CN110540247A - method and device for recycling ferrous sulfate monohydrate as byproduct of titanium dioxide plant - Google Patents
method and device for recycling ferrous sulfate monohydrate as byproduct of titanium dioxide plant Download PDFInfo
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- CN110540247A CN110540247A CN201910944014.1A CN201910944014A CN110540247A CN 110540247 A CN110540247 A CN 110540247A CN 201910944014 A CN201910944014 A CN 201910944014A CN 110540247 A CN110540247 A CN 110540247A
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- ferrous sulfate
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- sulfate monohydrate
- treatment agent
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- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 title claims abstract description 43
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000006227 byproduct Substances 0.000 title claims abstract description 24
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 21
- 238000004064 recycling Methods 0.000 title claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 42
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 238000006703 hydration reaction Methods 0.000 claims abstract description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000002699 waste material Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000013329 compounding Methods 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 22
- 235000010288 sodium nitrite Nutrition 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 15
- 239000002912 waste gas Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 10
- 150000002505 iron Chemical class 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000008399 tap water Substances 0.000 claims description 5
- 235000020679 tap water Nutrition 0.000 claims description 5
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 229920000592 inorganic polymer Polymers 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000008394 flocculating agent Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 239000010865 sewage Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 229940037003 alum Drugs 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical group [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- RBBDLPDTUTVRPO-UHFFFAOYSA-L potassium sodium dichlorate Chemical compound Cl(=O)(=O)[O-].[K+].Cl(=O)(=O)[O-].[Na+] RBBDLPDTUTVRPO-UHFFFAOYSA-L 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- AGXLJXZOBXXTBA-UHFFFAOYSA-K trisodium phosphate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O AGXLJXZOBXXTBA-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
the invention discloses a preparation method, application and a device of polymeric ferric sulfate, belonging to the technical field of comprehensive utilization of resources. The preparation method comprises the following steps: the method comprises the steps of pretreating ferrous sulfate monohydrate serving as a byproduct obtained by concentrating waste acid in a titanium dioxide factory in a working section, carrying out hydration reaction and catalytic oxidation reaction to prepare polymeric ferric sulfate, and further compounding the prepared polymeric ferric sulfate and ferric trichloride to prepare the water treatment agent. The polymeric ferric sulfate prepared by the invention belongs to a novel high-efficiency inorganic polymer ferric salt flocculating agent, has good water purification effect, does not contain harmful substances such as aluminum, chlorine, heavy metal ions and the like, and can be called a harmless, safe and reliable high-efficiency water treatment agent, and the water treatment agent prepared by compounding the polymeric ferric sulfate and ferric trichloride has the dephosphorization effect of more than 70 percent and has great industrial application value.
Description
Technical Field
the invention belongs to the technical field of comprehensive utilization of resources, and particularly relates to a method and a device for recycling ferrous sulfate monohydrate as a byproduct in a titanium dioxide factory.
Background
Titanium dioxide is an important inorganic pigment, and the production process mainly comprises a sulfuric acid method and a chlorination method. The chlorination production technology with little pollution and good product quality is monopolized by a few large foreign companies at present. The sulfuric acid method is adopted in the titanium dioxide production in China for the most part, a large amount of byproducts are generated in the titanium dioxide production by the sulfuric acid method, one of the byproducts is ferrous sulfate monohydrate, the acid content is high, the ferrous sulfate monohydrate cannot be directly utilized, however, serious environmental pollution is caused if the ferrous sulfate monohydrate is not recycled or further treated, meanwhile, precious resources are wasted, and great attention is paid to people due to the comprehensive utilization of the ferrous sulfate monohydrate serving as the byproduct of the titanium dioxide factory along the path of national sustainable development.
The polyferric sulfate is a polyhydroxy, multi-complex compound type cationic inorganic high molecular product with iron ions as cores, the product contains Fe3+, OH-, SO42-, Mg2+, Cl-, and other ions and compound forms, and the appearance and the properties of the liquid are as follows: a reddish brown liquid. The product has excellent dephosphorization effect, and is widely applied to the following aspects: the treatment of urban domestic sewage, the treatment of various industrial waste waters of paper making, petrochemical industry, mineral processing industry, dyeing industry and the like, and the treatment of sludge.
