WO2022104737A1 - 一种硫酸法钛白粉生产废水全资源循环利用的生产方法 - Google Patents
一种硫酸法钛白粉生产废水全资源循环利用的生产方法 Download PDFInfo
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- WO2022104737A1 WO2022104737A1 PCT/CN2020/130588 CN2020130588W WO2022104737A1 WO 2022104737 A1 WO2022104737 A1 WO 2022104737A1 CN 2020130588 W CN2020130588 W CN 2020130588W WO 2022104737 A1 WO2022104737 A1 WO 2022104737A1
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- titanium dioxide
- wastewater
- production
- sulfuric acid
- tank
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 212
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 123
- 239000002351 wastewater Substances 0.000 title claims abstract description 118
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000004064 recycling Methods 0.000 title claims abstract description 23
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical class [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 61
- 238000000926 separation method Methods 0.000 claims abstract description 57
- 239000012528 membrane Substances 0.000 claims abstract description 53
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 46
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 45
- 238000001556 precipitation Methods 0.000 claims abstract description 33
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 30
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 30
- 239000004571 lime Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 23
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 23
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 23
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 22
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 20
- 239000010440 gypsum Substances 0.000 claims abstract description 20
- 239000000706 filtrate Substances 0.000 claims abstract description 18
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 18
- 238000003763 carbonization Methods 0.000 claims abstract description 17
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 94
- 239000000243 solution Substances 0.000 claims description 57
- 238000006386 neutralization reaction Methods 0.000 claims description 37
- 238000005352 clarification Methods 0.000 claims description 20
- 235000017550 sodium carbonate Nutrition 0.000 claims description 20
- 239000012267 brine Substances 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 15
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000008213 purified water Substances 0.000 claims description 14
- 238000009993 causticizing Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000008267 milk Substances 0.000 claims description 11
- 235000013336 milk Nutrition 0.000 claims description 11
- 210000004080 milk Anatomy 0.000 claims description 11
- 235000019738 Limestone Nutrition 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 239000006028 limestone Substances 0.000 claims description 10
- 238000011085 pressure filtration Methods 0.000 claims description 9
- 238000001223 reverse osmosis Methods 0.000 claims description 9
- 229910052925 anhydrite Inorganic materials 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005374 membrane filtration Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004566 building material Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000011001 backwashing Methods 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 abstract description 4
- 230000003472 neutralizing effect Effects 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 18
- 239000011734 sodium Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000000108 ultra-filtration Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002455 scale inhibitor Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000005273 aeration Methods 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- DAAJPHTURITNKZ-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].C(=O)=O Chemical compound [O-2].[O-2].[Ti+4].C(=O)=O DAAJPHTURITNKZ-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- -1 calcium saturated calcium sulfate Chemical class 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 238000010850 salt effect Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
Definitions
- the invention relates to a production method for the treatment and recycling of production wastewater, in particular to a resource-based production method for the treatment and recycling of titanium dioxide production wastewater by sulfuric acid method and the recycling of wastewater containing calcium sulfate.
- the wastewater produced by sulfuric acid method titanium dioxide mainly comes from the metatitanic acid in the production process, the first washing liquid, the second washing filtrate and the washing liquid, the acid waste water produced by acid hydrolysis, the spray absorption water of the calcining tail gas, the sewage circulating drainage, and the floor washing. , Equipment flushing, desalination station regeneration wastewater and sporadic wastewater.
- the main pollutants in the waste water are H 2 SO 4 , TiO 2 , Fe 2+ , Fe 3+ , Na + and small and trace amounts of HSO 3 - , F - and Cl - and other harmful substances.
- the chemical reaction principle of the existing wastewater treatment method is as follows:
- titanium gypsum or "red mud”
- the pressure filtration filtrate is filtered by a clarifier or fiber filter due to the initial filtrate and filtered and a small amount of solids during filtration.
- Industrial wastewater that meets the national discharge standard is discharged to natural water bodies. Since the treated water cannot be recycled, the entry conditions for the titanium dioxide industry stipulate that the discharge amount of wastewater from titanium dioxide treated by sulfuric acid method must be less than 80 cubic meters. Applying and so on, the most effective production unit ton of titanium dioxide discharge and treatment wastewater is still about 60 cubic meters.
- the first is to use the ion exchange method to treat the usual raw water.
- the ton of titanium dioxide is calculated as 60 cubic meters, of which about 240 kg of saturated calcium sulfate needs to be removed, plus the soluble sulfates brought in due to the manufacture of rutile crystal seeds and post-treatment coating.
- anion and cation exchangers such as table salt, hydrochloric acid and sodium hydroxide, and at the same time, a large amount of concentrated brine containing calcium chloride is still discharged after the exchange, which is not only expensive, but also doubled.
- the quality of the effluent salt solution is unacceptable to the environment, and a lot of chemical resources are wasted.
