CN212559823U - Titanium white powder washing wastewater resource utilization processing system - Google Patents
Titanium white powder washing wastewater resource utilization processing system Download PDFInfo
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Abstract
The utility model provides a titanium white powder washing wastewater resource utilization processing system, titanium white powder washing wastewater is produced by titanium white powder washing in-process, including the waste water collecting tank, first heat transfer device, pretreatment systems, the system of receiving filtration, resin adsorption equipment, heat transfer system, reation kettle, first evaporation plant, crystallizer and the desicator that connect in order through the pipeline, the water outlet of receiving filtration system is linked together with reverse osmosis system's entry, reverse osmosis system's dense water outlet is linked together with membrane distillation plant's entry, membrane distillation plant's concentrate outlet is linked together with second evaporation plant's entry; the heat exchange system comprises a first heat exchange device and a second heat exchange device, the titanium dioxide washing wastewater recycling treatment system further comprises a filter pressing device, and the filter pressing device is communicated with a precipitation outlet of the pretreatment system. The utility model provides a system can the effective processing titanium white powder washing waste water, realizes the zero row utilization of waste water, and useless change is precious.
Description
Technical Field
The utility model belongs to coating waste water treatment field especially relates to a titanium white powder washing waste water resource utilization processing system.
Background
Titanium dioxide is widely used in the fields of manufacturing coatings, high-grade white paints, white rubber, synthetic fibers, welding electrodes, light reduction agents of rayon, fillers of plastics and high-grade paper and the like, and is also used in the industries of telecommunication equipment, metallurgy, printing and dyeing, enamel and the like.
The current common method for producing titanium dioxide is a sulfuric acid method. The main raw materials for producing titanium dioxide by a sulfuric acid method are titanium ore (ilmenite or acid-soluble titanium slag) and sulfuric acid, and the production process can be generally divided into ten major links: the method comprises the following steps of drying and crushing titanium ores, carrying out acidolysis on the titanium ores, purifying a titanium sulfate solution, crystallizing ferrous sulfate, hydrolyzing the titanium sulfate solution, washing and bleaching hydrated titanium dioxide, carrying out salt treatment, calcining and crushing, and carrying out surface treatment and crushing on titanium dioxide.
The waste acid discharged in the production process comes from a primary water washing procedure and a titanium dioxide hydrolysis process in the titanium sulfate solution purification process, the yield is 7-10t/t (titanium dioxide), the sulfuric acid content is 18-23%, and the FeSO4 content is about 80g/L (calculated by anhydrous FeSO 4). 20 percent of the total discharge amount of the waste acid can be directly returned to acidolysis acid preparation and used for adjusting the acidity coefficient of titanium liquid during leaching, and the rest waste acid can not be recycled. At present, most of domestic sulfuric acid process titanium dioxide factories supply the part of waste acid to nearby steel plants according to local conditions for pickling steel or supplying the waste acid to paper mills, dyeing mills and the like for treating alkaline waste water, but sometimes the problem cannot be solved due to small consumption, and the treatment methods of the part of waste acid mainly comprise the following steps:
1. waste acid concentration process
The waste acid concentration can adopt the methods of submerged combustion and vacuum concentration, the submerged combustion is to spray the high-temperature gas produced in the combustion chamber directly into the waste acid, so as to evaporate the water in the waste acid and play a role of concentrating the waste acid, because the concentration of sulfuric acid is improved, ferrous sulfate dissolved in the waste acid is separated out, but the concentration after the concentration of the method is not high, and the corrosion of equipment is very serious, the former Soviet Union uses the method to concentrate the waste acid to 55% for sale or for producing phosphate fertilizer, the vacuum evaporation concentration can respectively concentrate about 20% of the waste acid to 40%, 50%, 70% and even more than 90% according to the evaporation intensity and concentration grade. According to the method, in a multi-effect falling-film evaporator and a forced circulation concentrator, waste acid is concentrated to 70-80% by using steam as a heat source, a waste acid concentration pilot plant production device is established in Nanjing, Zhenjiang and the like in 80 s of the third design institute of the national department of chemical industry and the coating research of the ministry of the original chemical industry, the waste acid is settled and purified, then the waste acid is concentrated by a vacuum concentration method for more than 30%, then the waste acid is frozen at 0-5 ℃ to separate out ferric salt in the waste acid, meanwhile, the concentration of the waste acid can be increased to about 40%, and a second stage of concentration is added on the basis to increase the concentration of the waste acid to 40%, but the tube nest of the evaporator cannot be put into industrial production due to the fact that ferrous sulfate heptahydrate generated by dehydration of ferrous sulfate heptahydrate blocks the tube nest of the evaporator. The waste acid discharged in the titanium dioxide production is treated by adopting a concentration method and is popular in Europe and Japan, but waste acid concentration equipment is very expensive, energy consumption and operation cost are very high, and the cost of concentrated sulfuric acid is more expensive than that of purchased sulfuric acid, so that the factory in China is not in need of much liquid.
