CN113955808A - Method for producing polymeric ferric sulfate by using naturally oxidized and deteriorated ferrous sulfate as raw material - Google Patents
Method for producing polymeric ferric sulfate by using naturally oxidized and deteriorated ferrous sulfate as raw material Download PDFInfo
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- 229910000360 iron(III) sulfate Inorganic materials 0.000 title claims abstract description 92
- 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 88
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title claims abstract description 59
- 239000011790 ferrous sulphate Substances 0.000 title claims abstract description 55
- 235000003891 ferrous sulphate Nutrition 0.000 title claims abstract description 55
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 239000002994 raw material Substances 0.000 title claims abstract description 34
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 46
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000012043 crude product Substances 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 238000005189 flocculation Methods 0.000 claims abstract description 27
- 230000016615 flocculation Effects 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical group [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 40
- 235000010288 sodium nitrite Nutrition 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004568 cement Substances 0.000 claims description 4
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 230000006866 deterioration Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims 1
- 229910001447 ferric ion Inorganic materials 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 30
- 239000000126 substance Substances 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 42
- 238000003756 stirring Methods 0.000 description 21
- 235000013980 iron oxide Nutrition 0.000 description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 13
- 238000005086 pumping Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The method for producing the polymeric ferric sulfate by taking the naturally oxidized and deteriorated ferrous sulfate as the raw material comprises the following steps: 1) oxidizing ferrous sulfate into polymeric ferric sulfate by using naturally oxidized ferrous sulfate as a raw material through a conventional oxidation process reaction to obtain a crude product of a polymeric ferric sulfate solution; 2) adding Polyacrylamide (PAM) to carry out flocculation reaction, so that iron oxide impurities which cannot be filtered in the liquid polymeric ferric sulfate become filterable flocs; 3) and (3) removing iron oxide impurities in the crude product of the polymeric ferric sulfate solution by solid-liquid separation, wherein the filtrate is the finished product of the polymeric ferric sulfate. According to the method for producing the polymeric ferric sulfate by taking the naturally oxidatively deteriorated ferrous sulfate as the raw material, polyacrylamide is added into a polymeric ferric sulfate solution crude product after polymerization, so that iron oxide impurities which cannot be filtered in liquid polymeric ferric sulfate become filterable flocs, and then the iron oxide impurities are removed, so that the removal rate of the content of water insoluble substances in the solution is up to 93%, and the solid-liquid separation efficiency is improved.
Description
Technical Field
The invention relates to the technical field of polyferric sulfate coagulants, in particular to a method for producing polyferric sulfate by taking natural oxidative metamorphic ferrous sulfate as a raw material.
Background
The polyferric sulfate is a novel, high-quality and high-efficiency ferric salt inorganic polymeric flocculant, the morphological character of the polyferric sulfate is a faint yellow amorphous powdery solid which is very easy to dissolve in water, and a 10 percent (mass) aqueous solution is a reddish brown viscous transparent solution. The polymeric ferric sulfate can be used for the pretreatment of water supply for power production, the purification of domestic drinking water and the treatment of domestic sewage and industrial wastewater. The method also has wide application in the aspects of waste water recycling, casting, papermaking, medicine, leather making and the like.
The production process of the polyferric sulfate can be divided into a direct oxidation method and a catalytic oxidation method according to different oxidation modes, the production raw materials are very wide, and the method mainly comprises ferric oxide, ferrous oxide, ferroferric oxide, iron powder, steel pickling waste liquid, ferrous sulfate and the like, wherein the ferrous sulfate is most ideal, the production process is simple, the production conditions are mild, the product impurities are few, and the quality is high; however, ferrous sulfate is easy to oxidize and deteriorate naturally to generate a plurality of insoluble iron oxides, and a polyferric sulfate product produced by using deteriorated ferrous sulfate is a yellowish-brown suspended liquid in appearance, insoluble substances seriously exceed the standard, and the insoluble substances cannot be filtered and removed under normal conditions, so that the product quality is seriously influenced; if the deteriorated ferrous sulfate is not used, the waste is caused, and the environmental pollution is caused because the treatment is difficult.