- the second is to directly use reverse osmosis membrane to separate and treat wastewater according to the usual raw water treatment.
- concentration of the concentrated brine side of the membrane separation exceeds the saturated concentration of calcium sulfate, calcium sulfate is precipitated; due to the high concentration of the membrane surface and its surface energy
- the surface energy of the crystal nucleus (precursor) precipitated by supersaturated calcium sulfate is large, which rapidly deposits and scales on the membrane, preventing the passage of water molecules and reducing the separation efficiency of the membrane.
- the reverse osmosis membrane will be fouled and scrapped, and the required investment is large and the operating cost is high.
- a treatment method for titanium dioxide wastewater not only needs to add flocculant aluminum trichloride to the treated wastewater to flocculate the ultrafine suspended solids and then perform ultrafiltration, but also to prevent saturated calcium sulfate
- scale inhibitors need to be added; since the calcium sulfate content in the treated wastewater is as high as 4000mg/L, the converted calcium ion concentration is nearly 1200mg/L, a large and expensive scale inhibitor is required, which not only increases wastewater treatment Recycling costs, due to the presence of scale inhibitors in water, affects the use of circulating water, and even affects the quality of titanium dioxide production products, such as phosphorus-based scale inhibitors and aluminum trichloride flocculants, enter titanium dioxide from recycled water.
- the produced metatitanic acid is enriched, and the titanium dioxide microcrystalline particles with pigment properties cannot be calcined in the rotary kiln. Because phosphorus and aluminum are both control agents for controlling the particle size and crystal form of titanium dioxide production, the amount and instability will cause The quality of titanium dioxide is inferior; if an organic complexing agent is used, the molecular weight of the complexing agent is much larger than the molecular weight of the water molecular weight and the pore size of the membrane separation, which will block the membrane pores, also reduce the separation efficiency, and even cause the membrane material to be scrapped in a short time. In addition, the dense phase brine produced by it has a low concentration and has not been used yet. It is also discharged out, which does not reduce the absolute amount of solute discharge to the water body, and enters the water body and affects the environment.
- the third is to use ultrafiltration before membrane separation.
- Ultrafiltration is only effective for ultrafine solid particles, but is meaningless for saturated solutions or even supersaturated solutions; because the saturated concentration of calcium sulfate in the treated wastewater after separation of gypsum is relatively high.
- US patents US4966710 and US6086842 the former US4966710 uses sodium hydroxide to adjust the pH of the sodium sulfate solution to be magnesium and calcium in the precipitation solution, which is used to purify the sodium sulfate solution and reduce the chemical regenerant used for ion exchange regeneration, instead of using Impurities in the sodium carbonate precipitation solution; the latter US6086842 produces high-quality desulfurized gypsum without calcium sulfite for desulfurization tail gas, adopts sodium sulfate causticization cycle absorption, and does not use carbon dioxide in production to produce sodium carbonate.
- the sulfuric acid method titanium dioxide production wastewater using the carbon dioxide resources in the existing sulfuric acid method titanium dioxide production and the coupled production of lime raw material caustic solution and wastewater treatment, to remove the calcium ion content in the saturated calcium sulfate solution in the wastewater after separation of gypsum, It is returned to the gypsum, and the production coupling and its own waste and auxiliary resources are used, which is conducive to the recycling of all resources of the membrane separation treatment wastewater, and reduces the purchase cost of commercial chemicals; it solves the technology that the sulfuric acid method titanium dioxide neutralization treatment wastewater is difficult to recycle.
- the difficulty is to save the consumption of raw water resources in production, and eliminate the influence factors of the existing neutralization treatment wastewater on the environmental water body; The production process and technology production method of fully coupling and recycling its wastewater resources have not been reported.
- the coupled production technology overcomes the problems and deficiencies of difficult recycling and economical utilization of titanium dioxide wastewater by sulfuric acid method after neutralization and treatment, eliminates the influence factors of the existing treatment wastewater discharge on the environmental water body, and saves the production of a large amount of raw water resources used for production as the goal.
- the object of the present invention is to provide a production method for the full resource recycling of waste water produced by sulfuric acid method titanium dioxide.
- the method is to treat the wastewater after the titanium dioxide production wastewater of the sulfuric acid method is neutralized and precipitated with limestone and lime to separate gypsum, and add the sodium carbonate solution prepared by recycling itself to precipitate, wherein the concentration of saturated calcium sulfate left in the wastewater due to the separation of gypsum is carbonic acid.
- Calcium and sodium sulfate slurry; precipitation reaction slurry solution is clarified to separate calcium carbonate slurry and sodium sulfate solution.
- the clarified and separated calcium carbonate thick slurry is recycled back to the titanium dioxide wastewater to be used as calcium carbonate resources, and the separated sodium sulfate solution is subjected to membrane separation by reverse osmosis membrane.