2. Waste acid neutralization production gypsum
The process of producing gypsum by using waste acid neutralization is to neutralize the waste acid with lime milk to pH =2.5, and then to filter to obtain low-iron gypsum, the quality of which is basically the same as that of natural gypsum, and the gypsum can be used as building material.
3. Production of iron series pigment by waste acid
The waste acid contains ferrous sulfate besides sulfuric acid. The waste acid is utilized to react with the waste iron sheet and the scrap iron to obtain a ferrous sulfate solution, and then the ferrous sulfate solution is used as a raw material to produce iron series pigments such as iron oxide black, iron oxide red and the like. The iron oxide black is prepared by heating ferrous sulfate solution and excessive soda ash with water vapor (95 deg.C), filtering, washing with water, oven drying, and pulverizing. The simplest method for producing the iron oxide red is to dry and dehydrate ferrous sulfate to generate FeSO4.H2O, then calcine the raw iron oxide red at 800 ℃ to generate crude iron oxide red, and obtain a finished product after crushing, drying and re-crushing, wherein the waste gas SO3 can be recycled for preparing sulfuric acid, and the calcination method has important calcination temperature, and has a hue with a yellow phase at a lower temperature and a hue with a blue phase at a higher temperature. However, the method has high energy consumption, and needs to add a large amount of soda ash to neutralize iron, thereby causing high operation cost.
4. Ammonium sulfate and ferrous ammonium sulfate fertilizer produced by ammonia neutralization
The method for producing fertilizer by ammonia neutralization is a method adopted by chemical company in Japan, and patent 97106429.6 also discloses a method similar to chemical company in Japan, which introduces the method that ferrous sulfate is added into waste acid, liquid ammonia is directly added into the mixed solution, and then the material is directly sprayed and dried to obtain ammonium sulfate and ferrous ammonium sulfate. In addition, a method for producing liquid ammonium sulfate by using waste acid is also provided, and a titanium dioxide production line of Zibo drilling company Limited successfully performs pilot test on the method. The method is that waste acid is neutralized by ammonia water in a neutralization tank, then enters a first-stage aeration tank, is stirred by a small amount of compressed air, so that sulfuric acid and ammonia are fully reacted, and Fe2+ is converted into Fe3+At this time, the water still contains a small amount of sulfuric acid and Fe2+Therefore, secondary neutralization, aeration and filtration are arranged, so that qualified ammonium sulfate solution is obtained. This method is also a simpler and more efficient method, requiring strict control of the neutralization pH, otherwise large amounts of precipitates of iron salts belonging to the hazardous waste range will be produced.
In summary, most of the currently used waste acid treatment methods are neutralization, lime, liquid caustic soda or ammonia water are added, but the wastewater or waste acid contains a large amount of acid and also contains high-concentration iron ion concentration, and the titanium dioxide production wastewater is treated in a neutralization manner, so that the consumed alkali amount is large, and a large amount of iron slag is generated. In addition, disposal discharge of the wastewater after neutralization can also be a problem.