At present, the method for producing the polymeric ferric sulfate mainly comprises the following steps: 1) the iron filings and iron ore are directly reacted with sulfuric acid to generate ferrous sulfate, and then oxidant (sodium chlorate, potassium chlorate, hydrogen peroxide and the like) is added into a reaction system to oxidize ferrous ions into ferric ions, so as to obtain a polymeric ferric sulfate product. The iron and steel pickling waste liquid must adopt sulfuric acid pickling waste liquid, and according to its iron ion content and sulfuric acid concentration, the iron filings addition mode is adopted to regulate its internal system, and the iron filings and iron ore direct oxidation method is generally adopted to produce polymeric ferric sulfate product. The polymeric ferric sulfate produced by adopting the raw materials has large fluctuation of quality indexes of the raw materials, and a product with stable quality indexes is not easy to obtain. And because the iron sulfate belongs to waste materials and primary raw materials, the content of heavy metal ions contained in the iron sulfate is higher, and certain influence is formed on the heavy metal indexes of the produced polymeric ferric sulfate product. Meanwhile, the use and production of the raw materials have higher requirements on the source of the raw materials; 2) direct oxidation method: ferrous sulfate, sulfuric acid, water and the like are put into a reaction device, stirring is started, and an oxidant is added, wherein when hydrogen peroxide is used as the oxidant, the adding speed of the hydrogen peroxide must be controlled, so that oxygen generation (the oxygen cannot play an oxidizing role when no catalyst exists) is avoided, the single-batch secondary production time is long, the hydrogen peroxide cost is high, and further the production cost of the polymeric ferric sulfate is increased. The sodium (potassium) chlorate as oxidant also has the problem of high cost of oxidant and high cost of polymeric ferric sulfate. Potassium permanganate and manganese dioxide are used as oxidizing agents, so that the cost of polymeric ferric sulfate is high, and the influence of manganese ion residues is also existed, so that certain influence (in quality) can be formed on water treatment. Nitric acid is used as an oxidant, so that the production cost is high, the reaction is violent, the reaction pressure and temperature are high (the highest pressure can reach 0.2MPa, the temperature can reach 100 ℃), and the generated tail gas is more, thereby greatly influencing the safety and the environmental protection.
Disclosure of Invention
In view of the above, the present invention aims to provide a method and an apparatus for recycling ferrous sulfate monohydrate as a byproduct in a titanium dioxide plant.
In order to achieve the above purpose, the inventor of the present invention provides a technical solution of the present invention through long-term research and a great deal of practice, and the specific implementation process is as follows:
1. The method for recycling the ferrous sulfate monohydrate serving as a byproduct in a titanium dioxide factory comprises the following steps:
s1, mixing a byproduct ferrous sulfate monohydrate obtained by concentrating in a waste acid workshop section of a titanium dioxide factory with water to prepare a slurry, and then separating to obtain a washing clear liquid and the washed ferrous sulfate monohydrate;
s2, mixing the ferrous sulfate monohydrate washed in the s1 with water, stirring, and carrying out hydration reaction; then adding concentrated sulfuric acid to obtain a reaction intermediate product; meanwhile, sodium nitrite, namely NaNO2 is prepared into sodium nitrite solution;
s3, stirring the reaction intermediate product and introducing oxygen, then adding the sodium nitrite solution in batches, and carrying out circulating catalytic oxidation reaction to obtain polymeric ferric sulfate;
In the s1, the weight ratio of the byproduct ferrous sulfate monohydrate to water is 70-80: 20-35;
In the s2, the weight ratio of the washed ferrous sulfate monohydrate to the washed water to the concentrated sulfuric acid is 60-70: 20-30: 1-3;
In s3, the weight ratio of the reaction intermediate product to the sodium nitrite solution is 90-95: 1-5.