- the dilute phase liquid (purified water) obtained by membrane separation is returned to titanium dioxide production as process water, replacing the externally supplied raw water resources used in production.
- the concentrated salt solution containing sodium sulfate obtained by membrane separation is added with lime for causticization reaction to generate calcium sulfate precipitation and sodium hydroxide solution slurry, and the slurry is separated by pressure filtration; the separated calcium sulfate filter cake is recycled back to titanium dioxide wastewater In the slurry of neutralized and precipitated calcium sulfate, it is separated as the neutralized and precipitated wastewater gypsum; a part of the separated sodium hydroxide solution is returned to titanium dioxide as an alkali absorption liquid for acid hydrolysis and calcined acid tail gas washing, and a part is produced by titanium dioxide Carbon dioxide in the tail gas is carbonized, and sodium hydroxide is carbonized into sodium carbonate solution, which is used to remove saturated calcium sulfate in the treatment wastewater to become calcium carbonate precipitation to provide carbonate ion substances, which are recycled
- the production method for the coupled utilization of total resources of titanium dioxide production waste water by sulfuric acid method protected by the present invention not only solves the full recycling utilization of titanium dioxide production waste water, but also saves money. It meets the need for a large amount of raw water in titanium dioxide production, and achieves the reuse of production water and a large number of waste water reduction; and not only optimizes the production process of waste water treatment, but also makes full use of waste secondary resources carbon dioxide from the production of titanium dioxide drying tail gas, saving waste water treatment.
- the production principle of the present invention is as follows:
- Precipitation of sodium solution and calcium sulfate dihydrate carbon dioxide of reaction formula (5) is generated when the sodium hydroxide solution after separating calcium sulfate dihydrate is used to absorb titanium dioxide and post-processing the tail gas or limestone produced by drying combustion fuel and neutralize the precipitated calcium sulfate.
- the gas is carbonized according to the reaction equation (10) to obtain a sodium carbonate solution, and the obtained sodium carbonate solution is circulated back to the reaction equation (8) for removing the saturated calcium sulfate in the waste water and the filtrate.
- the waste water from titanium dioxide production by sulfuric acid method is added into the neutralization reaction tank, limestone, lime milk and air are added in sections to carry out neutralization, precipitation and oxidation reaction, and the slurry after the reaction and precipitation is sent to the filter press (1) for pressure filtration separation.
- the filter cake separated by pressure filtration is discharged as titanium gypsum and sent to cement and other building materials for use; the separated filtrate is sent to the sedimentation tank as treated wastewater, and the sodium carbonate solution sent by the carbonization tower and the carbonic acid after precipitating saturated calcium sulfate are added. Calcium is recycled back to the slurry, along with precipitation of calcium saturated calcium sulfate in solution.
- the material of precipitation calcium carbonate is sent to the clarification tank (1) for clarification; part of the clarified thick slurry is returned to the sedimentation tank as a circulating seed, and the saturated calcium sulfate is precipitated as calcium carbonate, and the rest is returned to the neutralization reaction tank to replace part of the lime milk for neutralization Waste water, clarified clear liquid is sent to membrane filter for membrane separation; dilute phase of membrane separation is returned to titanium dioxide production as purified water to replace the original process water; dense phase solution of membrane separation is sent to causticizing tank and lime milk is added for further purification.
- the causticized material is sent to the filter press (2) for pressure filtration, the separated filter cake is returned to the wastewater neutralization reaction tank and is incorporated into the neutralization slurry; the separated filtrate is used as a sodium hydroxide solution, and part of it is sent to the In the carbonization tower, carbon dioxide in the production tail gas is used for carbonization, and the carbonized solution is sent to the precipitation tank to precipitate calcium carbonate; part of it is returned to titanium dioxide to replace the purchased lye raw material.
- a production method for the coupled utilization of total resources of sulfuric acid method titanium dioxide production wastewater protected by the present invention not only solves the complete recycling utilization of titanium dioxide production wastewater, but also saves titanium dioxide.
- the production of white powder requires a large amount of raw water, which has achieved the reuse of production water and a large amount of emission reduction of waste water. It not only optimizes the production process of waste water treatment, but also makes full use of the waste secondary resource carbon dioxide of titanium dioxide production tail gas, which saves the production cost of waste water treatment.
- the demand for sodium hydroxide in the production of white powder maximizes the utilization of resources.
- the utilization and reuse rate of resources are improved, the economic benefit of the producer is increased, and the technical and economic purpose of coupling the waste water of titanium dioxide production by sulfuric acid method to recycle and reuse all resources is achieved.
- the waste water is titanium dioxide production waste water by sulfuric acid method and waste water containing calcium sulfate.
- the neutralizing agent includes lime, limestone and acetylene to produce calcium carbide slag and other basic calcium raw materials, preferably limestone and lime.
- the neutralization reaction tank can be a single reactor with stirring, or a plurality of reactors with stirring in series.
