CN113880208A - Polymeric aluminum ferric sulfate composite water purifying agent and preparation process thereof - Google Patents
Polymeric aluminum ferric sulfate composite water purifying agent and preparation process thereof Download PDFInfo
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- CN113880208A CN113880208A CN202111250672.4A CN202111250672A CN113880208A CN 113880208 A CN113880208 A CN 113880208A CN 202111250672 A CN202111250672 A CN 202111250672A CN 113880208 A CN113880208 A CN 113880208A
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- water purifying
- ferric sulfate
- purifying agent
- polymeric aluminum
- composite water
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 84
- 229910000360 iron(III) sulfate Inorganic materials 0.000 title claims abstract description 77
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000012629 purifying agent Substances 0.000 title claims abstract description 75
- 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 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000000243 solution Substances 0.000 claims abstract description 71
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002699 waste material Substances 0.000 claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 claims abstract description 36
- 239000000706 filtrate Substances 0.000 claims abstract description 28
- 239000007800 oxidant agent Substances 0.000 claims abstract description 25
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 239000012670 alkaline solution Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- -1 aluminum metals Chemical class 0.000 claims abstract description 9
- 239000003245 coal Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical group [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 17
- 239000002440 industrial waste Substances 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000003912 environmental pollution Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 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 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- GDPKWKCLDUOTMP-UHFFFAOYSA-B iron(3+);dihydroxide;pentasulfate Chemical compound [OH-].[OH-].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GDPKWKCLDUOTMP-UHFFFAOYSA-B 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention provides a polymeric aluminum ferric sulfate composite water purifying agent and a manufacturing process thereof, relating to the technical field of water purifying agents. The preparation process of the polymeric aluminum ferric sulfate composite water purifying agent comprises the following steps: adding a sulfuric acid I solution into waste residues containing iron and aluminum metals, treating for 2-3 hours in a constant-temperature water bath, adding an oxidant, reacting for 20-30 minutes, filtering to obtain a filtrate, cooling the filtrate to 60-70 ℃, adding an alkaline solution, adjusting the pH value of the whole solution to 3-4, curing for 3-4 hours, and drying to obtain the polymeric aluminum ferric sulfate composite water purifying agent. The invention also provides a polymeric aluminum ferric sulfate composite water purifying agent which has good water purifying effect, quick action, small dosage and low cost, can recover valuable metals in industrial waste residues and reduce solid residue discharge, and also has good economic benefit and environmental protection benefit.
Description
Technical Field
The invention relates to the technical field of water purifying agents, and particularly relates to a polymeric aluminum ferric sulfate composite water purifying agent and a manufacturing process thereof.
Background
Industrial waste residues are generated in the process of smelting metal ore by carrier gas, the waste residues often contain valuable metals such as aluminum, iron and the like and rare elements, are precious and rich secondary resources, and if the waste residues are directly used as wastes for treatment, not only can soil be alkalized, but also water sources are polluted, and the ecological environment is damaged. Moreover, the stockpiling of such industrial waste residues takes up a large amount of land, requiring relatively expensive maintenance. Under the condition that mineral resources are increasingly deficient, the recovery of valuable resources in the industrial waste residues is increasingly important, and if the valuable resources are reasonably utilized, the problem of environmental pollution can be solved, and the problem of resource shortage can be relieved.
In modern industrial production, the product is prepared fromThe development of the industry is accelerated, the amount of industrial wastewater treated daily is increased, and the industrial wastewater can seriously pollute natural environments such as rivers, soil and the like. The inorganic polymeric flocculant has the advantages of high efficiency, no toxicity, strong adaptability, low price and the like, and is widely used for treating various kinds of sewage and wastewater. In recent years, research on the preparation of inorganic polymeric flocculant from various industrial waste residues is rapidly developed. The Polymeric Aluminum Ferric Sulfate (PAFS) is a novel high-efficiency inorganic polymeric flocculant, and Fe is introduced based on the research of Polymeric Aluminum Sulfate (PAS)3+And (3) a copolymer formed by hydrolytic copolymerization with aluminum ions. The flocculant has the characteristics of high polyaluminium salt base and strong adaptability to raw water, and also has the advantages of high polyferric density and quick floc sedimentation; the method can overcome the defects of high concentration of residual aluminum and low settling speed of the water sample after aluminum salt treatment, and has wide application prospect. However, the reaction temperature of the prior art is not easy to be mastered in the actual production of the polymeric aluminum ferric sulfate, and no oxidant, Fe, is added in the production process2+Cannot be converted into Fe3+The polymerization effect can not be achieved, the water purification effect is influenced, the production efficiency is low, and the water purification effect is poor.