The waste acid workshop section is used for concentrating waste acid in a titanium dioxide factory to obtain a byproduct, the acid content of the byproduct is high, when the ferrous sulfate monohydrate and water are mixed to prepare a slurry, stirring is carried out, the stirring is kept in a slow speed state to ensure that the ferrous sulfate monohydrate can be fully washed and reacted, and the retention action of a filter press is adopted to separate the ferrous sulfate monohydrate slurry into a washing clear liquid and the washed ferrous sulfate monohydrate.
Preferably, in s1, washing clear liquid is recovered; in s2, water is a mixture of washing clear liquid and tap water.
preferably, the weight ratio of the washing clear liquid to the tap water is 15-20: 5-10.
Preferably, the weight ratio of the washing clear liquid to the tap water is 2: 1. Wherein, because the washing clear liquid contains acid, the aim is to fully utilize the waste water resource, and the advantages of resource recycling and production cost reduction are reflected.
preferably, in s2, the concentrated sulfuric acid is 98% by mass. The purpose of adding 98% concentrated sulfuric acid is to control the basicity of the final product by using sulfuric acid, so as to ensure that the basicity value meets the standard index requirements, and simultaneously, in the process of adding the concentrated sulfuric acid, heat can be released, so that the hydration reaction does not need external heating and external cooling.
preferably, in s2, the weight ratio of the washed ferrous sulfate monohydrate to the washed water to the washed concentrated sulfuric acid is 66:27: 1.
Preferably, in s2, the mass percentage of sodium nitrite in the sodium nitrite solution is 40%.
among them, in s2, the purpose of the hydration reaction is that the ferrous sulfate monohydrate is yellow slurry and cannot be directly reacted with sodium nitrite to obtain polymeric ferric sulfate, so the hydration reaction must be carried out to generate ferrous sulfate heptahydrate before the next reaction can be carried out.
Preferably, in the s3, the introduced oxygen is high-purity oxygen with the mass percentage of 99.99%, and the weight ratio of the oxygen to the reaction intermediate product is 1-3: 90-95.
In s3, the purpose of adding sodium nitrite is to accelerate the reaction speed by using sodium nitrite as a catalyst in order to accelerate the oxidation speed because the oxidation speed of ferrous iron by oxygen is slow.
Preferably, in the s3, the reaction temperature is less than 60 ℃, and the reaction pressure is less than 0.1 MPa.
2. polymeric ferric sulfate prepared by the recycling method.
3. The polymeric ferric sulfate prepared by the recycling method is applied to the preparation of water treatment agents.
4. A water treatment agent prepared by polymerizing ferric sulfate.
Preferably, the preparation method comprises the following steps: adding a ferric trichloride solution into the polymeric ferric sulfate for compounding, and stirring for 1-2 hours to obtain a water treatment agent; the weight ratio of the polymeric ferric sulfate to the ferric trichloride solution is 95: 5.
Preferably, the mass percentage of ferric trichloride in the ferric trichloride solution is 38%. Wherein, the added ferric trichloride can effectively improve the dephosphorization effect of the water treatment agent.
5. a preparation device of a water treatment agent comprises a ferrous sulfate monohydrate transfer tank, a filter press, a hydration reaction tank, a reaction kettle, a transfer tank, a compound tank and a water treatment agent storage tank which are connected in sequence.
Preferably, the device also comprises a clear liquid storage tank, a dissolving tank, an iron salt waste gas treatment device and an iron salt wastewater tank; the clear liquid storage tank is connected with the filter press and the hydration reaction tank; the dissolving tank and the ferric salt waste gas treatment device are both connected with the reaction kettle; the ferric salt wastewater pool is connected with a ferric salt waste gas treatment device; the iron salt waste gas treatment device comprises an oxygen tower, a reduction tower and an alkaline tower which are arranged in sequence.
Wherein, pressure in the reation kettle is controlled through the pressure release valve, and the gas of emission gets into and absorbs in the indisputable salt tail gas absorbing device, and simultaneously, accessible observation reaction pressure's change situation and the mode of sampling detection index confirm the reaction end, reduce suddenly as reaction pressure, then the pressure rises again, is the completion of reaction promptly.