SUMMERY OF THE UTILITY MODEL
The utility model aims to provide a simple, low energy consumption, low-cost titanium white powder washing waste water resource utilization processing system to exist not enough among the prior art.
Therefore, the utility model discloses a following technical scheme realizes:
the utility model provides a titanium white powder washing waste water utilization processing system, titanium white powder washing waste water is produced by titanium white powder washing in-process, its characterized in that: the titanium dioxide washing wastewater resource utilization treatment system comprises a wastewater collection tank, a first heat exchange device, a pretreatment system, a nanofiltration system, a resin adsorption device, a heat exchange system, a reaction kettle, a first evaporation device, a crystallizer and a dryer which are sequentially connected through pipelines, wherein a water production outlet of the nanofiltration system is communicated with an inlet of a reverse osmosis system, a concentrated water outlet of the reverse osmosis system is communicated with an inlet of a membrane distillation device, and a concentrated solution outlet of the membrane distillation device is communicated with an inlet of a second evaporation device; the heat exchange system comprises a first heat exchange device and a second heat exchange device, the effluent of the resin adsorption device enters a cooling water inlet of the first heat exchange device to reduce the temperature of the outlet wastewater of the wastewater collection tank, and simultaneously the effluent of the resin adsorption device is also improved; the titanium white powder washing wastewater resource utilization treatment system further comprises a filter pressing device, and the filter pressing device is communicated with a precipitation outlet of the pretreatment system.
When adopting above-mentioned technical scheme, the utility model discloses can also adopt or make up and adopt following technical scheme:
as the utility model discloses a preferred technical scheme: the pretreatment system is one or a combination of a sedimentation tank, a microfiltration device and an ultrafiltration device.
As the utility model discloses a preferred technical scheme: the nanofiltration system comprises a first-section nanofiltration device and a second-section nanofiltration device, wherein a nanofiltration adsorption device is further arranged on a connecting pipeline of the first-section nanofiltration device and the second-section nanofiltration device, a concentrated water outlet of the first-section nanofiltration device is communicated with an inlet of the nanofiltration adsorption device, a water outlet of the nanofiltration adsorption device is communicated with an inlet of the second-section nanofiltration device, a concentrated water outlet of the second-section nanofiltration device is communicated with an inlet of the resin adsorption device, and a water production outlet of the first-section nanofiltration device is communicated with an inlet of the reverse osmosis system; the nanofiltration adsorption device is internally provided with nanofiltration adsorption filler which is one or a combination of more of diatomite, activated carbon, zeolite and cellulose balls.
As the utility model discloses a preferred technical scheme: the resin adsorption device comprises a resin adsorption tank and a regeneration liquid tank, wherein the resin adsorption tank contains adsorption resin for adsorbing sulfuric acid, and the regeneration liquid tank is used for storing resin adsorption regeneration liquid.
As the utility model discloses a preferred technical scheme: and the inlet of the regeneration liquid tank is communicated with the water production outlet of the reverse osmosis system.
As the utility model discloses a preferred technical scheme: and a regenerated liquid outlet of the resin adsorption tank is communicated with an inlet of the nanofiltration system.
As the utility model discloses a preferred technical scheme: and a material feeding port and a catalyst feeding port are formed in the reaction kettle.
As the utility model discloses a preferred technical scheme: the first evaporation device is one or a combination of more of a membrane distillation evaporator, a mechanical vapor recompression technology evaporator or a multi-effect evaporator; the second evaporation device is one or the combination of two of a mechanical vapor recompression technology evaporator or a multi-effect evaporator.