Disclosure of Invention
The invention aims to provide a manufacturing process of a polymeric aluminum ferric sulfate composite water purifying agent, which not only improves the production efficiency, but also is easier to master the reaction temperature and improves the utilization rate of reactants.
The invention also aims to provide a polymeric aluminum ferric sulfate composite water purifying agent which has good water purifying effect, quick action, small using amount and low cost, can recover valuable metals in industrial waste residues and reduce solid residue discharge, and also has good economic benefit and environmental protection benefit.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a manufacturing process of a polymeric aluminum ferric sulfate composite water purifying agent, which comprises the following steps: adding a sulfuric acid I solution into waste residues containing iron and aluminum metals, treating for 2-3 hours in a constant-temperature water bath, adding an oxidant, reacting for 20-30 minutes, filtering to obtain a filtrate, cooling the filtrate to 60-70 ℃, adding an alkaline solution, adjusting the pH value of the whole solution to 3-4, curing for 3-4 hours, and drying to obtain the polymeric aluminum ferric sulfate composite water purifying agent.
The invention also provides a polymeric aluminum ferric sulfate composite water purifying agent which is prepared by the manufacturing process of the polymeric aluminum ferric sulfate composite water purifying agent.
The polymeric aluminum ferric sulfate composite water purifying agent and the preparation process thereof provided by the embodiment of the invention have the following beneficial effects:
on the one hand, in the manufacturing process of the polymeric aluminum ferric sulfate composite water purifying agent provided by the invention, waste residue is added into a sulfuric acid I solution for acid leaching for 2-3 hours, and the obtained solution mainly comprises Al2(SO4)3And Fe2(SO4)3And Fe (SO)4)2And the temperature of the whole reaction system can be kept constant by constant-temperature water bath heating treatment, and simultaneously, objects are heated uniformly, so that the uncontrollable property of excessive intensity and temperature caused by direct heating is avoided, the reaction temperature can be strictly controlled, and the constancy of the temperature of the whole reaction system is ensured. Then adding oxidant into the solution to react for 20-30 minutes to remove Fe in the solution2+Conversion to Fe3+Thereby improving the utilization rate of Fe. Remain filtrating after filtering, the reaction of the later stage of being convenient for after getting rid of insoluble dregs, and can improve the purity of final product, and then improve the water purification effect of product. And cooling the filtrate to 60-70 ℃, adding an alkaline solution to adjust the pH value of the filtrate to carry out hydrolytic polymerization reaction, wherein the hydrolysis reaction is favorably carried out at the temperature, and the generated basic aluminum and the basic iron have higher stability. With the addition of the alkaline solution, the pH value of the solution rises, and OH in the solution-The concentration is increased continuously so that [ Al (H)2O6)]3+、[Fe(H2O6)]3+The complex water ions in (1) are hydrolyzed to form a series of complex particles, while Al3+、Fe3+The cross copolymerization phenomenon can also occur during the hydrolysis and polymerization reaction to form a multinuclear, long-chain and more stable molecular chain, namely, the metal ions of the mononuclear complex are combined through the bridging action of the hydroxyl ligandThe polynuclear hydroxyl complex is formed, and the hydrolysis and the hydroxyl bridging are alternately carried out to finally generate polymeric aluminum ferric sulfate with infinite polymerization degree. Then drying the water purifying agent to obtain the polymeric aluminum ferric sulfate composite water purifying agent, wherein the dried composite water purifying agent is convenient to store and transport and has higher portability and practicability. In addition, the waste industrial waste residues are used as production raw materials, so that the resource is reasonably utilized, the problem of environmental pollution is solved, the problem of resource shortage can be relieved, the maintenance cost can be saved, and the method has very important environmental protection significance and economic benefit.
On the other hand, the invention also provides a polymeric aluminum ferric sulfate composite water purifying agent which has the characteristics of stronger hydrolytic capability, fast sedimentation, large and compact floc volume, good water purifying effect, fast action, small dosage and low cost, can recover valuable metals in industrial waste residues, reduce solid residue discharge amount and has good economic benefit and environmental protection benefit.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to specific examples.