At present, the technology for producing the polymeric ferric sulfate by using naturally oxidatively deteriorated ferrous sulfate as a raw material has not been reported, but how to efficiently utilize the deteriorated ferrous sulfate to produce the polymeric ferric sulfate is a practical problem which needs to be solved urgently by the market.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method for producing the polymeric ferric sulfate by using the naturally oxidized and deteriorated ferrous sulfate as the raw material is simple to operate and low in production cost, so that the phenomenon that the ferrous sulfate is abandoned and pollutes the environment due to natural oxidation and deterioration is avoided, and the actual problem of a polymeric ferric sulfate production enterprise is effectively solved.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the method for producing the polymeric ferric sulfate by taking the naturally oxidized and deteriorated ferrous sulfate as the raw material comprises the following steps:
1) preparation of a crude product of a polymeric ferric sulfate solution: oxidizing ferrous sulfate into polymeric ferric sulfate by using naturally oxidized ferrous sulfate as a raw material through a conventional oxidation process reaction to obtain a crude product of a polymeric ferric sulfate solution;
2) flocculation reaction: adding Polyacrylamide (PAM) into the crude product of the polymeric ferric sulfate solution obtained in the step 1) to perform a flocculation reaction, so that iron oxide impurities which cannot be filtered in the liquid polymeric ferric sulfate become filterable flocs;
3) solid-liquid separation: and (3) carrying out solid-liquid separation on the flocculated liquid obtained in the step 2), removing iron oxide impurities in the crude product of the polymeric ferric sulfate solution, and obtaining filtrate which is the finished polymeric ferric sulfate product.
In an exemplary embodiment, in step 2), the polyacrylamide is cationic polyacrylamide and nonionic polyacrylamide, and the dosage of the polyacrylamide is 3-10 PPM.
In an exemplary embodiment, in step 2), the polyacrylamide is completely dissolved into a transparent liquid by adding certain amounts of PAM and water into a PAM preparation tank before adding, and then is mixed with a crude polyferric sulfate solution.
In an exemplary embodiment, in the step 2), the flocculation time is 30-60 min.
In an exemplary embodiment, in step 3), the solid-liquid separation is positive pressure type, negative pressure type or centrifugal type, and the solid-liquid separator used in the step is any one of a plate-and-frame filter press, a positive pressure filter tank, a centrifuge or a negative pressure filter.
In a certain exemplary embodiment, in step 3), the filter residue after solid-liquid separation is sent to a cement plant for recycling.
In one exemplary embodiment, in step 1), the oxidation process is a direct oxidation process or a catalytic oxidation process.
The direct oxidation method is to directly oxidize ferrous ions into iron ions by using a strong oxidant, wherein the strong oxidant is hydrogen peroxide, sodium chlorate, potassium chlorate, sodium hypochlorite or potassium hypochlorite, the reaction is quick, the operation is simple, but the requirement on equipment is not high, but the production cost is high.
The catalytic oxidation method is to oxidize ferrous ions by oxygen under the action of a catalyst, wherein the catalyst is usually selected from sodium nitrite and nitric acid. The method selects sodium nitrite as a catalyst, is the most traditional production method, and has the advantages of simple process, mild reaction process, low requirement on equipment and low investment. The disadvantages are long oxidation time, high price of sodium nitrite and large dosage. At present, most manufacturers in China adopt the method to produce the products.
The method for producing the polymeric ferric sulfate by using the naturally oxidized and deteriorated ferrous sulfate as the raw material has the beneficial effects that:
1) by adding polyacrylamide into the polymerized crude product of the polymeric ferric sulfate solution, the iron oxide impurities which cannot be filtered in the liquid polymeric ferric sulfate become filterable flocs, and then the iron oxide impurities are removed, so that the removal rate of the content of the water-insoluble substances in the solution is up to 93 percent, and the solid-liquid separation efficiency is improved.
2) After polyacrylamide is adopted for flocculation, the content of water insoluble matters in the polymeric ferric sulfate produced by taking naturally oxidized and deteriorated ferrous sulfate as a raw material is lower than 0.2 percent, and the requirements of the national standard GB/T14591-2016 polymeric ferric sulfate are met.