As the utility model discloses a preferred technical scheme: the reverse osmosis system comprises a primary reverse osmosis device and a secondary reverse osmosis device, a reverse osmosis adsorption device is further arranged on a connecting pipeline of the primary reverse osmosis device and the secondary reverse osmosis device, a concentrated water outlet of the primary reverse osmosis device is communicated with an inlet of the membrane distillation device, a produced water outlet of the primary reverse osmosis device is communicated with an inlet of the reverse osmosis adsorption device, a water outlet of the reverse osmosis adsorption device is communicated with an inlet of the secondary reverse osmosis device, a concentrated water outlet of the secondary reverse osmosis device is communicated with an inlet of the primary reverse osmosis device, and a produced water outlet of the secondary reverse osmosis device is communicated with a regeneration liquid tank of the resin adsorption device; the reverse osmosis adsorption device is internally provided with reverse osmosis adsorption filler which is one or a combination of more of diatomite, activated carbon, zeolite and cellulose balls.
As the utility model discloses a preferred technical scheme: and the inlet of the reverse osmosis adsorption device is also communicated with the condensed water outlet of the first evaporation device.
The utility model provides a titanium white powder washing waste water utilization processing system can effective treatment titanium white powder washing waste water, realizes the zero-emission resource utilization of waste water, and useless change is precious. The acid in the wastewater is changed into high-concentration acid which can be returned to the front end of the process for acidolysis of titanium ore, the water in the wastewater reaches the standard of titanium dioxide washing water for titanium dioxide washing, the acid is used for titanium dioxide washing, the iron salt in the wastewater is changed into polymer product which can be sold as flocculant, and the titanium dioxide in the wastewater can be recovered. Compare traditional lime or add alkali neutralization system, through the utility model discloses can reduce the emission of the useless iron slag of per ton spent acid 0.95 kg at least, reduce the emission of 67 kg waste gypsum of per ton spent acid to and can reduce the emission of 900 kg waste water. Compare the evaporative concentration system, through the utility model discloses can be energy-conserving 50% at least, in addition, can not only effectively solve the problem that the evaporimeter blockked up, can produce the poly iron by-product again in order to gain the benefit.
Drawings
FIG. 1 is a schematic view of a titanium dioxide washing wastewater resource utilization treatment system provided by the utility model.
Detailed Description
The invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
A titanium dioxide washing wastewater resource utilization treatment system is characterized in that titanium dioxide washing wastewater is generated in the titanium dioxide washing process, the titanium dioxide washing wastewater resource utilization treatment system comprises a wastewater collection tank, a first heat exchange device, a pretreatment system, a nanofiltration system, a resin adsorption device, a heat exchange system, a reaction kettle, a first evaporation device, a crystallizer and a dryer which are sequentially connected through pipelines, a water production outlet of the nanofiltration system is communicated with an inlet of a reverse osmosis system, a concentrated water outlet of the reverse osmosis system is communicated with an inlet of a membrane distillation device, and a concentrated solution outlet of the membrane distillation device is communicated with an inlet of a second evaporation device; the heat exchange system comprises a first heat exchange device and a second heat exchange device, the effluent of the resin adsorption device enters a cooling water inlet of the first heat exchange device to reduce the temperature of the outlet wastewater of the wastewater collection tank, and simultaneously the effluent of the resin adsorption device is also improved; the titanium dioxide washing wastewater recycling treatment system further comprises a filter pressing device, the filter pressing device is communicated with a precipitation outlet of the pretreatment system, and the filter pressing device is a filter press.
In this embodiment: the pretreatment system is one or a combination of a sedimentation tank, a microfiltration device and an ultrafiltration device.
In this embodiment: the nanofiltration system comprises a first-section nanofiltration device and a second-section nanofiltration device, wherein a nanofiltration adsorption device is further arranged on a connecting pipeline of the first-section nanofiltration device and the second-section nanofiltration device, a concentrated water outlet of the first-section nanofiltration device is communicated with an inlet of the nanofiltration adsorption device, a water outlet of the nanofiltration adsorption device is communicated with an inlet of the second-section nanofiltration device, a concentrated water outlet of the second-section nanofiltration device is communicated with an inlet of the resin adsorption device, and a water production outlet of the first-section nanofiltration device is communicated with an inlet of the reverse osmosis system. The nanofiltration adsorption device is internally provided with nanofiltration adsorption filler which is one or a combination of more of diatomite, activated carbon, zeolite and cellulose balls.