The invention provides a manufacturing process of a polymeric aluminum ferric sulfate composite water purifying agent, which comprises the following steps: adding a sulfuric acid I solution into waste residues containing iron and aluminum metals, treating for 2-3 hours in a constant-temperature water bath, adding an oxidant, reacting for 20-30 minutes, filtering to obtain a filtrate, cooling the filtrate to 60-70 ℃, adding an alkaline solution, adjusting the pH value of the whole solution to 3-4, curing for 3-4 hours, and drying to obtain the polymeric aluminum ferric sulfate composite water purifying agent. Adding the waste residue into a sulfuric acid I solution for acid leaching treatmentFor 2-3 hours, the obtained solution mainly comprises Al2(SO4)3And Fe2(SO4)3And Fe (SO)4)2And the temperature of the whole reaction system can be kept constant by constant-temperature water bath heating treatment, and simultaneously, objects are heated uniformly, so that the uncontrollable property of excessive intensity and temperature caused by direct heating is avoided, the reaction temperature can be strictly controlled, and the constancy of the temperature of the whole reaction system is ensured. The temperature of the constant-temperature water bath treatment in the embodiment of the invention is 90-100 ℃, the whole reaction system starts to boil at the temperature, the collision among reactants is aggravated, simultaneously, the energy of the reactant molecules is increased, the percentage of the activated molecules is increased, the concentration of the activated molecules is increased, and the Al content is improved3+、Fe3+And Fe2+The dissolution rate of the method improves the utilization rate of the industrial waste residue. Further, the waste residue is ground and sieved, and the mesh number of the waste residue is 80-100 meshes. The waste residue is ground to reduce the particle size, increase the contact area of the I-sulfuric acid solution and the waste residue and improve Al3+、Fe3+And Fe2+The dissolution rate of the method can shorten the reaction time, and the particles with the mesh number are convenient for the later filtering operation.
Along with the reaction in the process of constant-temperature water bath treatment, ions in the sulfuric acid I solution are consumed to reduce the concentration of reactants so as to balance the reaction, wherein a small amount of Al3+、Fe3+Are not fully utilized. Therefore, in the embodiment of the invention, the solution of the sulfuric acid II is added at intervals of 30 minutes in the process of the constant-temperature water bath treatment, and the mass ratio of the solution of the sulfuric acid II to the solution of the sulfuric acid I is (0.2-0.3): 1. Therefore, the concentration of the sulfuric acid in the whole reaction system is supplemented, the reaction rate is accelerated, the reaction time is shortened, and the production efficiency is improved.
In detail, in the examples of the present invention, the mass fraction of the above-mentioned sulfuric acid I solution is 20 to 50 wt%. The mass fraction of the I sulfate solution is positively correlated with the concentration of the I sulfate solution, and when the concentration of the I sulfate solution is lower, Fe3+The dissolution rate is low, and most of the product is made of Fe2O3The monomer (b) has low basicity and poor turbidity removal effect; when inWhen the concentration of the sulfuric acid I solution is higher, SO contained in the sulfuric acid I solution4 2-If the content of (A) is too high, the content of basic ferric sulfate is reduced, the basicity is reduced, and the turbidity removal effect is poor. Therefore, when the mass fraction of the sulfuric acid I solution is 20-50 wt%, the basicity and the turbidity removal rate of the polymeric aluminum ferric sulfate composite water purifying agent are optimal.
To further improve Al3+、Fe3+And Fe2+In the embodiment of the invention, the waste residue is roasted before acid leaching treatment, the roasting temperature is 600-800 ℃, and the roasting time is 1-2 hours. Tests show that under the above-mentioned treatment conditions the interior aluminium and iron ions can be treated at high temp. to promote their activation so as to raise Fe content in waste slag2O3、Al2O3The leaching rate is low, the energy consumption is low in the roasting time, and the cost is relatively low.