- the neutralization reaction tank is preferably connected in series with a plurality of reaction tanks with agitators, and the neutralization pH is controlled according to different levels. 7.0-7.5.
- the filter press for separating gypsum is a common commercially available filter press with a diaphragm press, preferably provided with a back-blowing central hole system and a compressed air central filter cake drying system.
- the precipitation tank can be a single reactor with stirring, or a plurality of reactors with stirring in series; preferably more than two.
- the carbonization solution is added to the precipitation tank to precipitate calcium carbonate, and the thick slurry of the clarification tank can be added as crystal seed, or not; it is best to add thick slurry as crystal seed.
- the sodium carbonate added to the precipitation is that the molar ratio of saturated calcium sulfate (M Na2CO3 /M CaSO4 ) is 1.0-1.2, preferably 1.05-1.10, and thick slurry seeds are added to generate the calcium carbonate ratio ( M crystal /M raw ) is 1-3, preferably 1.5-2.
- M Na2CO3 /M CaSO4 saturated calcium sulfate
- M crystal /M raw is 1-3, preferably 1.5-2.
- the clarification tank (1) can be a continuous clarification tank and an alternately used parallel semi-continuous clarification tank, and the clarification residence time is 1-3 hours, preferably 1.0-1.5 hours.
- the membrane filter adopts a reverse osmosis membrane filtration separator, which can be single-stage or multi-stage, and the multi-stage is used for the post-treatment of titanium dioxide for the third washing water, and the rest are preferably single-stage, and the initial pressure of membrane filtration It is 1-2MPa, preferably 1.5MPa, the final pressure is 4-5MPa, preferably 4.5MPa, and the concentration ratio of the treated wastewater is 6-15 times, preferably 8-10 times.
- a reverse osmosis membrane filtration separator which can be single-stage or multi-stage, and the multi-stage is used for the post-treatment of titanium dioxide for the third washing water, and the rest are preferably single-stage, and the initial pressure of membrane filtration It is 1-2MPa, preferably 1.5MPa, the final pressure is 4-5MPa, preferably 4.5MPa, and the concentration ratio of the treated wastewater is 6-15 times, preferably 8-10 times.
- the conductivity of the membrane separation dilute phase is 60-120us/cm, preferably 80-100us/cm, which is directly returned to the titanium dioxide production process water.
- the causticizing tank adopts a series of multi-stage causticizing, and the number of stages is 2-5, preferably more than 3.
- the molar ratio (M Ca(OH)2 /M Na2SO4 ) of lime milk and sodium sulfate added to causticization is 1.1-1.4, preferably 1.15-1.25.
- the filter cake separated by the filter press (2) is returned to the neutralization reaction tank to react with the neutralization slurry; the filtrate is used as caustic lye, and part of the filtrate is returned to the production of titanium dioxide, and part is sent to the carbonization tower for carbonization ;
- the distribution ratio is determined according to the amount of saturated sulfuric acid that needs to be eliminated in the wastewater treatment.
- the carbon dioxide gas used in the carbonization of the carbonization tower can be the carbon dioxide gas produced by the use of calcium carbonate (limestone) in the post-processing dry tail gas of titanium dioxide production, rotary kiln calcination tail gas and waste water neutralization reaction; The value is controlled at 11.5-12.5, preferably at 12.
- the waste water produced by the sulfuric acid method titanium dioxide is subjected to lime neutralization reaction precipitation, and the gypsum is separated by a filter press.
- the treated wastewater solution mainly composed of sodium sulfate is obtained.
- the treated wastewater solution is filtered and purified by a membrane filter.
- the purified water obtained by membrane filtration is returned to titanium dioxide production and recycled as process water, and the treated wastewater is not discharged; the concentrated sodium sulfate solution obtained by membrane filtration and separation is added with lime for multi-stage causticization to obtain sodium hydroxide solution; sodium hydroxide solution Carbon dioxide in waste gas produced by titanium dioxide is carbonized to obtain sodium carbonate solution, which is returned to the precipitation tank for precipitation and treatment of saturated calcium sulfate in wastewater, so as to achieve the purpose of coupling and recycling all resources of titanium dioxide wastewater by sulfuric acid method.
- the method of the invention solves the problem of long-term difficulty in recycling caused by the concentration of saturated calcium sulfate in the neutralization of sulfuric acid method titanium dioxide and the concentration of saturated calcium sulfate in the wastewater due to the use of carbon dioxide resources in the existing sulfuric acid method titanium dioxide production and the coupled production of lime causticizing solution and wastewater treatment.
- the technical difficulty eliminates the influence factors of the existing neutralization treatment wastewater on the environmental water body, saves a large amount of raw water used in production, and saves water resources.