Drawings
FIG. 1 is a process flow diagram of a process for producing polymeric ferric sulfate (catalytic oxidation process) using naturally oxidatively deteriorated ferrous sulfate as a raw material in comparative example 2;
FIG. 2 is a process flow diagram of a method for producing polymeric ferric sulfate (catalytic oxidation method) using naturally oxidatively deteriorated ferrous sulfate as a raw material in example 1;
FIG. 3 is a process flow diagram of a method for producing polymeric ferric sulfate (direct oxidation method) using naturally oxidatively transformed ferrous sulfate as a raw material in example 2.
Detailed Description
The invention is further explained with reference to the drawings and the embodiments.
Comparative example 1
The production process of the polymeric ferric sulfate in the prior art comprises the following steps:
the method for producing the polymeric ferric sulfate by using the normal ferrous sulfate as the raw material comprises the following steps:
1) preparing a crude product of a polymeric ferric sulfate solution by a catalytic oxidation method: adding a certain amount of water and normal ferrous sulfate into a batching tank under stirring, slowly adding a certain amount of concentrated sulfuric acid while stirring, uniformly stirring, and conveying to a polymerization reaction kettle through a ferrous sulfate pump;
adding a certain amount of water into a sodium nitrite preparation tank, starting stirring, adding a certain amount of catalyst sodium nitrite, and conveying the sodium nitrite into a polymerization reaction kettle through a sodium nitrite pump after the sodium nitrite is completely dissolved;
and (3) gasifying the liquid oxygen in the liquid oxygen storage tank by a liquid oxygen vaporizer, introducing the gasified liquid oxygen into a polymerization reaction kettle for oxidative polymerization, controlling the introduction speed of the oxygen to enable the pressure to be 0.05 +/-0.1 MPa, sampling and analyzing to be qualified when the oxygen is hardly consumed, closing an oxygen valve, and finishing the polymerization reaction to obtain a crude product of the polymeric ferric sulfate solution.
2) Solid-liquid separation: and (2) after the polymerization reaction in the step 1) is finished, pumping the solution in the polymerization reaction kettle into a plate and frame filter (solid-liquid separator) with 750B filter cloth for solid-liquid separation, and taking the polymeric ferric sulfate solution to detect the water insoluble substance and the color of the polymeric ferric sulfate solution.
It should be noted that: the preparation of the polymeric ferric sulfate in this comparative example can also be replaced by conventional direct oxidation.
Comparative example 2
The method for producing the polymeric ferric sulfate by using the naturally oxidized and deteriorated ferrous sulfate as the raw material comprises the following steps of:
1) preparing a crude product of a polymeric ferric sulfate solution by a catalytic oxidation method: adding a certain amount of water and the ferrous sulfate which is naturally oxidized and deteriorated into a batching tank under stirring, then slowly adding a certain amount of concentrated sulfuric acid while stirring, and after uniformly stirring, conveying the mixture into a polymerization reaction kettle through a ferrous sulfate pump;
adding a certain amount of water into a sodium nitrite preparation tank, starting stirring, adding a certain amount of catalyst sodium nitrite, and conveying the sodium nitrite into a polymerization reaction kettle through a sodium nitrite pump after the sodium nitrite is completely dissolved;
and (3) gasifying the liquid oxygen in the liquid oxygen storage tank by using a liquid oxygen vaporizer, introducing the gasified liquid oxygen into a polymerization reaction kettle for oxidative polymerization, controlling the introduction speed of the oxygen to enable the pressure to be 0.05-0.1 Mpa, sampling and analyzing to be qualified when the oxygen is hardly consumed, closing an oxygen valve, and finishing the polymerization reaction to obtain a crude product of the polymeric ferric sulfate solution.
2) Solid-liquid separation: after the polymerization reaction in the step 1) is finished, pumping the solution in the polymerization reaction kettle into a solid-liquid separator (such as: a plate and frame filter with 750B filter cloth) for solid-liquid separation, and taking the polymeric ferric sulfate solution to detect the water-insoluble substance and the color.
It should be noted that: the preparation of the polymeric ferric sulfate in this comparative example can also be replaced by conventional direct oxidation.