The basicity of the polymeric ferric sulfate prepared by the method is 10-12.
The reaction principle of preparing the polymeric ferric sulfate by the ferrous sulfate monohydrate in the invention is as follows:
Hydration reaction of ferrous monohydrate: FeSO 4. mush 2O + 6H 2O. FeSO 4. mush 7H2O
Because the oxidation speed of ferrous iron by oxygen is slow, in order to accelerate the oxidation speed, sodium nitrite is used as a catalyst to accelerate the reaction speed, and the stepwise reaction comprises the following steps:
HSO+2NaNO＝2HNO+NaSO
HSO+2HNO+2FeSO＝Fe(SO)+2NO↑+2HO
2NO+O＝2NO
HSO+NO+2FeSO＝Fe(SO)+NO↑+HO
The total reaction is as follows:
The invention has the beneficial effects that:
1) In the method, the ferrous sulfate monohydrate which is a byproduct obtained by concentrating the waste acid in a titanium dioxide factory is used as a raw material to produce the polymeric ferric sulfate, the iron ion content of the polymeric ferric sulfate is relatively stable, no iron-containing raw material is required to be added externally, the formula system is stable, the production process is simple and stable to control, in addition, the content of heavy metal ions contained in the polymeric ferric sulfate is relatively low, no influence is caused on the heavy metal indexes of the yield of the produced polymeric ferric sulfate, the polymeric ferric sulfate can be safely used for drinking water treatment, and the secondary pollution of sewage treatment caused by the introduction of the heavy metal ions can not be caused when the polymeric ferric sulfate is applied to the sewage treatment;
2) The method comprises the steps of mixing ferrous sulfate and sulfuric acid generated after hydration, introducing oxygen into a reaction system, gradually adding sodium nitrite, dissociating the sodium nitrite into NO, reacting the NO with O2 to generate NO2, oxidizing Fe2+ again by NO2 until the Fe2+ is completely oxidized, wherein the whole reaction process belongs to a gas-liquid reaction, the absorption is thorough, the reaction speed is improved, the consumption of nitrogen oxide in the catalytic oxidation process is low, the nitrogen oxide can be recycled, the pressure in the whole reaction process is kept below 0.1MPa, and the temperature is below 60 ℃, so that the waste is not caused, and the pollution problem is not caused;
3) The polymeric ferric sulfate prepared by the invention belongs to a novel high-efficiency inorganic polymer ferric salt flocculant, has dense alum and dense alum flowers and is quick to settle; compared with water purification products such as ferrous sulfate, polyaluminium chloride and the like, especially the polyferric sulfate produced by other methods in the aspect of drinking water, the source-filtering ferric sulfate has better water purification performance, does not contain harmful substances such as aluminum, chlorine, heavy metal ions and the like, and can be called a harmless, safe and reliable high-efficiency water treatment agent, and the water treatment agent prepared by compounding the polyferric sulfate and ferric trichloride has the dephosphorization effect of more than 70 percent and has great industrial application value;
4) In the preparation device of the water treatment agent designed by the invention, the waste water is recycled, and the ferric salt waste gas treatment device is also arranged, wherein the waste gas passes through the oxidation tower, the reduction tower, the alkaline washing tower and the alkaline washing tower, the nitrogen-containing oxide in the gas discharged to the atmosphere is almost zero, and the remainder of the ferric salt waste gas treatment device is further treated by the ferric salt waste water tank, so that the advantages of zero emission and zero pollution are achieved.