Optionally, in the embodiment of the invention, the waste residue is red mud or coal gangue. With the development of the coal industry, a large amount of coal gangue is discharged every year, the coal gangue is accumulated on each mining area, not only is the land area invaded, but also the fertile farmland area is reduced, and if harmful gas generated by spontaneous combustion can cause environmental pollution. Utilizing Fe in coal gangue2O3、Al2O3The preparation of the polyaluminum ferric sulfate water purifying agent not only eliminates environmental pollution and changes waste into valuable, but also reduces production cost. Red mud is an insoluble residue, and the main component is SiO2、Al2O3、CaO、Fe2O3And the like.
After the waste residue and the sulfuric acid I solution are fully reacted, adding an oxidant into the mixture to react for 20-30 minutes so as to obtain Fe in the solution2+Conversion to Fe3+Thereby improving the utilization rate of the metallic iron. In detail, the oxidizer in the embodiment of the present invention is potassium chlorate, sodium hypochlorite or hydrogen peroxide. The addition of these oxidants to the I sulfate solution not only can rapidly add Fe2+Is oxidized into Fe3 +And the reaction can be more thorough, so that the reaction time is shortened, and the production efficiency is improved. Further, in the embodiment of the invention, the waste residue, the sulfuric acid I solution andthe mass ratio of the oxidant is 1 (5-8) to 0.3-0.8. When the amount of the oxidant added is insufficient, Fe2+Can not be completely oxidized into Fe3+Residual Fe2+More; when the amount of the oxidizing agent added is too large, Fe is contained in the solution2+Can be completely oxidized into Fe3+But it will cause waste of the oxidant and increase the production cost. Therefore, the addition of the oxidant according to the above proportion not only can enable Fe in the filtrate I2+Is completely oxidized, and the using amount of the oxidant can be saved.
Adding oxidant to react for 20-30 min, and converting Al and Fe in the reaction system into Al2(SO4)3And Fe2(SO4)3And Fe (SO)4)2Insoluble substances in the mixture can be removed after filtration, so that the later hydrolysis polymerization reaction is convenient to carry out, the purity of the final product can be improved, and the water purification effect of the product is further improved. After filtering, cooling the filtrate to 60-70 ℃, adding an alkaline solution to adjust the pH value of the filtrate to carry out hydrolytic polymerization reaction, wherein the hydrolysis reaction is favorably carried out at the temperature, and the generated basic aluminum and the basic iron have higher stability. With the addition of the alkaline solution, the pH value of the solution rises, and OH in the solution-The concentration is increased continuously so that [ Al (H)2O6)]3+、[Fe(H2O6)]3+The complex water ions in (1) are hydrolyzed to form a series of complex particles, while Al3+、Fe3 +The hydrolysis and polymerization reactions are carried out simultaneously, and a cross copolymerization phenomenon can also occur to form a polynuclear, long-chain and more stable molecular chain, namely, metal ions of the mononuclear complex are combined into a polynuclear hydroxyl complex through the bridging action of a hydroxyl ligand, and the hydrolysis and hydroxyl bridging actions are alternately carried out to finally generate polymeric aluminum ferric sulfate with infinite polymerization degree. Alternatively, the alkaline solution may be a sodium hydroxide solution, a calcium hydroxide solution, or the like, and is not particularly limited. Finally, the polymeric aluminum ferric sulfate composite water purifying agent can be obtained by drying the polymeric aluminum ferric sulfate composite water purifying agent, and the dried composite water purifying agent is convenient to store and transport and has higher portability and practicability. In addition, the invention takes the waste industrial waste residue as the production raw material, and not only carries out resource treatmentThe method has the advantages of reasonable utilization, solving the problem of environmental pollution, relieving the problem of resource shortage, saving maintenance cost and having very important environmental protection significance and economic benefit.
The invention also provides a polymeric aluminum ferric sulfate composite water purifying agent which is prepared by the manufacturing process of the polymeric aluminum ferric sulfate composite water purifying agent. The polymeric aluminum ferric sulfate composite water purifying agent has the characteristics of stronger hydrolytic capacity, fast sedimentation, large and compact floc volume, good water purifying effect, fast action, small dosage and low cost, can recover valuable metals in industrial waste residues, reduces solid residue discharge amount, and also has good economic benefit and environmental protection benefit.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment of the invention provides a manufacturing process of a polymeric aluminum ferric sulfate composite water purifying agent, which comprises the following steps:
pretreatment: grinding and sieving the red mud to obtain fine powder, wherein the sieving mesh number is 90 meshes;
roasting treatment: placing the fine powder in a high-temperature furnace, and roasting at the temperature of 750 ℃ for 1.5 hours;
preparing a polymeric aluminum ferric sulfate composite water purifying agent: adding 35 wt% of sulfuric acid I solution into the roasted fine powder, carrying out constant-temperature water bath treatment at the temperature of 95 ℃ for 2.5 hours, adding potassium chlorate, reacting for 25 minutes, filtering to obtain filtrate, cooling the filtrate to 65 ℃, adding an alkaline solution, adjusting the pH value of the whole solution to 3.5, curing for 3.5 hours, and drying to obtain the polymeric aluminum ferric sulfate composite water purifying agent.