Example 1
Referring to fig. 2, the method for producing polymeric ferric sulfate by using naturally oxidatively deteriorated ferrous sulfate as a raw material in the embodiment includes the following steps:
1) preparing a crude product of a polymeric ferric sulfate solution by a catalytic oxidation method: adding a certain amount of water and the ferrous sulfate which is naturally oxidized and deteriorated into a batching tank under stirring, then slowly adding concentrated sulfuric acid with the mass of 10 percent of that of the ferrous sulfate while stirring, uniformly stirring, and conveying the mixture into a polymerization reaction kettle through a ferrous sulfate pump;
adding a certain amount of water into a sodium nitrite preparation tank, starting stirring, adding a catalyst sodium nitrite which is 0.6 percent of the mass of ferrous sulfate, and conveying the sodium nitrite into a polymerization reaction kettle through a sodium nitrite pump after the sodium nitrite is completely dissolved;
and (2) gasifying liquid oxygen in the liquid oxygen storage tank by a liquid oxygen vaporizer, introducing the gasified liquid oxygen into a polymerization reaction kettle for oxidative polymerization, controlling the introduction speed of the oxygen to ensure that the pressure is 0.05 +/-0.002 Mpa and the temperature in the polymerization reaction kettle is 65 +/-2 ℃, sampling and analyzing the liquid oxygen to be qualified when the oxygen is hardly consumed, closing an oxygen valve, finishing the polymerization reaction to obtain a crude product of the polymeric ferric sulfate solution, taking the crude product of the polymeric ferric sulfate solution, and detecting the water-insoluble substances and the color of the crude product of the polymeric ferric sulfate solution.
2) Flocculation reaction: after the polymerization reaction in the step 1) is finished, starting a discharge pump of the polymerization reaction kettle, and pumping feed liquid into the flocculation reaction kettle; starting stirring of the PAM preparation tank, adding a certain amount of PAM and water into the PAM preparation tank, completely dissolving into transparent liquid, Pumping Acrylamide (PAM) solution in the PAM preparation tank into a flocculation reaction kettle to enable the concentration of polyacrylamide in the flocculation reaction kettle to be 7PPM, and carrying out flocculation reaction for 30 minutes under stirring;
3) solid-liquid separation: after the flocculation reaction in the step 2) is finished, pumping the solution in the flocculation reaction kettle into a plate-and-frame filter (solid-liquid separator) with 750B filter cloth for solid-liquid separation, removing iron oxide impurities in the crude product of the polymeric ferric sulfate solution, wherein the filtrate is the finished polymeric ferric sulfate product, collecting the filtrate into a storage tank of the finished polymeric ferric sulfate product, and taking the finished polymeric ferric sulfate product to detect water-insoluble substances and color and luster of the finished polymeric ferric sulfate product; and collecting filter residues and selling the filter residues to a cement factory.
The invention relates to a method for producing polymeric ferric sulfate by taking naturally oxidized and deteriorated ferrous sulfate as a raw material, which has the working principle that:
the ferrous sulfate and the sulfuric acid react with oxygen under the catalysis of sodium nitrite to polymerize into polymeric ferric sulfate. The chemical reaction formula of the process is as follows:
(1) catalytic oxidation reaction
2FeSO4+H2SO4+2NaNO2—→Fe2(SO4)3+Na2SO4+2NO+H2O
2NO+O2—→2NO2
2FeSO4+H2SO4+NO2—→Fe2(SO4)3+NO+H2O
2FeSO4+(1/2)O2+H2SO4—→Fe2(SO4)3+H2O
(2) Hydrolysis reaction
Fe2(SO4)3+nH2O—→Fe2(OH)n(SO4)3-n/2+(n/2)H2SO4
(3) Polymerisation reaction
m[Fe2(OH)n(SO4)3-n/2]—→[Fe2(OH)n(SO4)3-n/2]m
Forming flocs by polyacrylamide and the iron oxide in the ferric polysulfate solution, reducing the difficulty of filtering the crude ferric polysulfate solution, and simultaneously achieving the purposes of efficiently removing the iron oxide in the crude ferric polysulfate solution, reducing the turbidity of feed liquid and improving the color and luster of the feed liquid; and finally filtering and separating floc formed by complexing polyacrylamide iron oxide to obtain a high-quality polyferric sulfate finished product.
Example 2
Referring to fig. 3, the method for producing polymeric ferric sulfate by using naturally oxidatively deteriorated ferrous sulfate as a raw material in the embodiment includes the following steps:
1) preparing a crude product of a polymeric ferric sulfate solution by a direct oxidation method:
and adding water into the oxidant preparation tank, stirring, adding a sodium chlorate oxidant (hydrogen peroxide can be used as the oxidant) accounting for 5-7% of the weight of the ferrous sulfate, and completely dissolving the sodium chlorate oxidant to form a 20-50% sodium chlorate aqueous solution for later use.