- the invention adopts a large cycle of titanium dioxide production and wastewater treatment and a small cycle in wastewater treatment, which not only solves the problem of sulfuric acid method
- the technical problem of recycling waste water from titanium dioxide production, and the water consumption per unit of titanium dioxide production has been greatly reduced. It not only realizes the coupled utilization and reuse of all resources in wastewater, saves the use of resources, but also increases the economic benefits of producers. Not only significant energy saving and consumption reduction, but also significant economic benefits.
- the present invention not only innovates the utilization of resources by cyclically coupling the waste water of titanium dioxide production by the sulfuric acid method, but also greatly reduces the resource cost and the waste water discharge water cost, improves the economic and social benefits of production, and solves the problem that the traditional process cannot be recycled and the economic exploited technical difficulties.
- FIG. 1 Process flow chart of the traditional sulfuric acid method for titanium dioxide production wastewater treatment.
- FIG. 2 A production method process flow diagram of the present invention for the full resource recycling of titanium dioxide waste water by sulfuric acid method.
- 1600L per hour (specific gravity 1.05, containing sulfuric acid 36.96g/L, ferrous sulfate 16.80g/L, titanium sulfate 0.525g/L, see Table 1) and 29.0L of lime milk containing 170g/L calcium oxide per hour is neutralized in three series-connected 2000L bottoms with an air distribution pipe in a stirring neutralization reaction tank, and air is blown in for aeration oxidation to control the stay of the reaction material.
- the time was 1 hour, the pH value of the slurry was 7.5, and the slurry overflowed from the top of the third-stage neutralization reaction tank and entered the filter press pump tank and then continuously sent it to the filter press for pressure filter separation, obtaining 27.4 kg of water content 45% per hour.
- the filter cake and 1685L treated wastewater (specific gravity 1.005 and its composition are shown in Table 2).
- 1685L per hour of treated wastewater is continuously fed into the 5500Ld saturated calcium sulfate precipitation tank, and 146L of carbonized sodium carbonate solution with a concentration of 30g/L and 33L of clarified thick slurry with a concentration of 250g/L calcium carbonate are added every hour, and the precipitation reaction
- the material has a residence time of 1 hour, and is continuously sent to the clarification tank (1) for clarification to obtain 50L of calcium carbonate thick slurry with a concentration of 250g/L, 33L is circulated back to the sedimentation tank to provide crystal seeds, and 17L is circulated back to the acid waste water neutralization reaction tank.
- the clarified liquid from the clarification tank (1) is sent to the membrane separation device at 1814.2L per hour for separation.
- the initial filtration pressure is 1.5MPa, and after reaching the filtration pressure of 4.5MPa, backwashing and circulating filtration are performed.
- the purified water separated from the membrane filter is 1636L per hour, and the concentrated brine is 178L.
- the composition of the membrane separation influent, the separation purified water and the concentrated brine is shown in Table 3.
- the sodium sulfate concentration in the influent is 3.49g/L. It is only 16mg/L, the conductivity is 107us/cm, the concentration of sodium sulfate in concentrated brine increases to 34.72g/L, and the conductivity is 98000us/cm.
- the water recovery cycle returns titanium dioxide productivity at 90%.
- the concentrated brine separated by the membrane is 178L per hour, sent to the causticizing tank with stirring in 3 stages, and 4.3L lime milk containing CaO of 170g/L is added to each of the 3 stages, totaling 13.1L, for causticization, the material residence time 30 minutes each for a total residence time of 1.5 hours.
- the causticized slurry was sent to the filter press (2) for pressure filtration, and 16.80 kg of filter cake with a water content of 45% and 178.6 L of filtrate containing 20.1 g/L of sodium hydroxide were separated.
- the filtrate was carbonized with titanium dioxide dried tail gas to obtain 180L of a solution containing 26.43g/L of sodium carbonate, and 166L was separated and returned to the precipitation tank to precipitate saturated calcium sulfate solution, and the remaining 14L was used for other acidic tail gas washing instead of the original commercial hydroxide Sodium solution.
- the acid wastewater from the production of titanium dioxide by the sulfuric acid method is 240m3 per hour, and the main composition is shown in Table 4. It is neutralized with 36.5m3 of lime milk containing 200g/L calcium oxide per hour in four series of 180m3 with stirring.
- the neutralization reaction is carried out in the reaction tank.
- the bottom of the two-stage neutralization reaction tank is equipped with an air distribution pipe, and air is blown into the reaction tank for aeration oxidation.
- the residence time of the reaction material is controlled for 1.5 hours, and the pH value of the slurry is 7.5.
- the top of the four-stage neutralization reaction tank overflowed into the filter press pump tank and then was continuously sent to the filter press for pressure filter separation. 45.5 tons of filter cake with a water content of 45% and 253 tons of treated wastewater were obtained per hour.
- the composition is shown in Table 5.