In this example, a solution of sulfuric acid ii was added at intervals of 30 minutes during the constant temperature water bath treatment, the mass ratio of the solution of sulfuric acid ii to the solution of sulfuric acid i was 0.25:1, and the mass ratio of the waste residue, the solution of sulfuric acid i, and the oxidizing agent was 1:6: 0.5.
Example 2
The embodiment of the invention provides a manufacturing process of a polymeric aluminum ferric sulfate composite water purifying agent, which comprises the following steps:
pretreatment: grinding and sieving the coal gangue to obtain fine powder, and sieving the fine powder with a 80-mesh sieve.
Roasting treatment: the fine powder is placed in a high temperature furnace to be roasted for 1 hour at the temperature of 800 ℃.
Preparing a polymeric aluminum ferric sulfate composite water purifying agent: adding a sulfuric acid I solution with the mass fraction of 20 wt% into the roasted fine powder, carrying out constant-temperature water bath treatment at the temperature of 90 ℃ for 2 hours, adding sodium hypochlorite, reacting for 20 minutes, filtering to obtain a filtrate, cooling the filtrate to 60 ℃, adding an alkaline solution, adjusting the pH value of the whole solution to 4, curing for 3 hours, and drying to obtain the polymeric aluminum ferric sulfate composite water purifying agent.
In this example, a solution of sulfuric acid ii was added at intervals of 30 minutes during the constant temperature water bath treatment, the mass ratio of the solution of sulfuric acid ii to the solution of sulfuric acid i was 0.2:1, and the mass ratio of the waste residue, the solution of sulfuric acid i, and the oxidizing agent was 1:5: 0.3.
Example 3
The embodiment of the invention provides a manufacturing process of a polymeric aluminum ferric sulfate composite water purifying agent, which comprises the following steps:
roasting treatment: the waste slag containing iron and aluminum metals is placed in a high-temperature furnace to be roasted for 2 hours at the temperature of 600 ℃.
Preparing a polymeric aluminum ferric sulfate composite water purifying agent: adding 50 wt% of sulfuric acid I solution into the roasted waste residue, carrying out constant-temperature water bath treatment at the temperature of 100 ℃ for 3 hours, adding hydrogen peroxide for reaction for 20 minutes, filtering to obtain filtrate, cooling the filtrate to 60 ℃, adding an alkaline solution, adjusting the pH value of the whole solution to 3, curing for 4 hours, and drying to obtain the polymeric aluminum ferric sulfate composite water purifying agent.
In this example, a solution of sulfuric acid ii was added at intervals of 30 minutes during the constant temperature water bath treatment, the mass ratio of the solution of sulfuric acid ii to the solution of sulfuric acid i was 0.3:1, and the mass ratio of the waste residue, the solution of sulfuric acid i, and the oxidizing agent was 1:8: 0.8.
Example 4
The embodiment of the invention provides a manufacturing process of a polymeric aluminum ferric sulfate composite water purifying agent, which comprises the following steps:
pretreatment: grinding and sieving the waste residue to obtain fine powder, wherein the sieving mesh number is 100 meshes.
Preparing a polymeric aluminum ferric sulfate composite water purifying agent: adding 45 wt% of sulfuric acid I solution into the fine powder, carrying out constant-temperature water bath treatment for 2.5 hours, adding an oxidant, reacting for 23 minutes, filtering to obtain a filtrate, cooling the filtrate to 63 ℃, adding an alkaline solution, adjusting the pH value of the whole solution to 3.3, curing for 3 hours, and drying to obtain the polymeric aluminum ferric sulfate composite water purifying agent.