Adding a certain amount of water and the ferrous sulfate which is naturally oxidized and deteriorated into a polymerization reaction kettle under stirring, uniformly mixing, then slowly adding the prepared sodium chlorate aqueous solution under stirring, and carrying out polymerization reaction for 60min under stirring. Sampling, detecting and analyzing to be qualified, stopping stirring, finishing polymerization reaction to obtain a crude product of the polymeric ferric sulfate solution, taking the crude product of the polymeric ferric sulfate solution, and detecting the water-insoluble substance and the color of the crude product.
2) Flocculation reaction: after the polymerization reaction in the step 1) is finished, starting a discharge pump of the polymerization reaction kettle, and pumping feed liquid into the flocculation reaction kettle; starting stirring of the PAM preparation tank, adding a certain amount of PAM and water into the PAM preparation tank, completely dissolving into transparent liquid, pumping Polyacrylamide (PAM) solution in the PAM preparation tank into a flocculation reaction kettle to enable the concentration of polyacrylamide in the flocculation reaction kettle to be 4PPM, and carrying out flocculation reaction for 45 minutes under stirring;
3) solid-liquid separation: after the flocculation reaction in the step 2) is finished, pumping the solution in the flocculation reaction kettle into a plate-and-frame filter (solid-liquid separator) with 750B filter cloth for solid-liquid separation, removing iron oxide impurities in the crude product of the polymeric ferric sulfate solution, wherein the filtrate is the finished polymeric ferric sulfate product, collecting the filtrate into a storage tank of the finished polymeric ferric sulfate product, and taking the finished polymeric ferric sulfate product to detect water-insoluble substances and color and luster of the finished polymeric ferric sulfate product; and collecting filter residues and selling the filter residues to a cement factory.
Example 3
Referring to fig. 2, the method for producing polymeric ferric sulfate by using naturally oxidatively deteriorated ferrous sulfate as a raw material in this embodiment has the following differences compared with embodiment 1:
and step 2), the concentration of polyacrylamide in the flocculation reaction kettle is 10 PPM.
Example 4
Referring to fig. 2, the method for producing polymeric ferric sulfate by using naturally oxidatively deteriorated ferrous sulfate as a raw material in this embodiment has the following differences compared with embodiment 1:
and step 2), the concentration of polyacrylamide in the flocculation reaction kettle is 6 PPM.
Example 5
Referring to fig. 3, the method for producing polymeric ferric sulfate by using naturally oxidatively deteriorated ferrous sulfate as a raw material in this embodiment has the following differences compared with embodiment 1:
and step 2), the concentration of polyacrylamide in the flocculation reaction kettle is 8 PPM.
Example 6
Referring to fig. 3, the method for producing polymeric ferric sulfate by using naturally oxidatively deteriorated ferrous sulfate as a raw material in this embodiment has the following differences compared with embodiment 1:
and step 2), the concentration of polyacrylamide in the flocculation reaction kettle is 3 PPM.
TABLE 1 results of testing samples of the polymeric ferric sulfate solutions of comparative examples 1 to 2 and examples 1 to 6
Note: the above detection results are the detection average of 3 replicates.
As can be seen from table 1 above, polyacrylamide is added to the crude polyferric sulfate solution, and the flocculated polyferric sulfate solution is subjected to solid-liquid separation, so that iron oxide in the solution can be effectively complexed to form flocs, and then insoluble substances such as iron oxide and the like are removed by solid-liquid separation, wherein the content of the insoluble substances is equivalent to or even lower than that of a polyferric sulfate solution produced by using normal ferrous sulfate as a raw material.
The removal rate of water-insoluble substances increases with the increase of the addition amount of polyacrylamide by using 3-10 PPM of polyacrylamide.