Drawings
FIG. 1 is a process flow diagram for preparing a water treatment agent according to the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples so that those skilled in the art can better understand the present invention and can practice it, but the examples are not intended to limit the present invention.
example 1
The implementation process of the method and the device for recycling the byproduct ferrous sulfate monohydrate in the titanium dioxide factory comprises the following steps:
s1, taking a byproduct ferrous sulfate monohydrate obtained by concentrating the waste acid workshop section of the titanium dioxide factory as a raw material, preparing the byproduct ferrous sulfate monohydrate and water into slurry in a ferrous sulfate monohydrate transfer pool according to the weight ratio of 79:32, and separating by a filter press to obtain a washing clear liquid and the washed ferrous sulfate monohydrate; pumping the clear washing liquid into a clear liquid storage pool for recycling;
s2, putting the washed ferrous sulfate monohydrate and water in the s1 into a hydration reaction tank according to the weight ratio of 66:27, and stirring to perform hydration reaction; then adding concentrated sulfuric acid with the mass percentage content of 98%, wherein the weight ratio of the concentrated sulfuric acid to the washed ferrous sulfate monohydrate is 1:66, and obtaining a reaction intermediate product; meanwhile, in a dissolving tank, preparing NaNO2 into a sodium nitrite solution with the mass percentage of 40%;
s3, pumping the reaction intermediate product into a reaction kettle, starting a circulating pump, introducing oxygen into the reaction kettle, adding 40% sodium nitrite solution into the reaction kettle in batches, wherein the weight ratio of the 40% sodium nitrite solution to the reaction intermediate product is 94:1, controlling the temperature below 60 ℃ and the pressure below 0.1MPa, carrying out circulating catalytic oxidation reaction to obtain polymeric ferric sulfate, and after the reaction is finished, putting the polymeric ferric sulfate into a transfer pool; waste gas generated in the reaction kettle is sent into an iron salt waste gas device for treatment, then is discharged into the atmosphere, and the remainder after passing through the iron salt waste gas treatment device is further treated by an iron salt wastewater tank;
s4, pumping the polyferric sulfate in the transfer tank into a compound tank, stirring, adding 38% by weight of ferric trichloride solution for compounding, wherein the weight ratio of the 38% by weight of ferric trichloride solution to the polyferric sulfate is 95:5, stirring for 1h to obtain the water treatment agent, and pumping the water treatment agent into a water treatment agent storage tank after the water treatment agent is finished.
The polymeric ferric sulfate prepared by the embodiment belongs to a novel high-efficiency inorganic polymer ferric salt flocculant, has dense alum blossom, quick sedimentation and good water purification effect, has better water purification performance than that of polymeric ferric sulfate produced by other methods in the aspect of drinking water, especially compared with ferrous sulfate, polyaluminum chloride and other water purification products, does not contain aluminum, chlorine, heavy metal ions and other harmful substances, can be called as a harmless, safe and reliable high-efficiency water treatment agent, meets the national standard requirements, and has various technical indexes shown in table 1.
TABLE 1 product index of polyferric sulfate (GB14591-2006)
The water treatment agent prepared in the embodiment 1 is used for treating phosphorus-containing wastewater, and the specific treatment operation method comprises the following steps: weighing a water treatment agent, adding the water treatment agent into water for dissolving, preparing into a phosphorus removal agent solution with the percentage content of 2%, and carrying out a phosphorus removal experiment. The results are shown in Table 2. Wherein, No. 1 is self-made phosphorus-containing wastewater, and the preparation method comprises the following steps: adding 4.5g of diatomite in total into 20L of water, and adding 0.3g of trisodium phosphate decahydrate when the turbidity is detected to be about 100NUT to obtain the self-made phosphorus-containing wastewater.
TABLE 2
From the analysis in table 2, it can be seen that when the water treatment agent prepared in this example 1 is used for phosphorus removal experiments, phosphorus removal rates of the phosphorus-containing wastewater, the sewage of water utilities and the sewage of sewage treatment plants are all above 70%, and high-efficiency phosphorus removal effects are shown, and phosphorus content and turbidity in the treated sewage can reach the primary indexes of pollutant discharge standards (GB 18918-2002) of urban sewage treatment plants.
in conclusion, the water treatment agent prepared by the embodiment is prepared by compounding polymeric ferric sulfate and ferric trichloride, and can be widely applied to treatment of various industrial wastewater and sludge in the fields of urban domestic sewage treatment, papermaking, petrochemical industry, mineral processing industry, dyeing industry and the like.