In this embodiment: the resin adsorption device comprises a resin adsorption tank and a regeneration liquid tank, wherein the resin adsorption tank contains adsorption resin for adsorbing sulfuric acid, and the regeneration liquid tank is used for storing resin adsorption regeneration liquid.
In this embodiment: the inlet of the regeneration liquid tank is communicated with the water production outlet of the reverse osmosis system.
In this embodiment: the regenerated liquid outlet of the resin adsorption tank is communicated with the inlet of the nanofiltration system.
In this embodiment: a material feeding port and a catalyst feeding port are arranged on the reaction kettle.
In this embodiment: the first evaporation device is one or a combination of more of a membrane distillation evaporator, a mechanical vapor recompression technology evaporator or a multi-effect evaporator; the second evaporation device is one or the combination of two of a mechanical vapor recompression technology evaporator or a multi-effect evaporator.
In this embodiment: the reverse osmosis system comprises a first-stage reverse osmosis device and a second-stage reverse osmosis device, a reverse osmosis adsorption device is further arranged on a connecting pipeline of the first-stage reverse osmosis device and the second-stage reverse osmosis device, a concentrated water outlet of the first-stage reverse osmosis device is communicated with an inlet of the membrane distillation device, a produced water outlet of the first-stage reverse osmosis device is communicated with an inlet of the reverse osmosis adsorption device, a water outlet of the reverse osmosis adsorption device is communicated with an inlet of the second-stage reverse osmosis device, a concentrated water outlet of the second-stage reverse osmosis device is communicated to an inlet of the first-stage reverse osmosis device, and a produced water outlet of. The reverse osmosis adsorption device is internally provided with reverse osmosis adsorption filler which is one or a combination of more of diatomite, activated carbon, zeolite and cellulose balls.
In this embodiment: the inlet of the reverse osmosis adsorption device is also communicated with the condensed water outlet of the first evaporation device.
The above detailed description is provided for explaining the present invention, and is only a preferred embodiment of the present invention, but not for limiting the present invention, and any modifications, equivalent replacements, improvements, etc. made by the present invention are within the scope of the present invention.
Claims (10)
1. The utility model provides a titanium white powder washing waste water utilization processing system, titanium white powder washing waste water is produced by titanium white powder washing in-process, its characterized in that: the titanium dioxide washing wastewater resource utilization treatment system comprises a wastewater collection tank, a first heat exchange device, a pretreatment system, a nanofiltration system, a resin adsorption device, a heat exchange system, a reaction kettle, a first evaporation device, a crystallizer and a dryer which are sequentially connected through pipelines, wherein a water production outlet of the nanofiltration system is communicated with an inlet of a reverse osmosis system, a concentrated water outlet of the reverse osmosis system is communicated with an inlet of a membrane distillation device, and a concentrated solution outlet of the membrane distillation device is communicated with an inlet of a second evaporation device; the heat exchange system comprises a first heat exchange device and a second heat exchange device, the titanium dioxide washing wastewater recycling treatment system further comprises a filter pressing device, and the filter pressing device is communicated with a precipitation outlet of the pretreatment system.
2. The titanium dioxide washing wastewater resource utilization treatment system according to claim 1, characterized in that: the pretreatment system is one or a combination of a sedimentation tank, a microfiltration device and an ultrafiltration device.
3. The titanium dioxide washing wastewater resource utilization treatment system according to claim 1, characterized in that: the nanofiltration system comprises a first-section nanofiltration device and a second-section nanofiltration device, wherein a nanofiltration adsorption device is further arranged on a connecting pipeline of the first-section nanofiltration device and the second-section nanofiltration device, a concentrated water outlet of the first-section nanofiltration device is communicated with an inlet of the nanofiltration adsorption device, a water outlet of the nanofiltration adsorption device is communicated with an inlet of the second-section nanofiltration device, a concentrated water outlet of the second-section nanofiltration device is communicated with an inlet of the resin adsorption device, and a water production outlet of the first-section nanofiltration device is communicated with an inlet of the reverse osmosis system; the nanofiltration adsorption device is internally provided with nanofiltration adsorption filler which is one of diatomite, activated carbon, zeolite and cellulose balls.