Example 5
The embodiment of the invention provides a manufacturing process of a polymeric aluminum ferric sulfate composite water purifying agent, which comprises the following steps:
adding a sulfuric acid I solution into waste residues containing iron and aluminum metals, treating for 2.5 hours in a constant-temperature water bath, adding an oxidant, reacting for 28 minutes, filtering to obtain a filtrate, cooling the filtrate to 67 ℃, adding an alkaline solution, adjusting the pH value of the whole solution to 3.7, curing for 3.5 hours, and drying to obtain the polymeric aluminum ferric sulfate composite water purifying agent.
Effect example 1
The polymeric aluminum ferric sulfate composite water purifying agent of the embodiment 5 is tested by referring to the following related test method and the related test method of HB/T5565-2019 water treatment aluminum ferric sulfate, and the physical and chemical indexes of the polymeric aluminum ferric sulfate composite water purifying agent are detected, wherein the specific detection indexes are shown in Table 1.
(1) And (3) density measurement: the density of the polymeric aluminum ferric sulfate composite water purifying agent solution at 20 ℃ is measured by a hydrometer.
(2) And (3) pH measurement: the pH value of the polymeric aluminum ferric sulfate composite water purifying agent is measured by a pH meter.
TABLE 1 index and physicochemical Properties of the product
As can be seen from the data in Table 1, all the indexes of the prepared polymeric aluminum ferric sulfate composite water purifying agent meet the relevant indexes.
Effect example 2
The flocculation effect of the polymeric aluminum ferric sulfate composite water purifying agents of examples 1 to 5 was tested in the following manner, and the test results are shown in Table 2.
The test method comprises the following steps: weighing 1g of 200-mesh 300-mesh kaolin, drying the kaolin for 3 hours, putting the kaolin into a 2L volumetric flask, adding water to set to a scale, and shaking up to obtain a test stock solution. The test stock solution was pipetted into a new volumetric flask by 200mL, 6 sets and numbers 1 to 6 were pipetted, an equal amount of the polyaluminum ferric sulfate composite water-purifying agent of examples 1 to 5 was added to each of bottles 1 to 5, and a 1327-41-9 polyaluminum chloride water-purifying agent was added to bottle 6, and then the volumetric flask 1 to 6 was shaken for 10 minutes and then left to stand for 20 minutes to take out the supernatant and measure the residual turbidity. The test was repeated 4 times for each sample and averaged.
TABLE 2 flocculation results
| Bottle number | Reagent | Residual turbidity (. times.10)-6) |
| 1 | Example 1 | 1.2 |
| 2 | Example 2 | 1.5 |
| 3 | Example 3 | 1.8 |
| 4 | Example 4 | 1.9 |
| 5 | Example 5 | 2.1 |
| 6 | P874941 polymeric ferric sulfate water purifying agent | 3.7 |
The test results show that the modified polymeric ferric sulfate water purifying agent prepared by the embodiment of the invention has the advantages of good flocculation effect, low residual turbidity and excellent performance.
In summary, in the polymeric aluminum ferric sulfate composite water purifying agent and the manufacturing process thereof provided by the embodiments of the present invention, the manufacturing process of the polymeric aluminum ferric sulfate composite water purifying agent includes the following steps: adding a sulfuric acid I solution into waste residues containing iron and aluminum metals, treating for 2-3 hours in a constant-temperature water bath, adding an oxidant, reacting for 20-30 minutes, filtering, taking a filtrate, cooling the filtrate to 60-70 ℃, adding an alkaline solution, adjusting the pH value of the whole solution to 3-4, curing for 3-4 hours, drying to obtain a polymeric aluminum ferric sulfate composite water purifying agent, adding the waste residues into the sulfuric acid I solution, performing acid leaching for 2-3 hours, and adding Al into the obtained solution to perform acid leaching treatment for 2-3 hours2(SO4)3And Fe2(SO4)3And Fe (SO)4)2And the temperature of the whole reaction system can be kept constant by constant-temperature water bath heating treatment, and simultaneously, objects are heated uniformly, so that the uncontrollable property of excessive intensity and temperature caused by direct heating is avoided, the reaction temperature can be strictly controlled, and the constancy of the temperature of the whole reaction system is ensured. Then adding oxidant into the solution to react for 20-30 minutes to remove Fe in the solution2+Conversion to Fe3+Thereby improving the utilization rate of Fe. Filtering, retaining filtrate, removing insoluble residue to facilitate later reaction, and improving purity of final product, and further improving water purification of productAnd (5) effect. And