Compared with the prior art, the method takes the byproduct ferrous sulfate monohydrate obtained by concentrating the waste acid in the titanium dioxide factory as the raw material, and then carries out hydration reaction and catalytic oxidation reaction after pretreatment to prepare the polymeric ferric sulfate, and has the advantage of low impurity content. Furthermore, the prepared polymeric ferric sulfate and ferric trichloride are compounded to prepare the water treatment agent, so that the application range of the polymeric ferric sulfate is expanded. Meanwhile, in the pretreatment process, the produced wastewater is recycled, so that the advantage of resource recycling is reflected, and the produced tail gas is treated and then discharged into the atmosphere, so that the requirements of zero emission and zero pollution are met.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The method for recycling the ferrous sulfate monohydrate serving as a byproduct in a titanium dioxide factory is characterized by comprising the following steps of:
s1, mixing a byproduct ferrous sulfate monohydrate obtained by concentrating in a waste acid workshop section of a titanium dioxide factory with water to prepare a slurry, and then separating to obtain a washing clear liquid and the washed ferrous sulfate monohydrate;
s2, mixing the ferrous sulfate monohydrate washed in the s1 with water, stirring, and carrying out hydration reaction; then adding concentrated sulfuric acid to obtain a reaction intermediate product; meanwhile, sodium nitrite, namely NaNO2 is prepared into sodium nitrite solution;
s3, stirring the reaction intermediate product and introducing oxygen, then adding the sodium nitrite solution in batches, and carrying out circulating catalytic oxidation reaction to obtain polymeric ferric sulfate;
In the s1, the weight ratio of the byproduct ferrous sulfate monohydrate to water is 70-80: 20-35;
in the s2, the weight ratio of the washed ferrous sulfate monohydrate to the washed water to the concentrated sulfuric acid is 60-70: 20-30: 1-3;
in s3, the weight ratio of the reaction intermediate product to the sodium nitrite solution is 90-95: 1-5.
2. The method for recycling the ferrous sulfate monohydrate as the by-product in the titanium dioxide factory according to claim 1, wherein in s1, a washing clear solution is recycled; in s2, water is a mixture of washing clear liquid and tap water.
3. The method for recycling ferrous sulfate monohydrate as a byproduct of a titanium dioxide factory according to claim 2, wherein the weight ratio of the washing clear liquid to the tap water is 15-20: 5-10.
4. the method for recycling the ferrous sulfate monohydrate of the by-product in the titanium dioxide factory according to claim 1, wherein the weight ratio of the washed ferrous sulfate monohydrate, water and concentrated sulfuric acid in s2 is 66:27: 1.
5. polymeric ferric sulphate produced by a recycling method according to any one of claims 1 to 4.
6. Use of polymeric ferric sulphate produced by a recycling method according to any one of claims 1 to 4 in the production of a water treatment agent.
7. A water treatment agent prepared by using the polymeric ferric sulfate of claim 5.
8. A water treatment agent according to claim 7, characterized in that it is prepared by: adding a ferric trichloride solution into the polymeric ferric sulfate for compounding, and stirring for 1-2 hours to obtain a water treatment agent; the weight ratio of the polymeric ferric sulfate to the ferric trichloride solution is 95: 5.
9. a device for preparing a water treatment agent is characterized by comprising a ferrous sulfate monohydrate transfer tank, a filter press, a hydration reaction tank, a reaction kettle, a transfer tank, a compound tank and a water treatment agent storage tank which are connected in sequence; also comprises a dissolving tank; the dissolving tank is connected with the reaction kettle.
10. the apparatus for preparing a water treatment agent according to claim 9, further comprising a clear liquid storage tank, an iron salt waste gas treatment apparatus and an iron salt waste water tank; the clear liquid storage tank is connected with the filter press and the hydration reaction tank; the iron salt waste gas treatment device is connected with the reaction kettle; the ferric salt wastewater pool is connected with a ferric salt waste gas treatment device; the iron salt waste gas treatment device comprises an oxygen tower, a reduction tower and an alkaline tower which are arranged in sequence.
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