4. The titanium dioxide washing wastewater resource utilization treatment system according to claim 1 or 3, characterized in that: the resin adsorption device comprises a resin adsorption tank and a regeneration liquid tank, wherein the resin adsorption tank contains adsorption resin for adsorbing sulfuric acid, and the regeneration liquid tank is used for storing resin adsorption regeneration liquid.
5. The titanium dioxide washing wastewater resource utilization treatment system according to claim 4, characterized in that: and the inlet of the regeneration liquid tank is communicated with the water production outlet of the reverse osmosis system.
6. The titanium dioxide washing wastewater resource utilization treatment system according to claim 4, characterized in that: and a regenerated liquid outlet of the resin adsorption tank is communicated with an inlet of the nanofiltration system.
7. The titanium dioxide washing wastewater resource utilization treatment system according to claim 1, characterized in that: and a material feeding port and a catalyst feeding port are formed in the reaction kettle.
8. The titanium dioxide washing wastewater resource utilization treatment system according to claim 1, characterized in that: the first evaporation device is one or a combination of more of a membrane distillation evaporator, a mechanical vapor recompression technology evaporator or a multi-effect evaporator; the second evaporation device is one or the combination of two of a mechanical vapor recompression technology evaporator or a multi-effect evaporator.
9. The titanium dioxide washing wastewater resource utilization treatment system according to claim 1, characterized in that: the reverse osmosis system comprises a primary reverse osmosis device and a secondary reverse osmosis device, a reverse osmosis adsorption device is further arranged on a connecting pipeline of the primary reverse osmosis device and the secondary reverse osmosis device, a concentrated water outlet of the primary reverse osmosis device is communicated with an inlet of the membrane distillation device, a produced water outlet of the primary reverse osmosis device is communicated with an inlet of the reverse osmosis adsorption device, a water outlet of the reverse osmosis adsorption device is communicated with an inlet of the secondary reverse osmosis device, a concentrated water outlet of the secondary reverse osmosis device is communicated with an inlet of the primary reverse osmosis device, and a produced water outlet of the secondary reverse osmosis device is communicated with a regeneration liquid tank of the resin adsorption device; the reverse osmosis adsorption device is internally provided with a reverse osmosis adsorption filler which is one of diatomite, activated carbon, zeolite and cellulose balls.
10. The titanium dioxide washing wastewater resource utilization treatment system of claim 9, characterized in that: and the inlet of the reverse osmosis adsorption device is also communicated with the condensed water outlet of the first evaporation device.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939093A (en) * | 2021-03-31 | 2021-06-11 | 江苏镇钛化工有限公司 | A spent acid integrated processing device for titanium white powder production |
| CN113754121A (en) * | 2021-09-16 | 2021-12-07 | 中国恩菲工程技术有限公司 | System and method for treating hydrofluoric acid-containing wastewater |
-
2020
- 2020-04-30 CN CN202020718889.8U patent/CN212559823U/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939093A (en) * | 2021-03-31 | 2021-06-11 | 江苏镇钛化工有限公司 | A spent acid integrated processing device for titanium white powder production |
| CN112939093B (en) * | 2021-03-31 | 2024-05-24 | 江苏镇钛化工有限公司 | Comprehensive waste acid treatment device for titanium dioxide production |
| CN113754121A (en) * | 2021-09-16 | 2021-12-07 | 中国恩菲工程技术有限公司 | System and method for treating hydrofluoric acid-containing wastewater |
| CN113754121B (en) * | 2021-09-16 | 2022-11-15 | 中国恩菲工程技术有限公司 | System and method for treating hydrofluoric acid-containing wastewater |
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