cooling the filtrate to 60-70 ℃, adding an alkaline solution to adjust the pH value of the filtrate to carry out hydrolytic polymerization reaction, wherein the hydrolysis reaction is favorably carried out at the temperature, and the generated basic aluminum and the basic iron have higher stability. With the addition of the alkaline solution, the pH value of the solution rises, and OH in the solution-The concentration is increased continuously so that [ Al (H)2O6)]3+、[Fe(H2O6)]3+The complex water ions in (1) are hydrolyzed to form a series of complex particles, while Al3+、Fe3+The hydrolysis and polymerization reactions are carried out simultaneously, and a cross copolymerization phenomenon can also occur to form a polynuclear, long-chain and more stable molecular chain, namely, metal ions of the mononuclear complex are combined into a polynuclear hydroxyl complex through the bridging action of a hydroxyl ligand, and the hydrolysis and hydroxyl bridging actions are alternately carried out to finally generate polymeric aluminum ferric sulfate with infinite polymerization degree. Then drying the water purifying agent to obtain the polymeric aluminum ferric sulfate composite water purifying agent, wherein the dried composite water purifying agent is convenient to store and transport and has higher portability and practicability. In addition, the waste industrial waste residues are used as production raw materials, so that the resource is reasonably utilized, the problem of environmental pollution is solved, the problem of resource shortage can be relieved, the maintenance cost can be saved, and the method has very important environmental protection significance and economic benefit. The invention also provides a polymeric aluminum ferric sulfate composite water purifying agent which has good water purifying effect, quick action, small dosage and low cost, can recover valuable metals in industrial waste residues and reduce solid residue discharge, and also has good economic benefit and environmental protection benefit.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A manufacturing process of a polymeric aluminum ferric sulfate composite water purifying agent is characterized by comprising the following steps:
adding a sulfuric acid I solution into waste residues containing iron and aluminum metals, treating for 2-3 hours in a constant-temperature water bath, adding an oxidant, reacting for 20-30 minutes, filtering to obtain a filtrate, cooling the filtrate to 60-70 ℃, adding an alkaline solution, adjusting the pH value of the whole solution to 3-4, curing for 3-4 hours, and drying to obtain the polymeric aluminum ferric sulfate composite water purifying agent.
2. The process for preparing the polymeric aluminum ferric sulfate composite water purifying agent as claimed in claim 1, wherein the mass ratio of the waste residue, the sulfuric acid I solution and the oxidizing agent is 1 (5-8) to (0.3-0.8).
3. The process for preparing polymeric aluminum ferric sulfate composite water purifying agent as claimed in claim 1, wherein the waste residue is roasted at 600-800 deg.C for 1-2 hr.
4. The process for preparing the polymeric aluminum ferric sulfate composite water purifying agent according to claim 1, wherein the waste residue is ground and sieved, and the mesh number of the waste residue is 80-100 meshes.
5. The process for preparing the polymeric aluminum ferric sulfate composite water purifying agent according to claim 1, wherein the mass fraction of the sulfuric acid I solution is 20-50 wt%.
6. The process for preparing the polymeric aluminum ferric sulfate composite water purifying agent according to claim 1, wherein the temperature of the thermostatic waterbath treatment is 90-100 ℃.
7. The manufacturing process of the polymeric aluminum ferric sulfate composite water purifying agent according to claim 1, wherein the waste residue is red mud or coal gangue.
8. The process for preparing the polymeric aluminum ferric sulfate composite water purifying agent according to claim 1, wherein the oxidant is potassium chlorate, sodium hypochlorite or hydrogen peroxide.
9. The manufacturing process of the polymeric aluminum ferric sulfate composite water purifying agent as claimed in claim 1, wherein in the step of the constant temperature water bath treatment, a solution of sulfuric acid II is added at intervals of 30 minutes, and the mass ratio of the solution of sulfuric acid II to the solution of sulfuric acid I is (0.2-0.3): 1.
10. A polymeric aluminum ferric sulfate composite water purifying agent, which is characterized in that the polymeric aluminum ferric sulfate composite water purifying agent is prepared by the manufacturing process of the polymeric aluminum ferric sulfate composite water purifying agent according to any one of claims 1 to 9.
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