The applicant has also found that: when the addition amount of polyacrylamide is less than 3PPM, the amount of iron oxide formed flocs in the crude product of the polyferric sulfate solution is small, and the subsequent solid-liquid separation difficulty is still high; when the adding amount of the polyacrylamide is more than 10PPM, the amount of flocs formed by iron oxide in the crude product of the polyferric sulfate solution is extremely small, the viscosity of the solution is gradually increased, the filterability is gradually deteriorated, and the production cost is increased, so that the applicant believes that the polyacrylamide is cationic polyacrylamide and nonionic polyacrylamide, and the using amount of the polyacrylamide is 3-10 PPM.
The invention relates to a method for producing polymeric ferric sulfate by using natural oxidative modified ferrous sulfate as a raw material, which adjusts the addition amount and the concentration of polyacrylamide according to the content of water insoluble matters in a polymeric ferrous sulfate solution after the polymerization reaction of the natural oxidative modified ferrous sulfate, for example, the concentration of the polyacrylamide in a flocculation reaction kettle can be 4.5PPM, 5.8PPM or 9PPM, and the solid-liquid separator can also adopt other equipment in the prior art, such as a positive pressure filter tank, a centrifuge, a negative pressure filter and the like.
Claims (9)
1. The method for producing the polymeric ferric sulfate by taking the naturally oxidized and deteriorated ferrous sulfate as the raw material is characterized by comprising the following steps of:
1) preparation of a crude product of a polymeric ferric sulfate solution: oxidizing ferrous sulfate into polymeric ferric sulfate by using naturally oxidized ferrous sulfate as a raw material through a conventional oxidation process reaction to obtain a crude product of a polymeric ferric sulfate solution;
2) flocculation reaction: adding polyacrylamide into the crude product of the polymeric ferric sulfate solution in the step 1) to perform a flocculation reaction, so that iron oxide impurities which cannot be filtered in the liquid polymeric ferric sulfate become filterable flocs;
3) solid-liquid separation: and (3) carrying out solid-liquid separation on the flocculated liquid obtained in the step 2), removing iron oxide impurities in the crude product of the polymeric ferric sulfate solution, and obtaining filtrate which is the finished polymeric ferric sulfate product.
2. The method for producing polymeric ferric sulfate from natural oxidative deterioration ferrous sulfate as claimed in claim 1, wherein in step 2), the polyacrylamide is completely dissolved into a transparent liquid by adding a certain amount of PAM and water into a PAM preparation tank before adding, and then is mixed with the crude polymeric ferric sulfate solution.
3. The method for producing polymeric ferric sulfate from natural oxidative modified ferrous sulfate as claimed in claim 1 or 2, wherein in step 2), the polyacrylamide is cationic polyacrylamide and nonionic polyacrylamide, and the dosage of the polyacrylamide is 3-10 PPM.
4. The method for producing polymeric ferric sulfate from natural oxidative modified ferrous sulfate as claimed in claim 1 or 2, wherein the flocculation reaction time in step 2) is 30-60 min.
5. The method for producing polymeric ferric sulfate using naturally oxidatively deteriorated ferrous sulfate as a raw material according to claim 1 or 2, wherein in the step 3), the solid-liquid separation is positive pressure type, negative pressure type or centrifugal type, and the solid-liquid separator is any one of a plate-and-frame filter press, a positive pressure filter tank, a centrifuge or a negative pressure filter.
6. The method for producing polymeric ferric sulfate using naturally oxidatively deteriorated ferrous sulfate as a raw material according to claim 1 or 2, wherein in the step 3), the filter residue after solid-liquid separation is sent to a cement plant for recycling.
7. The method for producing polymeric ferric sulfate using naturally oxidatively deteriorated ferrous sulfate as a raw material according to claim 1 or 2, wherein in the step 1), the oxidation process is a direct oxidation method or a catalytic oxidation method.
8. The method for producing polymeric ferric sulfate using naturally oxidatively deteriorated ferrous sulfate as a raw material as claimed in claim 7, wherein said direct oxidation method is a method of directly oxidizing ferrous ions into ferric ions by a strong oxidizing agent, and said strong oxidizing agent is hydrogen peroxide, sodium chlorate, potassium chlorate, sodium hypochlorite or potassium hypochlorite.
9. The method for producing polymeric ferric sulfate using naturally oxidized and degenerated ferrous sulfate as raw material as claimed in claim 7, wherein said catalytic oxidation process is to oxidize ferrous ions with oxygen under the action of catalyst, and the catalyst is sodium nitrite or nitric acid.
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