- 253 tons of treated wastewater per hour are continuously fed into three saturated calcium sulfate precipitation tanks of 110m3 in series, and 4.6m3 of clarified thick slurry with a concentration of 300g/L calcium carbonate and 22m3 of carbonized slurry with a concentration of 35.6g/L are added every hour.
- the sodium carbonate solution and the precipitation reaction material have a residence time of 1 hour, and are continuously sent to the clarification tank (1) for clarification to obtain 6.8m3 of calcium carbonate thick slurry with a concentration of 300g/L, 4.6m3 of which are circulated back to the precipitation tank to provide crystal seeds, 2.2m3 It is recycled back to the wastewater neutralization reaction tank.
- the clarified liquid from the clarification tank ( 1 ) is 278m3 per hour and sent to the membrane separation device with a membrane separation area of 5000m2 for separation.
- the separated purified water is 255m3 per hour, and the concentrated brine is 23m3.
- the composition of brine is shown in Table 3.
- the concentration of sodium sulfate in the influent water is 4.80g/L
- the purified water is only 20mg/L
- the conductivity is 113us/cm.
- the concentration of sodium sulfate in the concentrated brine increases to 57.98g/L, and the conductivity is 98000us/cm.
- the water recovery cycle returns titanium dioxide productivity at 90%.
- the concentrated brine separated by the membrane is 23m3 per hour, sent to the causticizing tank of 15m3 with stirring in 5-stage series, and 0.63m3 of lime milk containing CaO of 200g/L is added to each of the 5-stages, for a total of 3.16m3, for causticization,
- the material residence time is 30 minutes each, and the total residence time is 2.5 hours.
- the causticized slurry is sent to the filter press (2) for pressure filtration, and 3.5 tons of filter cake with 50% water content and 21m3 of filtrate containing 29.4g/L sodium hydroxide are separated. 2.6m3 of the filtrate was separated and returned to the production of titanium dioxide, and the remaining 18.4m3 was carbonized with the titanium dioxide dried tail gas to obtain a solution containing 35.60g/L of sodium carbonate.
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Abstract
Description
组分 | 浓度(g/L) | 组分 | 含量(%) |
H 2SO 4 | 36.96 | MgSO 4 | 2.10 |
FeSO 4 | 16.80 | Al 2(SO 4) 3 | 1.05 |
Na 2SO 4 | 1.30 | CaSO 4 | 1.05 |
组分 | 浓度(g/L) | 组分 | 浓度(g/L) |
pH | 7.2 | MgSO 4 | 0.010 |
FeSO 4 | 0.001 | Al 2(SO 4) 3 | 0.010 |
Na 2SO 4 | 1.25 | CaSO 4 | 3.35 |
组分 | 进水浓度(g/L) | 净化水浓度(g/L) | 浓盐水浓度(g/L) |
pH | 7.6 | 7.2 | 7.8 |
Na 2SO 4 | 4.66 | 0.016 | 42.60 |
MgSO 4 | 0.005 | ‐‐ | |
CaSO 4 | ‐‐ | ‐‐ | ‐‐ |
电导率(us/cm) | 9000 | 107 | 98000 |
组分 | 浓度(g/L) | 组分 | 含量(%) |
H 2SO 4 | 41.06 | MgSO 4 | 1.10 |
FeSO 4 | 18.66 | Al 2(SO 4) 3 | 0.95 |
Na 2SO 4 | 1.54 | CaSO 4 | 1.55 |
组分 | 浓度(g/L) | 组分 | 浓度(g/L) |
pH | 7.0 | MgSO 4 | 0.010 |
FeSO 4 | 0.001 | Al 2(SO 4) 3 | 0.010 |
Na 2SO 4 | 1.46 | CaSO 4 | 3.65 |
组分 | 进水浓度(g/L) | 净化水浓度(g/L) | 浓盐水浓度(g/L) |
pH | 7.5 | 7.2 | 7.6 |
Na 2SO 4 | 4.80 | 0.016 | 57.98 |
MgSO 4 | 0.005 | ‐‐ | |
CaSO 4 | ‐‐ | ‐‐ | ‐‐ |
电导率(us/cm) | 10000 | 113 | 98000 |
Claims (10)
- 一种硫酸法钛白粉生产废水全资源循环利用的生产方法,包括:将硫酸法钛白粉生产废水与石灰石和石灰加入中和反应槽中进行沉淀反应,沉淀反应完全的反应物料送入压滤机进行过滤分离;分离的滤饼作为钛石膏送石膏建材和水泥建材使用,分离滤液作为处理后废水进行全循环利用的加工生产;将压滤机分离处理后的废水加入沉淀槽中,同时加入来自碳化塔的碳酸钠溶液,控制反应以沉淀处理废水中的饱和硫酸钙,使其生成溶解度更小的碳酸钙沉淀物料,沉淀物料送入澄清槽中进行澄清;澄清槽的重相底料碳酸钙料浆返回中和反应槽中,与钛白粉生产送来的废水进行中和反应;澄清槽的轻相清液送入膜分离器进行盐液的膜分离,膜分离的稀相(净化水)作为工艺水返回钛白粉生产工序,节约外供原水水资源,废水全利用;膜分离浓相硫酸钠溶液送入苛化槽,加入石灰乳进行苛化反应,生成沉淀硫酸钙和氢氧化钠溶液,将苛化料浆送入压滤机进行分离,分离滤饼返回石灰中和反应槽与钛白粉废水一道进行中和;分离滤液作为氢氧化钠溶液送入碳化塔,用钛白粉生产过程中产生的含二氧化碳的尾气进行碳化,转化成碳酸钠溶液,再循环到沉淀槽中沉淀处理废水中的饱和硫酸钙的钙离子;苛化分离的溶液视质量流情况,部分滤液可返回钛白粉生产作为稀碱液使用。
- 根据权利要求1所述的一种硫酸法钛白粉生产废水全资源循环 利用的生产方法,其特征在于:所述的生产废水是硫酸法钛白粉生产和需要进行中和处理的生产废水;用石灰中和反应的pH值为6‐8,最好为7.0‐7.5。
- 根据权利要求1‐2所述的一种硫酸法钛白粉生产废水全资源利用的生产方法,其特征在于:所述的处理废水是钛白粉生产废水经过石灰石和石灰中和、压滤机(1)分离石膏滤饼后的处理废水,其中含有饱和硫酸钙溶液及少量的可溶性硫酸盐杂质溶液,饱和硫酸钙的浓度范围在1‐5g/L,即1‐5Kg/m3。
- 根据权利要求1‐3任意一项所述一种硫酸法钛白粉生产废水全资源利用的生产方法,其特征在于:所述的沉淀槽加入来自碳化塔的碳酸钠溶液,其加入量与饱和硫酸钙的量摩尔比(M Na2CO3/M CaSO4)为1.0‐1.2,最好是1.05‐1.10,加入稠浆晶种以生成的碳酸钙比例(M 晶/M 生)为1‐3,最好1.5‐2。
- 根据权利要求1或4述的一种硫酸法钛白粉生产废水全资源利用的生产方法,其特征在于:所述澄清槽(1)澄清时间为1‐3小时,最好为1.5‐2.0小时;澄清槽(1)稠浆循环返回沉淀槽的量为总量的2/3,作为沉淀碳酸钙的晶种;总量的1/3循环返回反应中和槽与钛白粉生产废水一道反应;清液部分送入膜分离过滤器。
- 根据权利要求1‐5任意一项所述的一种硫酸法钛白粉生产废水全资源利用的生产方法,其特征在于:所述的澄清槽(1)分离的清液送入包含有预处理***、反渗透***及辅助加药、清洗、反洗等构成的反渗透膜分离装置中进行膜分离;膜过滤起始压力为1.5MPa,最 终压力为4-5MPa,最好为4.5MPa后进行反冲洗,处理废水浓缩倍数为6‐15倍,作为优选最好为8‐10倍。膜分离净化水直接返回钛白粉生产,作为工艺水循环利用;膜分离浓盐水为硫酸钠溶液,可作为苛化制备氢氧化钠和碳酸钠溶液用于消除处理废水中饱和硫酸钙,也可再浓缩富集。
- 根据权利要求1和5‐6任意一项所述的一种硫酸法钛白粉生产废水全资源利用的生产方法,其特征在于:所述法膜分离过滤可采取多级与单级分离;多级分离水可用在钛白粉后处理工艺;作为优选,所述的膜分离稀相(净化水)的电导率在60‐120us/cm,最好在80-100us/cm;净化水直接返回钛白粉生产工艺用水;膜分离浓相为硫酸钠盐溶液送苛化槽反应。
- 根据权利要求1‐6任意一项所述的一种硫酸法钛白粉生产废水全资源利用的生产方法,其特征在于:所述的苛化槽采用串联的多级苛化,级数在2‐5级,最好是3级以上;苛化加入石灰乳与硫酸钠的摩尔比(M Ca(OH)2/M Na2SO4)为1.1‐1.4,最好为1.15‐1.25;并按苛化级数进行石灰乳加量分配。
- 根据权利要求1和6‐7所述的一种硫酸法钛白粉生产废水全资源利用的生产方法,其特征在于:所述的苛化物料包含苛化生成的硫酸钙和没有参加反应的氢氧化钙送入压滤机(2)进行压滤,滤饼打浆循环返回中和反应槽中,滤液视其氢氧化钠的总量和需要沉淀饱和硫酸钙的量进行分流,部分送去碳化塔碳化,部分返回钛白粉生产代替生产需用碱液量。
- 根据权利要求1和6‐8所述的一种硫酸法钛白粉生产废水全资源利用的生产方法,其特征在于:所述的碳化塔碳化采用的二氧化碳气体,可以是钛白粉生产后处理干燥的尾气、偏钛酸转窑煅烧尾气、废水使用碳酸钙(石灰石)中和反应时产生的二氧化碳气体、燃烧燃料和产生锅炉的尾气;碳化度以pH值控制在11.5‐12.5,最好控制在12。
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CN116040687A (zh) * | 2022-11-01 | 2023-05-02 | 攀枝花末微环保科技有限公司 | 硫酸法钛白废酸的综合利用方法和硫酸法钛白生产工艺 |
CN116177779A (zh) * | 2022-12-09 | 2023-05-30 | 四川大学 | 钛白废水的回收利用方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5603839A (en) * | 1995-09-18 | 1997-02-18 | Cecebe Technologies Inc. | Process for the recovery of waste sulphuric acid |
CN102825058A (zh) * | 2012-09-05 | 2012-12-19 | 山东东佳集团股份有限公司 | 钛白粉酸性废水产生的硫酸钙废渣的循环利用方法 |
CN103058253A (zh) * | 2013-01-21 | 2013-04-24 | 菲徳勒环境生态工程(苏州)有限公司 | 一种利用钛白废水中游离硫酸制取石膏的方法 |
CN104086027A (zh) * | 2014-07-15 | 2014-10-08 | 铜陵化学工业集团有限公司 | 一种硫酸法钛白废水处理方法 |
CN110981056A (zh) * | 2019-12-05 | 2020-04-10 | 济南裕兴化工有限责任公司 | 一种硫酸法钛白水洗废水的处理方法 |
CN111362292A (zh) * | 2020-03-17 | 2020-07-03 | 中国科学院过程工程研究所 | 一种废硫酸生产低含水硫酸钙的连续化生产***与方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19812262A1 (de) * | 1998-03-20 | 1999-09-23 | Bayer Ag | Verfahren zur Aufarbeitung von Dünnsäure aus der TiO2-Herstellung |
JP2008143763A (ja) * | 2006-12-13 | 2008-06-26 | Toshibumi Kageyama | 二酸化チタンの製造の過程で生成する廃棄酸からの二酸化チタン、硫酸カルシウム及び酸化鉄の製造方法 |
CN106315910A (zh) * | 2015-07-06 | 2017-01-11 | 江苏金门能源装备有限公司 | 一种钛白废水的处理方法 |
CN109825711A (zh) * | 2019-03-14 | 2019-05-31 | 何耀 | 一种硫酸法钛白废酸资源化利用方法 |
-
2020
- 2020-11-20 WO PCT/CN2020/130588 patent/WO2022104737A1/zh active Application Filing
- 2020-11-20 JP JP2022550989A patent/JP2023509228A/ja active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5603839A (en) * | 1995-09-18 | 1997-02-18 | Cecebe Technologies Inc. | Process for the recovery of waste sulphuric acid |
CN102825058A (zh) * | 2012-09-05 | 2012-12-19 | 山东东佳集团股份有限公司 | 钛白粉酸性废水产生的硫酸钙废渣的循环利用方法 |
CN103058253A (zh) * | 2013-01-21 | 2013-04-24 | 菲徳勒环境生态工程(苏州)有限公司 | 一种利用钛白废水中游离硫酸制取石膏的方法 |
CN104086027A (zh) * | 2014-07-15 | 2014-10-08 | 铜陵化学工业集团有限公司 | 一种硫酸法钛白废水处理方法 |
CN110981056A (zh) * | 2019-12-05 | 2020-04-10 | 济南裕兴化工有限责任公司 | 一种硫酸法钛白水洗废水的处理方法 |
CN111362292A (zh) * | 2020-03-17 | 2020-07-03 | 中国科学院过程工程研究所 | 一种废硫酸生产低含水硫酸钙的连续化生产***与方法 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115417449A (zh) * | 2022-08-16 | 2022-12-02 | 宁波新福钛白粉有限公司 | 一种硫酸法钛白粉转窑尾气余热利用***及方法 |
CN115340165A (zh) * | 2022-08-17 | 2022-11-15 | 工大环境股份有限公司 | 一种煤化工废水丸粒pcr除硬耦合碳捕捉装置及方法 |
CN115385479A (zh) * | 2022-08-29 | 2022-11-25 | 工大环境股份有限公司 | 煤化工废水丸粒pcr除硬耦合碳捕捉多相反应装置及方法 |
CN116040687A (zh) * | 2022-11-01 | 2023-05-02 | 攀枝花末微环保科技有限公司 | 硫酸法钛白废酸的综合利用方法和硫酸法钛白生产工艺 |
CN116177779A (zh) * | 2022-12-09 | 2023-05-30 | 四川大学 | 钛白废水的回收利用方法 |
CN116177779B (zh) * | 2022-12-09 | 2024-04-19 | 四川大学 | 钛白废水的回收利用方法 |
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