) | Method for synthesizing water treatment agent by utilizing sulfuric acid waste liquid | |
| CN211169989U (en) | System for treating alkaline chemical nickel plating wastewater | |
| CN1233561C (en) | Method for preparing polymeric ferric sulfate by using partial oxidation process | |
| CN1958462A (en) | Method for preparing potassium ferrate by using waste liquid from acid washing steel | |
| CN106587314A (en) | Efficient phosphorus removal agent and preparation method thereof | |
| CN103030200A (en) | Method for producing poly-silicon rare earth chloride sulfate aluminum iron by using rare earth-containing sludge and electroplated and pickled acid-containing sewage | |
| CN107473486B (en) | Combined treatment method of desulfurization wastewater | |
| CN104261610A (en) | Novel coagulation treatment method for chemical waste water | |
| Son et al. | Removal of nitrogen and phosphate from fertilizer industry wastewater by magnesium ammonium phosphate formation and electrochemical treatment | |
| CN109607945B (en) | Method for improving biochemical efficiency of wastewater in photovoltaic and electronic industries | |
| CN111333215A (en) | Method for removing chemical oxygen demand of landfill leachate | |
| CN109574173A (en) | Efficient removing heavy metals, the organic coagulants of dephosphorization and its preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |