WO2022104737A1 - Procédé de production pour recyclage total des ressources des eaux usées provenant de la production de dioxyde de titane par procédé à l'acide sulfurique - Google Patents

Procédé de production pour recyclage total des ressources des eaux usées provenant de la production de dioxyde de titane par procédé à l'acide sulfurique Download PDF

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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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PCT/CN2020/130588
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English (en)
Chinese (zh)
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龚家竹
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成都千砺金科技创新有限公司
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Priority to JP2022550989A priority Critical patent/JP2023509228A/ja
Priority to PCT/CN2020/130588 priority patent/WO2022104737A1/fr
Publication of WO2022104737A1 publication Critical patent/WO2022104737A1/fr
Priority to US17/891,236 priority patent/US20220402786A1/en

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    • 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

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  • 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

L'invention concerne un procédé de production permettant le recyclage complet des ressources des eaux usées provenant de la production de dioxyde de titane par procédé à l'acide sulfurique. Le procédé consiste à neutraliser les eaux usées provenant de la production de dioxyde de titane de procédé à l'acide sulfurique avec de la chaux, à séparer les eaux usées de la sulfate de chaux au moyen d'un filtre-presse (2), à ajouter une solution de carbonate de sodium provenant d'une tour de carbonisation aux eaux usées pour un traitement de précipitation du sulfate de calcium saturé dans les eaux usées, à clarifier et à séparer les boues pour obtenir un précipité de carbonate de calcium et une solution de sulfate de sodium, à soumettre la solution de sulfate de sodium diluée séparée à une séparation par membrane au moyen d'un filtre à membrane, à ajouter de la chaux à une solution de sulfate de sodium en phase concentrée résultant de la séparation par membrane pour une réaction de caustification, à obtenir une solution d'hydroxyde de sodium en tant que filtrat, à soumettre celle-ci à une carbonisation avec un gaz résiduel contenant du dioxyde de carbone généré pendant le processus de production de dioxyde de titane pour obtenir une solution de carbonate de sodium, puis à renvoyer la solution de carbonate de sodium à l'étape de précipitation du sulfate de calcium saturé dans le processus de traitement des eaux usées. Grâce au procédé, la difficulté technique de l'incapacité de recycler économiquement les eaux usées neutralisées avec de la chaux pendant la production de dioxyde de titane du procédé à l'acide sulfurique est résolue, les facteurs influençant le rejet externe des eaux usées neutralisées existantes sur un plan d'eau environnant sont éliminés, et une grande quantité de ressources en eau brute utilisées pour la production sont économisées.
PCT/CN2020/130588 2020-11-20 2020-11-20 Procédé de production pour recyclage total des ressources des eaux usées provenant de la production de dioxyde de titane par procédé à l'acide sulfurique WO2022104737A1 (fr)

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PCT/CN2020/130588 WO2022104737A1 (fr) 2020-11-20 2020-11-20 Procédé de production pour recyclage total des ressources des eaux usées provenant de la production de dioxyde de titane par procédé à l'acide sulfurique
US17/891,236 US20220402786A1 (en) 2020-11-20 2022-08-19 Production method for full resource recycling of sulphate-process titanium dioxide production wastewater

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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
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系统及方法
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